US3314891A - Low foaming detergent - Google Patents

Low foaming detergent Download PDF

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US3314891A
US3314891A US50756165A US3314891A US 3314891 A US3314891 A US 3314891A US 50756165 A US50756165 A US 50756165A US 3314891 A US3314891 A US 3314891A
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phosphate
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Irving R Schmolka
Mason H Earing
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Wyandotte Chemicals Corp
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    • CCHEMISTRY; METALLURGY
    • C11ANIMAL AND VEGETABLE OILS, FATS, FATTY SUBSTANCES AND WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11DDETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D1/00Detergent compositions based essentially on surface-active compounds; Use of these compounds as a detergent
    • C11D1/02Anionic compounds
    • C11D1/34Derivatives of acids of phosphorus
    • C11D1/345Phosphates; Phosphites
    • CCHEMISTRY; METALLURGY
    • C11ANIMAL AND VEGETABLE OILS, FATS, FATTY SUBSTANCES AND WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11DDETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D1/00Detergent compositions based essentially on surface-active compounds; Use of these compounds as a detergent
    • C11D1/66Non-ionic compounds
    • CCHEMISTRY; METALLURGY
    • C11ANIMAL AND VEGETABLE OILS, FATS, FATTY SUBSTANCES AND WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11DDETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D1/00Detergent compositions based essentially on surface-active compounds; Use of these compounds as a detergent
    • C11D1/66Non-ionic compounds
    • C11D1/72Ethers of polyoxyalkylene glycols
    • CCHEMISTRY; METALLURGY
    • C11ANIMAL AND VEGETABLE OILS, FATS, FATTY SUBSTANCES AND WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11DDETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D3/00Other compounding ingredients of detergent compositions covered in group C11D1/00
    • C11D3/0005Other compounding ingredients characterised by their effect
    • C11D3/0026Low foaming or foam regulating compositions

Description

United States Patent 3,314,891 LOW FOAMING DETERGENT Irving R. Schmolka,.Grosse Ile, Mich., and Mason H. Earing, Danville, Ill., assignors to Wyandotte Chemicals Corporation, Wyandotte, Mich., a corporation of Michigan No Drawing. Filed Nov. 12, 1965, Ser. No. 507,561 14 Claims. (Cl. 252-89) This application is a continuation-impart of patent application Ser. No. 370,716, filed May 27, 1964, now abandoned, which, in turn, is a continuation-in-part of patent application Ser. No. 60,083, filed Oct. 3, 1960, now abandoned.

This invention relates in one aspect to detergent compositions and in a second aspect to low foaming deter: gent compositions especially adapted for use in automatic dishwashing machines.

It is knownin the prior art to employ, as automatic dishwashing detergents, alkaline detergent salts and mixtures of alkaline condensed phosphates, and alkaline detergent salts which may contain chlorinated trisodium phosphate. See, for example, U .8. Patent No. 2,689,225. It is also known that such compositions can optionally, but advantageously, be formulated with suit-able surface active agents as described in US. Patent No. 2,895,916. Aqueous solutions of the aforementioned compositions have good detergency, readily remove objectionable stains from plastic and ceramic dinnerware and are easily rinsed from glasses, "dishes and silverware without leaving undesirable films, streaks or spots thereon. Although these compositions have many advantageous features, nevertheless, they have the undesirable feature of foaming in the presence of raw egg soil. Since foaming can reduce the efficiency of the automatic dishwashing ma-. chine by retarding the mechanical action of the fine water sprays and by reducing the rate of rotation of the per forated spray arms in certain types of machines, it would be advantageous, therefore, to provide an automatic dish- Washing detergent which does not foam excessively-in the presence of raw egg soil or other proteinaceous matter.

Accordingly, it is a purpose of this invention to provide a composition which, when formulated with an automatic dishwashing detergent, will reduce foam during use thereof in the presence of proteinaceous matter.

In accordance with this invention, it has now been discovered that the foaming characteristics of an aqueous solution of an automatic dishwashing detergent containing alkaline detergent salts are substantially reduced in the presence of proteinaceous soil when this detergent is formulated with a composition containing a nonionic surface active agent and at least one alkyl phosphate ester having 18 carbon atoms in the alkyl radical or, more specifically, selected from the group consisting of stearyl acid phosphate and oleyl acid phosphate.

The nonionic surface active agents which are advantageously employed in the compositions of the invention are generally the polyoxyalkylene adducts of hydrophobic bases wherein the oxygen/carbon atom ratio in the oxyalkylene portion of the molecule is greater than 0.40. Those compositions which are condensed with hydrophobic bases to provide a polyoxyalkylene portion having an oxygen/carbon atom ratio greater than 0.40 inelude ethylene oxide, butadiene dioxide and glycidol, mixtures of these alkylene oxides with each other and with minor amounts of propylene oxide, butylene oxide, amylene oxide, styrene oxide, and other higher molecular weight al-kylene oxides. Ethylene oxide, for example,

3,314,891 Patented Apr. 18, 1967 is condensed with the hydrophobic base in an amount sufficient to impart water dispersibility or solubility and surface active properties to the molecule being prepared. The exact amount of ethylene oxide condensed with the hydrophobic base Will depend upon the chemical characteristics of the base employed and is readily apparent to those of ordinary skill in the art relating to the synthesis of oxyalkylene surfactant condensates.

Typical hydrophobic bases which can be condensed with ethylene oxide in order to prepare nonionic surface active agents include monoand po-lyalkyl phenols, polyoxypropylene condensed with a base having from about 1 to 6 carbon atoms and at least one reactive hydrogen atom, fatty acids, fatty amines, fatty amides and fatty alcohols. The hydrocarbon ethers such as the benzyl or lower alkyl ether of the polyoxyethylene surf-actant condensates are also advantageously employed inthe compositions of the invention.

Among the suitable nonionic surfactants are the polyoxyethylene condensates of alkyl phenols having from about 6 to 20 carbon atoms in the alkyl portion and from about 5 to 30 ethenoxy groups in the polyoxyethylene radical. The alkyl substituent on the aromatic nucleus may be octyl, diamyl, n-dodecyi, polymerized propylene such as propylene tetramer and trimer, isooctyl, nonyl, etc. The benzyl ethers of the poly-oxyethylene condensates of monoalkyl phenols impart good properties to the compositions of the invention and at typical product corresponds to the formula:

Higher polyalkyl oxyethylated phenols corresponding to the formula:

wherein R is hydrogen or an alkyl radical having from about 1 to 12 carbon atoms, R and R. are alkyl radicals having from about 6 to 16 carbon atoms and n has a value from about 10 to 40, are also suitable as nonionic surfactants. A typical oxyethylated polyalkyl phenol is dinonyl phenol condensed with 14 moles of ethylene oxide.

Other suitable nonionic surface active agents are co-v generic mixtures of conjugated polyoxyalkylene compounds containing in their structure at least one hydrophobic oxyalkylene chain in which the oxygen/carbon atom ratio does not exceed 0.40 and at least one ZhYdI'O': philic oxyalkylene chain in which the oxygen/carbon atom ratio is greater than 0.40.

Polymers of oxyalkylene groups obtained from propylene oxide, butylene oxide, am ylene oxide, styrene oxide, mixtures of such oxyalkylene groups with each other and with minor amounts of polyoxyalkylene groups obtained from ethylene oxide, butadiene dioxide, and glycidol are illustrative of hydrophobic oxyalkylene chains having an oxygen/carbon atom ratio not exceeding 0.40. Polymers of oxyalkylene groups obtained from ethylene oxide, butadiene dioxide, glycidol, mixtures of such oxyalkylene groups with each other and with minor amounts of oxyalkylene groups obtained from propylene oxide, butylene oxide, a-rny-lene oxide and styrene oxide are illustrative of 'hydrophilic oxyalkylene chains having an oxygen/ carbon atom ratio greater than 0.40.

Among the conjugated polyoxyalkylene compounds 'hich can be used in the compositions of the invention re those which correspond to the formula:

herein Y is the residue of organic compound having rom about 1 to 6 carbon atoms and one reactive hyrogen atom, 11 has an average value of at least about .4 as determined by hydroxyl number and m has a alue such that the oxyethylene portion constitutes about to 90 weight percent of the molecule. These surface ctive agents are more particularly described in US. 'atent No. 2,677,700.

Other conjugated polyoxyalkylene surface active agents lhich are most advantageously used in the compositions if the invention correspond to the formula:

vherein Y is the residue of an organic compound having rom about 2 to 6 carbon atoms and containing x re- .ctive hydrogen atoms in which x has a value of at least tbOlll'. 2, n has a value such that the molecular weight if the polyoxypropylene hydrophobic base is at least lbOll't 900 and in has a value such that the oxyethylene :ontent of the molecule is from about to 90 weight )ercent. Compounds falling within the scope of the lefinition for Y include, for example, propylene glycol, glycerine, pentaerythritol, trimethylolpropane, ethylene iiamine and the like. As already noted, the oxypropyl- :ne chains optionally, but advantageously, contain small amounts of ethylene oxide and the oxyethylene chains also optionally, but advantageously, contain small amounts of alkylene oxides such as propylene oxide and butylene oxide. These compositions are more particularly described in US. Patent No. 2,674,619. Additiona1 conjugated polyoxyalkylene surface active agents which are advantageously used in the compositions of this invention correspond to the formula:

wherein P is the residue of an organic compound having from about 8 to 18 carbon atoms and containing x reactive hydrogen atoms in which x has a value of 1 or 2, n has a value such that the molecular weight of the polyoxypropylene portion is at least about 58 and m has a value such that the oxyethylene content of the molecule is from about 10 to 90 weight percent and the formula:

wherein P is the residue of an organic compound having from about 8 to 18 carbon atoms and containing x reactive hydrogen atoms in which x has a value of 1 or 2, n has a value such that the molecular weight of the polyoxyethylene portion is at least about 44 and m has a value such that the oxypropylene content of the molecule is from about 10 to 90 weight percent. In either case the oxypropylene chains may contain optionally, but advantageously, small amounts of ethylene oxide and the oxyethylene chains may contain also optionally, but advantageously, small amounts of alkylene oxides such as propylene oxide, butylene oxide and higher alkylene oxides containing 8 to 18 carbon atoms in the alkyl chains.

Thus, cogeneric mixtures of conjugated polyoxyalkylene compounds containing in their structure the residue of an active hydrogen-containing compound and at least one hydrophobic chain of units selected from the group consisting of oxypropylene and oxypropylene-oxyethylene units in which the oxygen/carbon atom ratio does not exceed 0.40 and at least one hydrophilic chain of units selected from the group consisting of oxyethylene and oxyethylene-oxyp-ropylene units in which the oxygen/ carbon atom ratio is greater than 0.40 are suitable nonionic surface active agents.

Further suitable nonionic surface active agents are the .4 polyoxyethylene esters of higher fatty acids having from about 8 to 22 carbon atoms in the acyl group and from about 8 to 30 ethenoxy units in the oxyethy-lene portion. Typical products are the polyoxyethylene adducts of tall oil, rosin acids, lauric, stearic and oleic acids and the like. Additional nonionic surface active agents are the polyoxyethylene condensates of higher fatty acid amines and amides having from about 8 to 22 carbon atoms in the fatty alkyl or acyl group and about 10 to 30 ethenoxy units in the oxyethylene portion. Illustrative products are coconut oil fatty acid amines and amides condensed with about 10 to 30 moles of ethylene oxide.

Other suitable polyoxyalkylene nonionic surface active agents are the alkylene oxide adducts of higher aliphatic alcohols and thioalcohols having from about 8 to 22 carbon atoms in the aliphatic portion and about 3 to 50 oxyalkylene units in the oxyalkylene portion. Typicalproducts are synthetic fatty alcohols, such as n-decyl, nundecyl, n-dodecyl, n-tridecyl, n-tetradecyl, n-hexadecyl, n-octadecyl and mixtures thereof condensed with 3 to 50 moles of ethylene oxide, a mixture of normal fatty alcohols condensedwith 8 to 20 moles of ethylene oxide and capped with benzyl halide or an alkyl halide, a mixture of normal fatty alcohols condensed with 10 to 30 moles of a mixture of ethylene and propylene oxides, a mixture of several fatty alcohols condensed sequentially with 2 to 20 moles of ethylene oxide and 3 to 10 moles of propylene oxide, in either order; or a mixture of normal fatty alcohols condensed with a mixture of propylene and ethylene oxides, in which the oxygen/carbon atom ratio is less than 0.40, followed by a mixture of propylene and ethylene oxides in which the oxygen/ carbon atom ratio is greater than 0.40, or a linear secondary alcohol condensed with 3 to 30 moles of ethylene oxide, or a linear secondary alcohol condensed with a mixture Olf propylene and ethylene oxides, or a linear secondary alcohol condensed with a mixture of ethylene, propylene, and higher alkylene oxides.

The preferred alkyl phosphate esters which are used in the compositions of this invention are predominantly monostearyl phosphate which can contain, in addition thereto, diand tristearyl phosphates and monooleyl phosphates which can contain, in addition thereto, diand trioleyl phosphates.

The alkyl phosphate esters available on the market are generally mixtures of monoand dialkyl phosphate esters which may also contain some trialkyl phosphate. For purposes of this invention the preferred alkyl phosphate ester compositions can contain, in addition to the monoalkyl phosphate, up to about 50 mole percent of the dialkyl phosphate and up to about 5 weight percent of the trialkyl phosphate. In a preferred embodiment of this invention, at least 50 mole percent of the stearyl acid phosphate component is the monostearyl phosphate.

The salts and particularly the alkali metal salts of the alkyl phosphate esters may also be employed as is apparent to anyone skilled in the art. Accordingly, the expressions stearyl acid phosphate and oleyl acid phosphate, as used herein, include the salts of the stearyl and oleyl acid phosphates.

The compositions of the invention generally contain from about 50.0 to 99.9 weight percent of the nonionic surface active agent and from about 0.1 to 50.0 Weight percent of the alkyl phosphate ester. The compositions are readily prepared by blending the ingredients in the aforementioned proportions in a conventional mixing ap paratus at a temperature from about room temperature up to about C., depending upon the melting point of the materials used and, when desirable, following the blending step by a grinding or flaking step so as to obtain the blended ingredients in a suitable particle size. The composition is then added to the automatic dishwashing detergent in order to reduce foaming during use thereof. Also, the ingredients of the compositions of the invention can be added separately, in the proportions set forth, to

the automatic dishwashing detergent to accomplish defoaming.

The automatic dishwashing detergents to which the compositions of the invention are added in order to reduce foaming of aqueous solutions thereof in the presence of raw egg soil generally contain to 80 weight percent of an alkaline condensed phosphate salt such as tetrasodium pyrophosphate and those polyphosphates of the calcium and magnesium ion sequestering type whose Na O/P O ratios range from 1:1 to 1.67:1 and 20 to 100 weight percent of an alkaline detergent salt such as sodium carbonate, sodium bicarbonate and mixtures thereof, modified soda, diand trisodium orthophosphate, sodium metasilicate, sodium sesquisilicate, borax and sodium borate. In addition, these detergents often include 5 to 25 weight percent chlorinated trisodium phosphate. A mixture of lithium hypochlorite or chlorinated syanuric acid and trisodium phosphate can be used in place of chlorinated trisodium phosphate. An automatic dishwashing detergent of this type can be prepared by adding an aqueous silicate solution to substantially anhydrous sodium tripolyphosphate and subsequently adding chlorinated trisodium phosphate thereto under the conditions as described in US. Patent No. 2,895,916. Although the compositions of the invention can be added at any time during the preparation of the dishwashing detergent, they are preferably added simultaneously with the aqueous silicate solution.

A preferred automatic dishwashing composition characterized by low forming in the presence of proteinaceous matter comprises about 80 to 99.9 weight percent of the automatic dishwashing detergent of the type described above and about 0.1 to 20 weight percent of the composition of this invention.

It has been noted that the foaming characteristics of the above-described automatic dishwashing detergents in the presence of raw egg soil are reduced slightly by formul-at ing with either a nonionic surface active agent or specified alkyl phosphate ester but, as will be apparent from certain of the examples hereinafter set forth, the foaming characteristics of these detergents are substantially reduced when the detergents are formulated with a composition containing both a nonionic surface active agent and specified alkyl phosphate ester.

The foam characteristics of the detergent compositions were measured by observing the rate of rotation of the perforated spray arm of an automatic dishwashing ma chine during the washing cycle in which raw egg soil and detergent were present in definitive quantities. The rate of rotation of the spray arm is, of course, inversely proportional to the amount of foam present. In each of the subsequent examples, foam evaluation was carried out in a Hobart Kitchen Aid dishwasher. The procedure followed was to turn on the machine and, after part of the water had been added, turn off the machine and add the detergent composition and additives, if any, and 15 cc.

of raw egg. The dishwasher was then turned on again and the balance of the water added. The water was at a temperature of about 160 F. After the washing cycle started, the rate of rotation of the perforated spray arm was measured from the first to the second minute and from the third to the fourth minute. In the presence of excess foam, the rotor arm stopped or the foam overflowed. A spray arm rotation of about 70 rpm. or more is indicative that foam formation is being substantially depressed.

The following examples further illustrate the invention.

Example I This example sets forth the effect of 1) a nonionic surface active agent, (2) an alkyl phosphate ester having 18 carbon atoms in the alkyl radical, and (3) a mixture of a nonionic surface active agent and the alkyl phosphate ester as foam suppressing agents for an automatic dishwashing detergent.

The automatic dishwashing detergent employed in this example and referred to herein as Composition A contained the following ingredients in the proportions set forth:

Composition A: Parts by weight Chlorinated trisodium phosphate- 12 hydrate 7.2

Trisodium phosphate-12 hydrate 23.6 Sodium tripolyphosphate'6 hydrate 51.2 W-aterglass (1Na O/2SiO 50% solids 12.9

Composition A and Composition A formulated with additives (1), (2) and (3) above identified were evaluated for foaming characteristics in the presence of raw egg soil in a Hobart dishwasher in accordance with the procedure previously outlined and the ingredients, quantities thereof and results are set forth in Table 1.

Sodium chloride 1 The stearyl acid phosphate used in this example contained 78% by weight monostearyl acid phosphate, 17% by weight distearyl acid phosphate, balance tristearyl acid phosphate, phosphoric acid and impurit es.

N onionic 1 defines a mixture of nonionic Surface active agents consisting of (a) weight percent polyoxyethylene-polyoxypropylene-polyoxyethylene polyol wherein the average molecular weight of the polyoxypropylene base is about 1,750 and the polyoxyethylene content of the molecule is about 25 weight percent, and (b) 10 weight percent of a polyoxyethylene-polyoxypropylenepolyoxyethylene polyol wherein the average molecular weight of the polyoxypropylene base is about 1,750 and the polyoxyethylene content of the molecule is about 10 weight percent.

It will be noted from Table 1 that although the nonionic surface active agent and the phosphate separately had a slight foam suppressing effect on the dishwashing detergent, the combination of the nonionic and phosphate significantly and substantially reduced the foam characteristics of the detergent in the presence of egg soil. Thus, the combination of the nonionic surface active agent and the phosphate synergistically depresses foam formation of the detergent in the presence of raw egg soil.

Example 2 This example sets forth the effect of additional nonionic sur-face active agents alone and in admixture with an alkyl acid phosphate ester having 18 carbon atoms in the alkyl radical as foam suppressing agents for an automatic dishwashing detergent.

The automatic dishwashing detergent employed in this example and referred to herein as Composition B contained the following ingredients in the proportions set forth:

Composition B: Parts by weight Sodium tripolyphosphate 41.80 Trisodium phosphate-12 hydrate 11.30 Sodium metasilicate, anhydrous 14.70 Sodium sulfate .51 Sodium chloride .12

. 7 =thylene groups attached to the nitrogen. The general ormula is:

(CHzCH OhH RN\ (OH2CH2O) 'H vherein R represents the radical derived from the coconut )il; x plus y=l and the average molecular weight is 875.

Nonionic 3 defines an N-substituted fatty acid amide raving one fatty acyl group derived from coconut oil and :wo polyoxyethylene groups attached to the nitrogen. The general formula is: I

o (CH CHzO),H

RCN

(CH CH OMH wherein R'C represents the radical derived from the coconut oil, x plus 3 and the average molecular weight is 889.

The stearyl acid phosphate ester was the same as employed in Example 1.

It will be noted from Table 2 that although the nonionic surface active agents 2 and 3 alone had none or a negligible foam suppressing effect on the dishwashing detergent, the combination of either nonionic with the stearyl acid phosphate significantly and substantially reduced the foam characteristics of the detergent in the presence of egg soil. Thus, Examples 1 and 2 illustrate that the combination of various nonionic surface active agents with the alkyl phosphate ester depresses foam formation to a substantial degree as compared to any of the nonionic surface active agents alone in the presence of raw egg soil.

Examples 3-22 Examples illustrating the effectiveness of additional combinations of stearyl acid phosphate and oleyl acid phosphate with nonionic surface active agents as foam suppressing agents for automatic dishwashing detergents are provided in Table 3 below.

The following automatic dishwashing detergents, in dicated in Table 3 below as Compositions C, D, and E, were prepared containing the following ingredients and the proportions set forth:

Composition C: Parts by weight Compositions A and B set forth above in connection with Examples 13 and Compositions C, D, and E were formulated in the proportions shown in Table 3 below with various nonionic surface active agents and the specified alkyl phosphate esters.

The nonionic surface active agents, indicated by numbers ranging from 1-15 in Table 3 below, are as follows:

Nonionics l and 2 are described above in connection with Examples 1 and 2.

Nonionic 4 defines the benzyl ether of octylphenoxypolyethoxy ethanol having about 15 ethenoxy units in the oxyethylene portion.

Nonionic 5 defines the polyoxyethylene adduct of branched chain nonyl phenol having about 9 to 1'0 ethenoxy units in the oxyethylene portion.

Nonionic 6 defines the polyoxyethylene adduct of polyoxypropylene condensed with ethylene diamine wherein the oxypropylene hydrophobic base has a molecular weight of about 3600 and the oxyethylene content is about 15 weight percent of the molecule.

Nonionic 7 defines a heteric conjugated polyoxyalkylene polyl wherein a mixture of 90 weight percent propylene oxide and 10 weight percent ethylene oxide is condensed with trimethylolpropane so as to provide a hydrophobic base having a molecular weight of about 3200 and a mixture of 90 weight percent ethylene oxide and 10 weight percent propylene oxide is subsequently condensed With the hydrophobic base so as to provide a hydrophilic portion having a molecular weight of about 1280.

Nonionic 8 defines an ethoxylated synthetic fatty alcohol, consisting of a mixture of n-dodccanol, n-tetradecanol, n-hexadecanol and n-octadecanol, containing 60-65 percent by weight of ethylene oxide.

Nonionic 9 defines a polyoxyethylene ester of tall oil.

Nonionic 1O defines the polyoxyethylene adduct of a straight chain n-alkyl phenol having about 10l4 ethenoxy units in the oxyethylene portion and about 12-14 carbons in the alkyl portion.

Nonionic 11 defines polyethylene glycol tert. dodecyl thioether.

Nonionic 12 defines the polyoxyethylene adduct of a polyoxypropylene hydrophobic base having a molecular weight of about 1750 wherein the oxyethylene content is about 10 weight percent of the molecule.

Nonionic 13 defines a polyoxyalkylene polyol wherein a mixture of 1500 parts by weight of ethylene oxide and 500 parts by weight of propylene oxide is condensed with 500 parts by weight of a mixture of normal fatty alcohols having from 10 to 18 carbon atoms and, more specifically, a mixture of by weight 35 percent of a IO-carbon atom fatty alcohol, 15 percent of a 12-carbon atom fatty alcohol, 15 percent of a 16-carbon atom fatty alcohol, and 35 percent of an l8-carbon atom fatty alcohol.

Nonionic 14 defines a polyoxyalkylene polyol wherein 788 parts by weight of commercial lauryl alcohol is sequentially condensed with 1056 parts by weight of ethylene oxide and 696 parts by weight of propylene oxide.

Nonionic 15 defines a heteric conjugated polyoxyalkylene polyol wherein a mixture of 252 parts by weight of propylene oxide and 108 parts by weight of ethylene oxide is condensed with 600 parts by weight of a mixture of normal fatty alcohols having from 12 to 18 carbon atoms and, more specifically, a mixture of by weight 40 percent of a 12-carbon atom fatty alcohol, 30 percent of a 14-carbon atom fatty alcohol, 20 percent of a 16-carbon atom fatty alcohol, and 10 percent of an 18-carbon atom fatty alcohol to provide a hydrophobic base. A mixture of 1008 parts by weight ethylene oxide and 432 parts by weight propylene oxide is subsequently condensed with the hydrophobic base.

The stearyl acid phosphate is the same as that employed in Example 1.

The oleyl acid phosphate is a mixture of equimolar amounts of monooleyl acid phosphate and dioleyl acid phosphate.

TABLE 3 Base Nonionic Ester Example R.p.m. Water Temp,

No. (1st-2nd min.) F.

Composition Wt., gms. Designation Wt., gms. Material Wt., gms.

18. 6 1 0. 20 Stearyl acid phosphate 0.2 115 140 18. 6 1 0.30 do 0. 1 109 135 18.6 1 0. 35 -d 0.05 98 135 18. 6 2 0.20 0.2 100 135 18. 6 2 0. 30 0. 1 90 135 18. 6 4 0. 30 0. 05 78 160 18. 6 5 0. 30 0. 05 69 160 18.6 6 0. 30 0.05 80 160 18. 6 7 2. 25 0. 15 90 160 17.1 8 1. 35 0.35 89 160 18.3 9 1. 60 0. 20 99 160 17.1 10 0.30 0. 075 75 160 18. 6 11 0. 30 d0 0.10 64 160 25.0 12 1. 60 Oleyl acid phosphate. 0.05 73 160 18.3 13 0. 30 stearyl acid phosphate 0.05 71 140 18.3 13 0.30 Oleyl acid phosphate. 0.10 71 140 17.1 14 1.35 --.d0 0.35 106 140 17.1 14 0. 30 Stearyl acid phosphate- 0.10 87 140 20.0 15 0.90 O 0.10 98 140 20.0 15 0. 90 Oleyl acid phosphate 0.30 100 140 Examples 23-26 These examples illustrate that combinations of nonionic surface active agents and alkyl acid phosphate esters, which do not have 18 carbon atoms in the alkyl radical, do not have a significant foam suppressing effect on automatic dishwashing detergents.

A series of 18.6-gram portions of the automatic dishwashing detergent, set forth in Example 2 as Composition B, were formulated with 0.3 gram of the nonionic surface active agent set forth in Example 2 as Nonionic 2 and 0.1 gram of a lower alkyl phosphate ester indicated in Table 4 below. These formulations were evaluated for foam characteristics in the presence of egg soil in accordance with the procedure outlined in Example 1 at a water temperature of 140 F.

Thus, the objects of this invention have been accomplished, namely, a composition has been provided which, when formulated with an automatic dishwashing detergent, will substantially reduce foam formation during use thereof as is more particularly described herein.

What is claimed is:

1. A composition adapted to be formulated with automatic dishwashing detergents for reducing foam during use thereof in the presence of proteinaceous matter, comprising:

about 50.0 to 99.9 weight percent nonionic surface active component, selected, from the group consisting of polyoxyethylene condensates of alkyl phenols having from about '6 to 20 carbon atoms in the alkyl portion, the benzyl ethers of said polyoxyethylene condensates of alkyl phenols, cogeneric mixtures of conjugated polyoxyalkylene compounds containing in their structure the residue of an active hydrogen-containing compound and at least one hydrophobic chain of units selected from the group consisting of oxypropylene and oxypropylene-oxyethylene units in which the oxygen/ carbon atom ratio does not exceed 0.40 and at least one hydrophilic chain of units selected from the group consisting of oxyethylene and oxyethylene-oxypropylene units in which the oxygen/carbon atom ratio is greater than 0.40,

polyoxyethylene esters of higher fatty acids having from about 8 to 22 carbon atoms in the acyl group, polyoxyethylene condensates of higher fatty amines having from about -8 to 22 carbon atoms in the fatty alkyl group, polyoxyethylene condensates of higher fatty amides having from about 8 to 22 carbon atoms in the fatty acyl group, and alkylene oxide adducts of higher aliphatic compounds selected from the group consisting of alcohols and thioalcohols having from about 8 to 22 carbon atoms in the aliphatic portion, and about 0.1 to 50.0 weight percent alkyl phosphate ester component selected from the group consisting of stearyl acid phosphate and oley'l acid phosphate.

2. A composition in accordance with claim 1 wherein said surface active component is the polyoxyethylene condensate of an alkyl phenol having from about 6 to 20 carbon atoms in the alkyl portion.

3. A composition in accordance with claim 1 wherein said surface active component is the benzyl ether of a polyoxyethylene condensate of an allkyl phenol having from about 6 to 20 carbon atoms in the alkyl portion.

4. A composition in accordance with claim 1 wherein said surface active component is a cogeneric mixture of conjugated polyoxyal'kylene compounds containing in their structure at least one hydrophobic oxypropylene chain in which the oxygen/carbon atom ratio does not exceed 0.40 and at least one hydrophilic oxyethylene chain in which the oxygen/carbon atom ratio is greater than 0.40.

5. A composition in accordance with claim 1 wherein said surface active component is a polyoxyethylene ester of a higher fatty acid having from about 8 to 22 carbon atoms in the acyl group.

6. A composition in accordance with claim 1 wherein said surface active component is the ethylene oxide adduct of a higher aliphatic alcohol having from about 8 to 22 carbon atoms in the aliphatic portion.

7. The composition of claim 1 wherein said alkyl phosphate ester component consists essentially of up to about 50 mole percent dialkyl phosphate, up to about 5 weight percent trialkyl phosphate, balance monoalkyl phosphate.

8. A low-foaming, automatic dishwashing detergent, characterized by low foaming in the presence of proteinaceous matter, comprising:

about to 99.9 weight percent of Composition A containing 20 to percent of an alkaline detergent salt selected from the group consisting of sodium carbonate, sodium bicarbonate, modified soda, disodinm orthophosphate, trisodium orthophosphate, sodium metasilicate, sodium sesqui- 11 silicate, waterglass, borax, sodium borate, and mixtures thereof, and to 80 weight percent of an alkaline condensed phosphate salt selected from the group consisting of tetrasodium pyrophosphate and those polyphosphates of the calcium and magnesium ion sequestering type whose Na O/P O ratios range from 1:1 to 1.67:1, and about 0.1 to 20 weight percent of Composition B containing about 50.0 to 99.9 weight percent nonionic surface active component, selected from the group consisting of polyoxyethylene condensates of alkyl phenols having from about 6 to 20 carbon atoms in the alkyl portion, the benzyl ethers of said polyoxyethylene condensates of alkyl phenols, cogeneric mixtures of conjugated polyoxyalkylene compounds containing in their structure the residue of an active hydrogen-containing compound and at least one hydrophobic chain of units selected from the group consisting of oxypropylene and oxylpropylene-oxyethylene units in which the oxygen/carbon atom ratio does not exceed 0.40 and at least one hydrophilic chain of units selected from the group consisting of oxyethylene and oxyethylene-oxypropylene units in which the oxygen/carbon atom ratio is greater than 0.40, polyoxyethylene esters of higher fatty acids hav ing from about 8 to 22 carbon atoms in the acyl p,

. polyoxyethylene condensates of higher fatty amines having from about 8 to 22 carbon atoms in the fatty alkyl group,

polyoxyethylene condensates of higher fatty amides having from about 8 to 22 carbon atoms in the fatty acyl group, and alkyene oxide adducts of higher aliphatic compounds selected from the group consisting of alcohols and thioalcohols having from about 8 to 22 carbon atoms in the aliphatic portion, and about 0.1 to 50.0 weight percent higher alkyl phosphate ester component selected from the group consisting of stearyl acid phosphate and oleyl acid phosphate. 9. An automatic dishwashing detergent in accordance with claim 8 wherein said nonionic surface active component is a mixture of 90 weight percent of polyexythylene-polyoxypropylene-polyoxyethylene polyol wherein the average molecular weight of the polyoxypropylene base is about 1750 and the polyoxyethylene content of the molecule is about 25 weight percent and 10 weight percent of a polyoxyethylene polyoxypropylene polyoxyethylene polyol wherein the molecular weight of the oxypropylene base is about 1750 and the polyoxyethylene content of the molecule is about 10 weight percent.

10. An automatic dishwashing detergent in accordance with claim 8 wherein said surface active component is the benzyl ether of an octylphenoxy-polyethoxy ethanol containing about 12 to 20 ethoxy units.

1 1. The composition of claim 8 wherein said alkyl phosphate ester component consists essentially of up to about mole percent dialkyl phosphate, up to about 5 weight percent trialkyl phosphate, balance monoalkyl phosphate.

12. The composition of claim 7 wherein said alkyl phosphate ester is stearyl acid phosphate, at least 50 mole percent of which is monostearyl acid phosphate.

'13. The composition of claim 7 wherein said alkyl phosphate ester is oleyl acid phosphate.

14. The composition of claim 1 1 wherein said alkyl phosphate ester is. stearyl acid phosphate, at least 50 mole percent of which is monostearyl acid phosphate.

References Cited by the Examiner UNITED STATES PATENTS 2,005,619 6/1935 Graves 252-89 2,656,372 10/1953 Ernst et al. 252--89 2,674,619 4/ 1954 Lundsted. 2,677,700 5/1954 Jackson et al. 2,856,434 10/1958 Niderhauser et al. 2,895,916 7/1959 Milenkevich et al. 252-435 X 3,010,907 1 1/1961 Carroll 252- 3,048,548 8/1962 Martin et al. 252--135 FOREIGN PATENTS 354,300 8/1931 Great Britain.

OTHER REFERENCES Adler et al.: The Alkyl Esters of Phosphoric Acid, in Chemical Industries, October 1942, pp. 516-521, 557.

Ross: Chemical Antifoamin-g Agents, in Chemical Industries, May 1949, pp. 757-759.

ALBERT T. MEYERS, Primary Examiner.

Claims (1)

1. A COMPOSITION ADAPTED TO BE FORMULATED WITH AUTOMATIC DISHWASHING DETERGENTS FOR REDUCING FOAM DURING USE THEREOF IN THE PRESENCE OF PROTEINACEOUS MATTER, COMPRISING: ABOUT 50.0 TO 99.9 WEIGHT PERCENT NONIONIC SURFACE ACTIVE COMPONENT, SELECTED, FROM THE GROUP CONSISTING OF POLYOXYETHYLENE CONDENSATES OF ALKYL PHENOLS HAVING FROM ABOUT 6 TO 20 CARBON ATOMS IN THE ALKYL PORTION, THE BENZYL ETHERS OF SAID POLYOXYETHYLENE CONDENSATES OF ALKYL PHENOLS, CONGENERIC MIXTURES OF CONJUGATED POLYOXYALKYLENE COMPOUNDS CONTAINING IN THEIR STRUCTURE THE RESIDUE OF AN ACITVE HYDROGEN-CONTAINING COMPOUND AND AT LEAST ONE HYDROPHOBIC CHAIN OF UNITS SELECTED FROM THE GROUP CONSITING OF OXYPROPYLENE AND OXYPROPYLENE-OXYETHYLENE UNITS IN WHICH THE OXYGEN-CARBON ATOM RATIO DOES NOT EXCEED 0.40 AND AT LEAST ONE HYDROPHILIC CHAIN OF UNITS SELECTED FROM THE GROUP CONSISTING OF OXYETHYLENE AND OXYETHYLENE-OXYPROPYLENE UNITS IN WHICH THE OXYGEN/CARBON ATOM RATIO IS GREATER THAN 0.40, POLYOXYETHYLENE ESTERS OF HIGHER FATTY ACIDS HAVING FROM ABOUT 8 TO 22 CARBON ATOMS IN THE ACYL GROUP, POLYOXYETHYLENE CONDENSATES OF HIGHER FATTY AMINES HAVING FROM ABOUT 8 TO 22 CARBON ATOMS IN THE FATTY ACID GROUP, POLYOXYETHYLENE CONDENSATES OF HIGHER FATTY AMIDES HAVING FROM ABOUT 8 TO 22 CARBON ATOMS IN THE FATTY ACYL GROUP, AND ALKYLENE OXIDE ADDUCTS OF HIGHER ALIPHATIC COMPOUNDS SELECTED FROM THE GROUP CONSISTING OF ALCOHOLS AND THIOALCOHOLS HAVING FROM ABOUT 8 TO 22 CARBON ATOMS IN THE ALIPHATIC PORTION, AND ABOUT 0.1 TO 50.0 WEIGHT PERCENT ALKYL PHOSPHATE ESTER COMPONENT SELECTED FROM THE GROUP CONSISTING OF STEARYL ACID PHSOPHATE AD OLEYL ACID PHOSPHATES.
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DE19661617239 DE1617239B2 (en) 1964-05-27 1966-11-07
FR83334A FR1499000A (en) 1964-05-27 1966-11-10 New detergent compositions for washing machines raisselle
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US3468803A (en) * 1966-04-14 1969-09-23 Fmc Corp Dishwashing compositions
US3523902A (en) * 1965-04-07 1970-08-11 Wyandotte Chemicals Corp Controlled suds detergent
US4070298A (en) * 1976-07-26 1978-01-24 Olin Corporation Defoaming detergent additive
US4101457A (en) * 1975-11-28 1978-07-18 The Procter & Gamble Company Enzyme-containing automatic dishwashing composition
US4123395A (en) * 1975-11-28 1978-10-31 The Procter & Gamble Company Compositions containing nonionic surfactant and sulfonated aromatic compatibilizing agent
US4136045A (en) * 1976-10-12 1979-01-23 The Procter & Gamble Company Detergent compositions containing ethoxylated nonionic surfactants and silicone containing suds suppressing agents
US4206074A (en) * 1977-05-23 1980-06-03 Basf Aktiengesellschaft Extremely low-foaming surfactant system
US4263160A (en) * 1979-04-30 1981-04-21 Olin Corporation Process for the preparation of stable dispersions of alkyl phosphate esters
US4272394A (en) * 1979-11-19 1981-06-09 Basf Wyandotte Corporation Machine dishwashing detergents containing low-foaming nonionic surfactants
US4306987A (en) * 1979-11-19 1981-12-22 Basf Wyandotte Corporation Low-foaming nonionic surfactant for machine dishwashing detergent
US4313847A (en) * 1978-06-15 1982-02-02 Ici Americas Inc. Surfactant compositions
US4362642A (en) * 1976-01-23 1982-12-07 Lever Brothers Company Alkyl phosphoric acid polyvalent salts-mineral oil lather controlled detergent compositions
US4448706A (en) * 1982-05-10 1984-05-15 Basf Wyandotte Corporation Defoaming detergent additives containing bleached tallow acid phosphates
US4465613A (en) * 1976-01-23 1984-08-14 Lever Brothers Company Alkyl phosphoric salt-hydrocarbon wax lather controlled detergent compositions
US4539134A (en) * 1982-12-02 1985-09-03 Halliburton Company Methods and cleaning compositions for removing organic materials from metallic surfaces
US4588515A (en) * 1984-09-27 1986-05-13 The Procter & Gamble Company Granular automatic dishwasher detergent compositions containing smectite clay
US4601844A (en) * 1984-08-31 1986-07-22 The Procter & Gamble Company Granular automatic dishwasher detergent with alkyl phosphate and calcium ion source
US4614606A (en) * 1983-10-31 1986-09-30 Lever Brothers Company Liquid scouring compositions
US4726909A (en) * 1985-12-23 1988-02-23 Basf Corporation Low odor surfactant
US4740327A (en) * 1982-01-18 1988-04-26 Colgate-Palmolive Company Automatic dishwasher detergent compositions with chlorine bleach having thixotropic properties
US4846989A (en) * 1988-02-12 1989-07-11 Ecolab Inc. Solid cast warewashing composition and process for preparing the same
US4859358A (en) * 1988-06-09 1989-08-22 The Procter & Gamble Company Liquid automatic dishwashing compositions containing metal salts of hydroxy fatty acids providing silver protection
US4988452A (en) * 1988-06-09 1991-01-29 The Procter & Gamble Company Liquid automatic dishwashing detergent compositions containing bleach-stable nonionic surfactant
US5130043A (en) * 1988-06-09 1992-07-14 The Procter & Gamble Company Liquid automatic dishwashing compositions having enhanced stability
EP0699745A2 (en) 1994-08-31 1996-03-06 THE PROCTER & GAMBLE COMPANY Automatic dishwashing compositions comprising quaternary ammonium compounds bleach activators and quaternary ammonium
US5583097A (en) * 1994-04-22 1996-12-10 Ppg Industries, Inc. Deinking agent of nonionic surfactants
US5612305A (en) * 1995-01-12 1997-03-18 Huntsman Petrochemical Corporation Mixed surfactant systems for low foam applications
US6682881B2 (en) * 2001-03-14 2004-01-27 Fuji Photo Film Co., Ltd. Antifoaming agent composition for a silver halide photographic processing solution and process for processing a silver halide photographic material using same
US20080020961A1 (en) * 2006-07-21 2008-01-24 Rodrigues Klin A Low Molecular Weight Graft Copolymers
US20080020948A1 (en) * 2006-07-21 2008-01-24 Rodrigues Klin A Sulfonated Graft Copolymers
US20100069280A1 (en) * 2005-07-21 2010-03-18 Akzo Nobel N.V. Hybrid copolymers
US8636918B2 (en) 2011-08-05 2014-01-28 Ecolab Usa Inc. Cleaning composition containing a polysaccharide hybrid polymer composition and methods of controlling hard water scale
US8679366B2 (en) 2011-08-05 2014-03-25 Ecolab Usa Inc. Cleaning composition containing a polysaccharide graft polymer composition and methods of controlling hard water scale
US8841246B2 (en) 2011-08-05 2014-09-23 Ecolab Usa Inc. Cleaning composition containing a polysaccharide hybrid polymer composition and methods of improving drainage
US8853144B2 (en) 2011-08-05 2014-10-07 Ecolab Usa Inc. Cleaning composition containing a polysaccharide graft polymer composition and methods of improving drainage
US8945314B2 (en) 2012-07-30 2015-02-03 Ecolab Usa Inc. Biodegradable stability binding agent for a solid detergent
US9051406B2 (en) 2011-11-04 2015-06-09 Akzo Nobel Chemicals International B.V. Graft dendrite copolymers, and methods for producing the same
US9109068B2 (en) 2005-07-21 2015-08-18 Akzo Nobel N.V. Hybrid copolymer compositions
US9365805B2 (en) 2014-05-15 2016-06-14 Ecolab Usa Inc. Bio-based pot and pan pre-soak
EP3075832A1 (en) 2015-03-30 2016-10-05 Dalli-Werke GmbH & Co. KG Manganese-amino acid compounds in cleaning compositions

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FR2541908B1 (en) * 1983-03-04 1988-11-25 Ugine Kuhlmann Antifoam composition, process for its manufacture and its application

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Cited By (48)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3523902A (en) * 1965-04-07 1970-08-11 Wyandotte Chemicals Corp Controlled suds detergent
US3468803A (en) * 1966-04-14 1969-09-23 Fmc Corp Dishwashing compositions
US4101457A (en) * 1975-11-28 1978-07-18 The Procter & Gamble Company Enzyme-containing automatic dishwashing composition
US4123395A (en) * 1975-11-28 1978-10-31 The Procter & Gamble Company Compositions containing nonionic surfactant and sulfonated aromatic compatibilizing agent
US4465613A (en) * 1976-01-23 1984-08-14 Lever Brothers Company Alkyl phosphoric salt-hydrocarbon wax lather controlled detergent compositions
US4362642A (en) * 1976-01-23 1982-12-07 Lever Brothers Company Alkyl phosphoric acid polyvalent salts-mineral oil lather controlled detergent compositions
US4070298A (en) * 1976-07-26 1978-01-24 Olin Corporation Defoaming detergent additive
US4136045A (en) * 1976-10-12 1979-01-23 The Procter & Gamble Company Detergent compositions containing ethoxylated nonionic surfactants and silicone containing suds suppressing agents
US4206074A (en) * 1977-05-23 1980-06-03 Basf Aktiengesellschaft Extremely low-foaming surfactant system
US4313847A (en) * 1978-06-15 1982-02-02 Ici Americas Inc. Surfactant compositions
US4263160A (en) * 1979-04-30 1981-04-21 Olin Corporation Process for the preparation of stable dispersions of alkyl phosphate esters
US4306987A (en) * 1979-11-19 1981-12-22 Basf Wyandotte Corporation Low-foaming nonionic surfactant for machine dishwashing detergent
US4272394A (en) * 1979-11-19 1981-06-09 Basf Wyandotte Corporation Machine dishwashing detergents containing low-foaming nonionic surfactants
US4740327A (en) * 1982-01-18 1988-04-26 Colgate-Palmolive Company Automatic dishwasher detergent compositions with chlorine bleach having thixotropic properties
US4448706A (en) * 1982-05-10 1984-05-15 Basf Wyandotte Corporation Defoaming detergent additives containing bleached tallow acid phosphates
US4539134A (en) * 1982-12-02 1985-09-03 Halliburton Company Methods and cleaning compositions for removing organic materials from metallic surfaces
US4614606A (en) * 1983-10-31 1986-09-30 Lever Brothers Company Liquid scouring compositions
US4601844A (en) * 1984-08-31 1986-07-22 The Procter & Gamble Company Granular automatic dishwasher detergent with alkyl phosphate and calcium ion source
US4588515A (en) * 1984-09-27 1986-05-13 The Procter & Gamble Company Granular automatic dishwasher detergent compositions containing smectite clay
US4726909A (en) * 1985-12-23 1988-02-23 Basf Corporation Low odor surfactant
US4846989A (en) * 1988-02-12 1989-07-11 Ecolab Inc. Solid cast warewashing composition and process for preparing the same
US4859358A (en) * 1988-06-09 1989-08-22 The Procter & Gamble Company Liquid automatic dishwashing compositions containing metal salts of hydroxy fatty acids providing silver protection
US4988452A (en) * 1988-06-09 1991-01-29 The Procter & Gamble Company Liquid automatic dishwashing detergent compositions containing bleach-stable nonionic surfactant
US5130043A (en) * 1988-06-09 1992-07-14 The Procter & Gamble Company Liquid automatic dishwashing compositions having enhanced stability
US5583097A (en) * 1994-04-22 1996-12-10 Ppg Industries, Inc. Deinking agent of nonionic surfactants
EP0699745A2 (en) 1994-08-31 1996-03-06 THE PROCTER & GAMBLE COMPANY Automatic dishwashing compositions comprising quaternary ammonium compounds bleach activators and quaternary ammonium
US5612305A (en) * 1995-01-12 1997-03-18 Huntsman Petrochemical Corporation Mixed surfactant systems for low foam applications
US6682881B2 (en) * 2001-03-14 2004-01-27 Fuji Photo Film Co., Ltd. Antifoaming agent composition for a silver halide photographic processing solution and process for processing a silver halide photographic material using same
US9109068B2 (en) 2005-07-21 2015-08-18 Akzo Nobel N.V. Hybrid copolymer compositions
US9321873B2 (en) 2005-07-21 2016-04-26 Akzo Nobel N.V. Hybrid copolymer compositions for personal care applications
US20100069280A1 (en) * 2005-07-21 2010-03-18 Akzo Nobel N.V. Hybrid copolymers
US20110136718A1 (en) * 2005-07-21 2011-06-09 Akzo Nobel N.V. Hybrid copolymers
US8058374B2 (en) 2005-07-21 2011-11-15 Akzo Nobel N.V. Hybrid copolymers
US20080020961A1 (en) * 2006-07-21 2008-01-24 Rodrigues Klin A Low Molecular Weight Graft Copolymers
US8227381B2 (en) 2006-07-21 2012-07-24 Akzo Nobel N.V. Low molecular weight graft copolymers for scale control
US20080020948A1 (en) * 2006-07-21 2008-01-24 Rodrigues Klin A Sulfonated Graft Copolymers
US8674021B2 (en) 2006-07-21 2014-03-18 Akzo Nobel N.V. Sulfonated graft copolymers
US20110046025A1 (en) * 2006-07-21 2011-02-24 Akzo Nobel N.V. Low Molecular Weight Graft Copolymers
US8679366B2 (en) 2011-08-05 2014-03-25 Ecolab Usa Inc. Cleaning composition containing a polysaccharide graft polymer composition and methods of controlling hard water scale
US8853144B2 (en) 2011-08-05 2014-10-07 Ecolab Usa Inc. Cleaning composition containing a polysaccharide graft polymer composition and methods of improving drainage
US9309490B2 (en) 2011-08-05 2016-04-12 Ecolab Usa Inc. Cleaning composition containing a polysaccharide graft polymer compositon and methods of improving drainage
US8636918B2 (en) 2011-08-05 2014-01-28 Ecolab Usa Inc. Cleaning composition containing a polysaccharide hybrid polymer composition and methods of controlling hard water scale
US8841246B2 (en) 2011-08-05 2014-09-23 Ecolab Usa Inc. Cleaning composition containing a polysaccharide hybrid polymer composition and methods of improving drainage
US9309489B2 (en) 2011-08-05 2016-04-12 Ecolab Usa Inc Cleaning composition containing a polysaccharide hybrid polymer composition and methods of improving drainage
US9051406B2 (en) 2011-11-04 2015-06-09 Akzo Nobel Chemicals International B.V. Graft dendrite copolymers, and methods for producing the same
US8945314B2 (en) 2012-07-30 2015-02-03 Ecolab Usa Inc. Biodegradable stability binding agent for a solid detergent
US9365805B2 (en) 2014-05-15 2016-06-14 Ecolab Usa Inc. Bio-based pot and pan pre-soak
EP3075832A1 (en) 2015-03-30 2016-10-05 Dalli-Werke GmbH & Co. KG Manganese-amino acid compounds in cleaning compositions

Also Published As

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NL6615978A (en) 1967-05-16 application
BE689666A (en) 1967-05-16 grant
FR1499000A (en) 1967-10-20 grant
DE1617239B2 (en) 1974-02-21 application
GB1126888A (en) 1968-09-11 application
LU52349A1 (en) 1967-01-24 application
CA789509A (en) 1968-07-09 grant
DE1617239A1 (en) 1972-11-09 application

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