US2876201A - Detergent composition - Google Patents
Detergent composition Download PDFInfo
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- US2876201A US2876201A US497799A US49779955A US2876201A US 2876201 A US2876201 A US 2876201A US 497799 A US497799 A US 497799A US 49779955 A US49779955 A US 49779955A US 2876201 A US2876201 A US 2876201A
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- Prior art keywords
- ammonia
- composition
- detergency
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- C—CHEMISTRY; METALLURGY
- C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
- C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
- C11D3/00—Other compounding ingredients of detergent compositions covered in group C11D1/00
- C11D3/16—Organic compounds
- C11D3/37—Polymers
- C11D3/3746—Macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds
- C11D3/3757—(Co)polymerised carboxylic acids, -anhydrides, -esters in solid and liquid compositions
- C11D3/3765—(Co)polymerised carboxylic acids, -anhydrides, -esters in solid and liquid compositions in liquid compositions
Definitions
- the present invention relates to improved detergent compositions in the field of the so-called nonionic detergents.
- An object of the present invention is to raise the measured detergency value of nonionic detergents to a level far above that previously attainable.
- This and other objects of the invention are accomplished by the addition of a builder and a base to the nonionic detergent.
- the nonionic detergents are all condensation products of ethylene oxide and a nucleus which may vary from one product to another. Likewise, the number of mols of ethylene oxide used for each mole of the nuclear compound may vary.
- the nonionics which have been satisfactorily built to a high detergency value by the present invention are listed the following:
- the builder found most satisfactory for purposes of this invention is a 'water-soluble anionic polyelectrolyte, namely the sodium salt of styrene-maleic anhydride copolymer sold by Monsanto Chemical Company as Stymer S.
- the bases found useful for purposes of this invention appear'to be limited to ammonia and organic amides as ordinarily used bases such as the phosphates and the carbonates appear to impair rather than enhance the building properties of the Stymer S.
- detergency value is expressed in terms of a detergency ratio" based on controlled laundering of samples soiled with pigment. Detergency ratio is determined as follows:
- Amanthrene Olive Green B is a vat color having the formula: I V
- the mouth of the jar is covered with a stainless steel disc to prevent entrapment of theswatchin the lid of the jar.
- the launderometer is run for 30 minutes after which the samples are rinsed in the jars 3 times with 200 ml. water. Four samples are run for each detergent composition or concentration and the results averaged. The samples are allowed to dry at room temperature.
- the reflectances of the samples are measured with a Photovolt photoelectric reflectometer under a tristimulus green filter.
- the reflectance of each sample is measured before and after scouring. After the reflectance differences are formed and averaged, the detergency ratio is determined by the following formula.
- R is the reflectance increase produced by the detergent.- R is the reflectance increase produced by 0.25% tallowsoap.
- Example 1 To 0.2% of Triton X-100, which has an unbuilt detergency ratio of 85 at a wash temperature of 180 F. and of 90 at 140 F., was added .05% Stymer S and 0.1% NH as 28% NH OH. The detergency ratio of this composition, determined in accordance with the procedure outlined above, was 141 at a wash temperature of 140- F. and 170 at a wash temperature of 180 F. This example was repeated with the same compositionomitting the ammonia, and the detergency ratio was reduced to 128, at140 F. and 145 at 180 F.
- Example 2 To 0.2% Energetic W400, which has an unbuilt dc,- ter'gency ratio of 55 at a wash temperature of 180 F. and of 84 at 140 F., was added .05% Stymer S and 0.1 NH, as 28% NH OH. The detergency ratio of this composition determined in accordance with the procedure outlined above was 124 at a wash temperature of 140 F.
- Example 3 To 0.2% Sterox SK, which has an unbuilt detergency ratio of 21 at a wash temperature of 180 F. and of lit/14.0? F., was added .05% Stymer S and 0.1% NH, as, 28% NH QH. The detergency ratio of this OQmPOSition determined in accordance with the procedure outlined above was. 112 at a wash temperature of 140 F. and 121 at a wash temperature of 180 F. This example I, repeated with the. same composition omitting the 4- ammonia, and the detergency ratio was reduced to 79 at 140 F. and 66 at 180 F.
- Example 4 To 0.2% of Sterox A], which has an unbuilt detergency ratio of 63 at a wash temperature of 140 F., was added .05% Stymer S and 0.1% NH as 28% Nl-l Ol-l. The detergency ratio of this composition determined in accordance with the procedure outlined above was 132 at a wash temperature of 140 F. This example was repeated with the same composition omitting the ammonia, and
- the detergency ratio was reduced to 116 at 140- F.
- the entire example was then repeated three times, once with monoethanolamine substituted for the ammonia, once with diethanolamine substituted for the ammonia, and once with triethanolamine substituted for the ammonia. In all three instances the results obtained with the com-- positions containing the amines duplicated the results obtained with the composition containing the ammonia, within the range of ordinary experimental error.
- Example 5 ammonia, and the detergency ratio was reduced to- 104 at 140 F. and 129 at 180 F. The entire example was then repeated three times, once with monoe'thanoh.
- dure outlined above was 104 at awash temperature of 140 F. and 127 at a wash temperature of 180 F. example was repeated with the same composition omit-Q ting the ammonia, and the detergency ratio was reduced to 72 at 140 F. and 69 at 180 F. The entire example.
- cedure outlined above was 139 at a wash temperature of 140 F. and 154 at a wash temperature of 180' F. This example was repeated with the same composition omitting the ammonia, and the detergency ratio was reduced to 122 at 140 F. and 128 at 180 F. The entire example was then repeated three times, once with monoethanolamine substituted for the ammonia, once with diethanolamine substituted for the ammonia, and once with triethanolamine substituted for the ammonia. In all three instances the results obtained with the compositions containing the amines duplicated the results obtained with the composition containing the ammonia, within the range of ordinary experimental error.
- the quantity of nonionic and the quantity of builder used in the above examples has been arbitrarily chosen for test purposes and the invention should not be construed as limited thereto. It has been determined in the laboratory that increasing the quantity of either or both above the level shown in the examples will not substantially raise the detergency ratio of the composition. It has also been determined that lesser quantities of each will still give good results.
- the amount of nonionic detergent should not be less than 0.05 and the amount of builder should not be less than about .03% as its building action is gradually lowered as its concentration is lowered below 0.05%.
- the present invention provides a detergent composition comprising a nonionic active ingredient, a builder, and a limited number of bufiering bases which permits obtaining a new high in detergency value.
- a detergent composition consisting essentially of a water solution of at least 0.05% of a synthetic organic nonionic detergent, at least 0.03% of a water-soluble sodium salt of a styrene-maleic anhydride copolymer for building the detergency value of said detergent and a base selected from the group consisting of ammonia, monoethanolamine, diethanolamine and triethanolamine in an amount sufilcient to give the composition a pH above 9.
- composition as set forth in claim 1 wherein the base is monoethanolamine.
- composition as set forth in claim 1 wherein the base is diethanolamine.
- a composition as base is triethanolamine.
- a composition as base is ammonia.
Description
r h DETERGENT COMPOSITION Paul Feldmann, Danville, Va., assignor to Dan River Inc., Danville, Va., a corporation of Virginia No Drawing. Application March 29, 1955 Serial No. 497,799 I Claims. (Cl. 252-152) The present invention relates to improved detergent compositions in the field of the so-called nonionic detergents.
An object of the present invention is to raise the measured detergency value of nonionic detergents to a level far above that previously attainable. This and other objects of the invention are accomplished by the addition of a builder and a base to the nonionic detergent. The nonionic detergents are all condensation products of ethylene oxide and a nucleus which may vary from one product to another. Likewise, the number of mols of ethylene oxide used for each mole of the nuclear compound may vary. Among the nonionics which have been satisfactorily built to a high detergency value by the present invention are listed the following:
The cloud points are given to further characterize the detergents, it being known'that this temperature point is determined by the length of the polyoxyethylene chain which forms thesolubilizing group of the nonionic deterg'ent.
' The builder found most satisfactory for purposes of this invention is a 'water-soluble anionic polyelectrolyte, namely the sodium salt of styrene-maleic anhydride copolymer sold by Monsanto Chemical Company as Stymer S. The bases found useful for purposes of this invention appear'to be limited to ammonia and organic amides as ordinarily used bases such as the phosphates and the carbonates appear to impair rather than enhance the building properties of the Stymer S.
' It appears that the maximum detergency value of nonionics built in accordance with this invention is obtained.
at about pH 10. As the pH of the mixture is lowered from pH 10, the detergency value is progressively lowered also, but raising the pH above pH does not appear to effect any substantial change. It is believed that amines or ammonia are essential to maintain a bulfered solution in which the pH is held at or near the optimum, particularly in the presence of the ordinary contaminatin materials found in laundering dirty articles.
In the following description and examples detergency value is expressed in terms of a detergency ratio" based on controlled laundering of samples soiled with pigment. Detergency ratio is determined as follows:
' A sample of prepared and bleached type 180 cotton a 2 sheeting is padded with about 65% of its weight of a dispersion'of 30 grams Amanthrene Olive Green-B Paste per liter and allowed to dry at room temperature. Amanthrene Olive Green B is a vat color having the formula: I V
mouth of the jar is covered with a stainless steel disc to prevent entrapment of theswatchin the lid of the jar. The launderometer is run for 30 minutes after which the samples are rinsed in the jars 3 times with 200 ml. water. Four samples are run for each detergent composition or concentration and the results averaged. The samples are allowed to dry at room temperature.
Four samples are always run with 0.25% of an tallow soap'in distilled water as a standard.
The reflectances of the samples are measured with a Photovolt photoelectric reflectometer under a tristimulus green filter. The reflectance of each sample is measured before and after scouring. After the reflectance differences are formed and averaged, the detergency ratio is determined by the following formula.
R is the reflectance increase produced by the detergent.- R is the reflectance increase produced by 0.25% tallowsoap.
TABLE'A Detergency" Base: ratio Tetrasodium pyrophosphate 93 Borax 98 Soda ash 82' Disodium phosphate 107'" Ethanolamine Another stock selutionf of 0.2% Triton X-100 and 0.05% Stymer S was divided into five portions for dem- 1 onstrating the effect of pH in the laboratory. The pH of each portion was adjusted to the values shown in Table B below" with small amounts of hydrochloric acid or sodium hydroxide and the detergency ratio of each portion was determined by the procedures outlined above at a wash temperature of 180 F. The results are shown in Table B, below:
It should be noted that this procedure was for the purposes of laboratory evaluation only, as contaminants under ordinary laundry conditions might cause the pH to shift in either direction, depending on the nature of the .contaminating materials.
The invention will be better understood by reference to the following examples.
Example 1 To 0.2% of Triton X-100, which has an unbuilt detergency ratio of 85 at a wash temperature of 180 F. and of 90 at 140 F., was added .05% Stymer S and 0.1% NH as 28% NH OH. The detergency ratio of this composition, determined in accordance with the procedure outlined above, was 141 at a wash temperature of 140- F. and 170 at a wash temperature of 180 F. This example was repeated with the same compositionomitting the ammonia, and the detergency ratio was reduced to 128, at140 F. and 145 at 180 F. The entire example was then repeated three times, once with monoethanolamine substituted-for the ammonia, once with diethanolamine substituted for the ammonia, and once with triethanolamine substituted for the ammonia. In all three instances the results obtained with the compositions containing the amines duplicated the results obtained with the composition containing the ammonia, within the range of ordinary experimental error.
Example 2 To 0.2% Energetic W400, which has an unbuilt dc,- ter'gency ratio of 55 at a wash temperature of 180 F. and of 84 at 140 F., was added .05% Stymer S and 0.1 NH, as 28% NH OH. The detergency ratio of this composition determined in accordance with the procedure outlined above was 124 at a wash temperature of 140 F.
Example 3 To 0.2% Sterox SK, which has an unbuilt detergency ratio of 21 at a wash temperature of 180 F. and of lit/14.0? F., was added .05% Stymer S and 0.1% NH, as, 28% NH QH. The detergency ratio of this OQmPOSition determined in accordance with the procedure outlined above was. 112 at a wash temperature of 140 F. and 121 at a wash temperature of 180 F. This example I, repeated with the. same composition omitting the 4- ammonia, and the detergency ratio was reduced to 79 at 140 F. and 66 at 180 F. The entire example was then repeated three times, once with monoethanolamine substituted for the ammonia, once with diethanolamine substituted for the ammonia, and once with triethanolamine substituted for the ammonia. In all three in stances the results obtained with the compositions containing the amines duplicated the results obtained with the composition containing the ammonia, within the range of ordinary experimental error.
Example 4 To 0.2% of Sterox A], which has an unbuilt detergency ratio of 63 at a wash temperature of 140 F., was added .05% Stymer S and 0.1% NH as 28% Nl-l Ol-l. The detergency ratio of this composition determined in accordance with the procedure outlined above was 132 at a wash temperature of 140 F. This example was repeated with the same composition omitting the ammonia, and
the detergency ratio was reduced to 116 at 140- F. The entire example was then repeated three times, once with monoethanolamine substituted for the ammonia, once with diethanolamine substituted for the ammonia, and once with triethanolamine substituted for the ammonia. In all three instances the results obtained with the com-- positions containing the amines duplicated the results obtained with the composition containing the ammonia, within the range of ordinary experimental error.
Example 5 ammonia, and the detergency ratio was reduced to- 104 at 140 F. and 129 at 180 F. The entire example was then repeated three times, once with monoe'thanoh.
amine substituted for the ammonia, once with diethanol-..
amine substituted for the ammonia, and once with triethanolamine substituted for the ammonia. In all three instances the results obtained with the compositions con-. taining the amines duplicated the results obtained with the composition containing the ammonia, within the range of ordinary experimentz :rror.
Example 6.
To 0.2% of Nonic 261, which has an unbuilt deter: gency ratio of 44 at a wash temperature, of 180 F. and
of 25 at 140 F., was added .05,% Stymer S and 0.1% NH as 28% NH OH. The detergency ratio ofithis, composition determined in accordance with the.
dure outlined above was 104 at awash temperature of 140 F. and 127 at a wash temperature of 180 F. example was repeated with the same composition omit-Q ting the ammonia, and the detergency ratio was reduced to 72 at 140 F. and 69 at 180 F. The entire example.
was then repeated three times, once with monoethanolamine substituted for the ammonia, once with diethanolamine substituted for the ammonia, and once with triethanolamine substituted for the ammonia. all three instances the results obtained with the compositions con; taining the amines duplicated the results obtained withthe composition containing the ammonia, within the-rangeof ordinary experimental error.
detergency ratio of 71 at a wash temperature oi 180? FI and of at F., was added 05% Stymer-:5 and 01% a a 2 H4OH- The c ers ncy r io ats compos ion de ermine in. ccordance-l with 2&
cedure outlined above was 139 at a wash temperature of 140 F. and 154 at a wash temperature of 180' F. This example was repeated with the same composition omitting the ammonia, and the detergency ratio was reduced to 122 at 140 F. and 128 at 180 F. The entire example was then repeated three times, once with monoethanolamine substituted for the ammonia, once with diethanolamine substituted for the ammonia, and once with triethanolamine substituted for the ammonia. In all three instances the results obtained with the compositions containing the amines duplicated the results obtained with the composition containing the ammonia, within the range of ordinary experimental error.
The quantity of nonionic and the quantity of builder used in the above examples has been arbitrarily chosen for test purposes and the invention should not be construed as limited thereto. It has been determined in the laboratory that increasing the quantity of either or both above the level shown in the examples will not substantially raise the detergency ratio of the composition. It has also been determined that lesser quantities of each will still give good results. The amount of nonionic detergent should not be less than 0.05 and the amount of builder should not be less than about .03% as its building action is gradually lowered as its concentration is lowered below 0.05%.
Thus it will be seen that the present invention provides a detergent composition comprising a nonionic active ingredient, a builder, and a limited number of bufiering bases which permits obtaining a new high in detergency value.
I claim:
1. A detergent composition consisting essentially of a water solution of at least 0.05% of a synthetic organic nonionic detergent, at least 0.03% of a water-soluble sodium salt of a styrene-maleic anhydride copolymer for building the detergency value of said detergent and a base selected from the group consisting of ammonia, monoethanolamine, diethanolamine and triethanolamine in an amount sufilcient to give the composition a pH above 9.
2. A composition as set forth in claim 1 wherein the base is monoethanolamine.
3. A composition as set forth in claim 1 wherein the base is diethanolamine.
4. A composition as base is triethanolamine.
5. A composition as base is ammonia.
References Cited in the file of this patent UNITED STATES PATENTS set forth in claim 1 wherein the set forth in claim 1 wherein the 2,047,398 Voss July 14, 1936 2,205,021 Schuette June 18, 1940 2,702,277 Kinney Feb. 15, 1955
Claims (1)
1. A DETERGENT COMPOSITION CONSISTING ESSENTIALLY OF A WATER SOLUTION OF AT LEAST 0.05% OF A SYNTHETIC ORGANIC NONIONIC DETERGENT, AT LEAST 0.03% OF A WATER-SOLUBLE SODIUM SALT OF A STYRENE-MALEIC ANHYDRIDE COPOLYMER FOR BUILDING THE DETERGENCY VALUE OF SAID DETERGENT AND A BASE SELECTED FROM THE GROUP CONSISTING OF AMMONIA, MONOETHANOLAMINE, DIETHANOLAMINE AND TRIETHANOLAMINE IN AN AMOUNT SUFFICIENT TO GIVE THE COMPOSITION A PH ABOVE 9.
Priority Applications (1)
Application Number | Priority Date | Filing Date | Title |
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US497799A US2876201A (en) | 1955-03-29 | 1955-03-29 | Detergent composition |
Applications Claiming Priority (1)
Application Number | Priority Date | Filing Date | Title |
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US497799A US2876201A (en) | 1955-03-29 | 1955-03-29 | Detergent composition |
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US2876201A true US2876201A (en) | 1959-03-03 |
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US497799A Expired - Lifetime US2876201A (en) | 1955-03-29 | 1955-03-29 | Detergent composition |
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Cited By (1)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US3278444A (en) * | 1964-06-22 | 1966-10-11 | Kelite Chemicals Corp | Detergent composition |
Citations (3)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US2047398A (en) * | 1930-06-26 | 1936-07-14 | Ig Farbenindustrie Ag | Artificial resins and process of making them |
US2205021A (en) * | 1934-11-02 | 1940-06-18 | Ig Farbenindustrie Ag | Production of condensation products |
US2702277A (en) * | 1955-02-15 | Detergent composition |
-
1955
- 1955-03-29 US US497799A patent/US2876201A/en not_active Expired - Lifetime
Patent Citations (3)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US2702277A (en) * | 1955-02-15 | Detergent composition | ||
US2047398A (en) * | 1930-06-26 | 1936-07-14 | Ig Farbenindustrie Ag | Artificial resins and process of making them |
US2205021A (en) * | 1934-11-02 | 1940-06-18 | Ig Farbenindustrie Ag | Production of condensation products |
Cited By (1)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US3278444A (en) * | 1964-06-22 | 1966-10-11 | Kelite Chemicals Corp | Detergent composition |
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