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Publication numberUS3692684 A
Publication typeGrant
Publication dateSep 19, 1972
Filing dateMar 17, 1970
Priority dateOct 1, 1969
Also published asDE2026739A1, DE2026739B2, DE2026739C3
Publication numberUS 3692684 A, US 3692684A, US-A-3692684, US3692684 A, US3692684A
InventorsHentschel Gerhard Oskar
Original AssigneeValter Sven Erwin Hentschel
Export CitationBiBTeX, EndNote, RefMan
External Links: USPTO, USPTO Assignment, Espacenet
Detergent
US 3692684 A
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Description  (OCR text may contain errors)

United States Patent 3,692,684 DETERGENT Gerhard Oskar Hentschel, Goteborg, Sweden, assignor to Valter Sven Erwin Hentschel, Goteborg, Sweden No Drawing. Filed Mar. 17, 1970, Ser. No. 20,425 Claims priority, application Switzerland, Oct. 1, 1969, 13,492/ 69 Int. Cl. Clld 3/20 US. Cl. 252-89 3 Claims ABSTRACT OF THE DISCLOSURE A detergent containing alkaline salts of organic, aliphatic and/or aromatic carboxylic acids and/or anhy, drides of the same with one or several carboxylic groups. These salts replace in the detergent previously used phosphates which caused a eutrophication and endangered the ecology.

BACKGROUND OF THE INVENTION The present invention relates to a washing dish-washing and cleaning detergent in the shape of powders, granules or pastes or liquids, the phosphates previously used in such a detergent being completely or partly replaced by chemicals which are more suitable from the eutrophic point of view.

The purpose of the phosphates in detergent compositions is to soften the water and to keep thehardening agents in the water in solution. Further, the phosphates have a certain dispersion effect on the dirt particles and improves the effects of the tensides in certain respects.

The phosphates form nutrient salts for the watercourses and when waste water is discharged into such watercourses, this results in overnutrition with an increased propagation of algae and a filling as a result (eutrophica- 3,692,684 Patented Sept. 19, 1972 DETAILED DESCRIPTION OF THE INVENTION The carboxylic acids which should preferably be used according to the invention are the following aliphatic acidsz. lactic acid, acetic acid, tartaric acid and citric acid, and the following aromatic acids: benzoic acid, phthalic acid and tri-, tetra-, pentaand hexa-carboxylic acids and their alkaline salts. However, the invention is not restricted to the acids enumerated in the aforegoing but also other.

carboxylic acids which are not dangerous from toxicologic point of view may be used. One condition is of course that they could be accepted from water care'point of view. They must also give a satisfactory washing result.

COOH-groups give the best results in surface Washing and at the same time many of these acids are toxicologically and allergologically undangerous and do not endanger water care. Several of these carboxylic acids occur in nature and form so to say a natural component of the plants and animals.

The anionic, double-ionic or nonionic tensides which may be present in the detergents according to the inventhem water soluble, this group being of anionic or nonionie character. As anionic active detergent soaps, sulphonates and glp hates are of importance. Also phosphate tion). For this reason it is important to keep the phosphate contents as low as possible or to replace the phosphates completely in detergent compositions. In the detergent industry one has tried to accomplish this by introducing nitrilotriacetates (NTA) and replacing large parts of the phosphates therewith. As the decomposition of NTA in recipients and purifying plants is not completely known and the watercourses thereby are fed with nitrogen and nitrogen compounds, also NTA increases the algae growth why this solution of the eutrophication problem still is unsolved. Further, one does not know anything about the reactions between trace elements in natural watercourses and NTA.

SUMMARY OF THE INVENTION The present invention relates to detergent compositions which contain alkaline salts of aliphatic and aromatic car boxylic acids and/or their anhydrides having as a maximum eight carbon atoms in the hydrophobic part or having one or several carboxylic groups or the free acids in a mixture with the alkaline salts of inorganic acids, e.g. carbonates and silicates. In order to improve the effect of said carboxylic acid salts it has turned out to be suitable to add multivalent higher alcohols up to an amount of 25%, preferably 0.58% as calculated on the quantity of said salts. Said acids are used because they contain only tensides cou be used. The sulphonates may comprise alkylaryl sulphonates, alkyl sulphonates, alkene sulphonates and oxyalkane sulphonates. Also sulphonated esters may be used. The sulphates may comprise e.g. alkylene sulphate, fatty alcohol ether sulphate, sulphated amides of fatty acids, sulphated monoglycerides, sulphating products of ethoxylated and/or propoxylated fatty alcohols, alkyl phenols, fatty acid amines, etc. Sulphonates of fatty acid esters of oxethane sulphonic acid and dioxypropane sulphonic acid, fatty alcoholic esters of lower aliphatic and aromatic thiomonoand dicarboxylic acids as well as condensation products of fatty acids with aminoethane sulphonic acids may be used. Synthetic capillary active carboxylates and condensation products of fatty acids with aminocarboxylic acids or with protein hydrolysates as well as phosphate esters of fatty alcohols and fatty acids may be used.

As nonionic tensides one may use e.g. alkylic phenol, fatty alcohol, alkyl amino, fatty acid, fatty acid alkylol amide fatty amide polyglycolethers, phosphate esters of ethoxylated fatty alcohols, block polymerisates of ethylene oxide and propylene oxide etc.

Also amphoteric tensides may be used such as imidazoline derivatives of fatty acids, carboxybetaines, compounds with the phosphoric acid groups in the acid test or with sulphonic or sulphuric acid groups.

Foam stabilizers or foam inhibitors as well as corrosion inhibitors may be included and so may dirt carrying sub- It has turned out in practice that acids with several enzymes, dyes and water. Also different types of bleaching agents containing oxygen or chlorine and activators and stabilizers belonging thereto.

In order to improve the effect of the carboxylic acid salts there is added a multivalent higher alcohol in an amount up to 25%, preferably 0.58% as calculated on the quantity of said salts. The multivalent alcohols are selected from the group consisting of sorbitol, mannitol, pentaerythritol, trimethylol propane, trirnethanol ethane, hexanetriol and butane triol.

As a conclusion it could be said that all tensides and aids used in connection with detergents and cleaning agents may be combined with the principle of the present invention and that the above enumeration .is. not to be considered as any restriction whatsoever.

The following examples are intended to illustrate the invention:

Sodium silicate, cryst. CMC, perfume, opt. brightening agent, enzymes,

and water l1 EXAMPLE 2 Large-scale detergent, granules Parts Fatty alcohol polyglycol ether having 30 mols EO (ethylene oxide) 12 Tallow fatty alcohol i 2 Cumol sulphonate ,3 Na-adipate 3 Na-K-tartrate 7 Na-acetate 10 Calcined soda 2O Na-bicarbonate .4 10 Na-percarbonate l5 Na-silicate '10 CMC, perfume, opt. brightening agent, Mg-silicate,

enzymes, and water Q. 8

EXAMPLE 3 Detergent for ordinary washing, sprayed I Parts Na-dodecyl benzene sulphonate .Q 10 Fatty alcohol polyglycol ether 5 Xylene sulphonate 7 SEHITJ'I'WBW 2 Phosphate ester of ethoxylated fatty alcohol 2 Na-perborate 15 Na-citrate 30 Mannitol 5 Na-silicate 10 EDTA or NTA 3 Na-salt of benzene tetracarboxylic acid 2 CMC, opt. brightening agent, Mg-silicate 9 EXAMPLE 4 Small-washing detergent, gran.

Parts Alkylbenzene sulphonate, 50% 12 Fatty alcohol polyglycol ether 6 Thiosuccinic acid semiester of fatty acid polyglycol ether, Na-salt Coconut fatty acid monoethanol amide or fatty acid amide polyglycol ether 2 Na-silicate 6 Mannitol 2.5 Na-citrate 21 Benzene hexacarboxylic acid 3.5 Gran. soda l0 Sesquicarbonate 14 Sodium sulphate calc. 13 CMC, opt. brightening agent, perfume, water 7 EXAMPLE 5 Pre-washing detergent, powder, gran.

Parts Alkylsulphate, Na-salt 4 Laurie acid monoethanol amide thiosuccinic semiester, Na-salt 2 Fatty acid polyglycol ester 4 Soda gran. 20 Sodium bicarbonate 2O Na-disilicate 15 Na-acetate 20 Potassium biphthalate 5 Pentaerythrite 4 CMS, opt. brightening agent, enzymes, water 6 EXAMPLE 6 Liquid washing and cleansing agent Parts Mixture of alkane and alkene sulphonates 7 Dialkyl phenolpolyglycol ether 3 Undecylene acid monoethanol amide thiosuccinic acid semiester, Na-salt 3 Fatty acid aminoxide 2 Pine-oil 3 Ethyldiglycol 3 Sodium lactate 10 Sorbitol 2 Water, perfume, dyes, ammonia etc. 67

EXAMPLE 7 Dish-washing machine detergent Parts Polypropylene-ethylene oxide-addition product 3 Sodium alkylic polyglycol etherphosphate 3 Na-acetate 25 Na-sulphate 25 Na-citrate 30 Perfumes, dyes, bactericides, water l4 EXAMPLE 8 Washing and cleansing paste Parts Fatty acid imidazoline derivate, 50% 10 Succinic acid-Z-ethyl hexylic monoester 3 Undecylene acid monoethanol amide 3 Fatty acid condensation product with methyl taurine l6 Glycol derivate 7 Na-citrate 11 1,4-butane dicarboxylic acid 2 CMC 3 Water 45 What I claim is: 1. A detergent composition consisting essentially of: a water-soluble surface active agent have 8 to 30 6 carbon atoms in the hydrophobic group thereof, 3. The detergent composition of claim 2 wherein said selected from the group consisting of an anionic wetsurface active agent is a sodium soap. ting agent, a nonionic wetting agent, an amphoteric wetting agent and mixtures thereof in an amount of References Cited from about 10 to about 32 parts per 100 parts of 5 UNITED STATES PATENTS composition; an alkaline salt of a carboxylic acid selected from the 2264103 11/1941 TPcker I 252' 89 2,740,727 4/1956 Littleton et al 252-8.6 group consisting of lactic acid, acetic acid, tartaric 2,838,455 6/1958 Tompkins 2528.6 acld, citric and, butane dicarboxylrc acid, adipic 2,311 008 2/1943 T k H 252 89 acid, benzoic acid, phthalic acid, benzene tricar- 10 3'308O67 3/1967 25289 boxylic acid, benzene tetracarboxylic, benzene pen- 3459670 8/1969 C 252-89 tacarboxylic, benzene hexacarboxylic acid and mix at er tures thereof, said alkaline salt being present in an amount of from about 10 to about 30 parts per 100 OTHER REFERENCES parts of i i 15 Chemmumque, vol. 10, No. 1, February 1962, Atlas a polyhydric alcohol selected from the group consisting Publ- PP- of sorbitol, mannitol, pentaerythritol, trimethylol propane, trimethylol ethane, hexanetriol and butane MAYER WEINBLATF Pnmary Exammer triol, said polyhydric alcohol being present in said W, E, SCHULZ, A i t t E i composition in an amount of 0.5% to 25% by 20 weight of the salt of said carboxylic acid thereof. US. Cl. X.R.

2. The detergent composition of claim 1 wherein said 21058; 252-8.6

surface active agent is an anionic wetting agent.

UNITED STATES PATENT OFFICE CERTIFICATE OF CORRECTION Patent No. 3,692 ,684 Dated September 19, 1972 Inventor(s) Gerhard Oskar Hentschel It is certified that error appears in the above-identified patent and that said Letters Patent are hereby corrected as shown below:

In Column 1, line 6, after the word "application" delete "Switzerland" and insert "Sweden" In Column 4, line 32 "CMS" should be CMC In Column 4, line 75, "have" should be having Signed and sealed this 6th day of February 1973.

(SEAL) Attest:

ROBERT GOTTSCHALK EDWARD M.PLETCHER,JR.

Commissioner of Patents Attesting Officer FORM po'wso H0459) USCOMM-DC 60376-P69 [1.5, GOVERNMENT PRINTING OFFICE: 959 0-365-334

Referenced by
Citing PatentFiling datePublication dateApplicantTitle
US3844982 *May 11, 1971Oct 29, 1974Procter & GambleBuilt detergent composition
US3852220 *Jan 12, 1972Dec 3, 1974Marathon Oil CoIsocyanurate-based polyelectrolyte detergent composition
US3859224 *Sep 21, 1972Jan 7, 1975Hoechst AgDetergent composition containing, as a builder, the sodium salt of glycerol tricitrate
US3872020 *Sep 8, 1972Mar 18, 1975Dai Ichi Kogyo Seiyaku Co LtdDetergent compositions
US3896040 *Dec 11, 1972Jul 22, 1975Danesh AndreDetergent composition
US3915879 *Apr 5, 1974Oct 28, 1975Lever Brothers LtdDetergent compositions
US3920569 *Feb 9, 1973Nov 18, 1975Lever Brothers LtdDetergent composition having substituted phthalic acid salt builder
US3951877 *Jul 13, 1973Apr 20, 1976Lion Fat & Oil Co., Ltd.Heavy-duty granular detergent composition with sodium citrate builder
US3953352 *May 31, 1974Apr 27, 1976Kao Soap Co., Ltd.Coating a pyrrolidone-carboxylic acid compound
US3962149 *Oct 12, 1973Jun 8, 1976Colgate-Palmolive CompanyNon-phosphate spray dried detergents containing dicarboxylic acid salts
US3971728 *May 17, 1974Jul 27, 1976Ethyl CorporationSequestering agent
US4009114 *Oct 3, 1975Feb 22, 1977Colgate-Palmolive CompanyNon-phosphate detergent composition
US4013579 *May 31, 1974Mar 22, 1977Kao Soap Co., Ltd.Acidic cleaning composition
US4040972 *Mar 5, 1976Aug 9, 1977Deutsche Gold- Und Silber-Scheideanstalt Vormals RoesslerIon-exchanging aluminum silicate with hydrophilic surfaces
US4088593 *Mar 30, 1977May 9, 1978Henkel Kommanditgesellschaft Auf Aktien (Henkel Kgaa)Washing, rinsing, cleaning agent
US4102799 *Mar 5, 1976Jul 25, 1978Colgate-Palmolive CompanyAutomatic dishwasher detergent with improved effects on overglaze
US4123375 *Nov 19, 1976Oct 31, 1978Henkel Kommanditgesellschaft Auf AktienDishwasher detergent with clear rinsing effect and method of machine washing dishes
US4210550 *Jul 14, 1978Jul 1, 1980Akzo N.V.And one or more of adipic, succinic, and glutaric acids
US4239552 *Jul 23, 1979Dec 16, 1980Basf AktiengesellschaftMachine dishwashing, using polyhydric alcohols, carboxylic acids and or esters of these as rinsing agents
US4239641 *Jul 23, 1979Dec 16, 1980Basf AktiengesellschaftOf aqueous detergent and cleanser slurries
US4252663 *May 2, 1974Feb 24, 1981Ab Helios, Kemisk-Tekniska FabrikerNonionic etherified or esterified polyoxyalkylene glycol surfactant, alkali metal carboxylate builder
US4395365 *Aug 19, 1981Jul 26, 1983Nissan Motor Co., Ltd.Metal cleaning composition containing a fatty acid succrose ester and other detergent components
US4594175 *Aug 29, 1984Jun 10, 1986Economics Laboratory, Inc.Mechanical dishwashing rinse composition having a low foaming sulfonic acid rinsing agent, a hydrotrope and a source of active halogen
US4612137 *Aug 23, 1985Sep 16, 1986Kao CorporationAnti-yellowing detergent composition containing citrate and isocitrate
US4613448 *Mar 29, 1979Sep 23, 1986The Colgate-Palmolive Co.Tetrahydroxysuccinic acid as builder
US4902439 *Apr 15, 1988Feb 20, 1990Ciba-Geigy CorporationDetergent composition for washing off dyeings obtained with fibre-reactive dyes, process for the preparation thereof and use thereof
US4935158 *Oct 30, 1986Jun 19, 1990Aszman Harry WSolid detergent cleaning composition, reusable cleaning pad containing same and method of manufacture
US4983315 *Aug 10, 1989Jan 8, 1991The Procter & Gamble CompanyBiodegradation
US5427707 *Jun 22, 1994Jun 27, 1995Colgate Palmolive Co.Thixotropic aqueous compositions containing adipic or azelaic acid stabilizer
Classifications
U.S. Classification510/477, 510/532, 510/467, 210/699, 510/351, 510/292, 510/283, 510/423, 510/318, 510/228, 510/481, 510/404, 510/488
International ClassificationC11D3/20, C11D1/04, C11D1/02, C11D3/00
Cooperative ClassificationC11D3/2065, C11D3/2075, C11D3/221
European ClassificationC11D3/20E, C11D3/20B3, C11D3/22B