EP0414581B1 - Bei niedrigen Temperaturen wirksame Bleichmittelzusammensetzungen für Textilien - Google Patents
Bei niedrigen Temperaturen wirksame Bleichmittelzusammensetzungen für Textilien Download PDFInfo
- Publication number
- EP0414581B1 EP0414581B1 EP90401635A EP90401635A EP0414581B1 EP 0414581 B1 EP0414581 B1 EP 0414581B1 EP 90401635 A EP90401635 A EP 90401635A EP 90401635 A EP90401635 A EP 90401635A EP 0414581 B1 EP0414581 B1 EP 0414581B1
- Authority
- EP
- European Patent Office
- Prior art keywords
- bleaching
- catalytic
- complexes
- compositions
- complex
- 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.)
- Expired - Lifetime
Links
- 239000000203 mixture Substances 0.000 title claims abstract description 80
- 238000004061 bleaching Methods 0.000 title claims abstract description 47
- 239000004753 textile Substances 0.000 title claims abstract description 5
- 239000003599 detergent Substances 0.000 claims abstract description 37
- 238000005406 washing Methods 0.000 claims abstract description 28
- 229910052751 metal Inorganic materials 0.000 claims abstract description 26
- 239000002184 metal Substances 0.000 claims abstract description 26
- 239000003054 catalyst Substances 0.000 claims abstract description 23
- -1 peroxide compounds Chemical class 0.000 claims abstract description 12
- 150000002978 peroxides Chemical group 0.000 claims abstract description 12
- 239000002243 precursor Substances 0.000 claims abstract description 10
- 150000002739 metals Chemical class 0.000 claims abstract description 5
- 150000003839 salts Chemical class 0.000 claims description 24
- 230000003197 catalytic effect Effects 0.000 claims description 21
- 150000001768 cations Chemical class 0.000 claims description 18
- 239000003945 anionic surfactant Substances 0.000 claims description 15
- 239000000470 constituent Substances 0.000 claims description 15
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- 239000002736 nonionic surfactant Substances 0.000 claims description 14
- 239000010457 zeolite Substances 0.000 claims description 13
- 125000004432 carbon atom Chemical group C* 0.000 claims description 9
- 125000000129 anionic group Chemical group 0.000 claims description 7
- 239000007844 bleaching agent Substances 0.000 claims description 7
- 150000004985 diamines Chemical class 0.000 claims description 6
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 claims description 5
- 229910000323 aluminium silicate Inorganic materials 0.000 claims description 5
- 229910052802 copper Inorganic materials 0.000 claims description 5
- 239000010949 copper Substances 0.000 claims description 5
- 150000002191 fatty alcohols Chemical class 0.000 claims description 5
- 239000003446 ligand Substances 0.000 claims description 5
- PWHULOQIROXLJO-UHFFFAOYSA-N Manganese Chemical compound [Mn] PWHULOQIROXLJO-UHFFFAOYSA-N 0.000 claims description 4
- 229920000388 Polyphosphate Polymers 0.000 claims description 4
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- 125000002947 alkylene group Chemical group 0.000 claims description 4
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- 230000015572 biosynthetic process Effects 0.000 claims 1
- 230000000694 effects Effects 0.000 abstract description 7
- 238000000354 decomposition reaction Methods 0.000 abstract description 5
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- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 description 7
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- YGUMVDWOQQJBGA-VAWYXSNFSA-N 5-[(4-anilino-6-morpholin-4-yl-1,3,5-triazin-2-yl)amino]-2-[(e)-2-[4-[(4-anilino-6-morpholin-4-yl-1,3,5-triazin-2-yl)amino]-2-sulfophenyl]ethenyl]benzenesulfonic acid Chemical compound C=1C=C(\C=C\C=2C(=CC(NC=3N=C(N=C(NC=4C=CC=CC=4)N=3)N3CCOCC3)=CC=2)S(O)(=O)=O)C(S(=O)(=O)O)=CC=1NC(N=C(N=1)N2CCOCC2)=NC=1NC1=CC=CC=C1 YGUMVDWOQQJBGA-VAWYXSNFSA-N 0.000 description 4
- 239000000654 additive Substances 0.000 description 4
- 125000000217 alkyl group Chemical group 0.000 description 4
- ORTQZVOHEJQUHG-UHFFFAOYSA-L copper(II) chloride Chemical compound Cl[Cu]Cl ORTQZVOHEJQUHG-UHFFFAOYSA-L 0.000 description 4
- 235000014113 dietary fatty acids Nutrition 0.000 description 4
- 239000000194 fatty acid Substances 0.000 description 4
- 229930195729 fatty acid Natural products 0.000 description 4
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- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 4
- 229910001868 water Inorganic materials 0.000 description 4
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- RPNUMPOLZDHAAY-UHFFFAOYSA-N Diethylenetriamine Chemical compound NCCNCCN RPNUMPOLZDHAAY-UHFFFAOYSA-N 0.000 description 3
- 229920002125 Sokalan® Polymers 0.000 description 3
- 239000002253 acid Substances 0.000 description 3
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- 235000019832 sodium triphosphate Nutrition 0.000 description 3
- 239000000243 solution Substances 0.000 description 3
- 241000894007 species Species 0.000 description 3
- 150000003467 sulfuric acid derivatives Chemical class 0.000 description 3
- 239000003760 tallow Substances 0.000 description 3
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 description 2
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 description 2
- 239000004721 Polyphenylene oxide Substances 0.000 description 2
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 description 2
- PMZURENOXWZQFD-UHFFFAOYSA-L Sodium Sulfate Chemical compound [Na+].[Na+].[O-]S([O-])(=O)=O PMZURENOXWZQFD-UHFFFAOYSA-L 0.000 description 2
- 102000005158 Subtilisins Human genes 0.000 description 2
- 108010056079 Subtilisins Proteins 0.000 description 2
- 239000002280 amphoteric surfactant Substances 0.000 description 2
- 238000006555 catalytic reaction Methods 0.000 description 2
- 239000003093 cationic surfactant Substances 0.000 description 2
- 229910052681 coesite Inorganic materials 0.000 description 2
- 229910052906 cristobalite Inorganic materials 0.000 description 2
- 229960003280 cupric chloride Drugs 0.000 description 2
- HNPSIPDUKPIQMN-UHFFFAOYSA-N dioxosilane;oxo(oxoalumanyloxy)alumane Chemical class O=[Si]=O.O=[Al]O[Al]=O HNPSIPDUKPIQMN-UHFFFAOYSA-N 0.000 description 2
- 229940071106 ethylenediaminetetraacetate Drugs 0.000 description 2
- 159000000011 group IA salts Chemical class 0.000 description 2
- 229910001385 heavy metal Inorganic materials 0.000 description 2
- AMWRITDGCCNYAT-UHFFFAOYSA-L hydroxy(oxo)manganese;manganese Chemical compound [Mn].O[Mn]=O.O[Mn]=O AMWRITDGCCNYAT-UHFFFAOYSA-L 0.000 description 2
- 238000010348 incorporation Methods 0.000 description 2
- 230000002401 inhibitory effect Effects 0.000 description 2
- 150000002500 ions Chemical class 0.000 description 2
- 239000000463 material Substances 0.000 description 2
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- MGFYIUFZLHCRTH-UHFFFAOYSA-N nitrilotriacetic acid Chemical compound OC(=O)CN(CC(O)=O)CC(O)=O MGFYIUFZLHCRTH-UHFFFAOYSA-N 0.000 description 2
- 230000003287 optical effect Effects 0.000 description 2
- 230000003647 oxidation Effects 0.000 description 2
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- 229920006395 saturated elastomer Polymers 0.000 description 2
- 239000000377 silicon dioxide Substances 0.000 description 2
- 229910052682 stishovite Inorganic materials 0.000 description 2
- 150000003871 sulfonates Chemical class 0.000 description 2
- 230000009466 transformation Effects 0.000 description 2
- 229910052905 tridymite Inorganic materials 0.000 description 2
- XFNJVJPLKCPIBV-UHFFFAOYSA-N trimethylenediamine Chemical compound NCCCN XFNJVJPLKCPIBV-UHFFFAOYSA-N 0.000 description 2
- UNXRWKVEANCORM-UHFFFAOYSA-I triphosphate(5-) Chemical compound [O-]P([O-])(=O)OP([O-])(=O)OP([O-])([O-])=O UNXRWKVEANCORM-UHFFFAOYSA-I 0.000 description 2
- ZMLPKJYZRQZLDA-UHFFFAOYSA-N 1-(2-phenylethenyl)-4-[4-(2-phenylethenyl)phenyl]benzene Chemical group C=1C=CC=CC=1C=CC(C=C1)=CC=C1C(C=C1)=CC=C1C=CC1=CC=CC=C1 ZMLPKJYZRQZLDA-UHFFFAOYSA-N 0.000 description 1
- SLICILBTKABSTQ-UHFFFAOYSA-N 2,3,9,10-tetramethyl-1,4,8,11-tetrazacyclotetradeca-1,3,8,10-tetraene Chemical compound CC1=NCCCN=C(C)C(C)=NCCCN=C1C SLICILBTKABSTQ-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
- NIXOWILDQLNWCW-UHFFFAOYSA-N 2-Propenoic acid Natural products OC(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 description 1
- XSVSPKKXQGNHMD-UHFFFAOYSA-N 5-bromo-3-methyl-1,2-thiazole Chemical compound CC=1C=C(Br)SN=1 XSVSPKKXQGNHMD-UHFFFAOYSA-N 0.000 description 1
- 241000251468 Actinopterygii Species 0.000 description 1
- BVKZGUZCCUSVTD-UHFFFAOYSA-L Carbonate Chemical compound [O-]C([O-])=O BVKZGUZCCUSVTD-UHFFFAOYSA-L 0.000 description 1
- 244000060011 Cocos nucifera Species 0.000 description 1
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- 229940120146 EDTMP Drugs 0.000 description 1
- 102000004190 Enzymes Human genes 0.000 description 1
- 108090000790 Enzymes Proteins 0.000 description 1
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 description 1
- IAYPIBMASNFSPL-UHFFFAOYSA-N Ethylene oxide Chemical compound C1CO1 IAYPIBMASNFSPL-UHFFFAOYSA-N 0.000 description 1
- WAEMQWOKJMHJLA-UHFFFAOYSA-N Manganese(2+) Chemical compound [Mn+2] WAEMQWOKJMHJLA-UHFFFAOYSA-N 0.000 description 1
- CERQOIWHTDAKMF-UHFFFAOYSA-N Methacrylic acid Chemical compound CC(=C)C(O)=O CERQOIWHTDAKMF-UHFFFAOYSA-N 0.000 description 1
- BPQQTUXANYXVAA-UHFFFAOYSA-N Orthosilicate Chemical compound [O-][Si]([O-])([O-])[O-] BPQQTUXANYXVAA-UHFFFAOYSA-N 0.000 description 1
- 235000019482 Palm oil Nutrition 0.000 description 1
- ABLZXFCXXLZCGV-UHFFFAOYSA-N Phosphorous acid Chemical group OP(O)=O ABLZXFCXXLZCGV-UHFFFAOYSA-N 0.000 description 1
- ZLMJMSJWJFRBEC-UHFFFAOYSA-N Potassium Chemical compound [K] ZLMJMSJWJFRBEC-UHFFFAOYSA-N 0.000 description 1
- OFOBLEOULBTSOW-UHFFFAOYSA-N Propanedioic acid Natural products OC(=O)CC(O)=O OFOBLEOULBTSOW-UHFFFAOYSA-N 0.000 description 1
- BLRPTPMANUNPDV-UHFFFAOYSA-N Silane Chemical compound [SiH4] BLRPTPMANUNPDV-UHFFFAOYSA-N 0.000 description 1
- 239000004115 Sodium Silicate Substances 0.000 description 1
- QAOWNCQODCNURD-UHFFFAOYSA-L Sulfate Chemical compound [O-]S([O-])(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-L 0.000 description 1
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- 230000009471 action Effects 0.000 description 1
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- BVKZGUZCCUSVTD-UHFFFAOYSA-N carbonic acid Chemical class OC(O)=O BVKZGUZCCUSVTD-UHFFFAOYSA-N 0.000 description 1
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- NFDRPXJGHKJRLJ-UHFFFAOYSA-N edtmp Chemical compound OP(O)(=O)CN(CP(O)(O)=O)CCN(CP(O)(O)=O)CP(O)(O)=O NFDRPXJGHKJRLJ-UHFFFAOYSA-N 0.000 description 1
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- UPBDXRPQPOWRKR-UHFFFAOYSA-N furan-2,5-dione;methoxyethene Chemical compound COC=C.O=C1OC(=O)C=C1 UPBDXRPQPOWRKR-UHFFFAOYSA-N 0.000 description 1
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- VZCYOOQTPOCHFL-UPHRSURJSA-N maleic acid Chemical compound OC(=O)\C=C/C(O)=O VZCYOOQTPOCHFL-UPHRSURJSA-N 0.000 description 1
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- XJRBAMWJDBPFIM-UHFFFAOYSA-N methyl vinyl ether Chemical compound COC=C XJRBAMWJDBPFIM-UHFFFAOYSA-N 0.000 description 1
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- 239000000178 monomer Substances 0.000 description 1
- 230000007935 neutral effect Effects 0.000 description 1
- 150000002825 nitriles Chemical class 0.000 description 1
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- 239000002540 palm oil Substances 0.000 description 1
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- JRKICGRDRMAZLK-UHFFFAOYSA-L persulfate group Chemical group S(=O)(=O)([O-])OOS(=O)(=O)[O-] JRKICGRDRMAZLK-UHFFFAOYSA-L 0.000 description 1
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- AOHJOMMDDJHIJH-UHFFFAOYSA-N propylenediamine Chemical compound CC(N)CN AOHJOMMDDJHIJH-UHFFFAOYSA-N 0.000 description 1
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- DZCAZXAJPZCSCU-UHFFFAOYSA-K sodium nitrilotriacetate Chemical compound [Na+].[Na+].[Na+].[O-]C(=O)CN(CC([O-])=O)CC([O-])=O DZCAZXAJPZCSCU-UHFFFAOYSA-K 0.000 description 1
- 229960001922 sodium perborate Drugs 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
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- 235000011152 sodium sulphate Nutrition 0.000 description 1
- MZSDGDXXBZSFTG-UHFFFAOYSA-M sodium;benzenesulfonate Chemical compound [Na+].[O-]S(=O)(=O)C1=CC=CC=C1 MZSDGDXXBZSFTG-UHFFFAOYSA-M 0.000 description 1
- NASFKTWZWDYFER-UHFFFAOYSA-N sodium;hydrate Chemical compound O.[Na] NASFKTWZWDYFER-UHFFFAOYSA-N 0.000 description 1
- YKLJGMBLPUQQOI-UHFFFAOYSA-M sodium;oxidooxy(oxo)borane Chemical compound [Na+].[O-]OB=O YKLJGMBLPUQQOI-UHFFFAOYSA-M 0.000 description 1
- 239000007921 spray Substances 0.000 description 1
- 229910001220 stainless steel Inorganic materials 0.000 description 1
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- DIORMHZUUKOISG-UHFFFAOYSA-N sulfoformic acid Chemical compound OC(=O)S(O)(=O)=O DIORMHZUUKOISG-UHFFFAOYSA-N 0.000 description 1
- 239000013589 supplement Substances 0.000 description 1
- 235000013616 tea Nutrition 0.000 description 1
- 150000003510 tertiary aliphatic amines Chemical class 0.000 description 1
- 150000004685 tetrahydrates Chemical class 0.000 description 1
- VZCYOOQTPOCHFL-UHFFFAOYSA-N trans-butenedioic acid Natural products OC(=O)C=CC(O)=O VZCYOOQTPOCHFL-UHFFFAOYSA-N 0.000 description 1
- 239000001993 wax Substances 0.000 description 1
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Images
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
- C11D3/39—Organic or inorganic per-compounds
- C11D3/3902—Organic or inorganic per-compounds combined with specific additives
- C11D3/3905—Bleach activators or bleach catalysts
- C11D3/3932—Inorganic compounds or complexes
Definitions
- the present invention relates to detergent compositions having a bleaching effect on textiles, suitable for containing a bleaching system based on peroxide compounds and divalent metal complexes with atomic number between 25 and 29 (or their precursors), which have, under washing conditions, a positive net charge and act as catalysts for the decomposition of peroxides, increasing the bleaching efficiency of detergent compositions at low temperatures.
- peroxide compounds in compositions for washing clothes and other compositions intended for domestic or industrial use has been known for a long time, these compounds being particularly useful for removing stains having a significant content of colored materials, such as stains from coffee, tea, fruit, wine and cosmetics.
- peroxides such as hydrogen peroxide, mineral persalts such as perborates, percarbonates, persulfates, perphosphates and the like, and organic percarboxylic acids.
- Another solution described for improving the behavior of detergents with peroxidized bleaching agents consists in incorporating into the formulation of small quantities of metal cations in the form of coordination complexes, so that the intrinsic capacity of the metal cations to decompose the peroxides remains controlled, which makes it possible to obtain a beneficial effect on the efficiency of the bleaching of the peroxides, as described, for example, British patent n ° 984,459, the US patents n 3 3 156 654 and n 3 352 634, the application EP Patent No. 0 272 030 and DE-An Patent Application No. 30 02 271.
- Said complexes do not act by regulating the amount of free metal so that the latter is that which effectively catalyzes the decomposition; instead, it is the complexes themselves, or the complex species which they produce in solution, which catalyze this decomposition on the substrates to be bleached, so that a bleaching efficiency can be obtained at low temperatures. higher than that obtained with a catalysis by free metal.
- the problem of making reactive additives compatible in finished formulations is not limited to ensuring the stability of the formulations; it is also a question of obtaining the stability of the various constituents in the washing bath, where they are in much more intimate contact because they are dissolved there.
- the object of the present invention is thus to produce a stable detergent and bleaching composition which contains a bleaching system consisting of a peroxidized compound and a soluble salt of a divalent heavy metal cation with atomic number between 25 and 29 and a sequestering agent capable of forming, with the metal salt, in the washing bath, a catalytic complex comprising a positive residual charge, and which is capable of providing maximum bleaching efficiency in hard water and at low temperatures.
- the metal cation salt and the sequestering agent can be incorporated into the detergent and bleaching compositions as such or in the form of the preformed complex.
- detergent compositions which contain a bleaching system based on a peroxide compound and a catalytic metal complex or its precursors, according to what has been described in the above paragraph, and which are suitable for enhancing the efficiency of the bleaching system in the washing operation.
- anionic surfactants which are another of the key ingredients in the majority of detergent formulations, can also impede the catalytic activity of the bleaching catalysts described above.
- the content of alkaline earth cations in the washing bath which is usually designated by the term "hardness” also has a negative influence on the catalytic bleaching activity. This fact worsens because of the impossibility of adding large quantities of powerful sequestering agents to the detergent compositions in question, because said sequestering agents destroy the catalytic complexes by competing with the ligands of which they are made up.
- Zeolites contain zeolites, replacing mineral phosphates, as detergency builders. Zeolites have a good detergency builder power without having a sequestering power which would allow them to compete with the ligands of the catalytic complex, inactivating the latter.
- zeolites have the additional beneficial effect, when used to absorb the bleaching catalyst on themselves, thereby incorporating it into detergent compositions.
- Said additional beneficial effect consists in a reduction in the rate of decomposition of the bleaching peroxides, so that one takes advantage of their bleaching power in a more effective manner.
- zeolites as a support for bleaching catalysts of the type of salts of free metal cations is described in European patent applications Nos . 224 952 and 224 953, where compositions containing manganese (+2) absorbed on are described. zeolites, so that the oxidation of manganese to manganese oxide is avoided, which can cause stains on fabrics, by further improving the storage stability of the bleaching compositions which contain said system.
- compositions described in the present invention said drawbacks are not encountered, since the metal catalysts used do not undergo transformation by oxidation into species capable of causing stains on the washed fabrics.
- compositions in question can contain any type of cationic, amphoteric, zwitterionic, nonionic and anionic surfactants.
- anionic surfactants have a negative effect on catalysis, as indicated above.
- strong sequestering agents can only be included in detergent compositions which contain bleaching catalysts in very small quantities, less than 0.2% by weight of the composition, since they enter in competition with the ligands which form the catalytic complex, inhibiting the activity of the latter.
- compositions according to the invention may contain, in addition, constituents such as surfactants from other categories, foaming regulators, bleaching activators of the peroxide precursor type, polymers which inhibit encrustation and redeposition, structuring and / or alkaline salts, optical brighteners, photoactivators, tinting agents, colorants, perfumes and, in general, any type of additive that is commonly used in detergents.
- constituents such as surfactants from other categories, foaming regulators, bleaching activators of the peroxide precursor type, polymers which inhibit encrustation and redeposition, structuring and / or alkaline salts, optical brighteners, photoactivators, tinting agents, colorants, perfumes and, in general, any type of additive that is commonly used in detergents.
- the bleaching catalysts suitable for practicing the present invention are those formed from the salts of divalent metal cations having an atomic number between 25 and 29 with sequestering agents which form with said cations complexes which, at the usual alkaline pH in the washing, have a positive residual charge and have free coordination positions, or may undergo transformation, in the washing bath, into species which have said free coordination positions.
- Said catalysts can be incorporated into the formulations which are the subject of the present invention, either in the form of the preformed complexes, or in the form of the precursors of the said complexes, in which case the latter are formed when the compositions are placed in aqueous solution.
- precursors of catalytic complexes should be understood to mean the salts of divalent cations with atomic number between 25 and 29 and the sequestering agents which form with said salts the complexes described in the above paragraph.
- these complexes are those formed by the salts of divalent metals with atomic number between 25 and 29 with diamines in which the nitrogen atoms are separated by a chain of at most five atoms, these diamines may or may not be substituted substituted, the substituents possibly comprising functional groups by means of which the diamines may or may not establish additional attachment points with the divalent metal with which they form the complexes.
- these complexes are those formed by divalent copper or divalent manganese with polyamines such as ethylenediamine, diethylenetriamine, 1,3-propylenediamine, 1,2-propylenediamine and 1,2-cyclohexylenediamine.
- Additional examples are the complexes formed by macrocyclic compounds such as 1,4,8,11-tetraaza-2,3,9,10-tetramethylcyclotetradeca-1,3,8,10-tetraene and the salts of divalent copper and divalent manganese.
- the peroxidized bleaching agents suitable for practicing the present invention are mineral persalts, both those which are real persalts and those which are compounds of addition of mineral salts and of hydrogen peroxide.
- Examples of this type of bleach are alkaline perborates, such as sodium perborate, mono- or tetrahydrate, and alkaline percarbonates.
- the mineral phosphates mentioned in the description include orthophosphates, pyrophosphates and polyphosphates of alkali metals, and in particular sodium and potassium tripolyphosphates in their different degrees of hydration.
- alkaline aluminosilicates ion exchangers or zeolites it is possible to use both the crystallines and the amorphous ones or that amorphous / crystalline mixtures, both of natural origin and of synthetic origin.
- zeolites of formula (Na20) P ,,, (AI203) y, (SiO2) ,, WH20, in which x is equal to 1, y has a value of 0.6 to 1 , 3 and is preferably about 1, za a value from 1 to 4 and preferably from 2 to 3 or about 2, and wa a value from 0 to 9 and preferably from 2.5 to 6.
- the aluminosilicates of this type are commercially available products and are usually called zeolites A and X or their mixtures.
- the surfactant system includes different types of compounds.
- synthetic anionic surfactants those suitable for use in the present invention including the soluble salts of alkylbenzenesulfonates, alkylsulfates, alkyl (polyether) sulfates, a-olefinesulfonates, paraffin sulfonates, alkylglyceryl ether sulfonates, a-sulfocarboxylates and their esters, sulfates and sulfonates of fatty acid monoglycerides, alkylphenol (polyether) sulfates and the like.
- alkali metal alkylbenzenesulfonates are preferred, the alkyl chain of which is essentially linear and contains a number of carbon atoms between 10 and 14.
- surfactants used are nonionic surfactants, among which can be used those of the polyoxyalkylenated fatty alcohol type with a number of moles of alkylene oxide per mole of fatty alcohol of between 2 and 20, and preferably between 3 and 15, and said fatty alcohols having straight or partially branched chains having a number of carbon atoms between 8 and 22.
- nonionic surfactants are the products of the oxyethylenation of lauryl alcohol and the products of l oxyethylenation of synthetic alcohols found on the market under brands such as Dobanol R , Synperonic R , Lutensol R or LiaI R.
- nonionic surfactants are reaction products of alkylene oxides with alkylphenols in which the alkyl radical contains a number of carbon atoms between 7 and 11, so that the number of moles of oxide d alkylene per mole of alkylphenol is between 3 and 20, and preferably between 5 and 12.
- soaps of fatty acids saturated or unsaturated, comprising a number of carbon atoms between 8 and 24.
- alkaline salts of fatty acids mainly saturated, which preferably contain between 10 and 20 carbon atoms
- alkali salts of mixtures of fatty acids derived from tallow and coconut and palm oils being particularly preferred.
- Aminopolycarboxylic acids or their salts such as ethylenediaminetetraacetic or nitrilotriacetic acid, and the like, are suitable for use as potent sequestering agents.
- Organic phosphonic acids or their salts and hydroxycarboxylates or their salts are also suitable.
- proteolytic or amylolytic enzymes such as those found on the market under the brands Maxatase R and Alcalase R.
- Cationic surfactants of the quaternary ammonium salt type in which at least one or two of the alkyl radicals are linear or partially branched C s -C is carbon chains, can also be incorporated.
- amphoteric surfactants which can also be used, are the water-soluble derivatives of secondary and tertiary aliphatic amines in which the aliphatic radical may comprise a straight or branched chain, and, among the water-soluble derivatives, one of the substituents contains from 8 to 18 carbon atoms and another consists of an anionic group such as, for example, a carboxy, sulfonate, phosphate or phosphonate group.
- surfactants known as surfactants with hybrid or zwitterionic ions such as the water-soluble derivatives of cationic aliphatic compounds with the quaternary ammonium, phosphoric and sulphonic groups, in which the radicals can comprise a linear or branched chain and in which one aliphatic substituents contains 8 to 18 carbon atoms and another contains an anionic group which is soluble in water.
- Substances that help prevent redeposition of soiling on fabrics during the washing process can also be added.
- Examples are cellulose derivatives like its carboxyalkylated or hydroxyalkylated compounds.
- compositions of the present invention is the structuring salts, among which there are a large number of mineral salts which are neutral to hydrolysis and which have a high solubility in water.
- structuring salts among which there are a large number of mineral salts which are neutral to hydrolysis and which have a high solubility in water.
- Alkalizing agents suitable for these compositions are the alkali metal salts derived from carbonic, orthosilicic, metasilicic acids and the like.
- Anionic fluorescent brighteners also known as optical brighteners, can also be used.
- these type of products those which are most suitable are the water-soluble sulfonated derivatives of stilbenes and the water-soluble sulfonated derivatives of distyrylbiphenyl.
- these products sold by Ciba-Geigy, among which we can cite those of the brands Tinopal R 5BMS, Tinopal R DMS, Tinopal R LMS-X and Tinopal R CBS-X.
- Said polymers are the water-soluble salts of polycarboxylic homo- or copolymers having a configuration such that the carboxylic radicals are separated from one another by one or two carbon atoms.
- Products of this type are homo or copolymers of monomer units such as, for example, maleic anhydride, maleic acid, methylvinyl ether, acrylic acid, methacrylic acid, and the like. These products are found on the market under names such as Sokalan R , Gantrez R , Primal R and the like.
- foam regulators other than soaps or nonionic surfactants having a high degree of oxyethylenation, such as, for example, waxes, saturated hydrocarbons, esters of phosphoric acid and silicones.
- silicones such as combinations of dialkylpolysiloxanes with finely divided silica and silane silicas or, alternatively, copolymers of dialkylpolysiloxanes with glycol or ethylene oxide radicals.
- Said special silicones are marketed by the firm Dow Corning under the references Q2-3092, DB-100, DC-190, DC-193, DC-198. Said silicones can be used as presented by the supplier, or else protected by granulation and coating with inert materials to avoid their interaction with the constituents of the detergent composition.
- compositions according to the invention are indicated and the reflectance results of EMPA-114 fabrics of 10 ⁇ 10 cm washed with said compositions bleaching detergents.
- EMPA-114 corresponds to standard cotton fabrics stained with red wine according to the standards of the Eidgenôssiche Materialierithese of Switzerland.
- Detergent compositions are prepared according to the following formulations:
- Examples 1 to 7 correspond to compositions according to what is described in the present invention and, for this reason, all these compositions provide a high bleaching efficiency in washing EMPA-114 stains, which leads to reflectance values high.
- Example 8 corresponds to a detergent composition which does not fulfill the conditions of the present invention.
- Example 9 corresponds to reference compositions and contains only perborate and a catalyst in the absence of any other constituent, and offers the same concentration of perborate in the bath. as the compositions of Examples 1 to 8.
- compositions of Examples 1 to 9 are studied by washing with them standard stains by means of the washing process described below.
- a dose of 210 grams of the detergent composition to be studied is introduced into the detergent compartment of a Zanussi 630 stainless steel washing machine and a washing cycle is programmed at a temperature of 30 ° C for 70 minutes, after which rinse cycles, which last a total of 40 minutes.
- the fabrics are removed from the washing machine and dried at room temperature.
- the reflectance measurements are made in an Ultrascan device from the company Hunterlab, with a halogen lamp of the JCR type of 9.5 V and 55 W, with a light of the D65 / 10 ° type, inclusion of brightness and of a filter. ultraviolet.
- Examples 1 to 7 which correspond to detergent bleaching compositions which meet the conditions described in the present invention, provide reflectances of the washed fabrics higher than those which is obtained by washing with a composition which contains only perborate and a catalyst (Example 9).
- the composition of Example 8 which does not meet the conditions of the present invention, provides an even lower reflectance than that obtained with the reference composition of Example 9.
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- Chemical & Material Sciences (AREA)
- Inorganic Chemistry (AREA)
- Life Sciences & Earth Sciences (AREA)
- Engineering & Computer Science (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Oil, Petroleum & Natural Gas (AREA)
- Wood Science & Technology (AREA)
- Organic Chemistry (AREA)
- Detergent Compositions (AREA)
Claims (8)
Applications Claiming Priority (2)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
ES8902082A ES2016465A6 (es) | 1989-06-14 | 1989-06-14 | Composiciones detergentes y blanqueantes para el lavado de textiles eficaces en aguas duras y a bajas temperaturas, y utilizacion de las mismas. |
ES8902082 | 1989-06-14 |
Publications (3)
Publication Number | Publication Date |
---|---|
EP0414581A1 EP0414581A1 (de) | 1991-02-27 |
EP0414581B1 true EP0414581B1 (de) | 1995-09-20 |
EP0414581B2 EP0414581B2 (de) | 2003-10-15 |
Family
ID=8262530
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
EP90401635A Expired - Lifetime EP0414581B2 (de) | 1989-06-14 | 1990-06-13 | Bei niedrigen Temperaturen wirksame Bleichmittelzusammensetzungen für Textilien |
Country Status (4)
Country | Link |
---|---|
EP (1) | EP0414581B2 (de) |
AT (1) | ATE128178T1 (de) |
DE (1) | DE69022515T3 (de) |
ES (2) | ES2016465A6 (de) |
Families Citing this family (8)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CA2085642A1 (en) * | 1991-12-20 | 1993-06-21 | Ronald Hage | Bleach activation |
GB9127060D0 (en) * | 1991-12-20 | 1992-02-19 | Unilever Plc | Bleach activation |
US6069123A (en) * | 1995-06-30 | 2000-05-30 | Procter & Gamble Company | Peroxygen bleach-containing prespotting compositions with polyamine stabilizers providing improved fabric/color safety |
ES2233987T3 (es) * | 1996-09-26 | 2005-06-16 | Henkel Kommanditgesellschaft Auf Aktien | Combinacion de productos activos cataliticamente para reforzar el efecto de blanqueo. |
US6069122A (en) * | 1997-06-16 | 2000-05-30 | The Procter & Gamble Company | Dishwashing detergent compositions containing organic diamines for improved grease cleaning, sudsing, low temperature stability and dissolution |
US6727212B2 (en) | 1997-11-10 | 2004-04-27 | The Procter & Gamble Company | Method for softening soil on hard surfaces |
CA2333610A1 (en) | 1998-06-02 | 1999-12-09 | Joanna Margaret Clarke | Dishwashing detergent compositions containing organic diamines |
GB0103526D0 (en) * | 2001-02-13 | 2001-03-28 | Unilever Plc | Composition and method for bleaching a substrate |
Family Cites Families (4)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
DE3002271A1 (de) * | 1980-01-23 | 1981-07-30 | VEB Waschmittelwerk Genthin, Stammbetrieb, DDR 3280 Genthin | Bleichmittel |
US4478733A (en) * | 1982-12-17 | 1984-10-23 | Lever Brothers Company | Detergent compositions |
GB8329762D0 (en) * | 1983-11-08 | 1983-12-14 | Unilever Plc | Manganese adjuncts |
US4655782A (en) * | 1985-12-06 | 1987-04-07 | Lever Brothers Company | Bleach composition of detergent base powder and agglomerated manganese-alluminosilicate catalyst having phosphate salt distributed therebetween |
-
1989
- 1989-06-14 ES ES8902082A patent/ES2016465A6/es not_active Expired - Fee Related
-
1990
- 1990-06-13 AT AT90401635T patent/ATE128178T1/de active
- 1990-06-13 DE DE69022515T patent/DE69022515T3/de not_active Expired - Lifetime
- 1990-06-13 EP EP90401635A patent/EP0414581B2/de not_active Expired - Lifetime
- 1990-06-13 ES ES90401635T patent/ES2078955T5/es not_active Expired - Lifetime
Also Published As
Publication number | Publication date |
---|---|
ATE128178T1 (de) | 1995-10-15 |
DE69022515T3 (de) | 2004-06-03 |
EP0414581B2 (de) | 2003-10-15 |
EP0414581A1 (de) | 1991-02-27 |
DE69022515D1 (de) | 1995-10-26 |
ES2078955T5 (es) | 2004-05-16 |
ES2078955T3 (es) | 1996-01-01 |
DE69022515T2 (de) | 1996-05-15 |
ES2016465A6 (es) | 1990-11-01 |
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