US3749682A

US3749682A - Detergent composition

Info

Publication number: US3749682A
Application number: US00165584A
Authority: US
Inventors: E Tanner
Original assignee: Lever Brothers Co
Current assignee: Lever Brothers Co
Priority date: 1970-08-12
Filing date: 1971-07-23
Publication date: 1973-07-31
Anticipated expiration: 1990-07-31
Also published as: FR2104227A5; GB1354498A; NO135323C; BE771251A; NO135323B; CA941709A; NL156185B; JPS5238045B1; AT310333B; SE390421B; DE2139923B2; NL7110923A; DE2139923A1; CH565859A5

Abstract

A DETERGENT COMPOSITION WITH GOOD ANTI-SOIL-REDEPOSITION CHARACTERISTICS FOR SYNTHETIC AND SIMILAR FABRICS IS PROVIDED BY INCORPORATING THEREIN A SMALL PROPORTION OF A COPOLYMER OF VINYLPYRROLIDONE AND VINYLACETATE. GENERALLY THE VINYLPYRROLIDONE/VINYLACETATE COPOLYMERS INCORPORATED HAVE AN AVERAGE MOLECULAR WEIGHT WITHIN THE RANGE OF ABOUT 10,000 TO ABOUT 400,000, PREFERABLY FROM ABOUT 20,000 TO ABOUT 200,000.

Description

United States Patent 3,749,682 1 DETERGENT COMPOSITION Emil Tanner, Basel, Switzerland, assignor to Lever Brothers Company, New York, N.Y.

No Drawing. Filed July 23, 1971, Ser. No. 165,584 Claims priority, application Great Britain, Aug. 12, 1970, 38,797 7 0 Int. Cl. Clld 3/28 U.S. Cl. 252-524 6 Claims ABSTRACT OF THE DISCLOSURE A detergent composition with good anti-soil-rcdeposition characteristics for synthetic and similar fabrics is provided by incorporating therein a small proportion of a copolymer of vinylpyrrolidone and vinylacetate. Generally the vinylpyrrolidone/vinylacetate copolymers incorporated have an average molecular weight within the range of about 10,000 to about 400,000, preferably from about 20,000 to about 200,000.

BACKGROUND OF THE INVENTION Field of the invention Detergent compositions.

Description of the prior art Modern textiles, particularly those composed of synthetic fabrics or a mixture of natural and synthetic fabrics, or chemically modified cotton, show a tendency to greying on washing.

Hitherto sodium carboxymethylcellulose has been used extensively in detergent compositions to reduce redeposition of soil during the washing process. However, whereas it is a very effective anti-redeposition agent for cotton and similar fabrics, it is ineffective as an anti-redeposition agent for synthetic, especially polyester fabrics. In recent years vinyl compounds, viz, polyvinyl alcohol and polyvinylpyrrolidone have been proposed as soil-suspending agents for the prevention of soil redeposition, the suc cess of which has been very slight. Moreover, it has now been established that, particularly the higher molecular weight polyvinyl alcohols show drawbacks during the processing and use of detergent compositions containing these materials. These substances tend to agglomerate in the slurry, which may be caused by their susceptibility of being salted out by electrolytes. The result is that coarse particles are formed which in some instances grow into large lumps attaching to the stirring elements of the slurry mixer. When added as a fine powder to the final composition to overcome this difficulty, their tendency to agglomerate still causes the formation of undissolved flakes during the washing process, which tend to attach to the laundry article, particularly to knitted fine wash garments.

Applicant has found that copolymers of vinylpyrrolidone and vinylacetate are good anti-redeposition agents for synthetic fabrics without showing the above drawbacks.

SUMMARY OF THE INVENTION The present invention relates to detergent compositions containing vinylpolymers as an anti-redeposition agent. Copolymers of vinylpyrrolidone and vinylacetate are good anti-redeposition agents for synthetic and similar fabrics.

Accordingly an object of the present invention is to provide a detergent composition having satisfactory anti-soilredeposition characteristics for modern textiles, and so reducing the tendency to greying of these fabrics on repeated washings.

3,749,682 Patented July 31, 1973 ice It has been found that copolymers of vinylpyrrolidone and vinylacetate are good anti-redeposition agents for synthetic and similar fabrics without showing the drawbacks of known agents. These copolymers used in small amounts already prevent redeposition of soil on synthetic fabrics as sodium carboxymethylcellulose does on cotton. The specific or exact degree of polymerisation is not critical provided the material has the desired water solubility. Generally the suitable vinylpyrrolidone/vinylacetate copolymers have an average molecular weight usually within the range of about 10,000 to about 400,000 and preferably from about 20,000 to about 200,000. Such copolymers are known commercially but their use as anti-redeposition agents has not hitherto been disclosed. Their degree of efiectiveness in reducing redeposition of soil depends on the ratio of vinylpyrrolidone (VP and vinylacetate (VA) portion in the copolymer. Optimum of activity was noted at a VPzVA mol ratio of 50:50. The preferred copolymers of the invention are those having VPzVA mol ratios of between 10:90 and :10, more preferably between 30:70 and 70:30.

The VP/VA copolymers can be incorporated in liquid as well as particulate or solid detergent compositions. Used in particulate detergent compositions they may be admixed with the other ingredients in the conventional manner during the slurry-making preparation, followed by spray-drying. Some degree of hydrolysis of the acetateportion of the copolymer may have occurred during the processing, without affecting the physical properties of the slurry or of the powder characteristics and its performance. The spray-dried powder shows no increase in hygroscopicity at all by the VP/VA copolymer content and maintains its free-flowing properties on storage.

The invention therefore provides a detergent composition comprising essentially a detergent active compound and a copolymer of vinylpyrrolidone and vinylacetate as hereinbefore defined.

Generally the amount of the vinylpyrrolidonelvinylacetate copolymer used as anti-redeposition agent in the composition should be a minor proportion of the composition, e.g. 0.1 to 5.0% by weight of the detergent composition, preferably from 0.2% up to 2.0%

The detergent active compound in the composition according to the invention can be any of the conventional anionic, nonionic, cationic or ampholitic detergent active compounds normally included in fabric washing detergent compositions. Examples of suitable detergent active compounds are: alkylaryl sulphonates; alkyl or alkane sulphonates; alkyl sulphates; alkyl phosphates; the mixtures of anionic detergent active compounds produced by the sulphonation with sulphur trioxide, and subsequent hydrolysis and neutralisation of unsaturated hydrocarbons (commonly called oefine sulphonates); ethoxylated alcohols; ethoxylated alkyl phenols; ethoxylated amines; ethoxylated fatty acid amides; sulphates and phosphates of these ethoxylated materials; amine oxides; isothionates; C -C fatty acid soaps; taurines; betaines and sulphobetaines. Mixtures of these detergent active compounds may be used, if desired. They normally comprise 2 to 60% by weight of the detergent composition, but soap powders or soap flakes generally have a much higher active detergent content i.e. up to In addition to the detergent active compound and the VP/VA copolymer, a composition of the invention may comprise any of the other conventional detergent composition ingredients, such as fatty acid amide lather boosters, e.g. coconut ethanolamide and palmkernel ethanolamide; inorganic and organic detergency builders such as sodium tripolyphosphate, trisodium orthophosphate and sodium nitrilotriacetate; hydrotropes such as sodium xylene sulphonate, sodium toluene sulphonate etc.; additives for inhibiting corrosion and fabric damage such as silicates; inorganic salts such as sodium sulphate and sodium carbonate; bleaches such as sodium perborate, sodium percarbonate and sodium chlorocyanurates; and, usually present in minor amounts, perfumes, colourants, fiuorescers, germicides, enzymes and other anti-redeposition agents, such as sodium or potassium carboxymethylcellulose. This latter agent may be present in the composition in amounts of the same order as the anti-redeposition agent of the invention, viz 0.1-5.0% by weight, without aflecting each others performance.

The following examples illustrate aspects of the invention in greater detail.

EXAMPLES III The anti-redeposition characteristics of two VP/ VA copolymers were compared with those of polyvinylpyrrolidone in a conventional nonionic base powdered detergent formulation using the following test method. A bowl washing machine provided with a mechanical stirrer was used.

(=chemically modified cross-linked Example 1 2 A B Components (percent):

N ouylphenol-lO ethylene oxide 10. 0 10.0 10.0 10. 0 10. 0

Sodium carbonate 6.0 6.0 G. 0 6.0 6. 0

Sodium sulphate. 24.0 24.0 24.0 24.0 24. 0

Proteolytic enzyme 2. 2 2. 2 2. 2 2. 2 2. 2

Water, perfume, etc. 3. 8 3.8 3.8 3. 8 3.8

Anti-rcdeposition age 0.2 0.2 0.2 0.2

1 Example 1: VP/V A copolymer 60:40 (obtained from Badische Anilin und Soda Fabriken and sold under the trade name Luviskol VA 64). Example 2: VP/VA copolymer 50:50 (obtained from General Aniline & Film Corp. and sold under the trade name Elia E-535). Example A: Polyvinylpyrrolidone (obtained from BASF and sold under the trade name Luviskol K Example B: Polyvinylpyrrolidone (obtained from BASF and sold under the trade name Luvislrol K 90).

The above table clearly shows the good anti-redeposition effect of the copolymers according to the invention in a nonionic detergent composition.

EXAMPLES III-VI The anti-redeposition characteristics of four VP/VA copolymers were compared with those of other polymeric compounds in a conventional powdered detergent com- 75 position containing soap, using the test method as explained in Examples I-II.

3 4 5 6 D E F Components (percent):

Sodium Cn-alkylbenzene sulphonate 7.0 7.0 7.0 7. 0 7. 0 7. 0 7. 0 Nonylphenol oxide 3.5 3. 5 3. 5 3. 5 3. 5 3.5 3.5 Soap (Cit-C19 fatty acids) 11.5 11.5 11.5 11.5 11.5 11.5 11.5 Sodium tripolyphosphate. 50.0 50. 0 50.0 50. 0 50.0 50.0 50. 2 Sodium sulphate 6. 9 6. 9 6.9 6. 9 6. 9 6. 9 6. 9 Waterglass (SiOzzNazO 2.3:1) 6.0 6.0 6.0 6.0 6.0 6 0 Sodium carboxymethylcellulose 1.8 1.8 1.8 1.8 1.8 1.8 Ethyleuediamine tetraacetic acid 0. 2 0.2 0. 2 0. 2 0.2 0.2 Water, perfume, etc 12.9 12.9 12. 9 12. 9 12. J 12.9 12. 9 Anti-redeposition agent 0.2 0.2 0.2 0.2 0.2 0.2

1 Example 3: VP/VA copolymer 50:50(ex GAF; sold under the trade name Ella E 535). Example 4: VP/VA copolymcr 20:80-(ex BASF; sold under the trade name Luviskol VA 28). Example 5: VP/VA copolymer 50:50(ex BASF; sold under the trade name Luviskol VA 55E). Example 6: VP/VA copolymer 60:40-(ex BASF; sold under the trade name Luviskol VA 64). Example D: Alkylmonoester of poly(methylvinylether)(ex GAF, sold under code number ES 225). Example E: zgglrggf-acrylic ester copolymer(ex I'Ioechst, sold under code number The above Table II shows that even in soap containing compositions the effect of the VP/VA copolymers is still clearly noticeable.

EXAMPLE VII The anti-redeposition characteristics of composition of Example V was tested in washing naturally soiled fabrics in a Schulthess drum-type Washing machine set for the synthetic wash cycle with a maximum temperature of 60 C. The whiteness degree after 25 and 50 washes, measured with the Elrepho-photometer were compared with a similar composition without a VP/VA copolymer being present, except for sodium carboxymethylcellulose which was present as an anti-redeposition agent for cotton fabrics in conventional compositions (composition F). These results are shown in Table III.

Test conditions Normally soiled white laundry goods were washed together with samples of cotton, nylon, polyester and Splendesto fabrics.

wash load: 4 kg.

detergent product concentrations: 5 g./ litre water hardness: 20 German hardness bath ratio: 1:6

washing temperature: 60 C.

TABLE III [Whitening degree measured with the Elrepho-photomotcr] After 25 washes After 50 washes Comp. 5 Comp. F Comp. 5 Comp. F

with without; with Without VP/VA VP/VA DitI. VP/VA VP/VA Ditt.

Cotton.-... 178 174 4 171 166 5 Nylon 141 123 18 138 127 11 Polyester... 155 5 161 150 11 174 1 179 174 5 Splendesto..

5 EXAMPLES VIII-XI The following powder detergent compositions were made without difficulty and were equally good in powder structure and performance.

Example 8 9 EXAMPLES XII-XIV Liquid preparations incorporating VP/VA copolymers devised for fine laundering.

Example 12 13 14 Components (percent):

Dodecyl benzene sulphonate. 7. 10. 0 10. 0 Lauryl ether sulphate 3. 0 5. 0 Lauryl sulphate-.. 4. 0 Nonylphenol-ll ethylene oxide 5. 0 5. 0 4. 0 Alkylether phosphate 15. 0 Urea 5. 0 3. 0 5. 0 Sodiumxylene sulphonat 3. 0 5.0 E thyl alcohol 6. 0 5. 0 Ethylene diamine tetraacetata.-- 0. 2 0. 2 Thickening agent 0. 8 Sodium nitrilotrlacetate. 10. 0 Sodium tripolyphosphate.. 15.0 Antl-redeposition agent I 0. 5 1. 0 0. 8 Sodium carboxymethylcellulose. 1. 0 Water plus perfume 65. 5 56. 0 59. 0

1 Example 12: VP/VA copolymer 50:50 ex BASF. Example 13: VP/VA (igpggmer 20:80 ex BASF. Example 14: VP/VA copolymer 60:40 ex What is claimed is:

1. A detergent composition consisting essentially of 2 percent to 95 percent by weight of a detergent active compound selected from the group consisting of anionic, nonionic, ampholitic detergents and mixtures thereof; and 0.1 percent to 5.0 percent by weight of a copolymer of vinylpyrrolidone and vinylacetate, said copolymer having an average molecular weight within the range of 10,000 to 400,000 and a vinylpyrrolidone/vinylacetate ratio of between :90 and 90:10.

2. A detergent composition according to claim 1, wherein said copolymer has an average molecular weight within 6 the range of 20,000 to 200,000, and a vinylpyrrolidone/ vinylacetate ratio of between 30:70 to :30.

3. A detergent composition according to claim 1, wherein said copolymer has a vinylpyrrolidone/vinylacetate ratio of 50:50.

4. A detergent composition according to claim 1, wherein the proportion of said copolymer is 0.2% to 2.0% by weight of the detergent composition.

5. A detergent composition consisting essentially of 2 percent to 95 percent by weight of a detergent active compound selected from. the group consisting of anionic, nonionic, ampholitic detergents and mixtures thereof; a copolymer of vinylpyrrolidone and vinylacetate having an average molecular weight within the range of 10,000 to 400,000, in an amount of 0.1% to 5.0% by weight of the composition, and an alkali metal carboxymethylcellulose in an amount of 0.1% to 5.0% by weight of the composition.

6. A detergent composition consisting essentially of 2 to 60% by weight of a detergent active compound, selected from the group consisting of anionic, nonionic, cationic, ampholitic detergents and mixtures thereof, 0.1 to 5.0% by weight of a copolymer of vinylpyrrolidone and vinylacetate having an average molecular weight within the range of 10,000 to 400,000, and the balance being primarily water-soluble inorganic and organic detergency builder salts and water, said detergency builder salts being selected from the group consisting of sodium phosphates, nitrilotriacetates, sodium sulphate, sodium carbonate, sodium silicates and mixtures thereof.

References Cited UNITED STATES PATENTS 3,144,391 8/1964 Goff 424-71 3,558,499 1/1971 Galvin 252545 3,254,028 5/ 1966 Wixon 252524 3,000,830 9/ 1961 Fong 252524 2,667,473 1/ 1954 Morner 16787.2

OTHER REFERENCES PVP/VA Copolymer, GAF Technical Bulletin 7543- 031, 1966.

LEON D. ROSDOL, Primary Examiner E. L. ROLLINS, Assistant Examiner U.S. Cl. X.R.

252-DIG. 15, 110, 117, 527, 542, 546; 424-