US3894960A

US3894960A - Activated peroxygen detergent

Info

Publication number: US3894960A
Application number: US255359A
Authority: US
Inventors: Frederick William Gray; Paul Sheldon Grand
Original assignee: Colgate Palmolive Co
Current assignee: Colgate Palmolive Co
Priority date: 1972-05-22
Filing date: 1972-05-22
Publication date: 1975-07-15
Anticipated expiration: 1992-07-15

Abstract

Laundry detergent compositions of low phosphate content and high sodium silicate content, containing peroxygen compound and activator therefore in minor amount.

Description

United States Patent [1 1 [111 3,894,960 Gray et al. July 15, 1975 1 ACTIVATED PEROXYGEN DETERGENT 3,655,567 4/1972 Gray 252/99 175] inventors: Frederick William Gray, Summit;

Paul Sheldon Grand, South Bound Brook both of Ni Primary ExammerMayer Wemblatt I Attorney, Agent, or FirmHerbert 8 Sylvester;

[73] Assrgnee: Colgate-Palmolive Company, New Murray M. Grill; Ronald S. Come" York, N.Y.

1122] Filed: May 22, 1972 121] App]. No.: 255,359

[57] ABSTRACT \[52] US. Cl. 252/99; 252/95; 252/187 1511 Int. Cl. Clld 7/18; c1 1d 7/38 Laundry detergent composltwns of low phosphate [581 Field of Search 252/99, 95, 187 Content and high Sodium Silicate Content, Containing peroxygen compound and activator therefore in minor [56] References Cited amount UNITED STATES PATENTS 3.637339 1/1972 Gray 252/99 UX 5 Claims, N0 Drawings ACTIVATED PEROXYGEN DETERGENT This invention relates to laundry detergent compositions which contain little or no phosphate builder and which are mixtures of organic sulfonate or sulfate detergents with sodium silicate in large amounts. Certain particularly useful compositions of this type are described in the following three copending applications of Paul S. Grand, all filed on Nov. 12, 1971: Ser. No. 198.454 (Sulfate Detergent Compositions) Ser. No. 198.455 (Sulfonate Detergent Compositions) and Ser. No. 198,456 (Detergent Compositions); and in the continuations-in-part of said applications (having the same titles) being filed on or about May 22, 1972. The entire disclosures of the aforesaid Grand applications are incorporated herein by reference.

These compositions are particularly suitable for use in such amounts that the concentration of sulfonate or sulfate detergent in the wash water is within the range of about 0.02 to about 0.1%. Similarly the concentration of sodium silicate in the wash water is generally within the range of about 0.02 to 0.1%, more preferably about 0.03 to 0.06%. The sodium silicate is preferably the principal builder in the composition and is preferably present in an amount which is at least two thirds the amount of sulfonate detergent. For a composition to be used in 0.15% concentration in the wash water the proportion of sodium silicate is generally above 20% and below 50%.

It has been found that excellent stain removal is attained when such laundry detergent compositions are employed with a peroxygen compound in minor amount with an activator for said peroxygen compound, which activator is a peracid precursor. The amount of peroxygen compound is generally within the range of amounts representing about 5 to 30 parts of active oxygen per million parts of the wash water, more preferably about to 20 ppm of active oxygen based on the weight of wash water. For compositions to be used at 0.15% concentration in the wash water and containing sodium perborate tetrahydrate (having about 10% active oxygen), a 20 ppm concentration of active oxygen is supplied by the presence of about (e.g., 13%) sodium perborate tetrahydrate in the composition.

The mol ratio of activator to active oxygen (of the peroxygen compound) is preferably at most about 1:1 particularly in view of the relatively high cost of the activators. it has been found that good results can be obtained, at correspondingly lower cost, when lower ratlos are employed. Thus one may use such ratios as 1:2, 1:3, 1:4, 1:6, or 1:8 or even lower ratios, e.g., 1:20 or 1:60. These ratios also have the advantage, of being usable for the washing of wash loads containing colored fabrics. particularly when the acyl moiety of the activator is one which (like benzoyl or -m-chlorobenzoyl) yields a peracid of such strength tht it may tend to remove the dye from dyed fabrics (e.g., blue dyed cotton percale) when it is used in 1:1 mol ratio.

Activators which are peracid precursors, are well known in the art. They are described, for instance, in a series of articles by Gilbert in Detergent Age, June 1967 p. 18-20, July 1967 p. 30-33, August 1967 p. 26. 2.7 and 67. which explains that such compounds include esters. anhydrides and amides. A listing of some of the commonly known activators is also found in the U.S. Pat. No. to Woods 3,632,634. Other disclosures of suitable activators are found in Canadian Pat. No.

844,481 which describes such amides (N-acyl compounds) as the N-acyl azoles; U.S. Pat. No. 3,061,550 which describes certain acylated imides; British Pat. No. 907,376 describing certain N-acyl compounds such as tetraacetyl ethylenediamine, tetraacetyl methylenediamine, etc; published Swedish Pat. application No. 17880/68 describing acylated glycolurils such as tetraacetylglycoluril; and French Pat. No. 1,590,335, describing N-acyl compounds having a mchlorobenzoyl acyl group.

Particularly useful activators are of the amide type, well known in the art (and discussed in the patents and publications cited above) which have a monovalent carboxylic acyl group directly attached to a nitrogen atom and which, as mentioned above, form peracids on reaction with the peroxy compound in solution. in the most common such compounds the acyl group is acetyl or benzoyl or substituted benzoyl. It is within the broader scope of this invention, however, to use other types of peracid-forming activators, e.g., esters of anhydrides, (e.g., p-sulfophenyl ethyl carbonate). Various examples of activators are also given in Gray U.S. Pat. No. 3,637,339 of Jan. 25, 1972.

Preferred peroxygen compounds are sodium perborate, tetrahydrate and sodium percarbonate (e.g., Na

It is within the broader scope of the invention to use other forms of sodium perborate, e.g., sodium perborate monohydrate, or other activatable peroxy compounds; such compounds, e.g., urea-hydrogen peroxide and other peroxyhydrates, are well known in the art. The cation of the peroxygen compounds need not be Na; it may be, for example, K, Ca, Mg or H.

The invention is illustrated by the following Examples. In these Examples, and in the rest of application as well, all proportions are by weight unless otherwise indicated.

EXAMPLE 1 The accompanying Table 1 gives results obtained (in three series of runs) in tests of various detergent compositions for their effectiveness in the removal of stain on 3 X 6 inch coffee-tea stained cotton fabrics of predetermined reflectance (Rd) values, in a 10 minute washing in a vessel (a Tergotometer) at a temperature of 120F, followed by a 5 minute rinse in fresh water at F, (after which the swatches are dried, the Rd values are again recorded on 21 Gardner Color Difference Meter, and the average ARd value is determined.) In each case the amount of water in the wash vessel is one liter, the total amount of each Detergent is 1500 mg (giving a concentration of 0.15%). The activator used is m-chlorobenzoyl dimethylhydantoin.

The Silicate Detergent A contains 18% sodium linear dodecybenzenesulfonate, 25% sodium silicate of Na O:SiO mol ratio 1:2.35, 4% nonionic detergent (Neodol 45-1 1), 2% sodium carboxymethylcellulose, 6% soap, about 5% moisture and the balance sodium sulfate. The Silicate Detergent B is similar except that its content of sodium linear dodecylbenzenesulfonate is 25% and its content of soap is 1%. The High Phosphate (TPP) Detergent contains 10% alkylbenzenesulfonate, 2% nonionic detergent, 2% soap, 33% freshly added pentasodium tripolyphosphate (TPP) and the balance sodium sulfate and about 8% moisture. The High Phosphate (pyro) Detergent is 3 4 similar except that it contains 33% freshly added soi- The foregoing table indicates that despite a reduction dum pyrophosphate in place of the 33% TPP in the proportion of activator (in a system containing The 150 ppm hardness water and 300 ppm hardness about 15 ppm of active oxygen and water of convenwater are prepared by adding calcium and magn i tional hardness) the silicate system still gives good salts in appropriate amounts to New Brunswick tap wa' 5 bleachingter. Hardness is in ppm calculated as calcium carbonate EXAMPLE n (e.g. l00 ppm is equivalent to 40 ppm of Ca ion).

New Brunswick tap water has a hardness of about 100 ppm calculated as calcium carbonate and a copper content of less than 1 ppm. A typical chemical analysis of the New Brunswick tap water is as follows. all figures A test similar to that used in Example 1 (except that the washing time is minutes) is carried out with the seven compositions (a through g) tabulated below. The same compositions are also tested under the same con- (except pH) being in parts per milli unless th wi ditions, using clean blue percale swatches in place of indicated: total hardness 90, alkalinity 38, C0 8, pH the coffee-tea stained swatches. The results are given 7.6, chlorine 1.0, iron 0.05, manganese 0,00, on med in Table ll. It will be apparent that the use of a l:l mol oxygen 0.6, dissolved oxygen 15.0, chloride 25, tot l 15 ratio of the m-chlorobenzoyl activator caused undesirsolids 165, organic and volatile 40, min r l matter 125 able bleaching of the blue percale in the concentrations free ammonia 0.048, albumoid ammonia 0.015. nitrites mploy in his est.

TABLE II ARd VALUES OBTAINED ON WASHING WlTH Amount (mg) pesent per liter ofdwash solution a e f g Silicate Detergent A 1000 I000 I000 lOOO I000 1000 1000 NBenzoyl-Zmethylimidazole I 60 mChlorobenzoyldimethylhydantoin 50 87 120 60 Sodium perborate tetrahydrate 70 50 70 70 I00 100 EDTA* 20 20 20 20 20 20 20 Approximate mol ratio of l:l l:l l:l 1:2 l:l 1:2

activatorzperborate A Rd (coffee-tea) ll 67 9.3 l 1.3 9.0 l l.l 8.7 ARd (blue percale) 02 I4 2.2 3.1 0.7 0.4 O.2 Ab (blue percale) (H 1.6 3.4 4 8 0.5 0.3 0.8

pH for all runs: 9.8 0.l

EDTA is ethylenediaminetetraacetic acid sodium salt; it is a sequestering agent. which efi'cctively removes metal ions such as heavy metal ions (e.g. Fe ions) from the water as nitrogen 0.00, nitrates as nitrogen 0.20. A typical The peroxygen compound and activator may be ini l l i f thi water Supply i h figures again cluded in the compositions of the aforesaid Grand pain ppm) is: sulfates 45. silica l5. calcium 23.2. magnetent pp i n y imply including said peroxygen compound and activator in place of an equal amount sium 7.776.

of the diluent (e.g., sodium sulfate) in said composi- 40 TABLE I Rd VALUES OBTAINED ON WASHING WITH l500mg of l500mg of ISOOmg of Detergent" Detergent Detergent" l500mg of alone plus the 150 mg Detergent plus I perborate plus plus the I50 mg mg sodium mg activator perborate plus perborate (1:3 activator: 250 mg activator tetrahyperborate mol (l:l mol Detergent drate ratio) ratio) Series Water Silicate Detergent A 0.6, 0 7 ()9. l0 7.2 8.] l -0.5 l Silicate Detergent B 0.7, -l.() 0.9. I8 50 6| l 0.2 l I New V High phosphate 07, 07 ll. |.7 2.4 6.6 Brunswick (TPP) Detergent 0.] 9 tap water (hardness High phosphate 0.2 0.8 I5) 30 4.8 about (pyro) Detergent ppm) l Silicate Detergent A 3.1, 3.7 ll New l Brunswick High phosphate l tap water (TPP) Detergent l.5

Zero hardness l50 ppm hardness 300 ppm hardness Silicate Detergent A 3.7 4.6 5.3 Hi h phosphate (TP) Detergent 3.4 2.0 L0 lll as in- High Phosphate dicated 4.5 3.0 4.4 l at left (pyro) Detergent tions. The amounts of sodium silicate and sulfonate or sulfate detergent in the resulting composition will be greater than the amount of peroxygen compound; the ratio of the amount of sodium silicate to the amount of peroxygen compound ratio will generally be at least about 2:1 (e.g., about 2:1 to 4:1) and the ratio of the total amount of surface active detergent (including nonionic detergent and soap, for instance) to the amount of peroxygen compound will generally also be at least about 2:1 (e.g., about 2:1 to 4:1). The sodium silicate preferably has an Na O:SiO ratio of about 1:2 to 1:3.

1n some cases either the activator or peroxygen compound or both may be suitably encapsulated (e.g., by means of a polymeric coating) to improve the storage stability of the composition with respect to moisture and other influences.

The washing temperatures may be the same as those taught in the art for use with activated peroxygen compositions, e.g., below l60F and usually above room temperature, e.g., 90 or 100F to 150F, such as 105 pr 120 or 150F.

It is understood that the foregoing detailed description is given merely by way of illustration and that variations may be made therein without departing from the spirit of the invention. The Abstract given above is merely for the convenience of technical searchers and is not to be given any weight with respect to the scope of the invention.

We claim:

1. Built laundry detergent composition consisting essentially of (a) water soluble anionic sulfonate or sulfate detergent, (b) sodium silicate as the principal builder salt, (c) a peroxygen compound and (d) an activator for said peroxygen compound, said activator having a carboxylic acyl group, said peroxygen compound being one which reacts with said activator to form the corresponding percarboxylic acid on addition of said composition to the wash water, the ratio of c to d being from about 8:1 to 2:1 of the stoichiometric ratio for said reaction, the ratio (a b):c being at least 2:1 and the ratio hr being over 1:1, and wherein said sodium silicate has an Na O:SiO- ratio of about 1:2 to 1:3.

2. Composition as in claim 1 in which the peroxygen compound is sodium perborate or sodium percarbonate and the activator is one which reacts therewith to form a perbenzoic acid.

3. Composition as in claim 2 in which the activator is a m-chlorobenzoyl amide.

4. A composition as in claim 2 in which said bzc ratio is at least 2:1.

5. Built laundry detergent composition consisting essentially of (a) water soluble sodium linear alkylbenzenesulfonate detergent, (b) sodium silicate as the principal builder salt, (c) a peroxygen compound and (d) m-chlorobenzoyl dimethylhydantoin as activator for said peroxygen compound, said peroxygen compound being one which reacts with said activator to form the corresponding percarboxylic acid on addition of said composition to the wash water, the ratio of c to d being from about 8:1 to 2:1 of the stoichiometric ratio for said reaction, the ratio (a b):c being at least 2:1 and the ratio h:c being over 1:1 wherein said sodium silicate has an Na O:SiO ratio of about 1:2 to 1:3, and said composition also containing nonionic detergent and sodium carboxymcthylcellulose.

Claims

1. BUILT LAUNDRY DETERGENT COMPOSITION CONSISTING ESSENTIALLY OF (A) WATER SOLUBLE AIONIC SULFONATE OR SULFATE DETERGENT, (B) SODIUM SILICATE AS THE PRINCIPAL BUILDER SALT, (C) A PEROXYGEN COMPOUND AND (D) AN ACTIVATOR FOR SAID PEROXYGEN COMPOUND SAID ACTIVATOR HAVING A CARBOXYLIC ACYL GROUP, SAID PEROXYGEN COMPOUND BEING ONE WHICH REACTS WITH SAID ACTIVATOR TO FORM THE CORRESPONDING PERCARBOXYLIC ACID ON ADDITION OF SAID COMPOSITION TO THE WASH WATER, THE RATIO OF C TO D BEING FROM ABOUT 8:1 TO 2:1 OF THE STOICHIOMETRIC RATIO FOR SAID REACTION, THE RATIO (A + B):C BEING AT LEAST 2:1 AND THE RATIO B:C BEING OVER 1:1, AND WHEREIN SAID SODIUM SILICATE HAS AN NA2O:SIO2 RATIO OF ABOUT 1:2 TO 1:3.

3. Composition as in claim 2 in which the activator is a m-chlorobenzoyl amide.

4. A composition as in claim 2 in which said b:c ratio is at least 2:1.

5. Built laundry detergent composition consisting essentially of (a) water soluble sodium linear alkylbenzenesulfonate detergent, (b) sodium silicate as the principal builder salt, (c) a peroxygen compound and (d) m-chlorobenzoyl dimethylhydantoin as activator for said peroxygen compound, said peroxygen compound being one which reacts with said activator to form the corresponding percarboxylic acid on addition of said composition to the wash water, the ratio of c to d being from about 8:1 to 2: 1 of the stoichiometric ratio for said reaction, the ratio (a + b):c being at least 2:1 and the ratio b:c being over 1:1 wherein said sodium silicate has an Na2O:SiO2 ratio of about 1:2 to 1:3, and said composition also containing nonionic detergent and sodium carboxymethylcellulose.