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Publication numberUS3816319 A
Publication typeGrant
Publication dateJun 11, 1974
Filing dateMay 26, 1971
Priority dateMay 27, 1970
Also published asCA957308A1, DE2124587A1, DE2124587B2, DE2124587C3
Publication numberUS 3816319 A, US 3816319A, US-A-3816319, US3816319 A, US3816319A
InventorsDecamps A, Delattre M, Sarot P
Original AssigneeSolvay
Export CitationBiBTeX, EndNote, RefMan
External Links: USPTO, USPTO Assignment, Espacenet
Activation of peroxide washing and bleaching baths
US 3816319 A
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Description  (OCR text may contain errors)

ite States Patent 1 Sarot et a1.

[ June 11, 1974 ACTIVATION OF PEROXIDE WASHING AND BLEACI-IING BATHS [75] Inventors: Pierre Sarot, Vilvoorde; Michel Delattre, Rixensart; Alain Decamps, Brussels, all of Belgium [73] Assignee: Solvay & Cie, Brussels, Belgium [22] Filed: May 26, 1971 [21] App]. No.: 146,932

[30] Foreign Application Priority Data May 27, 1970 France 70.19481 [52] US. Cl 252/95, 252/99, 252/186, 260/566 AE, 8/111 [51] Int. Cl .C1ld 7/54 Primary Examiner-Mayer Weinblatt Attorney, Agent, or Firm-Lobato and Zelnick [57] ABSTRACT The acylation products of dioximes are used as activators for washing and bleaching baths containing a peroxide compound.

8 Claims, 5 Drawing Figures slelslsle PATENTEDJUH 1 1 m4 SHEET 1 OF 5 PATENTEDJUN 11 I974 31818319 PATENTEDJIJHH an 7 3316319 sum 30F 5 PATENTEDJUM 1 1974 I I 18161319 SHEET MF 5 PATENTED H v 3816319 SHEEISOF 5 ACTIVATION OF PEROXIIDE WASHING AND BLEACHING BATHS BACKGROUND OF THE INVENTION The present invention relates to a process for the activation of peroxide compounds in aqueous solutions used for washing and bleaching, or for disinfection and decontamination, and also to solid compositions containing both a peroxide compound and the activator.

In washing and bleaching products it is known to use peroxide compounds such as hydrogen peroxide, so-

dium peroxide, sodium perborate, sodium percarbonate, urea peroxide, etc. These peroxide compounds provide a satisfactory bleaching action when the washing liquid is used at or close to boiling temperature, but

their action is relatively slow at lower temperatures and for treatments of short duration. This disadvantage is important because of the increasing use of washing machines the operating temperature of which is for example from 30 to 60C. and the washing time from to minutes.

It is for this reason that it has been proposed to add activators which even at low temperature permit washing and bleaching by means of liquids containing peroxide compounds while providing under these conditions good bleaching action and also satisfactory removal of stains. As examples of known activators, mention may be made of the anhydrides of lower carboxylic acids, for example, acetic anhydride, substances containing one or more nitrogen atoms and at least two acyl groups bonded to the same nitrogen atom, particularly tetraacetylethylenediamine, and also acylated derivatives of 2,4,6-trihydroxy-l,3,5-triazine, preferably trisacetyl cyanurate. Among these compounds the acetylated derivatives are the most effective, but their penetrating odor considerably limits their utility.

SUMMARY OF THE INVENTION It has now been found that the acylation products of dioximes, particularly the reaction products of glyoximes and an acylation agent constitute remarkable activators for washing and bleaching baths containing peroxide compounds.

According to the invention, a peroxide compound in an aqueous medium is activated by the reaction product of a dioxime and an acetylation agent.

Also according to the invention, a solid composition useful for producing washing and bleaching baths is comprised of a solid peroxide compound and the reaction product of a dioxime with an acylation agent, which is effective as an activator for the peroxide compound.

BRIEF DESCRIPTION OF THE DRAWINGS Each of the figures is a diagram wherein the time of soaking in hours (abscissa) has been plotted against the soil eliminated in percent (ordinate) In FIG. 1, curves I and II concern soaking with a peroxide compound without an activator, curves III and IV concern soaking with a peroxide compound in the presence of 0.1 g. of an acylated dioxime, curves V and VI concern soaking in the presence of a peroxide compound and 0.5 g. of an acylated dioxime and curves VII and VIII concern soaking in the presence of a peroxide compound and 1.0 g. of an acylated dioxime. The soil to be eliminated is tea (curves I, III, V and VII) and wine (curves II, IV and VI).

In each of FIGS. 2, 3, 4 and 5, curve I concerns soaking with a peroxide compound without activation and curves II, III and IV concern soaking with a peroxide compound in the presence of diacetylated dimethylgloxime, diacetylated glyoxime and diacetylated methylethylglyoxime, respectively.

In FIGS. 2 and 4, the diagrams concern tests of fabrics soiled with tea and in FIGS. 3 and 5, the diagrams concern tests of fabrics soiled with red wine.

DESCRIPTION OF THE INVENTION Up to the present time, it has not been possible to determine the structure of the acylation products of dioximes which, according to the invention have been found to be highly effective as activators for peroxides, so that it is not known whether these compounds are di-N-acylated dioximes or di-O-acylated dioximes.

Among the acylation products of dioximes according to the invention the preferred compounds are acylation products, the acyl group of which contains from two to four carbon atoms, particularly acetylation products. The compounds which can be used according to the invention are preferably the diacylated products of glyoxime and dialkylglyoximes in which the alkyl group contains from one to 12, preferably from one to four carbon atoms.

A particularly suitable compound is diacetylated dimethylglyoxime, the formula of which is probably one of the following:

This compound is'easily obtained by reacting acetic anhydride with dimethylglyoxime by the usual acetylation techniques. Its composition has been determined by elementary analysis and mass spectrometry. It is obtained in the form of a white powder of crystalline appearance an surprisingly is practically odorless, so that it has an undeniable advantage in the present application. The use of the activators according to the invention makes it possible to obtain a sufficient degree of whiteness even at relatively low temperatures, so that in the process according to the invention the objects to be treated may be brought into contact with an aqueous solution containing the peroxide compound and the activator at temperatures between ambient temperature and C.

The process according to the invention is effective for bleaching paper pulp, textile materials, greases, oils, and all materials as well as all compounds usually bleached by means of peroxide solutions. These aqueous solutions of peroxide compounds and activators may also be used for decontamination and disinfection.

The amount of peroxide compound varies wih the nature of the objects to be treated and the degree of whiteness which is desired; thus, for the decoloration of oils and greases it may be necessary to use larger amounts of peroxide compounds than for the bleaching of textile materials.

The diacylated dioximes used as activators in the present invention are effective even when they are present in the washing and bleaching baths at the rate of 0.05 mole per gram-atom of active oxygen; it is obvious that larger amounts may be used, but it scarcely appears advantageous to use more than one mole of activator per gram-atom of active oxygen.

For the purpose of carrying out the process according to the invention, the activators proposed may be added to the washing and bleaching baths at the time of use.

When the activators proposed are in solid form, which is most frequently the case, they may also be mixed, preferably provided with a protective coating which is soluble in water or capable of dispersion therein, such as certain polyethylene glycols, polyvinyl alcohol, or other similar materials with the washing or bleaching powders containing peroxide compounds, so as to have available a pulverulent mixture ready for the preparation of the washing or bleaching bath by dissolving in water.

Such ready-to-use mixtures may contain, in addition to the peroxide compound and the activator, anionic or non-ionic detergents having a washing action, alkaline substances regulating pH, and assisting the washing action, for example, carbonates, phosphates, pyrophosphates, tripolyphosphates, and silicates, antiredeposition agents such as carboxymethyl cellulose, optical bleaching products, proteolytic and/or amylolytic enzymes, stabilizers, anti-corrosive agents, etc.

The following examples further illustrate the best mode currently contemplated for carrying out the invention, except of course those examples wherein no activator has been used or wherein an activator known in the art has been used for the purposes of comparison. The examples which illustrate the invention must not be construed as limiting the invention in any manner.

EXAMPLE 1 In this example, the activities imparted by diacetylated dimethylglyoxime (DMGA) and by a known activator, triacetylcyanurate (TACA), to a perborate washing powder containing no activator and used for washing clothes under mild temperature conditions are compared.

The washing tests were carried out in a General Electric WA 55013" washing machine which treats the cloths in the following manner:

filling, maximum duration 5 minutes;

washing with 75 liters of preheated water, time: 14


draining of water, time: about 1 minute;

rinsing for a period of 15 minutes with cold water;

spin drying for 5 minutes.

The total duration of a washing cycle is therefore about 40 minutes.

The water feeding the machine has a hardness of 16 to 17 French hydrotimetric degrees; its temperature in the machine is 40C. i 1C.

The washing powder used at the rate of 2 g. per liter of 150 g. per cycle is a commercial product. Its composition, determined by analysis is as follows, in percent by weight:

sodium pyrophosphate 5 10 sodium sulphate tetrahydrated sodium perborate 20 water of crystallization, celluose derivatives, optical bleaching agent, etc. 10 100 The material to be washed is composed of two parts: a white load and various test pieces intended to evaluate washing effectiveness.

The load, with a total weight of 3.5 kg., is composed of various pieces of about cm. in length and 50 cm. in width. These pieces are of mixed cloth based on cotton (65 percent) and polyester (35 percent). The whiteness of the cloth, measured by its reflectance in blue light, is 88.0 i 0.1 percent referred to magnesium oxide.

Various test pieces of about square cm. (12.5 cm. X 8 cm.) are sewn on the load. Fifteen types of test pieces were used at the rate of 10 test pieces per type. The fabrics to be tested were distributed in the following four groups;

First group: test pieces intended to measure the detergent effectiveness of the washing product.

Second group: fabrics covered with soil sensitive to the action of the enzymes used in washing powders.

Third group: test pieces soiled by products capable of decoloration by oxidation.

Fourth group: white fabrics serving to evaluate the amount of soil redeposition during washing.

The first group comprises three different cottons covered with pigmentary soil based on lampblack. These fabrics were prepared by the following specialized organizations: EMPA (Switzerland), TEST FABRICS (U.S.A.), and WFK KREFELD (West Germany).

The second group comprises EMPA l 12 and 1 l6 soiled cottons. One of the cottons is impregnated with soil containing blood, milk, India ink, etc.; the other is soiled with cocoa.

The third group is composed of mixed cloth soiled with seven different stains; the staining was obtained by impregnating the fabric with a concentrated solution of the staining element, padding the impregnated cloth and drying in the open air, this staining cycle being repeated three times in succession. Four stains were made with natural fruit jucies blackcurrant, bilberry, cherry, and grape and the other three are based on tea, coffee and red wine.

In the fourth group, three types of white fabrics were used to evaluate the antiredeposition power of the washing product; two test pieces are cotton and a third is a mixed cotton-polyester fabric.

The effect of the washing treatment on the various test pieces is measured by the variation of their whiteness. The latter is always determined on the hidden face of the test piece, that is to say the face in permanent contact with the load. Whiteness is measured with the aid of an ELREPHO reflectometer (Zeiss) giving diffused lighting of the test piece and having an effective wavelength of 457 nanometers; the values obtained for refiectances are given in percent, referred to magnesium oxide.

For each soiled test piece the rate of soil elimination in percent, that is to say the ratio,

Table 1a Activator Not of Relative efficiency (unactivated powder washing r 100, result after 3 cycles) cycles Detergent Enzyme Bleaching Antiredepaction action action osition action TACA 0.4 3 88 109 205 100 g./l. DMGA 1 107 167 89 (soil eliminated/soil to be eliminated) X 100, It is therefore seen that, in relation to the results obis given by the formula. tained after three washing cycles with the aid of an un activated perborate powder, the powder activated with DMGA has a bleaching power twice as great after only reflectance after Wahin refiecta ce before bnshigng n two washlng cycles. For an equal number of cycles the g X100. r powder contammg DMGA has a detergent power aluut reflectance (before formatlon Of most identical to that of the powder without activator shuns) reflectance blefore w i (the differences measured are not visible to the eye);

' the enzymatic and antiredeposition powers are im- The mean rate of S011 elimination 18 equal to the arith-. proved respectively by 26 and 18 percent metic mean of the above results for all the test pieces of the same group. EXAMPLE 2 1n the case of unsoiled fabrics, the soil to be elimiin hi example, h i fluen f h di i d dina ted obviously corresponds to initial reflectance, and methyigiyoxime (DMGA) Content on the activation f S011 eliminated or gain in whiteness corresponds to the 30 a perborate washing powder i determined in addition, difference between reflectance after washing and initial Comparative tests are i d out i h h T CA ireflectance ously mentioned and with tetraacetylethylenediamine The relative efficiency 01 the various washing pow- TAED) dfirs expressed by the 1 [1111111131169 y 100, The washing tests were carried out in a Launder-O- tween the mean rates of elimination of soil with the aid 35 meter i h h id f a perbgrate w hi g p wd of an activated powder and of an unactivated powder. The Launder meieii a laboratory washing chine manufactured and sold by Atlas Electric Devices The tests carried out made it possible to compare the (USA). The Washing Conditions are as fohows; following products:

perborate powder without activation, perborate powder activated by trisacetylcyanurate lsmperfllure 1C. 40 mlnutes 15 water used, hardness French degrees 16-17 perborate powder activated by discetylated dimethylvqlume cm. 250 l i (DMGA) perborate washing powder jl, 2

Test pieces to be washed Detailed results of the tests relating to the fourth (100 cm about 0.6 g.)

' mixed cotton-polyester fabric soiled with wine 1 g i n gaijg l gzjz x of mixed cotton-polyester fabric soiled with tea 1 Table l I Number of successive washing cycles Test piece:

Mixed 0 3 3 1 2 3 cotton/polyester fabric (/35) Activator in g.[1. Nature Nil TACA 0 4 DMGA 0 35 of stains soil soil elimsoil elimsoil e1im soil elimsoil elimto be elimination e1imination elimination elimination e1im ination elimininated rate inated rate inated rate inated rate inated rate ated Blackcurrant 60.8 1.3 2.1 11.0 18.1 5.8 9.5 9 5 15.6 12.1 19.9 Grape 50.5 20.9 41.4 34.6 68.5 27.4 54.3 31.3 62.0 33.6 66.5 Bilherry 59.2 14.4 24.3 24.7 41.7 22.2 37.5 26.3 44.4 29.5 49.8 Tea 66.2 0.0 0.0 10.8 16.3 8.6 13.0 13.2 19.9 17.5 26.4 Wine 39.5 0.7 1.8 11.2 211.4 10.0 25.3 13.6 34.4 16.6 42.0 Coffee 61.4 26.9 43.8 40.1 65.3 33.6 54.7 37.5 61.1 40.4 65.8 (herry 52.5 11.8 22.5 20.9 39.8 16.9 32.2 19.6 37.3 21.8 41.5 mean: 19.4 mean: 39.7 mean: 32.4 mean: 39.3 mean: 44.4

In addition, the results obtained with the four groups The washing powder used 18 the same as that deof test pieces are summarized in Table 1a. scribed in Example 1. The test pieces sub ected to washing were soiled as indicated in Example 1; they perborate powder was nevertheless replaced by a perwere, however, subjected to supplementary aging for 4 carbonate washing powder. This powder was used at hours at 70C. the rate of 1.88 g./l. so as to give the washing solution The results obtained are given in Tables 2 and as the Same OXldlZmg POWer as 1n EXamPle The p follow: 5 bonate powder had the followmg compos1tion:

I Table 2 Activator, g.l. Mixed cotton-polyester fabric (6535) soiled with Tea Wine Soil to be eliminated 69.3 43.9

Soil Elimination Soil Elimination eliminated rate of soil eliminated rate of in 7: soil in 7:

Nil 3.3 4.8 9.3 21.2 DMGA 0.1 7.1 10.2 16.9 38.5 0.2 127 I83 20.2 46.0 0.3 13.3 19.2 22.1 50.3 04* 15.9 22.9 21.3 48.5 TACA 0.4 13.0 18.8 19.4 44.2 TAED 0.4 12.4 17.9 19.5 44.4

mean of five tests Key.

Soil to be eliminated: difference between initial reflectance and that after formation of stains Soil eliminated: difference between reflectance after washing and that before washing.

Table 2a summarizes the values of Table 2, expressed surface active organic materials, 21

sodium silicate 5 1n terms of relat1ve efficlency. sodium tripolyphosphm 32 T bl 2 sodium pyrophosphate 5 sodium sulphate l l sodium percarbonate (containing 14% of active oxygen) 15 Activator. g./l. Relative efficiency of the activated powder Water of Crystallization cellulose refers to the same powder wnqout actwator w l derivatives, Optical whitener etc. Ld "'10 DMGA 0.1 215 182 35 2 217 8:; g; 238 The results obtamed, as set forth 1n Tables 3 and 3a 0.4 482 229 clearly show the considerable increase in efficiency im- T QES i3: 5% parted to the percarbonate washing powder by the use of DMGA.

Table 3 Activator. g./l. Mixed cotton-polycster fabric (6535) soiled by Tea Wine Soil to be eliminated 69.3 43.9

Soil Elimination Soil Elimination eliminated rate of soil eliminated rate of in 7: soil in 7? N11 3.3 4.8 10.0 22.8 DMGA=' 0.1 8.2 11.8 13.1 29.8 0.2 11.7 16.9 16.7 38.0 0.3 13.8 19.9 18.4 41.9 0.4 14.9 21.5 20.1 45.8

()mean of two tests It is found that the use of small amounts of diacety Table 3a shows the preceding results expressed in lated dimethylglyoxime, of the order of 25 percent by terms of felatlve efficlencyweight referred to the sodium perborate, that is, 0.2 mole of activator per gram-atom of active oxygen, makes it possible for the efficiency of the washing solu- Table 30 tion containing perborate to be practically doubled. Moreover, the additional activity imparted to the powcfficlency (powder w1thout activator der mcreases with the amount of acttvator present. Tea wine EXAMPLE 3 DMGA 0 1 248 131 0.2 355 167 The tests described 1n th1s example were carrled out 8-3 418 184 .4 452 201 under the same conditions as those of Example 2. The

Tests carried out with the object of determining the action of DMGA on the efficiency of proteolytic en- EXAMPLE 4 EXAMPLE 5 The tests of Example 5 were carried out under the same conditions as those indicated in Example 2. The

zymes which are sometimes introduced into washing 5 only change relates to the quality of the water. The water used in this example has a very high hardness of powders.

The washing tests were carried out in a Launder-O- meter under the following conditions:

Temperature C. 30 duration minutes 30 water used. hardness French degrees 17-1 8 amount cm. 250

Washing powder: perborate (see Example 1 for composition g./1. '2 or pcrcarhonate (see Example 3 for composition) g./1. 1.88 proteolytic enzymes at 300,000 units Delft/g. g./1. 0.02 Test pieces to be washed (about 100 cm.):

EMPA 112 number 1 EMPA 116 number 1 The DMGA is used at the rate r0.4 g./1. of washin liquid.

36 French hydrotimetric degrees.

The results of the tests shown in Table indicate that Table 5 g DMGA is also very efficient in very hard water.

Mixed cottonpolyester fabric (-35) soiled by tea Soil to be eliminated:

Soil eliminated, without activator i.e. 1.0%

with DMGA 0.4 g./l. (mean 01'4 tests) 12.6 i.e. 18.2% Relative efficiency, without activator with DMGA 1820 Mixed cotton-polyester fabric (65-35) soiled bv wine Soil to be eliminated: 44.0 Soil eliminated, without activator i.e. 1.4%

with DMGA 0.4 g./1. (means of 4 tests) 15.6 i.e. 35.5% Relative efficiency. without activator 100 with DMGA 2600 EXAMPLE 6 The results obtained are indicated in Table 4. They show that DMGA does not harm the action of enzymes in perborate or percarbonate biological powders.

Soaking tests were carried out in cold water under the following conditions:

Temperature C. Time hours Water used, hardness French degrees quantity cm.

Pcrhorate powder (see Example I for composition) Test pieces (about I emf, 0.6 g.) Mixed cotton-polyester fabric soiled by wine Mixed cotton-polyester fabric soiled by tea The results are shown in FIG. I. In this and the following diagram the abscissae represent the soaking time in hours, while the ordinates represent the soil eliminated in percent. Curves I, III, V and VII relate to fabric soiled by tea, while curves II, IV and VI relate to fabric soiled by wine. Curves I and II show soaking tests without activator; curves III and IV were obtained in the presence of 0.1 g. of DMGA per liter; curves V and to 3 I8 1000 Number 6 Number 6 The results obtained are shown in the accompanying diagrams (FIGS. 2 to 5). Diagrams 2 and 3 relate to a concentration of activator of 0.25 g./I. while diagrams 4 and 5 were obtained with an activator concentration of 0.5 g./l.

Diagrams 2 and 4 relate to soaking tests with fabrics soiled with tea, diagrams 3 and 5 to fabrics soiled with red wine.

Curves I relate to tests carried out without activator, curves II to tests carried out with DMGA, III with DAG and IV with MEGA.

These diagrams clearly show the considerable increase in efficiency of a soaking powder when one of these three activators is introduced into it.

Table 6 expresses these results in terms of relative ef ficiency.

Table 6a indicates the time required for a soaking Table 6 Nature of Concentration of Relative Efficiency After 3 hours Activator Activator of Soaking:

g./l. TEA WINE nil (I) 0 I00 I00 DMGA (II) 0.25 I76 264 0.50 239 386 DAG (Ill) 0.25 I76 264 0.50 23] 368 MEGA (IV) 025 I76 243 EXAMPLE 7 The tests described in this example were carried out under the same conditions as indicated in Example 6.

powder containing one of the three diacetylated glyoximes to eliminate an amount of soil equivalent to that removed by the same unactivated powder after soaking for 3 hours.

Table 6a Nature of Concentration Soaking time equivalent to a soaking Activator of Activator of 3 hours without activator. minutes g./I. TEA WINE DMGA (II) 0.50 l4 l3 DAG (III) 0.50 36 I4 MEGA (IV) 0.50 42 22 The only change relates to the temperature of the test, which is 22C.

Two other acetylated glyoximes were tested under the same conditions as DMGA. namely. diacetylated glyoximc (DAG) and diucctylatcd methylcthylglyoximc (MEGA).

l. A process for the activation, in an aqueous medium, of an active oxygen releasing compound selected from the group consisting of hydrogen peroxide, sodium perborate and sodium percarbonate, which comprises activating said active oxygen releasing compound by an activator selected from the group consisting of diacylated glyoxime and diacylated dialkylglyoxime wherein the alkyl group contains from one to four carbon atoms and the acyl group contains from two to four carbon atoms, said activator being present in a quantity corresponding to about 0.05-1 mole per gramatom of active oxygen contained in said active oxygen releasing compound.

2. A process according to claim 1 in which the activator is diacetylated methylethylglyoxime.

3. A process according to claim 1 in which the activator is diacetylated glyoxime.

4. A process according to claim 1 in which the activator is diacetylated dimethylglyoxime.

ide compound is hydrogen peroxide.

6. A process according to claim 1 in which the peroxide compound is sodium perborate.

v 7. A process according to claim 1 in which the peroxide compound is sodium percarbonate.

8. A solid composition for producing-washing and bleaching baths by dissolution in water comprising an active oxygen releasing compound selected from the group consisting of sodium perborate and sodium percarbonate and an activator selected from the group consisting of diacylated glyoxime, diacylated dialkylglyoxime wherein the alkyl group contains from one to four carbon atoms and the acyl group contains from two to four carbon atoms, said activator being present in a quantity corresponding to about 0.05-1 mole per gram-atom of active oxygen contained in said active oxygen releasing compound.

Referenced by
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US3957670 *Dec 4, 1974May 18, 1976Hoechst AktiengesellschaftActivators for inorganic per-compounds
US3975153 *Aug 25, 1975Aug 17, 1976Fmc CorporationActivation of peroxygen bleaches using isophorone enol acetates and isophorone oximinoacetate
US4021361 *Aug 25, 1975May 3, 1977Fmc CorporationAcylated adduct of nitromethane and cyclohexanone or cyclopentanone
US4064062 *Dec 15, 1975Dec 20, 1977Colgate-PalmoliveStabilized activated percompound bleaching compositions and methods for manufacture thereof
US4164395 *Oct 16, 1978Aug 14, 1979Fmc CorporationPeroxygen bleaching and compositions therefor
US4778618 *Nov 6, 1986Oct 18, 1988The Clorox CompanyAnd source of hydrogen peroxide; bleaching textiles over nide temperature range
US4859800 *Apr 30, 1987Aug 22, 1989The Clorox CompanyPhenoxyacetate peracid precursors
US4956117 *May 19, 1989Sep 11, 1990The Clorox CompanyBleaches
US4957647 *Apr 14, 1989Sep 18, 1990The Clorox CompanyAcyloxynitrogen peracid precursors
US5049305 *Jun 25, 1990Sep 17, 1991Zielske Alfred GBleach
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US5380457 *Jun 3, 1994Jan 10, 1995The Clorox CompanyAcyloxynitrogen peracid precursors
US6025023 *Dec 23, 1998Feb 15, 2000Valente; GabrieleMethod for decorating stone-like materials and a machine for carrying out this method
US6448062Oct 29, 1999Sep 10, 2002Metrex Research CorporationSimultaneous cleaning and decontaminating compositions and methods
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US6596683Dec 22, 1998Jul 22, 2003The Procter & Gamble CompanyGranulating a detersive material comprising a detergent surfactant and a builder; and coating an inorganic aqueous solution on the granules substantially to coat the granules
US6858572Mar 8, 2000Feb 22, 2005The Procter & Gamble CompanyProcess for producing coated detergent particles
US7022660Mar 8, 2000Apr 4, 2006The Procter & Gamble CompanyProviding a particle core of a detergent active material and at least partially covered by a particle coating layer of a water soluble coating material including double salt combinations of alkali metal carbonates and sulfates that reduces the surface area of the particle.
USRE32672 *Aug 4, 1987May 24, 1988Allergan, Inc.Method for simultaneously cleaning and disinfecting contact lenses using a mixture of peroxide and proteolytic enzyme
EP2059581A2 *Aug 14, 2007May 20, 2009American Sterilizer CompanyA one part, solids containing decontamination blend composition
U.S. Classification252/186.38, 564/159, 510/313, 252/186.43, 510/314, 8/111, 252/186.41, 564/254
International ClassificationC11D3/39, C11D3/386, C11D3/38
Cooperative ClassificationC11D3/38609, C11D3/3917
European ClassificationC11D3/39B2D6, C11D3/386A