US3580850A - Stabilized nonionic surfactants in solid formulations containing active chlorine compounds - Google Patents

Abstract

A SOLID BUILT DETERGENT FORMULATION CONSISTING OF A LOW FOAMING NONIONIC SURFACTANT CONTAINING A MINOR AMOUNT OF AN ANTIOXIDANT, AN ACTIVE CHLORINE AGENT, AND AN ALKALINE BUILDER, THE ANTIOXIDANT SERVING TO STABILIZE THE SURFACTANT AGAINST DEGRADATION CAUSED BY THE OXIDATIVE OR OTHER AGGRESSIVE EFFECTS OF THE CHLORINE.

Description

3,588,858 Patented May 25, 1971 Int. Cl. Clld 7/56 U.S. Cl. 252-99 2 Claims ABSTRACT OF THE DISCLOSURE A solid built detergent formulation consisting of a low foaming nonionic surfactant containing a minor amount of an antioxidant, an active chlorine agent, and an alkaline builder, the antioxidant serving to stabilize the surfactant against degradation caused by the oxidative or other aggressive effects of the chlorine.

It has long been recognized that for many cleaning and sanitizing operations there are available three broad classes of highly effective materials: low foaming nonionic surfactants, active chlorine-releasing compounds, and alkaline builders. Each of these substances contributes usefully to the removal of soils. The alkaline builders are the primary detersive agents, and are responsible for effecting the removal of the bulk of most soils. The active chlorine compounds aid in the removal of stains and food films, and contribute sanitizing activity. In operations involving agitation of the detergent, such as spraying, pumping, or recirculating, the low foam nonionic inhibits the tendency of alkaline solutions of food salts to foam and improves the detergency and rinsing qualities of detergent solutions. Logically, it would appear that a combination of all three cleaning agents would provide the most satisfactory effect of all. But heretofore such a combination in a single granular dishwashing or other cleaning product has not been successfully attainable by means which are economically feasible.

A principal obstacle has been the incompatibility of the nonionic surfactant and the active chlorine compound. During storage a significant loss of the chlorine inevitably occurs and this results in a loss of cleaning, bleaching or sanitizing capacities. Upon storage the surfactant also tends toward a significant loss of performance such as by foaming excessively, a lessening of the ability to deform waters containing foam-causing substances, and overall loss in detergency. In fact, in some cases the degradation of the surfactants is so bad that a given surfactant cannot be used for its intended purpose.

The problem just described is not new to the art. It has been described and solved previously, albeit the solu tion was by means other than the present invention, an illustration being U.S. Pat. No. 3,306,858. That patent teaches the concept of incorporating an organic surface active agent with a solid carrier, coating the mixture with a substance that is impervious to chlorine attack during storage, and then combining the encapsulated material with a chlorine releasing agent. While such means are effective in providing adequate stability, the operation is difficult and much too costly to be economically feasible in most instances.

As pointed out in U.S. Pat 3,306,858 the desire to combine organic surface active agents and chlorine releasing agents in a single product, along with alkaline builders, is that both classes of materials have certain highly useful properties in dishwashing and other detergent applications. The surface active agents function to emulsify food soils, to inhibit foam caused by food soils, to promote wetting of dinnerware so as to eliminate or minimize spotting, and generally to improve the overall detergency of the composition for soil removal. The chlorine releasing agents improve detergency by their oxidizing action on food soils, particularly proteins, to convert them to a more soluble form. The active chlorine also serves to bleach out stains on dinnerware, as those caused by coffee or tea, and to minimize spotting on such ware by preventing build-up of soil films on their surfaces.

The obstacles to the effective combination of the surface active and chlorine-releasing agents include the fact that the preferred surfactants are organic nonionic polyether type materials which are readily susceptible to attack by active chlorine agents such as the hypochlorite ion. As a consequence of such reactions, the surfactants break down and in a relatively short period lose their desirable properties. The active chlorine content also is decreased as a result of the reaction with the surfactants so that by the time the detergent product is used by the ultimate consumer it frequently is substantially devoid of the desirable properties imparted by both the surfactant and the chlorine-releasing agents.

The present invention provides an improved, comparatively economical means for preparing detergent compositions suitable for dishwashing and similar applications in which organic nonionic surface active agents are compounded with chlorine releasing agents to form a suitable product which may be stored without undesired and significantly unacceptable reaction between these normally incompatible components. The present invention, moreover, provides detergent formulations of the type containing the otherwise noncompatible constituents as described previously, but which exhibit none of the aforementioned undesirable characteristics.

In essence, my invention consists in a modification of the surfactant which is combined with alkaline builders and chlorine-releasing agents, resulting in a product which thus consists of four main classes of materials instead of three as in the prior art. The modification consists of the addition to the surfactant of a minor amount of a composition which I call an antioxidant. The mechanism of the reaction by which the novel products of my invention are protected against chlorine attack, is not known with absolute certainty. However, because of the fact that the classes of compounds which I have found to stabilize nonionic surfactants against aggressive chlorine attack happen to have antioxidant properties, and a theoretical analysis of the causes of that stabilizing effect indicate an antioxidative action is taking place, I find it convenient to term the compositions in question antioxidants.

In any event the observable net effect of the addition of one or more of these antioxidants to a nonionic surfactant is to reduce tremendously the chemical attack on the surfactant by active chlorine compounds in powdered alkaline formulations which occurs when no antioxidant is present. Moreover, this has been accomplished without adding to the loss of any of the active chlorine that is furnished by the chlorine releasing agent; in fact, in many instances the opposite result occurs for the amount of chlorine loss is reduced when compared with chlorine losses from formulations identical with the present invention except for the lack of the antioxidant. This in itself is as surprising as it is beneficial since antioxidants are materials which are themselves easily oxidized and thus would be expected to react with the chlorine re leasing agents and thereby accelerate the chlorine loss.

The four main classes of materials which are incorporated into the detergent formulation of the present invention have many sub-classes and components thereof which may be utilized. For example, among the alkaline builders which may be employed (generally at levels of about 92 to about 98% by Weight of the entire composition) in the present invention are diand tri-sodium and potassium orthophosphates, alkaline condensed phosphate salts such as tetrasodium or tetrapotassium pyrophosphates, sodium tripolyphosphate, and sodium hexametaphosphate, sodium and potassium hydroxides, sodium carbonate and bicarbonate, alkali metal borates, and alkali metal silicates. Both anhydrous and hydrated builders may be employed.

Among the many chlorine-releasing (or active chlorine) agents which can be utilized (generally at levels of about 1 to about 3 weight percent) in the present invention are sodium and potassium dichloroisocyanurate, diand trichlorocyanuric acid, trichloro melamine, Chloramine T (sodium N-chloro-p-toluene-sulfonamide), dichlorodimethyl hydantoin, sodium, calcium and lithium hypochlorites, and the like. The chlorine-releasing agent can be combined with the alkaline builder, an example being chlorinate trisodium phosphate (which is a composition consisting of hydrated trisodium phosphate and sodium hypochlorite in intimate association in a crystalline form).

There are a great many classes of nonionic surface active agents which can be utilized (generally at levels of about 1 to about 5 weight percent), but all have one characteristic in common: they are all low foaming compositions. By this is meant they will all produce less than 3.0 cm. of foam when measured by the Hamilton-Beach test (described below and also in US. Pat. 3,021,372) under certain use conditions. Surfactants which produce more than that amount of foam, when so tested, are essentially useless in the practice of the present invention. Data showing the criticality of this foaming capacity, or index, are set forth in Table I below.

Illustrative of the great variety of low foaming nonionic surface active agents which are useful in this invention are the following classes of compounds:

(1) Block copolymers of ethylene oxide and propylene oxide or butylene oxide (e.g., Pluronics, the trade mark for products disclosed in US. Pat. 2,674,619 as compounds Of the formula HO'(C H4O) (C3H O) (C2H4O) --H, where y is at least 15, and (C H O) I equals to 90% of the total weight of the compound; Product E-97, the trade designation for a polyoxyalkylene polymer having the formula:

where x, y and z are integers such that the average molecular weight of the compound ranges from 3600 to 4400).

(2) Polyethylene oxide and/ or propylene oxide adducts of low molecular weight polyhydroxy or polyamine compounds.

(3) Terminated nonionics of the type where R is alkoxy, alkyl phenoxy or alkyl amine of which the alkyl group contains 818 C atoms; R is H or CH R is benzyl or a substituted benzyl, an alkyl chain of 1-8 C atoms, a halogen, a propylene oxide chain of 3 or more units, a lactam radical, or an alkyl acetal radical whose alkyl group consists of 1 to 8 C atoms; and x is 3 or higher.

(4) Acetylenic diols of at least 7 C atoms, and their ethylene oxide adducts.

31 R (GHzCIkhCHA where R, R and x are as indicated in No. 3 above, and A is either H or an alkyl group of 1 to 3 C atoms.

Variations within the foregoing classes of compounds may occur and are fully within the purview of the present invention. For instance, the amount of ethylene oxide in a given compound will depend upon the alkyl chain length or exact terminating group (e.g., benzyl, butyl, polypropylene oxide chain, etc.) employed. On the minimum side it should be understood that sufficient units of ethylene oxide must be incorporated in the surfactants to give them desired surface active properties. As for the maximum end of the range, the level of ethylene oxide units must not exceed that which will cause the end product to foam in excess of the 3.0 cm. limit described above as determined by the I-Iamilton-Beach test. Simple go and no go tests will make selection of acceptable limits for the ethylene oxide content in a given compound a relatively routine procedure.

Among the antioxidants which can be utilized (general- 1y at about 1 to about 10 weight percent based on weight of nonionic surfactant) in the present invention are substituted phenols, organic phosphites, amides, organic sulfur compounds, and aromatic amines. There are numerous classes of substituted phenols which may be employed. For example, one such class of compounds is represented by the formula:

in which R to R inclusive, may each be OH, alkyl, alkoxy or alkyl amine. Another such class consists of alkylphenol-formaldehyde condensates. Specific examples of compositions encompassed by these classes are: di-tbutyl-p-cresol, 2,6 di-t-butyl 3 dimethylamino methyl phenol, p-t-octyl, dodecyl and butyl phenol-formaldehyde condensates, 1,2,3 trihydroxy benzene, 1,4 dihydroxy benzene, p-ethoxy phenol, etc. Still other such classes are known to the art, and some of them may be exemplified by the following compositions: 1,1,3 tris (2 methyl-4- hydroxy-S-t-butyl phenyl) butane and 3,3,5,5 (tetra-tbutyl) 4,4 dihydroxy biphenyl. 1

Some of the organic phosphites are encompassed by the formula in which R, R" and R are alkyl, cycloalkyl, aryl, alkoxyalkyl, aralkyl or tetrahydrofurfuryl, and X is oxygen or sulfur, and examples are trimethyl phosphite and thiophosphite, triethyl phosphite and thiophosphite, tributyl and triisobutyl phosphite, trisecondary and tritertiary butyl phosphite, tributyl trithiophosphite, tributyl mono and dithiophosphite, trihexyl phosphite and trithiophosphite, tricyclohexyl phosphite and trithiophosphite, tri-Z-ethylhexyl phosphite and trithiophosphite, triisooctyl phosphite, tridecyl phosphite and dithiophosphite, trilauryl phosphite and mono, diand trithiophosphite, trioctadecyl phosphite and trithiophosphite, trieicosanyl,

phosphite, phenyl didecyl phosphite and trithiophosphite, phenyl dilauryl and distearyl phosphite, phenyl distearyl trithiophosphite, diphenyl decyl and lauryl phosphite, diphenyl stearyl phosphite and trithiophosphite, triphenyl phosphite, triphenyl mono-, diand trithiophosphite, tri-o-, mand p-cresyl phosphite, tri-p-cresyl dithiophosphite, tri-p-octyl-phenyl trithiophosphite, tri-p-octylphenyl phosphite, triethoxyethyl phosphite, tributoxyethyl phosphite, tritetrahydrofurfuryl phosphite, tritetrahydrofurfuryl trithiophosphite, triphenyl ethyl phosphite, S-phenyldilauryl monothiophosphite, S-phenyl-didecyl monothiophosphite, S,S-diphenyl lauryl dithiophosphite, S,S-diphenyldecyl dithiophosphite, tri a-naphthyl phosphite, tri-B-naphthyl phosphite, S,S-diphenyldecyl dithiophosphite, phenyldilauryl trithiophosphite, phenyldilauryl trithiophosp'hite, tri-p-dodecylphenyl phosphite, tri-oand m-chlorophenyl phosphite, diphenyl lauryl trithiophosphite, S-lauryl diphenyl monothiophosphite, tri-p-chlorophenyl phosphite, tri-p-methoxyphenyl trithiophosphite, tri-p-methoxyphenyl phosphite, S,O-diphenyl-S-lauryl dithiophosphite, tri-omethoxyphenyl dithiophosphite, S,O-dilaurylphenyl dithiophosphite. Other useful phosphate esters are cyclic phosphites, or pentaerythritol derivatives of one of the following formulae 00112 CH2O where R and R" are as defined above and can be methyl, ethyl, propyl, butyl, isobutyl, secondary butyl, tertiary butyl, amyl, hexyl, heptyl, octyl, isooctyl, 2-ethylhexyl, decyl, isodecyl, lauryl, tetradecyl, cetyl, octadecyl (stearyl), eicosanyl, ethoxyethyl, butoxyethyl, methoxyethyl, tetrahydrofurfuryl, phenylethyl, aryl or haloaryl, e.g., phenyl, o-tolyl (o-cresyl), m-tolyl, p-tolyl, o-ethylphenyl, p-ethylphenyl, p-t-butylphenyl, o-t-butylphenyl, m-t-butylphenyl, p-octylphenyl, p-nonylphenyl, p-decylphenyl, p-dodecylphenyl, benzylphenyl, o-phenylphenyl, p-phenylphenyl, o-chlorophenyl, m-chlorophenyl, p-chlorophenyl, o-brornophenyl, p-fluorophenyl, m-iodophenyl, o-, pand m-methoxyphenyl, a-naphthyl and ,B-naphthyl. In the formulae -R R R R R and R are hydrogen or alkyl groups of 1 to 20 C atoms, and X is oxygen or sulfur. More examples of phosphites coming within the purview of the preceding formula may be found in U.S. Pat. 3,205,269.

Examples of the other classes of antioxidants are thiourea (amides), dilauryl thiodipropionate (organic sulfur compounds), and o-phenylene diamine (aromatic amines).

The choice of the antioxidants, surfactants, alkaline builders and chlorine releasing agents which should be selected for incorporation in a particular composition normally would be based upon a number of factors including odor, degree of discoloration, solubility, detergency, cost, etc. If desired, other additives may be incorporated as, for example, anti-tarnishing agents, anti-caking agents, perfumes, and agents to prevent removal of dinnerware ovenglaze (viz, sodium aluminates, boric acid, and aluminum acetate).

The data which are recorded in the tables below clearly exemplify the invention and illustrate its improvement over the prior art in terms of its stabilization of the surfactant against degradative attack by chlorine. The data in each instance were based upon tests run as follows. The antioxidants in each instance were dissolved in the nonionic surfactant at the desired level, generally at a 5% level based on the surfactant. The nonionic surfactants, which generally were present at from 1 to 5% level in the detergent, were mixed with one or more of the alkaline builder ingredients which are present at levels of 92-98%. The solid chlorine-releasing agent was added last, at the l3% level, all the ingredients were mixed together preliminary to storage under various conditions, and this was followed by evaluation of the properties of the end products.

The storage conditions were of two types: (a) a highly accelerated test at 60 C. in sealed glass jars, and (b) a 14 day or 28 day test in flasks covered with a paperpolyethylene laminate, which permits the entry of water vapor, at 38 C. and relative humidity.

As mentioned above, a critical requirement of the present invention is the use of a low foaming surface active agent. A comparison of widely divergent foaming values of diiferent detergents is given in Table I. The measurement of the foam values recorded in that table and in the others which follow it was made by the Hamilton-Beach test method. According to that procedure, 0.72 gram of the detergent formulation was added to 200 ml. of Water (0.36 weight percent detergent) in a test cell at 50 C., mixing with a Hamilton-Beach mixer for 3 minutes, then stopping the agitation and recording the foam height after 5 seconds. Food soil defoaming was measured using the same procedure except that increments of powdered milk (added as a 10% dispersion in Water) are added after one minute periods of agitation. When the foam height exceeds 4.0 cm. (5 sec. value), the solution is no longer considered to be defoamed.

1 (1) All of the surface active agents are noniouics except Nos. 5 and 6 which are anionic. Only Nos. 1-3 are suitable; 4-6 definitely would be useless, particularly in high pressure machine applications of detergent solutions; (2) In these tests the surface active agent was present in the amount of 0.0075 weight percent, and the alkaline builder (30/25/41 sodium trlpolyphosphate/sodium metesilicate anhydrous/sodium hydroxide) was present in the amount of 0.36 weight percent.

A liquid condensate of polypropylene oxide and ethylene oxide wherein the polyoxypropylene group has a molecular weight of 1,501 to 161800 and the condensate contains 20 to 30% by weight of ethylene 0x1 e.

Table II, which follows, reflects experiments involving three different chlorine-releasing agents and three combinations of alkaline builders and two storage test conditions, some with and some without antioxidants. In the cases where no antioxidant was utilized there was a significant loss of performance (i.e. an objectionable increase in foam and a decrease in ability to defoam milk soil), and also a noticeable loss of active chlorine content. In the identical tests, except that 5% of an antioxidant was incorporated into the surfactant before preparing the formulation, the loss of defoaming ability of the surfactant was reduced from 33 to 92% below the loss levelobtained when no antioxidant was present.

TABLE II Initial values Stored Percent antioxidant 2 Percent Percent Percent added to Formulamilk loss of loss of surfactant 3 tion 4 Foam defoamed Foam defoaming active 01 Test condition: 1 4 3 O. 7 .0 96 25 A i i o. a .46 0. 4 4 5 0 0. 1 55 l. l 73 27 B (5] 0. 4 0. 6 40 17 1 68 i 5 i .61 2s 1 A=14 days at 38 C. and 80% relative humidity.

B=3 days at 60 C. in sealed containers.

1 p-t-Octyl phenolformaldehyde condensate (low molecular weight polymer; molecular weight about 2,000).

C=2/30/25/41/2 surfactant/sodium tn'polyphosphate/sodium metasilicate anhydrous/sodium hydroxide] potassium diehloroisocyanurate.

D=2/30/25/4l/2 surfactant/sodium tripolyphosphate/sodium metasilicate anhydrous/sodium carbonate] sodium dichloroisocyanurate.

E=2l30l30l38 surfactant/sodium tripolyphosphate/sodium metasilicate pentahydrate/chlorinated trisedium phosphate.

Table III, which follows, contains data showing how sixteen different compounds representing five major types of antioxidants, significantly reduced the extent of loss of soil defoaming activity after storage in one formulation employing one specific surfactant and one specific chlorine releasing agent. At a level of 5% antioxidant in the surfactant all the antioxidants gave at least a 24% reduction in loss compared to the surfactant minus the antioxidant. A few examples illustrate the effect of increasing the amount of the antioxidant to %which was to further reduce the chlorine loss.

TABLE III 1 Reduction in phenol. p-t-Ocgyl phenolformaldehyde condens e. 1,2,3 trihydroxy benzene 1,4 dihydroxy benzene p-Ethoxy phenol. Antioxidant 431 4 Irganox 858 Organic phosphites:

Triphenyl phosphite [(CuHsO) 2POCH2]4C l6 Organic sulfur com propionate.

l6 Aromatic amine; o-phenylene diamine 7 42 l Formulation 2/30/25/41/2 surfactant/sodium tripolyphosphatelsodium metasilicate anhydrous/sodium hydroxide/potassium dichloro lsoeyanurate; surfactant is DCQHNK)QHZCH(OH3)]2(OCH2OHZ)I2 OCH2C5H5; stored 3 days at 60 C. in sealed ar.

2 Percent loss of defoaming activity of formulation without antioxidant minus the percent loss with antioxidant added to the surfactant.

3 Low molecular polymer; molecular weight about 5,000. I

4 A hindered phenol type of antioxidant manufactured by Uniroyal (U.S. Rubber 00.).

5 A complex polyphenol type of antioxidant manufactured by Geigy Chemical Corp.

0 An organic phosphite type of antioxidant manufactured by Uniroyal (U.S. Rubber Co.).

7 Tested at 3% level in surfactant.

Table IV, which follows, contains test data based on the use of two additional examples of substituted phenol antioxidants along with examples of two antioxidants from Table III, but under different test conditions.

TAB LE IV 1 Reduction in percent loss of defoaming activity after storage Formula- Formula- N o. Antioxidant composition tion 2 0 tion 3 F 5 4 p-t-0cty1phenolformaldehyde conden- 56 64 sa e. 17 p-godecyl phenolformaldehyde con- 47 71 ens 'e. 18 p-t-Butyl phenolformaldehyde con- 43 08 dcnsate. 14 Thiourea 44 53 1 Surfactant used was n-OuH WCHzCHzO)1uCH2OuH formula trons, which included 5% antioxidant in surfactant, were stored for 14 days at 38 C. and relative humidity.

2 See Table II for composition.

3 Same composition as Formulation D in Table II except for use of potassium dichloroisocyanurate as chlorine releasing agent.

4 See Table III.

Table V, which follows, shows that mixtures of antioxidants, as well as single compounds are useful.

TABLE V 1 Mixtures of antioxidants Reduction of percent Antioxidants 2 Ratio loss 3 1 Same conditions as Table III, 5% total antioxidant in surfactant.

Numbers refer to correspondingly numbered compositions in Table III.

3 Defoaming activity after storage.

In Table VI, which follows, the data recorded are the results of use of one antioxidant to stabilize five different organic nonionic surfactants. This effect is thus shown to be general and thus applicable to low foam nonionics of all kinds.

TABLE VI consisting of the following groups of compounds:

(1) block copolymers of ethylene oxide and oxide or butylene oxide;

Surfactant p-t-Octyl phenyl (CH2OH20)1BCH2C9H5 -C 1oO[CHzCH(CHa)O]2(CH2OH2O)12CHzCaH Samg as above o n-CrsHwO (CH2CH20)10CH2C6H5 n-CnHrsO (CHzCHz )r0- 3): n-CuHzsO (CH2C )1o[C 2C (C s) 11 (C s) 0 C2 5 1 Numbers refer to correspondingly numbered compositions in Table III hunndity.

3 Defoaming after storage.

In Tables VII and VIII, which follow, the effect of varying the percent of antioxidant present with surfactant is demonstrated. From 1 to 10% was shown to have a beneficial effect. Higher levels may be useful but would raise Formulation C (from Table II), stored 14 days at 38 C. and 80% relative humidity.

2 Percent antioxidant (No. 5 in Table III) added to surfactant prior to preparing formulation; surfactant was nC H O (CH CH O)1 CH O H 3 Foam before storage was 0.5-0.8 cm.

TABLE VIII Foam Percent loss of Reduction after 3 in percent storage, Active loss of cm. chlorine Defoaming defoaming t t' idant: 2 Percen an 10x 3. 5 3 8 n 0. 7 21 28 70 0. 6 5 6 92 1 Formulation C, stored 28 days at 38 C. and 80% relative humidity; surfactant iS 11C9H190[CH2CH(CH3) 12( H CHzOh2 H2C5H5.

2 Percent antioxidant (No. 5 in Table III).

3 Foam before storage is 0.1-0.5 cm.

I claim:

1. The detergent composition consisting essentially of the following components:

(a) the alkaline builder ranges from about 92% to about 98% by weight and is selected from the class consisting of diand tri-sodium and potassium orthophosphates, alkaline condensed phosphate salts, sodium and potassium hydroxides, sodium carbonate and bicarbonate, alkali metal borates, and alkali metal silicates,

(b) the active chlorine agent ranges from about 1% to about 3% by weight and is selected from the class consisting of sodium and potassium dichlorisocyanurates, di and trichlorocyanuric acid, trichloro melamine, sodium N-chloro-p-toluene sulfonamide, dichlorodimethyl hydantoin, and sodium, calcium and lithium hypochlorites,

(c) the surface active agent ranges from about 1% to about 5% by weight and is selected from the class 2 See Tables II and IV for composition of detergent formulations; stored 14 days at 38 C. and relative (2) polyethylene oxide and/or propylene oxide ad ducts of low molecular weight polyhydroxy or polyamine compounds;

(3) terminated nonionics of the type R1 R(oH2( JHo),R where R is alkoxy, alkyl phenoxy or alkyl amine of which the alkyl group contains 8-18 C atoms; R is H or CH R is benzyl, an alkyl chain of 1-8 C atoms, a halogen, a propylene oxide chain of 3 or more units, a lactam radical, or an alkyl acetal radical whose alkyl group consists of l- 8 C atoms; and x is 3 or larger;

(4) acetylenic diols of at least 7 C atoms, and

their enthylene oxide adducts; and

where R, R and x are as indicated in (3) above,

and A is either H or an alkyl group of l-3 C atoms; and

(d) the antioxidant is selected from the class consisting of substituted phenols selected from one of p-toctyl phenolformaldehyde condensate, p-dodecyl phenol-formaldehyde condensate, pt-butyl phenol-formaldehyde condensate, all said condensates having a molecular weight averaging about 2000; organic phosphites consisting of compounds having the formulae:

RIII X in which R, R", R' are alkyl, cycloalkyl, aryl, alkoxy alkyl, aralkyl or tetrahydrofurfuryl, and x is oxygen or sulfur, thiourea; and O-phenylene diamine.

2. The detergent composition consisting essentially of the following components:

(a) the alkaline builder ranges from about 92% to about 98% by weight and is selected from the class consisting of diand tri-sodium and potassium or thophosphates, alkaline condensed phosphate salts, sodium and potassium hydroxides, sodium carbonate and bicarbonate, alkali metal borates, and alkali metal silicates;

(b) the active chlorine agent ranges from about 1% to about 3% by weight and is selected from the class consisting of sodium and potassium dichlorisocyanurates, diand trichlorocyanuric acid, trichloro melamine, sodium N-chloro-p-toluene sulfonamide, dichlorodimethyl hydantoin, and sodium, calcium and lithium hypochlorites;

1 1 1 2 (c) the surface active agent ranges from about 1% to about 5% by weight and is a terminated nonionic of References Cited the yp UNITED STATES PATENTS f 3,288,576 11/1966- Pierron et a1 252- 400X R(CHZCHO);R2 5 3,356,612 12/1967 Guthrie 25299 3,422,030 1/1969 Riley, J1. 252-40O where R is alkoxy or alkyl phenoxy, of WhlCh the 3,298,964 1/1967 szczepanek et ah 252 40Q alkyl group constains 8-18 carbon atoms; R is H or 3; R2 is y and X is 3 or g e MAYER WEINBLATI, Primary Examiner (d) the antioxidant is one of p-t-octyl phenol formalde- 10 hyde condensate havin a molecular weight of about US. Cl. X.'R.

2000, or triphenyl phosphite, or a mixture of the two. 252-18 40