DETERGENT
United States Patent 3816318
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.
US Patent References:
Production of dicarboxylic acids and esters thereof
Hill et al. - December 1937 - 2101217
Monoalkenyl-succinic acid mono-ester salts
Kyrides - July 1945 - 2380699
Process for producing sugar esters
Haas et al. - July 1959 - 2893990
2,2'-oxodisuccinic acid, derivatives thereof, and process for preparing
Berg - April 1964 - 3128287
/3661787.html
Brown - May 1972 - 3661787
Production of dicarboxylic acids and esters thereof
Hill et al. - December 1937 - 2101217
Monoalkenyl-succinic acid mono-ester salts
Kyrides - July 1945 - 2380699
Process for producing sugar esters
Haas et al. - July 1959 - 2893990
2,2'-oxodisuccinic acid, derivatives thereof, and process for preparing
Berg - April 1964 - 3128287
/3661787.html
Brown - May 1972 - 3661787
Application Number:
05/263442
Publication Date:
06/11/1974
Filing Date:
06/16/1972
View Patent Images:
Export Citation:
Assignee:
Hentschel, Walter S. E. (Gothenburg, SW)
Primary Class:
Other Classes:
560/180, 560/193, 510/477, 510/361, 510/505, 510/404, 510/223, 510/320, 510/229, 510/318, 510/488, 510/351
International Classes:
C11D3/00; C11D3/20; C11D1/83
Field of Search:
252/89 260/485R
US Patent References:
| 3692684 | September 1972 | Hentschel |
Primary Examiner:
Schulz, William E.
Attorney, Agent or Firm:
Harness, Dickey & Pierce
Claims:
What I claim is
1. Detergent compositions for washing, dish-washing and cleaning purposes in the form of powders, pastes, or liquids, consisting essentially of water softeners, anionic and non-ionic detergents and detergent effect intensifiers, wherein said water softeners and said detergent effect intensifiers are monoesters produced through esterifying dibasic or tribasic organic aliphatic carboxylic acids having up to nine carbon atoms in the hydrocarbon moiety and/or dibasic or tribasic aromatic carboxylic acids with alcohols having one or several hydroxylic functions and one to eight carbon atoms in the hydrocarbon moiety, said monoesters being present in said detergent compositions in amounts of between 5 and 30 percent.
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 1, 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, hexanetriol, butane-1.2.4-triol.
10. The detergent composition of claim 8, wherein the polyvalent alcohols are present in amounts of between 0.5 and 8 percent.
1. Detergent compositions for washing, dish-washing and cleaning purposes in the form of powders, pastes, or liquids, consisting essentially of water softeners, anionic and non-ionic detergents and detergent effect intensifiers, wherein said water softeners and said detergent effect intensifiers are monoesters produced through esterifying dibasic or tribasic organic aliphatic carboxylic acids having up to nine carbon atoms in the hydrocarbon moiety and/or dibasic or tribasic aromatic carboxylic acids with alcohols having one or several hydroxylic functions and one to eight carbon atoms in the hydrocarbon moiety, said monoesters being present in said detergent compositions in amounts of between 5 and 30 percent.
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 1, 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, hexanetriol, butane-1.2.4-triol.
10. The detergent composition of claim 8, wherein the polyvalent alcohols are present in amounts of between 0.5 and 8 percent.
Description:
BACKGROUND OF THE INVENTION
The present invention relates to washing, dish-washing 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-, penta- and hexabenzene-carboxylic 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 alakaline salts of acid esters exhibit both lipophilic properties (alkyl groups) and hydrophilic 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 5 -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 4 and R the alcohol rest having one to eight carbon atoms.
Examples of monoesters:
X--o 2 c--ch--ch--co 2 --r
1. sodium ethylene dicarboxylic acid monoethylester Na--O 2 C--CH=CH--CO 2 --CH 2 H 5
2. potassium ethylene dicarboxylic acid monoethyl ester K--O 2 C--CH=CH--CO 2 --CH 3
3. potassium ethylene dicarboxylic acid monobutyl ester K--O 2 C--CH=CH--CO 2 --C 4 H 9
X--o 2 c--ch 2 --ch(oh)--co 2 --r
4. sodium oxyethane dicarboxylic acid 1.4-monoethyl ester Na--O 2 C--CH 2 --CH(OH)--CO 2 --CH 3
5. sodium oxyethane dicarboxylic acid monoisoamyl ester Na--O 2 C--CH 2 CH(OH)--CO 2 --C 5 H 11
X--o 2 c--ch 2 --ch 2 --co 2 --r
6. ammonium ethane dicarboxylic acid monopropyl ester NH 4 --O 2 C--CH 2 --CH 2 --CO 2 --C 3 H 7
7. potassium ethane dicarboxylic acid monoethyl ester K--O 2 C--CH 2 --CH 2 --CO 2 --C 2 H 5
X--o 2 c--ch(oh)--ch(oh)--co 2 --r
8. sodium dioxi-succinic acid monomethyl ester Na--O 2 C--CH(OH)--CH(OH)--CO 2 --CH 3
9. potassium dioxy-succinic acid monosecbutylester K--O 2 C--CH(OH)--CH(OH)--CO 2 --CH(CH 3 )C 2 H 5
X--o 2 c--ch 2 =c(co 2 h)--ch 2 --co 2 --r
10. sodium 1.2.3.-propene tricarboxylic acid monoethyl ester Na--O 2 C--CH 2 =C(CO 2 H)--CH 2 --CO 2 --C 2 H 5
X--o 2 c--ch 2 --ch(co 2 h)--ch 2 --co 2 --r
11. ammonium tricarballylacid monohexylic ester NH 4 O 2 C--CH 2 --CH(CO 2 H)--CH 2 --CO 2 --C 6 H 13
X--o 2 c--ch 2 --c(oh)--co 2 h--ch 2 --co 2 --r
x--o 2 c--c(oh)--ch 2 --co 2 h--ch 2 --co 2 --r
12. sodium-2-hydroxypropane tricarboxylic acid monoisoamylester Na--O 2 C--CH 2 --C(OH)--CO 2 H--CH 2 --CO 2 --C 5 H 11
13. potassium-2-hydroxypropane tricarboxylic acid monopropylester K--O 2 C--CH 2 --C(OH)--CO 2 H--CH 2 --CO 2 --C 3 H 7
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 strengthen 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, amphoteric 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 thiomono- and -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 dirt-carrying 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
Detergent composition for ordinary washing, sprayed:
10 parts Na-dodecylbenzenesulphonate
5 parts fattyalcoholpolyglycolether
7 parts zylenesulphonate
2 parts sodiumsoap, 80%
2 parts phosphateesters of etoxylated fatty alcohol
15 parts sodium perborate
15 parts sodium ethanedicarboxylicacidmonopropylester
15 parts potassium-2-hydroxypropane tricarboxylicacid monoamylester
5 parts sodium citrate
10 parts sodium silicate
3 parts EDTA or NTA
2 parts sodium salt of benzenetetracarboxylicacid
9 parts CMC, optical brightener, magnesium silicate
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
15 parts sodium disilicate
20 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 ethylenedicarboxylicacid-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 70°-74°C
1 part fattyaciddiethanol amide
2 parts Na-toluene sulphonate
6 parts sodium soap
20 parts sodium perborate
10 parts K-1.2.3.-propenetricarboxylicacid monobutylester
20 parts sodium dioxysuccinicacid monomethylester
5 parts sodium tripolyphosphate
4 parts d-sorbitol
10 parts sodium silicate, cryst.
11 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 monomethyl-2-hydroxypropane tricarboxylic acid ester
14 parts perfume, dyes, bactericides, water
EXAMPLE 7
Washing and cleaning paste
10 parts fattyacidimidazolinederivate, 50%
3 parts succinic acid-2-ethyl hexylicmonoester
3 parts undecyleneacidmonoethanolamide
16 parts fattyacidcondensationproduct with methyl taurine.
7 parts hexanediol
6 parts sodium monoethyl ethenedicarboxylicacidester
5 parts sodium oxyethanedicarboxylicacid 1.4.-monobutylester
2 parts adipinic acid
3 parts CMC
45 parts water
EXAMPLE 8
Liquid washing and cleansing agent
7 parts of a mixture of alkane and alkenesulphonates
3 parts dialkylphenolpolyglycolether
3 parts undecyleneacidmonoethanolamidethiosuccinicacidsemiester, sodium salt
2 parts fattyacidamineoxide
3 parts pine-oil
3 parts ethyldiglycol
10 parts NH 4 -monopropyl oxyethanedicarboxylicacidester
2 parts sorbite
67 parts water, perfume, dyes, ammonia, etc.
To show the effects of the detergent of Example 4 above as compared with known detergents containing phosphates and NTA the following washing test results are given:
TABLE I ______________________________________ Detergent Dosage Prewash gr/k Main Wash gr/k ______________________________________ I 6 26 II 6 24 III 6 25 IV 7 27 ______________________________________
TABLE 2 ______________________________________ Washing programme and conditions Automatic Laboratory Coloured White Washing Machine Washing Washing ______________________________________ Filling Weight 2.5 k 2.5 k Filling Factor 1:14 1:14 Bath Conditions 1:6 1:6 Water Hardness 5.4°dH 5.4°dH Total Washing Time 66 min. 75 min. Prewash 19 min. 17 min. Heating Time 13 min. 11 min. Max. Washing Temperature 45°C less 40°C less than 5 min. than 5 min. Main Wash 24 min. 34 min. Heating Time 12 min. 23 min. Max. Washing Temperature 60°C less 85°C less than 10 min. than 10 min. Rinsing 18 min. 18 min. 1st Rinse 4 min. 4 min. 2nd, 3rd, and 4th Rinses 4 min. each, with throughflow Spin-drying 5 min. 5 min. ______________________________________
TABLE 3 ____________________________________________________________ ______________ Percentage of Stains Removed Coloured Washing White Washing Unstained Unwashed I II III IV I II III 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 Blood 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-Ink 90.3 9.2 85.1 47.7 84.6 60.0 81.8 80.1 85.2 73.9 Bleachable Stains Bleaching Test 85.3 28.0 23.2 26.0 28.2 27.8 32.5 41.6 39.1 39.8 Cotton, Baw 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 II Detergent on soap base, containing 10% tripolyphosphate and 20% Na-perborate III Detergent synthetic, containing 30% tripolyphosphate and 25% Na-perborate IV Detergent synthetic, containing 18% NTA, 10% tripolyphosphate and 20% Na-perborate
TABLE 4 ______________________________________ Incineration after 10 washes Coloured Washing Prewash 45°C/Main Wash 60°C Test 1 Test 2 Average Value ______________________________________ I 0.15% 0.12% 0.13% II 0.06% 0.05% 0.06% III 0.05% 0.05% 0.05% IV 0.05% 0.05% 0.05% White Washing Prewash 40°C/Main Wash 85°C Test 1 Test 2 Average Value ______________________________________ I 0.08% 0.09% 0.09% II 0.10% 0.08% 0.09% III 0.07% 0.06% 0.07% IV 0.07% 0.05% 0.06% ______________________________________
The above results show that the substitutes for phosphates and NTA as taught by the present invention provide a detergent possessing equally good washing results without increasing incrustation, as is apparent from Table 4. The detergent in accordance with the invention thus provides excellent washing results without polluting the water recipients with nutrient salts containing phosphor and nitrogen.
The present invention relates to washing, dish-washing 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-, penta- and hexabenzene-carboxylic 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 alakaline salts of acid esters exhibit both lipophilic properties (alkyl groups) and hydrophilic 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 5 -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 4 and R the alcohol rest having one to eight carbon atoms.
Examples of monoesters:
X--o 2 c--ch--ch--co 2 --r
1. sodium ethylene dicarboxylic acid monoethylester Na--O 2 C--CH=CH--CO 2 --CH 2 H 5
2. potassium ethylene dicarboxylic acid monoethyl ester K--O 2 C--CH=CH--CO 2 --CH 3
3. potassium ethylene dicarboxylic acid monobutyl ester K--O 2 C--CH=CH--CO 2 --C 4 H 9
X--o 2 c--ch 2 --ch(oh)--co 2 --r
4. sodium oxyethane dicarboxylic acid 1.4-monoethyl ester Na--O 2 C--CH 2 --CH(OH)--CO 2 --CH 3
5. sodium oxyethane dicarboxylic acid monoisoamyl ester Na--O 2 C--CH 2 CH(OH)--CO 2 --C 5 H 11
X--o 2 c--ch 2 --ch 2 --co 2 --r
6. ammonium ethane dicarboxylic acid monopropyl ester NH 4 --O 2 C--CH 2 --CH 2 --CO 2 --C 3 H 7
7. potassium ethane dicarboxylic acid monoethyl ester K--O 2 C--CH 2 --CH 2 --CO 2 --C 2 H 5
X--o 2 c--ch(oh)--ch(oh)--co 2 --r
8. sodium dioxi-succinic acid monomethyl ester Na--O 2 C--CH(OH)--CH(OH)--CO 2 --CH 3
9. potassium dioxy-succinic acid monosecbutylester K--O 2 C--CH(OH)--CH(OH)--CO 2 --CH(CH 3 )C 2 H 5
X--o 2 c--ch 2 =c(co 2 h)--ch 2 --co 2 --r
10. sodium 1.2.3.-propene tricarboxylic acid monoethyl ester Na--O 2 C--CH 2 =C(CO 2 H)--CH 2 --CO 2 --C 2 H 5
X--o 2 c--ch 2 --ch(co 2 h)--ch 2 --co 2 --r
11. ammonium tricarballylacid monohexylic ester NH 4 O 2 C--CH 2 --CH(CO 2 H)--CH 2 --CO 2 --C 6 H 13
X--o 2 c--ch 2 --c(oh)--co 2 h--ch 2 --co 2 --r
x--o 2 c--c(oh)--ch 2 --co 2 h--ch 2 --co 2 --r
12. sodium-2-hydroxypropane tricarboxylic acid monoisoamylester Na--O 2 C--CH 2 --C(OH)--CO 2 H--CH 2 --CO 2 --C 5 H 11
13. potassium-2-hydroxypropane tricarboxylic acid monopropylester K--O 2 C--CH 2 --C(OH)--CO 2 H--CH 2 --CO 2 --C 3 H 7
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 strengthen 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, amphoteric 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 thiomono- and -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 dirt-carrying 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
Detergent composition for ordinary washing, sprayed:
10 parts Na-dodecylbenzenesulphonate
5 parts fattyalcoholpolyglycolether
7 parts zylenesulphonate
2 parts sodiumsoap, 80%
2 parts phosphateesters of etoxylated fatty alcohol
15 parts sodium perborate
15 parts sodium ethanedicarboxylicacidmonopropylester
15 parts potassium-2-hydroxypropane tricarboxylicacid monoamylester
5 parts sodium citrate
10 parts sodium silicate
3 parts EDTA or NTA
2 parts sodium salt of benzenetetracarboxylicacid
9 parts CMC, optical brightener, magnesium silicate
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
15 parts sodium disilicate
20 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 ethylenedicarboxylicacid-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 70°-74°C
1 part fattyaciddiethanol amide
2 parts Na-toluene sulphonate
6 parts sodium soap
20 parts sodium perborate
10 parts K-1.2.3.-propenetricarboxylicacid monobutylester
20 parts sodium dioxysuccinicacid monomethylester
5 parts sodium tripolyphosphate
4 parts d-sorbitol
10 parts sodium silicate, cryst.
11 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 monomethyl-2-hydroxypropane tricarboxylic acid ester
14 parts perfume, dyes, bactericides, water
EXAMPLE 7
Washing and cleaning paste
10 parts fattyacidimidazolinederivate, 50%
3 parts succinic acid-2-ethyl hexylicmonoester
3 parts undecyleneacidmonoethanolamide
16 parts fattyacidcondensationproduct with methyl taurine.
7 parts hexanediol
6 parts sodium monoethyl ethenedicarboxylicacidester
5 parts sodium oxyethanedicarboxylicacid 1.4.-monobutylester
2 parts adipinic acid
3 parts CMC
45 parts water
EXAMPLE 8
Liquid washing and cleansing agent
7 parts of a mixture of alkane and alkenesulphonates
3 parts dialkylphenolpolyglycolether
3 parts undecyleneacidmonoethanolamidethiosuccinicacidsemiester, sodium salt
2 parts fattyacidamineoxide
3 parts pine-oil
3 parts ethyldiglycol
10 parts NH 4 -monopropyl oxyethanedicarboxylicacidester
2 parts sorbite
67 parts water, perfume, dyes, ammonia, etc.
To show the effects of the detergent of Example 4 above as compared with known detergents containing phosphates and NTA the following washing test results are given:
TABLE I ______________________________________ Detergent Dosage Prewash gr/k Main Wash gr/k ______________________________________ I 6 26 II 6 24 III 6 25 IV 7 27 ______________________________________
TABLE 2 ______________________________________ Washing programme and conditions Automatic Laboratory Coloured White Washing Machine Washing Washing ______________________________________ Filling Weight 2.5 k 2.5 k Filling Factor 1:14 1:14 Bath Conditions 1:6 1:6 Water Hardness 5.4°dH 5.4°dH Total Washing Time 66 min. 75 min. Prewash 19 min. 17 min. Heating Time 13 min. 11 min. Max. Washing Temperature 45°C less 40°C less than 5 min. than 5 min. Main Wash 24 min. 34 min. Heating Time 12 min. 23 min. Max. Washing Temperature 60°C less 85°C less than 10 min. than 10 min. Rinsing 18 min. 18 min. 1st Rinse 4 min. 4 min. 2nd, 3rd, and 4th Rinses 4 min. each, with throughflow Spin-drying 5 min. 5 min. ______________________________________
TABLE 3 ____________________________________________________________ ______________ Percentage of Stains Removed Coloured Washing White Washing Unstained Unwashed I II III IV I II III 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 Blood 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-Ink 90.3 9.2 85.1 47.7 84.6 60.0 81.8 80.1 85.2 73.9 Bleachable Stains Bleaching Test 85.3 28.0 23.2 26.0 28.2 27.8 32.5 41.6 39.1 39.8 Cotton, Baw 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 II Detergent on soap base, containing 10% tripolyphosphate and 20% Na-perborate III Detergent synthetic, containing 30% tripolyphosphate and 25% Na-perborate IV Detergent synthetic, containing 18% NTA, 10% tripolyphosphate and 20% Na-perborate
TABLE 4 ______________________________________ Incineration after 10 washes Coloured Washing Prewash 45°C/Main Wash 60°C Test 1 Test 2 Average Value ______________________________________ I 0.15% 0.12% 0.13% II 0.06% 0.05% 0.06% III 0.05% 0.05% 0.05% IV 0.05% 0.05% 0.05% White Washing Prewash 40°C/Main Wash 85°C Test 1 Test 2 Average Value ______________________________________ I 0.08% 0.09% 0.09% II 0.10% 0.08% 0.09% III 0.07% 0.06% 0.07% IV 0.07% 0.05% 0.06% ______________________________________
The above results show that the substitutes for phosphates and NTA as taught by the present invention provide a detergent possessing equally good washing results without increasing incrustation, as is apparent from Table 4. The detergent in accordance with the invention thus provides excellent washing results without polluting the water recipients with nutrient salts containing phosphor and nitrogen.