US3708427A

US3708427A - Washing and cleansing compositions

Info

Publication number: US3708427A
Application number: US00096267A
Authority: US
Inventors: G Jakobi; P Berth
Original assignee: Henkel AG and Co KGaA
Current assignee: Henkel AG and Co KGaA
Priority date: 1969-12-20
Filing date: 1970-12-08
Publication date: 1973-01-02
Anticipated expiration: 1990-01-02
Also published as: BE760534A; FR2073910A5; AT303238B; CH554938A; BR7024775D0; NL7017039A; ES386638A1; DE1964024A1

Abstract

BUILDER SALT-CONTAINING WASHING AND CLEANSING COMPOSITIONS COMPRISING (A) ONE PART BY WEIGHT OF A CAPILLARYACTIVE COMPOUND SELECTED FROM THE GROUP CONSISTING OF ANIONIC SURFACE-ACTIVE COMPOUNDS, NON-IONIC SURFACES-ACTOVE COMPOUNDS AND AMPHOTERIC SURFACE-ACTIVE COMPOUNDS AND (B) 0.5 TO 20 PARTS BY WEIGHT OF A MIXTURE OF BUILDER SALTS CONSISTING OF (1) FROM 20% TO 75% BY WEIGHT OF SAID MIXTURE OF PENTASODIUM TRIPHOSPHATE (2) FROM 10% TO 60% BY WEIGHT OF SAID MIXTURE OF SODIUM CLITRATE, AND ''3) FROM 3% TO 50% BY WEIGHT OF SAID MIXTURE OF SODIUN METASILICATE HAVING A RATIO NA20:SI02OF 1:1.

Description

WASHING AND CLEANSING COMPOSITIONS Gunter Jakobi, Hilden Rhineland, and Peter Bertn,

Leichlingen, Germany, assignors to I-Ienkel & Cie.

GmbH, Dusseldorf-Holthausen, Germany No Drawing. Filed Dec. 8, 1970, Ser. No. 96,267

Claims priority, application Germany, Dec. 20, 1969,

P 19 64 024.5 Int. Cl. Clld 7/18, 7/56 US. Cl. 252-99 6 Claims ABSTRACT OF THE DISCLOSURE THE PRIOR ART As is known, washing and cleansing agents often contain larger amounts of condensed alkali metal phosphates, particularly pentasodium triphosphate, also known as sodium tripolyphosphate. The phosphates are utilized in the washing agent compositions to complex and bind the hardness constituents of tap water and to increase the cleansing activity of the surface-active detergents. For various reasons, however, an increase of the phosphate content of the agents above a certain percentage should not be attempted or a decrease in respect to the share customary up to now should not be attempted. Therefore, the objective existed, partly to replace the polyphosphates, contained in the washing and cleansing agents, by other substances, free of phosphates, and to improve at the same time the cleansing power and the biological degradability of the mixtures.

OBJECTS OF THE INVENTION An object of the invention is the obtaining of a washing and cleansing composition containing builder salts which has a lower phosphate content and an improved cleansing activity and capability to complex and bind the hardness constituents of tap water.

Another object of the invention is the obtaining of builder salt-containing washing and cleansing compositions comprising (a) one part by weight of a capillaryactive compound selected from the group consisting of anionic surface-active compounds, non-ionic surface-active compounds and amphoteric surface-active compounds and (b) 0.5 to 20 parts by weight of a mixture of builder salts consisting of (1) from 20% to 75% by weight of said mixture of pentasodium triphosphate (2) from 10% to 60% by weight of said mixture of sodium citrate, and (3) from 3% to 50% by weight of said mixture of sodium metasilicate having a ratio Na O:SiO of 1:1.

These and other objects of the invention will become more apparent as the description thereof proceeds.

3,708,427 Patented Jan. 2, 1973 It has now been found that the drawbacks of the prior art have been overcome and the above objects achieved by builder salt-containing washing and cleansing compositions comprising (a) one part by weight of a capillaryactive compound selected from the group consisting of anionic surface-active compounds, non-ionic surface-active compounds, and amphoteric surface-active compounds and (b) from 0.5 to 20 parts by weight of a mixture of builder salts consisting of (1) from 20% to preferably from 30% to 65%, by weight of said mixture of pentasodium tdphosphate, (2) from 10% to 60%, preferably from 15% to 50%, by weight of said mixture of sodium citrate and (3) from 3% to 50%, preferably from 5% to 40%, by weight of said mixture of sodium meta silicate (Na O:SiO =l:1).

Of particular interest are washing agents with a low foaming power, suitable for use in drum-washing machines. So far as the capillary-active surface-active substances utilized in the washing agents have a tendency for strong foaming, the agents should contain 0.01 to 1 part by weight of at least one foam inhibitor. Suitable foam inhibitors are saturated fatty acids with 18 to 24 carbon atoms or their alkali metal salts, which particularly contain higher amounts of arachinic acid, behenic acid and lignocerinic acid and can be obtained, for instance, from hardened peanut, rape and fish oil. Further suitable foam inhibitor are the tria'zine derivatives, such as N,N', N"-trialkylmelamine or 2,4 diaminoalkyl-6-chloro-1,3,5- triazine, in which the alkyls have 6 to 24 carbon atoms, also propoxylated and/or butoxylated melamines with 6 to polyglycolether groups, for example, melamine re= acted with 10 to 100 mols of propylene oxide or one reacted with 6 to 30 mols of butylene oxide, or one reacted first with 3 to 30 mols of propylene oxide and subsequent ly with 3 to 30 mols of butylene oxide. Also mixtures of the above-named foam inhibitors may be used advantageously. Preferably, the amount of the foam inhibitors added is calculated to be from 1% to 30% by weight based on the amount of the foaming surface-active substances in the washing agent composition.

Optionally, paraffin hydrocarbons, halogenated paraffins, higher molecular weight fatty acid esters or triglycerides or dicarboxylic acid esters of higher molecular weight fatty alcohols may also be used as foam reducing agents or in a mixture with the above-named foam inhibitors. The foam reducing effect of these substances is, however, less than that of the above named foam inhibitors, particularly if the washing agents are free of soap. Appropriately they are, therefore, only used in agents containing soap.

The washing and cleansing agents can contain conventional anionic basic detergent substances of the sulfonate or sulfate type. Primarily alkylbenzene sulfonates, for example, dodecylbenzene sulfonate are suitable, also olefin sulfonates, such as, for example, are obtained by sulfonation of primary and secondary aliphatic monoolefins with gaseous sulfur trioxide and subsequent alkaline or acidic hydrolysis, as well as alkylsulfonates obtainable from nalkanes by sulfochlorination or sulfoxidation and subsequent hydrolysis or neutralization, or by addition of bisulfite to olefins. Also suitable are a-sulfofatty acid esters, primary and secondary alkylsulfates and the sulfates of ethoxylated or propoxylated higher alcohols. Other com-= pounds of this class which can be optionally present in the washing composition are the higher molecular weight sulfated partial ethers and partial esters of polyhydric alcohols, such as the alkali metal salts of the monoalkylethers or mono fatty acid esters of the glycerine monosulfuric acid esters, or l,Z-dihydroxypropanesulfonic acid. Also sulfates of ethoxylated or propoxylated fatty amides and alkylphenols as well as fatty acid taurides and fatty acid isothionates are suitable.

Other appropriate anionic basic detergent ingredients are alkali metal soaps of natural or synthetic fatty acids, such as sodium soaps of coconut, palm kernel, or tallow fatty acids. As amphoteric detergent components, alkyl betaines and particularly alkyl sulfobetaines are suitable, for example, 3 (N,N-dimethyl-N-alkylammonium)-propane l-sulfonate and 3-(N,N-dimethyl-N-alkylammonium)-2-hydroxypropane-l-sulfonate.

The anionic basic detergent ingredients can be present in the form of their alkali metal salts such as the sodium and potassium, and ammonium salt, as well as salts of organic bases, such as mono-, diand triethanolamine. Inasmuch as the named anionic and amphoteric compounds have an aliphatic hydrocarbon radical, the latter should preferably be straight-chained and should have from 8 to 22 carbon atoms. In the compounds with araliphatic hydrocarbon radicals, such as alkylphenyl radicals, the preferred straight alkyl chains contain an average of from 6 to 16 carbon atoms.

Asnon-ionic surface-active basic detergent ingredients, primarily suitable are the polyglycolether derivatives of alcohols, fatty acids and alkylphenols which contain 3 to 30 glycol ether groups and 8 to 20 carbon atoms in the hydrocarbon radical. Particularly suitable are polyoxyethyleneglycolether derivatives in which the number of oxyethylene groups is to and whose hydrocarbon radicals are derived from straight-chain primary alcohols with 12 to 18 carbon atoms, or from alkylphenols with a straight-chain alkyl chain of 6 to 14 carbon atoms. By the addition of 3 to 15 mols of propylyene oxide to the last named polyethyleneglycolethers, or by converting them into acetals, detergents are obtained which are distinguished by a special low foaming power.

Other suitable non-ionic basic detergent ingredients are the water-soluble polyethylene oxide adducts, containing to 250 ethyleneglycolether groups and 10 to 100 propyleneglycolether groups adducted to polypropylene glycol, ethylenediamine polypropyleneglycol and alkylenepolypropyeneglycol with 1 to 10 carbon atoms in the alkylene chain. The compounds utilized usually contain 1 to 5 oxyethylene units per oxypropylene unit. Also suitable as nonionic compounds are those of the amine oxide and sulfoxide types, which, if necessary can be ethoxylated.

By a suitable combination of different surface-active basic detergent substances with one another, increases in activity may be obtained in many cases, for example, an improved washing power or a reduced foaming capacity. Such improvements are possible, for example, by a combination of anionic compounds with non-ionic and/or amphoteric compounds, by a combination of different nonionic compounds, or by mixtures of basic detergent substances of the same type which differ in regard to the number of carbon atoms or the number and position of double bonds or branching of chains.

Depending on their use, the cleaning compositions of the invention may also contain oxygen-yielding or active chlorine-containing bleaching agents such as hydrogen peroxide, alkali metal perborates, particularly sodium perborate, alkali metal percarbonates, alkali metal perphosphates, urea perhydrate, alkali metal persulfate, alkali metal hypochlorites, chlorinated trisodium phosphate and chlorinated cyanuric acid and its alkali metal salts. The percompounds can be present in admixture with bleaching agent activators.

In addition to the surface-active compounds, builder salts, foam inhibitors and bleaching agents, the washing and cleaning agents of the invention may contain other customary washing agent ingredients. These include sodium sulfate, silicates, such as magnesium silicate, utilized as a perborate stabilizer, and Water glass, utilized as a corrosion inhibitor, with a Na O:SiO ratio of from 1:3 to 1:3.5. In addition, the agents may contain tetrasodium pyrophosphate which might be formed during the compounding, particularly with the hot spray-drying of the liquid washing agent concentrates, by a partial hydrolysis of the sodium triphosphate.

Further suitable mixture ingredients are antigreying compounds, such as sodium cellulose glycolate, as well as the water-soluble alkali metal salts of synthetic polymers which contain free carboxylic groups. To them belong the polyesters of the polyamides of triand tetracarboxylic acids and dihydric alcohols or diamines, also polymeric acrylic, methacrylic, maleic, fumaric, itaconic, citraconic and aconitic acids, as well as the mixed polymerizates of the above-named unsaturated carboxylic acids or their mixed polymerizates with olefins.

For a further improvement of the dirt loosening properties of the washing and cleaning compositions of the invention, they may also contain enzymes from the class of the proteases, lipases and amylases, which may be ob tained from animal and vegetable origin, for example, from digestive ferments or yeasts, such as pepsin, pancreatin, trypsin, papain, catalase and diastase. Preferably, enzymic active substances are obtained from strains of bacteria or fungi, such as Bacillus sublilis and Streptomyces griseus, which substances are relatively stable towards alkalis, percompounds and anionic detergent substances and are not appreciably inactivated even at temperatures between 45 C. and 70.

Further suitable components of the mixtures are optical brighteners of the bis-(triazinyl)-4,4'-diaminostilbenedisulfonic acid type according to the following formula in which X and Y represent the following: -NH -NHCH NHCH CH OH,

N(CH CH OH) 'morpholino, dimethylmorpholino, NHC H -NH-C H S0 H, OCH Cl, where X and Y are the same or different. Compounds in which X represents an anilino and Y a diethanolamino or morpholino group are specially suitable.

In addition, optical brighteners of the diarylpyrazoline type according to the following formula may be present;

In the formula, Ar and Ar represent aryl residues, such as phenyl, diphenyl or naphthyl, which may carry further substituents such as hydroxy, alkoxy, hydroxyalkyl, amino, alk'ylamino, acylamino, carboxyl, sulfonic acid and sulfonamide groups or halogen atoms. 1,3-diarylpyrazolines are preferably used in which Ar is p-sulfonamidophenyl and Ar is p-chlorophenyl. In addition, whiteners suitable for the brightening of other types of fibers may be present, for example, such as of the type of naphthotriaziolestilbene sulfonates, ethylene-bis-benzimidazoles, ethylene-bis-benz oxazoles, thiophene'bis-benzoxazoles, dialkylaminocow marins, and cyanoanthracenes. These brighteners or their mixtures can be present in the washing composition in amounts from 0.01% to 1.5% by weight, preferably from 0.1% to 1% by weight.

For stabilizing of the optical brighteners, the agents can also contain complexing agents. To these belong the alkali metal salts of ethylenediaminetetraacetic acid, which are preferably used. In addition, the alkali metal salts of diethylenetriaminepentaacetic acid as well as the higher homologs of the named aminopolycarboxylic acids can be present. Suitable homologs can, for instance, be prepared by polymerization of an ester, amide or nitrile of N-acetic acid-aziridine and subsequent saponification to carboxylic acid salts, or by reacting a polyamine with a molecular weight of from 500 to 100,000 with alkali metal chloroacetates or bromoacetates in an alkaline medium. Other suitable complexing agents are the alkali metal salts of aminopolyphosphonic acids, particularly aminotri(methylene-phosphonic acid), ethylenediaminetetra-(methylenephosphonic acid), l-hydroxyethane-l,l-diphosphonic acid, methylene-diphosphonic acid, ethylene-diphosphonic acid as well as the higher homologs of the named polyphosphonic acids. Also mixtures of the above-named complexing agents are usable.

Furthermore, bactericidal substances, particularly halo genated diphenylethers, halogenated diphenylurea derivatives and halogenated salicyclic acid anilides can be present. For the improvement of the hand, non-quaternary, higher molecular weight, ammonium compounds may be added, such as the tallow fatty acid amide of the aminoethylethanolamines.

The washing and cleaning agents may be present in liquid, pasty or, preferably, solid form, for example, pul verulent, granulated or lump form, and particularly spray dried. For better solubility, liquid preparations may contain solvents miscible with water, especially ethanol and isopropanol, as well as solution aids such as the alkali metal salts of benzene-, toluene-, xyleneor ethylbenzenesulfonic acid.

In the preparation of the washing agents of the invention, the sodium citrate, as such, is mixed directly with the other washing agent ingredients or with the aqueous pasty washing agent mixture, or the free citric acid is added to these mixtures, provided that they contain an excess of alkaline-reacting compounds required for neutralization, for instance, sodium hydroxide or sodium carbonate. In this case the salt is formed during the preparation or the use of the agent.

If the agents contain foam inhibitors from the class of substituted triazines or melamines, the latter are advantageously admixed to the washing agent ingredients present as powder or granulate, or to a part of them, granulated upon them or in melted form or, after dissolving in a volatile solvent, sprayed upon them.

The quantitative composition of the agents of the invention corresponds preferably to the following recipe:

1 part by weight of a surface-active compound which consists by weight of up to 100%, preferably 5% to 70%, of compounds of the sulfonate and/or sulfate type, up to 100%, preferably 5% to 40%, of non-ionic compounds of the polyglycolether type, and up to 100%, preferably to 50%, of soap,

0.5 to 20, preferably 1 to 10, parts by weight of the builder salt mixture consisting of pentasodium triphosphate, sodium citrate, and sodium metasilicate,

0.01 to 1 part, preferably an amount which is 1% to 30%, by weight of the surface-active detergents, of foam inhibitors, preferably from the class of saturated fatty acids with 18 to 24 carbon atoms and their alkali metal soaps, as well as of the substituted triazines, obtainable by the reaction of 1 mol of cyanuric chloride with 2 to 3 mols of a primary monoamine, or by propoxylation and/ or butoxylation of melamine,

ISO

6 O to 5, preferably 0.5 to 3, parts by weight of sodium perborate with or without crystalline water,

0 to 3, preferably 0.1 to 2, parts by weight of other washing agent ingredients which have preferably the following composition:

0.1% to of neutral salts, particularly sodium sulfate,

0 to 40% of tetrasodium pyrophosphate,

0 to 10% of sodium ethylenediaminetetraacetate,

0 to 40% of magnesium silicate,

0.1% to 20% of greying inhibitors, particularly sodium carboxymethylcellulose 0 to 20% of enzymes, and

0 to 10% of at least one optical brightener.

The agents according to the invention possess a high cleansing power and an improved dirt-carrying power. The effects are greater than if each of the three components of the salt mixture, named under (bl, were present alone. On the basis of the reduced phosphate content, the washing agents are distinguished by a good biological degradability and they do not promote the undesirable growth of algae and plants in rivers and lakes burdened by sewage. In comparison with mixtures which contain as builder salts, exclusively or predominately, sodium triphosphate, they cause in repeated application, a reduction in fabric incrustation and in damage of the textile fibers.

The following examples are illustrative of the practice of the invention without, however. being deemed limitative in any respect.

EXAMPLES 1--16 The washing agents used had the compositions shown in Table I (data in percent by Weight).

TAB LE I Ingredients A B C D The olefin sulfonate was derived from straight-chain C C olefins (average chain length C The alkane sulfonate was a product prepared from n-paraiiins of a chain length of c,,-c,, by sulfoxidation and contained secondary sulfonate groups. The abbreviation EtO stands for ethylene oxide groups. No optical brightener was added to the agents A, B and C in order not to partially mask the results of the determination of the degree of whiteness by fluorescence phenomena.

The composition of the mixture designated by builder salts can be found in Table II. The compounds were used as sodium salts,

For the determination of the washing power, textile samples of cotton that had been homogenously soiled with a mixture of dust and skin fat were washed in a laboratory washing machine (Launderometer'). The washing agents concentration was 4 gm./liter. The weight ratio of washing liquor to textile was 12:1. The temperature was C., and the washing time 15 minutes. The tap water used had a hardness of 16 dH (corresponding to mgm. CaO/l.). The whiteness degree of the threetimes rinsed and then dried fabric was determined by photometer. The results are summarized in Table II. Each test series was preceded by comparative tests in which the builder consisted of only one component. The results demonstrate the superiority of the mixture of builder salts of the invention.

TABLE I1 Composition of the builder salts Metasilicate, percent Triphosphate, percent Citrate,

percent Degree of whiteness The preceding specific embodiments are illustrative of the practice of the invention. It is to be understood, however, that other expedients known to those skilled in the art, or disclosed herein, may be employed without departing from the spirit of the invention or the scope of the appended claims.

We claim:

1. Builder salt-containing washing and cleansing compositions consisting essentially of (a) one part by weight of a capillary-active compound selected from the group consisting of anionic surface-active compound, non-ionic surface-active compounds and amphoteric surface-active compounds and (b) 0.5 to 20 parts by weight of a mixture of builder salts consisting of (1) from 40% to 65% by weight of said mixture of sodium tripolyphosphate, (2) from 17% to 50% by weight of said mixture of sodium citrate, and (3) from 5% to 40% by weight of said mixture of sodium metasilicate having a ratio Na O:SiO of 1:1.

2. The builder salt-containing washing and cleansing compositions of claim 1 having a further content of from 0.01 to 1 part by weight of at least one foam inhibitor selected from the group consisting of saturated fatty acids having 18 to 24 carbon atoms and their alkali metal soaps, N,NN"-trialkylmelamines and 2,6-diaminoalkyl-o-chlorotriazines wherein the alkyl radicals have 6 to 24 carbon atoms, and alkoxylated melamines having from 6 to 100 polyglycolether groups selected from the group consisting of propyloxylated melamines, butyloxylated melamines and propyloxylated, butyloxylated melamines.

3. The builder salt-containing washing and cleansing compositions of claim 1 wherein capillary-active compounds are selected from the group consisting of sulfate and sulfonate anionic surface-active compounds, polyglycolether non-ionic surface-active compounds and soaps.

4. The builder salt-containing washing and cleansing compositions of claim 1 having a further content of from 0.1 to 5 parts by weight of sodium perborate.

5. The builder salt-containing washing and cleansing compositions of claim 3 wherein said capillary-active compounds consist of a mixture of from 25% to by weight of sulfonate and sulfate anionic surface-active compounds, from 5% to 40% by Weight of polyglycolether non-ionic surface-active compounds and from 10% to 50% by weight of soap.

6. Builder salt-containing washing and cleansing compositions consisting essentially of (a) one part by weight of a mixture of capillary-active compounds consisting of from 25% to 70% by weight of sulfonate and sulfate anionic surface-active compounds, from 5% to 40% by weight of polyglycolether non-ionic-active compounds and from 10% to 50% by weight of soap, (b) from 1 to 10 parts by weight of a mixture of builder salts consisting of from 40% to 65% of sodium tripolyphospbate, from 17% to 50% by weight of sodium citrate and from 5% to 40% by weight of sodium metasilicate having a ratio of Na O:SiO of 1 to 1, (c) from 1% to 30%, based on the weight of said mixture of capillary-active compounds of a foam inhibitor selected from the group consisting of saturated fatty acids having 18 to 24 carbon atoms and their alkali metal soaps, N,N,N"-trialkylmelamines and 2, 6-diaminoalkyl-6-chloro-triazines wherein the alkyl radicals have 6 to 24 carbon atoms, and alkoxylated melamines having from 6 to polyglycolether groups selected from the group consisting of propyloxylated melamines, butyloxylated melamines and propyloxylated, butyloxylated melamines, (d) from 0.5 to 3 parts by weight of sodium perborate and (e) from 0.1 to 2 parts by weight of other washing agent ingredients consisting of 0.1% to 80% by weight of neutral salts, 0 to 40% by weight of tetrasodium pyrophosphate, 0 to 10% by weight of sodium ethylene-diaminetetraacetate, 0 to 40% by weight of magnesium silicate, 0.1% to 20% by weight of greying inhibitors, 0 to 20% by weight of enzymes and 0 to 10% by weight of optical brighteners.

References Cited UNITED STATES PATENTS 31,579,484 5/1971 Collier 252-99 X 38,578,598 5/1971 Burke 202-99 X 2,311,008 2/1943 Tucker 202-132 X 3 ,235,505 2/1966 Tuvell 202-135 2,264,103 11/1941 Tucker 202-132 X MAYER WEINBLATT, Primary Examiner US. Cl. X.R, 25'2 132, 135