|Publication number||US3816318 A|
|Publication date||Jun 11, 1974|
|Filing date||Jun 16, 1972|
|Priority date||Jun 16, 1972|
|Publication number||US 3816318 A, US 3816318A, US-A-3816318, US3816318 A, US3816318A|
|Original Assignee||Hentschel W|
|Export Citation||BiBTeX, EndNote, RefMan|
|Referenced by (13), Classifications (17)|
|External Links: USPTO, USPTO Assignment, Espacenet|
United States Patent 1191 a 1111 3,816,318 Hentschel June 11, 1974  DETERGENT 2,893,990 7/1959 Haas et al. 252/89 UX  Inventor: Gerhard Oskar Hentschel,
Gothenburg, Sweden 3,692,684 9/1972 Hentschel 252/89  Assignee: Walter S. E. Hentschel, Gothenburg,
Sweden; a part interest 22 Filed: June 16, 1972 21 Appl. No.: 263,442
[52 US. (:1. 252/89, 260/485 R 51 1m. (:1 ..'Clld1/83  Field of Search 252/89; 260/485 R  References Cited UNITED STATES PATENTS 2,101,217 12/1937 Hill et a1. 260/485 R 2,380,699 7/1945 Kyrides 260/485 R Primary Examiner-William E. Schulz Attorney, Agent, or Firm1-1arness, Dickey & Pierce [5 7 ABSTRACT Detergent compositions containing monoesters produced through esterifying dibasic or polybasic organic aliphatic carboxylic acids and/or dibasic or polybasic aromatic carboxylic acids with alcohols. These monoesters replace in the detergent previously used phosphates which caused eutrofication and endangered the ecology.
10 Claims, N0 Drawings DETERGENT BACKGROUND OF THE INVENTION The present invention relates to washing, dishwashing and cleaning detergent compositions in the form of powders, granules, pastes, or liquids, in which the phosphates previously used in such detergents are completely or partly replaced by chemicals which are more suitable from the eutrophic point of view. The invention discloses the replacement of the phosphates which are undesirable from the eutrophic point in view by aliphatic carboxylic acids and/or their salts, such as lactic acid, acetic acid, tartaric acid and citric acid, or by aromatic carboxylic acids such as, e.g., benzoic acid, phthalic acid and tri-, tetra-, pentaand hexabenzenecarboxylic acids and/or their salts.
SUMMARY OF THE INVENTION The present invention concerns the use of the salts of particularly the fruit acids as these have proved most suitable as substitutes for phosphates. The reason herefor is that they decompose easily biologically, forming few toxic substances, and they do not pollute lakes and rivers with phosphor or nitrogen.
DETAILED DESCRIPTION OF A PREFERRED EMBODIMENT To increase the washing efficiency of these carboxylic acids it has proved suitable to let the carboxylic acids or part of the carboxylic acids incorporated in the detergent compositions react with lower alcohols to form monoesters. The a'lakaline salts of acid esters exhibit both lipophilic properties (alkyl groups) and hyd'rophilic properties (carbonyl group, COONa). Since the dirt particles generally are embedded in fat these monoesters have proved suitable for use in a system consisting of mixture of fat and water wherein the alkyl group imparts the lipophilic properties to the molecule whereas the esterified COOH-groups impart the typical acid character to the molecule, i.e., its capability of forming complex heavy metal ions. Owing to the strengthened lipophilic property the dispersing and emulsifying properties of such compounds are hightened. The reason for the restriction to monoesters in this connection is that the higher esters are much less soluble and for this reason do not provide the same efficiency in detergents. In addition, the biological decomposibility of the compound must be taken into consideration. Furthermore, the biological oxygen consumption, the so called, BO -values, is lower in the case of monoesters than in the case of higher esters.
.The esters are generally produced by esterifying the anhydrous acid with its respective alcohol and with a suitable catalyst or while using other suitable methods.
In the formulae given below X represents Na, K, or
NH, and R the alcohol rest having one to eight carbon atoms.
Examples of monoesters: XO CCH--CHCO -R 1. Sodium ethylene dicarboxylic acid monoethylester NaO- CCH=CH-CO CH H 2. Potassium ethylene dicarboxylic acid monoethyl ester KO CCl-l=CH-CO CH V 3. Potassium ethylene dicarboxylic acid monobutyl ester XO C-CH -CI-I(OI-I)CO R 4. Sodium oxyethane dicarboxylic acid monoethyl Na-O CCH CH(OH)-CO CH 5. Sodium oxyethane dicarboxylic acid monoisoamyl ester 6. Ammonium ethane dicarboxylic acid monopropyl ester NH4-O2C CH2CH2CO2C3H7 7. Potassium ethane dicarboxylic acid monoethyl ester KO2C-CH2CH2 CO2C2H5 8. Sodium dioxi-succinic acid monomethyl ester Na-O C-CH(OH)CH(OH)CO -CH 9. Potassium dioxy-succinic acid monosecbutylester K-O CCH(OI-I)CH(Ol-l- )CO CH(CH )C I-I 10. Sodium l.2.3.-propene tricarboxylic acid monoethyl ester NaO CCH =C(CO I-I)CH- 2 2 2 s 11. Ammonium tricarballylacid monohexylic ester l2. Sodium-Z-hydroxypropane tricarboxylic acid monoisoamylester NaO C-Cl-I C(Ol-l)-CO HCH- 2 2 5 11 l3. Potassium-2-hydroxypropane tricarboxylic acid monopropylester KO CCH -C(OH)CO HCI-I CO C H Naturally, the invention is not limited to the monoesters enumerated above but also other carboxylic acid monoesters which are harmless from a toxicological point of view may be used. One condition is, of course, that they are acceptable from a water-preservation point of view. In addition, they must give satisfactory washing results. Experiments have shown that to strenester gthen the efficiency of these esters it is advantageous to add polyvalent higher alcohols in amounts up to 25 percent, preferably between 0.5 and 8 percent, calculated on the amount of the above esters.
The anionic, amphote ric or nonionic surfactants which may be present in the detergents in accordance with the invention contain in their molecule at least one hydrophobic group having eight to 30 carbon atoms and a group making them water-soluble, this group being of anionic or nonionic character. Soaps, sulphonates, and sulphates are of importance as anionic active detergents. Also phosphate surfactants could be used. The sulphonates may be alkylaryl sulphonates, alkyl sulphonates, alkene sulphonates, oxyalkene sulphonates and oxyalkane sulphonates. Also sulphonated esters may be used. The sulphates may be, e.g., alkyl 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 amides, and so on. 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 are useable. Synthetic, capillary-active carboxylates as well as condensation products of fatty acids with amino-carboxylic acids or with protein hydrolysates as also phosphate esters of fatty alcohols and fatty acids may be used.
As nonionic surfactants may be used, e.g., alkyl phenols, fatty alcohols, alkyl amines, fatty acids and fatty acid alkylol amides, fatty amides polyglycol esters, phosphate esters of ethoxylated fatty alcohols, block polymerisates of ethylene oxide and propylene oxide, etc.
Also amphoteric surfactants may be used, such as imidazoline derivates of fatty acids, carboxybetaines, compounds with the phosphoric acid groups in the acid rest, or with sulphonic or sulphuric acid groups.
Foam stabilizers of foam inhibitors as well as corrosion inhibitors may be included and so may dirtcarrying substances, optical brighteners, perfumes, bactericides, enzymes, dyes, and water. Also different types of'bleaching agents containing oxygen or chlorine and activators and stabilizers belonging thereto may be included.
In summary, all surfactants and aids used in connection with detergents and cleaning agents may be combined in accordance with the principle of the present invention and the enumeration given above is not to be considered as any restriction whatsoever.
The following examples illustrate the invention:
EXAMPLE 1 9 parts CMC, optical brightener, magnesium silicate ordinary washing,
EXAMPLE 2 Pre-washing-detergent, powder, gran.
4 parts alkylsulphate, sodium salt 2 parts lauricacidmonoethanolamidethiosuccincisemiester, sodium salt 4 parts fattyacidpolyglycolester 20 parts sodiumcarbonate, gran.
20 parts sodiumbicarbonate l5 parts sodium disilicate parts sodium monoisoamyl-2-hydroxypropane tricarboxylicacidester 5 parts sodium ethanedicarboxylicacid monoethylester 4 parts pentaerythritol 6 parts CMC, optical brightener, enzymes, water EXAMPLE 3 Small-washing detergent, gran. 12 parts alkylbenzenesulphonate, 50% 6 parts fattyalcoholpolyglycolether 3 parts thiosuccinicacidsemiester of fatty acid polyglycolether, sodium salt 2 parts coconutfattyacidmonoethanolamide or fatty acidamidepolyglycolether 6 parts sodium silicate 2,5 parts mannitol 16 parts sodium citrate 5 parts sodium monobutyl benzenehexacarboxylicacidester 3,5 parts benzenehexacarboxylic acid 10 parts sodium carbonate, gran.
14 parts sodium sesquicarbonate 13 parts sodium sulphate calc.
7 parts optical brightener, perfume, water EXAMPLE 4 Large-scale detergent, gran.
12 parts fatty alcoholpolyglycolether having 30 mols EO (ethylene oxide) 2 parts tallowfattyalcohol 3 parts cumolsulphonate 10 parts sodium monoethylester 5 parts Potassium ethylenedicarboxylicacid monomethylester 5 parts sodium acetate 20 parts sodium carbonate, calc.
10 parts sodium bicarbonate 15 parts sodium percarbonate 10 parts sodium disilicate 8 parts CMC, perfume, optical brightener, magnesium silicate, enzymes, and water EXAMPLE 5 Large-scale detergent, powder 6 parts dodecylbenzenesulphonate, calculated as containing 100% 5 parts alkylphenolpolyglycolether, turbidity point 1 part fattyaciddiethanol amide 2 parts Na-toluene sulphonate 6 parts sodium soap 20 parts sodium perborate 10 parts K-l.2.3.-propenetricarboxylicacid monobutylester 20 parts sodium dioxysuccinicacid monomethylester ethylenedicarboxylicacid- 5 parts sodium tripolyphosphate 4 parts d-sorbitol 10 parts sodium silicate, cryst.
l 1 parts CMC, perfume, optical brightener, enzymes,
and water EXAMPLE 6 Machine Dish-washing detergent 3 parts polypropylene-ethylene oxide-addition product 3 parts sodium alkylpolyglycoletherphosphate 25 parts sodium acetate 25 parts sodium sulphate 15 parts sodium monoethyltricarballylacid monohexylicester 15 parts sodium monomethyI-Z-hydroxypropane tricarboxylic acid ester 14 parts perfume, dyes, bactericides, water EXAMPLE 7 TABLE 2 7 Washing and cleaning paste 10 parts fattyacidimidazolmedenvate, 50% washing programme and commons 3 parts SUCClnlC ac1d-2-ethyl hexylicmonoester 5 Aummatic Lah niini Coloured White 3 parts undecyleneacidmonoethanolamide wash'ng Muchme whhmg washmg 16 parts fattyacidcondensationproduct w1th methyl Filling weight 25 k taurine. Filling Factor H4 H4 Bath Conditions 1:6 1:6 7 parts hexanedlol Water Hardness 5.4dH 5.4dH 6 parts sodium monoethyl ethenedicarboxyhcactd- Total Washing Time 66 min. 7 75 min. ester. Prewash l9 min. 17 min. Heating Time l3 min. ll min. 5 parts Sodium OXYethanedlcarboxyhcacld -f Max. Washing Temperature 45C less 40C less monobutylester than 5 min. than 5 min.
- Main Wash 24 min. 34 min. 2 parts adlplmc acld Heating Time 12 min. 23 min.. 3 parts CMC 15 Max. Washing Temperature 60C less 85C less than 10 min. than l0 min. 45 Parts water Rinsing 18 min. 18 min.
lst Rinse 4 min. 4 min. EXAMPLE 8 2nd, 3rd. and 411i Rinses 4 min. each, Y with throughflow Liquid washing and cleansing agent Spin-drying 5 mi 5 min, 7 parts of a mixture of alkane and alkenesulphonates 20 i TABLE 3 Perce n tagg of Stains Removed I Coloured Em MLu L a Unstained Unwashed 11 111 Iv 11 11 111 IV Pigment Stains EMPA-standard stains 85.3 15.5 90.8 88.8 92.1 88.2 93.5 93.7 94.8 92.9 Protein Stains 810011 90.3 14.2 98.2 89.9 95.7 95.7 98.4 98.9 96.6 97.2 Chocolate 90.3 26.8 39.1 48.5 77.6 49.4 45.0 79.0 82.4 72.7 BlOOd-Milk-|nk 90.3 9.2 85.1 47.7 84.6 60.0 81.8 80.| 85.2 73.9 Bleachablc Stains Bleaching Test 85.3 28.0 23.2 26.0 28.2 27.8 32.5 41.6 39.1 39.8 Cotton. BflW 90.3 59.4 21.4 18.5 24.2 23.1 39.8 41.2 39.3 39.8 Red Wine 90.3 40.5 60.4 62.9 72.1 66.0 92.9 92.3 92.2 92.4
I Detergent of Example 4 ll Detergent on soap base. containing 1071 tripolyphnsphatc and 20% Na-perborate Ill Detergent synthetic. containing tripolyphosphate and 25% Na-perbomte IV Detergent synthetic. containing lll'1.NTA. 10% lripoiyphnsphnte and 209: Na-perborate 3 parts dialkylphenolpolyglycolether I w v i 7 '7 7 TABLE 4 3 parts undecyleneacidmonoethanolamidethiosucv cinicacidsemiester, sodium salt Incineration after 10 washes 2 parts fattyacidamineoxide 5Q COlOUl'Ed Washing v Prewash C/Main wash 60C 3 parts p Test 1 Test 2 Average Value 3 parts-ethyldiglycol 1 0.15% 0.12% 0.13% 11 0.06% 0.05% 0.06% 10 parts NH monopropyl oxyethanedicarboxyllca m 005% 005% 005% cldesler 1v 0.05% 0.05% 0.05% 2 parts sorb1te w p h 40C/M w h 85C 67 parts water. perfume, dyes, ammonia, etc. as mg Tesl F Tmt 2 am j value To show the effects of the detergent of Example 4 I above as compared with known detergents 'containing i 8%? 8'83; 383;:
o 1 phosphates and NTA the following washing test results m 0,07% 0,06% 0.07% are given: I 1v 0.07% 0.05% (1.06%
TABLE I I 1 r The above results show that the substitutes for phos- Delefgem Dosage Pmwflsh 8 k B phates and NTA as taught by the present invention pro- I 6 vide a detergent possessing equally good washing re- 11 -6 24 sults without increasmg incrustation, as is apparent K. g from Table 4. The detergent in accordance with the invention thus provides excellent washing results without .to eight carbon atoms in the hydrocarbon moiety,
said monoesters being present in said detergent compositions in amounts of between Sand percent.
m 2. Detergent compositions as claimed in claim 1, wherein said carboxylic acids are oxycarboxylic acids.
3. Detergent compositions as claimed in claim 1,; wherein the free carboxylic groups of said monoesters are at least partly neutralized by means of alkalis.
4. Detergent compositions as claimed in claim 1, which contain monoesters.
5. Detergent compositions as claimed in claim I. wherein said monoesters are a mixture.
6. Detergent compositions as claimed in claim 5, wherein said monoesters are a mixture together with the salts of said carboxylic acids.
7. Detergent compositions as claimed in claim 5, wherein said monoesters are a mixture together with said free carboxylic acids.
8. Detergent compositions as claimed in claim 1, additionally containing polyvalent alcohols in amounts up to 25 percent calculated on said carboxylic acids.
9. Detergent compositions as claimed in claim 8, wherein said polyvalent alcohols are sorbitol, mannitol,
pentaerythritol, trimethyl propanol, trimethyl ethanol,
tween 0.5 and 8 percent.
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|US4039464 *||Jan 28, 1974||Aug 2, 1977||Texaco Inc.||Detergent builders and compositions containing the same|
|US4271032 *||Jul 5, 1979||Jun 2, 1981||Texaco Inc.||Polycarboxylic acids and esters in detergent formulations and their use|
|US4369329 *||Mar 10, 1980||Jan 18, 1983||Bayer Aktiengesellschaft||Substituted tartaric acid esters, a process for their production and their use as polymerization initiators|
|US4395365 *||Aug 19, 1981||Jul 26, 1983||Nissan Motor Co., Ltd.||Metal cleaning composition containing a fatty acid succrose ester and other detergent components|
|US4714565 *||Apr 25, 1986||Dec 22, 1987||The Procter & Gamble Company||Homogeneous concentrated liquid detergent compositions containing a monoester of a dicarboxylic acid|
|US4732703 *||Feb 3, 1987||Mar 22, 1988||Lever Brothers Company||Liquid detergent compositions containing stabilizers to prevent phase separation|
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|US6176244 *||Jul 31, 1998||Jan 23, 2001||Epenhuysen Chemie N.V.||Machine dish-washing process|
|U.S. Classification||510/221, 510/229, 560/180, 510/361, 510/223, 510/351, 560/193, 510/320, 510/505, 510/404, 510/477, 510/488, 510/318|
|International Classification||C11D3/20, C11D3/00|