US 3309319 A
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United States Patent 3,309,319 DETERGENT-WHITENER COMPGSITKONS Todd L. Coward, Cincinnati, Ohio, and Norman R. Smith, Konigshach, Germany, assignors to The Procter & Gamhie Company, Cincinnati, Ohio, a corporation of bio o Drawing. Fiied Sept. 23, 1965, Ser. No. 489,726 It) Claims. (Cl. 252-137) This invention relates to a detergent composition comprising a mixture of detergent materials which provide superior whitening eifectiveness on nylon for a certain stilbene whitener compound.
Those compounds which have optical whitening properties when deposited on fabrics are complex and expensive chemicals. Full utilization of their advantageous whitening properties requires that they be used in detergent systems from which they are effectively and efiiciently deposited on the cloth being laundered. blylon is an especially difiicult textile material for efiicient whitener deposition. It is difiicult to predict, among the many different optical whitening materials, those wh ch are susceptible to efi'lcient deposition and those for wlnch deposition may be improved by any particular detergent formulations.
Accordingly, it is an object of this invention to provide a detergent composition especially formulated with a s ecific stilbene optical whitener which composition has superior and unexpected characteristics regarding the whitening of nylon fabric.
This and other objects are achieved with the detergent comprising an organic anionic synthetic detergent compound and at least one of a certain class of zwitterionic and sernipolar detergent compounds hereinafter more fully described, in a weight ratio range of 4:1 to 1:4, together with a minor amount of a certain stilbene whitener.
The stilbene whitener used in the compositions of this invention is 4,4 bis[(4,6-di-anilino-s-triazin-Z-yl)amino]-2,2'-stilbene disulfonate, preferably the disodium salt.
It has the following chemical structure:
H N III i N where M (monovalent salt) is alkali metal, such as sodium or potassium, or ammonium or triethanolammonium. This optical whitener is well known per se as a whitener and is available under the trade names Calcofluor White PG concentrate, Blancophor CN-76, Hiltamine Artic White EP, Tinopal TAS and Cellu-Brite. Hereinafter this will be referred to as stilbene whitener.
This stilbene whitener, when deposited on fabrics such as nylon in an ordinary detergent system such as one based on sodium dodecyl benzene sulfonate, is a moderately efficient whitener. It is also moderately efiicient when deposited on such fabrics from detergent systems based on some zwitterionic or semipolar detergent compounds. Quite surprisingly, however, it was found that stilbene whitener provided superior whitening efficacy when deposited on nylon fabric during laundering with a detergent composition based on a 4:1 to 1:4 by weight mixture of an anionic detergent compound and a zwitter- "ice ionic or semi-polar detergent compound of the sultaine, betaine, amine oxide, phosphine oxide or sulfoxide classes as hereinafter more fullydescribed. It was further surprisingly found that this improved nylon whitening effectiveness from this particular mixture of detergent compounds was apparently unique 'with the stilbene whitener and this surprising whitening property was not observed in these detergent mixtures with other conventional optical whitening compounds. No explanation can be offered for this particular result since the complexities of optical whitening compounds per se and their behavior in various detergent systems and on various fabrics is not subject to any known set of principles. Stilbene whitener provides an optical whitening functioning for nylon fabric in the detergent systems of this invention superior to that which results when this same material is deposited from a detergent system containing either an anionic detergent compound alone or one of the specified zwitterionic or semi-polar detergent compounds alone or from some other detergent system such as a nonionic ethoxylate detergent system or a cationic detergent system.
The stilbene whitener is used in an amount ranging from about 0.05% to about 2% of the total Weight of the mixture of anionic detergent and zwitterionic or semipolar detergent.
This ternary mixture, i.e., stilbene whitener+anionic synthetic detergent-l-zwitterionic or semi-polar detergent, is preferably used in aqueous laundering solution at a weight concentration ranging from about 0.05% to about 2%. The washing solution temperature preferably ranges from about F. to about F. Under these conditions the whitening effect on nylon fabric is surprisingly superior.
The organic anionic synthetic detergent of this inventron can be any of the variety of such detergent compounds which are widely known and used. The selectlon of any particular anionic detergent compound does not appear to be critical, but for their preferred detergency characteristics the following anionic detergent compounds are especially desirable. The anionic class of organic synthetic detergents can be broadly described as the water-soluble salts, particularly the alkali metal salts, of organic sulfuric reaction products having in their molecular structure an alkyl radical containing from about 8 to about 22 carbon atoms and a radical selected from the group consisting of sulfonic acid and sulfuric acid ester radicals. Important examples of these synthetic detergents are the sodium or potassium alkyl sulfates, especially those obtained by sulfating tallow or coconut oil fatty alcohols; sodium or potassium alkyl benzene sulfonates, in which the alkyl group in a straight or branched chain contains from about 9 to about 16 carbon atoms; potassium or sodium salts of sulfonated a olefins containing from 10 to 18 carbon atoms, especially those described in copending application of Pflaumer et al. Ser. No. 423,364 filed Jan. 4, 1965; sodium alkyl glyceryl ether sulfonates, especially those ethers of the higher alcohols derived from tallow and coconut oil; sodium coconut oil fatty acid monoglyceride sulfates and sulfonates; sodium or potassium salts of sulfuric acid esters of the reaction product of one mole of a high er fatty alcohol (e.g., tallow or coconut oil alcohols) and one to five (e.g. three) moles of ethylene oxide; sodium or potassium salts of sulfated condensation products of one mole of alkyl phenol with l to 5 moles ethylene oxide, e.g. those products with an average of about four units of ethylene oxide per molecule and in which the alkyl radicals contain about 9 carbon atoms; the reac-' tion product of fatty acids esterified with isethionic acid and neutralized with sodium hydroxide where, for example, the fatty acids are derived from coconut oil; sodium or potassium salts of fatty acid amide of a methyl taurine in which the fatty acids, for example, are derived from coconut oil; and others known in the art, a number being specifically set forth in United States Letters Patent Numbers 2,486,921, 2,486,922 and 2,396,278.
The preferred anionic synthetic detergents in this invention are sodium dodecyl benzene sulfonate, sodium tallow alkyl sulfate and the sodium salt of sulfonated a tetradecene.
The zwitterionic quarternary ammonium compounds which are used in the compositions of this invention are compounds of the general formula wherein R is an alkyl radical having from about 10 to about 18 carbon atoms, R and R are each alkyl radicals having from about 1 to about 3 carbon atoms, R is an alkylene or hydroxyalkylene radical having from 1 to 4 carbon atoms, and X is SO= SO= or COO=. R is preferably a propene or 2-hydroxypropene radical.
Compounds which conform to the above general formula are characterized by the presence of both positive and negative charges which are internally neutralized (i.e., zwitterionic). When the anion X is S= or SO= these compounds are referred to as sultaines. The term betaine is employed when the anion X is COO=. The following structural formulas are illustrative of the two types and their inner salt character.
R2 R2 R NR;S o R NR4C 0 R3 0 R: O
Sultaines Betaines Examples of compounds falling within this definition are 3-(N,N-dimethyl-N-hexadecylammonio) propane-1- sulfonate and 3-(N,N-dlmethyl-N-dodecylammonio) 2- hydroxy propane -l-sulfonate and which are especially preferred for their excellent cool water detergency characteristics. The most marked improved whitening results in the composition and process of this invention are obtained with the anionic-zwitterionic detergent system.
The semi-polar compounds of the compositions of this invention comprise the amine oxide, phosphine oxide and sulfoxide classes defined as follows.
Tertiary amine oxides are those corresponding to the following general formula R R R N+O, wherein R is an alkyl or hydroxyalkyl radical of from about to about 18 carbon atoms, and R and R are each methyl, ethyl or hydroxyethyl radicals. R is preferably dodecyl. The arrow in the formula is a conventional representation of a semi-polar bond. Examples of amine oxides suitable for use in this invention include dimethyldodecyl amine oxide, dimethyl-2-hydroxydodecyl amine oxide, dimethyldecyla-mine oxide, dimet-hyltetradecylamine oxide, dimethylhexadecylamine oxide and dodecyl diethanolamine oxide.
Tertiary phosphine oxides are those corresponding to the following general formula R R R P+O wherein R is an alkyl, aikenyl or monohydroxyalkyl radical ranging from 10 to 18 carbon atoms in chain length and R and R are each alkyl or monohydroxyalkyl groups containing from 1 to 3 carbon atoms. R is preferably dodecyl. The arrow in the formula is a conventional representation of a semi-polar bond. Examples of suitable phosphine oxides are:
dodecyldimethylphosphine oxide, tetradecyldimethylphosphine oxide,
tetradecylmethylethylphosphine oxide, cetyldimethylphosphine oxide, stearyldimethylphosphine oxide, cetylethylpropylphosphine oxide, dodecyldiethylphosphine oxide, tetradecyldiethylphosphine oxide, dodecyldipropylphosphine oxide, dodecyldi(hydroxymethyl) phosphine oxide, dodecyidi(2-hydroxyethyl) phosphine oxide, tetra-decylmethyl-2-hydroxypropyl phosphine oxide, oleyldimethylphosphine oxide, and 2-hydroxyldodecyldimethylphosphine oxide.
Dialkyl sulfoxides, R R S+O, are those containing one short chain alkyl (R e.g. methyl or ethyl, and one long hydrophobic chain (R which can contain ether linkages and hydroxy groups and which contain from about 10 to about 18 carbon atoms, e.g. alkyl, hydroxyalkyl or alkoxyhydroxyalkyl. R is preferably dodecyl, hydroxydodecyl or dodecoxyhydroxypropyl. Examples include:
octadecyl methyl sulfoxide dodecyl methyl sulfoxide tetradecyl methyl sulfoxide 3-methoxytridecyl methyl sulfoxide 3-hydroxytridecyl methyl sulfoxide 3-hydroxy-4-do-decoxybutyl methyl sulfoxide In the above described zwitterionic and semi-Polar compounds the short chain groups, i.e., R R R R R R and R are preferably methyl for greater water solubility.
The ternary mixture compositions of this invention, i.e., anionic detergent, zwitterionic or semi-polar detergent and stilbene whitener, are advantageously employed with water-soluble detergency builder salts to form built laundry detergent compositions, especially for washing and whiten= ing nylon. Preferably the ratio of ternary mixture to builder salt ranges from about 1:05 to about 1:10. Ordinarily detergent compositions employ from about 10% to about 25% of the ternary mixture, from about 20 to about 60% builder, the balance being essentially a diluent such as water or Na SO The pH of such built compositions usually ranges from about 8 to about 12.
Examples of water-soluble inorganic alkaline detergency builder salts are alkali metal carbonates, phosphates, polyphosphates, and silicates. Specific examples of such salts are sodium and potassium tripolyphosp'hates, carbonates, pyrophosphates, phosphates,-and hexametaphosphates.
Examples of organic alkaline sequestrant builder salts are (1) alkali metal amino polycarboxylates [e.g., sodium and potassium ethylene diaminetetraacetates, N-(2-hydroxyethyl)-ethylene diamine triacetates, nitrilo triacetates, and N-(Z-hydroxyethyl)-nitrilo diacetates]; (2) alkali metal salts of phytic acid (e.g., sodium and potassium phytates-see US. Patent 2,739,942); (3) Watersoluble salts of ethane-l-hydroxy-l,l-diphosphonate (e.g., the trisodium and tripotassium salts) as described in US. Patent 3,159,581; (4) water-soluble salts of methylene diphosphonic acid (e.g., trisodium and tripotassium methylene diphosphonate and the other salts described in the copending application of Francis L. Diehl, Serial No. 266,025, filed March 18, 1963); (5) water-soluble salts of substituted methylene diphosphonic acids (e.g., trisodium and tripotassium ethylidene, isopropylidene, benzylmethylidene, and halomethylidene diphosphonates and the other substituted methylene diphosphonates disclosed in the copending application of Clarence H. Roy, Serial No. 266,055, filed March 18, 1963); (6) water-soluble salts of polycarboxylate polymers and copolymers as described in the copending application of Francis L. Diehl, Serial No. 269,359, filed April 1, 1963 (e.g., polymers of itaconic acid; aconitic acid; maleic acid; mesaconic acid; fumaric acid, methylene malonic acid; and cinronic acid and copolymers with themselves and other compatible monomers such as ethylene).
Mixtures of organic and/or inorganic builders can be used and are generally desirable. Especially preferred are the mixtures of builders disclosed in the copending application of Burton H. Gedge, Ser. No. 398,705, filed Sept. 23, 1964, e.g. ternary mixtures of sodium tripolyphosphate, sodium nitrilotriacetate, and trisodium ethane- 1-hydroxy-1,l, diphosphonate.
ther minor ingredients can also be added to the compositions of this invention including: soil suspending agents such as carboxymethylcellulose; other optical brighteners; dye; antibacterial agents; oxygen bleaches; tarnish inhibitors such as benzotriazole. The total amount of these minor ingredients is preferably less than 5 to by weight of the composition. The composition can also contain 2l0% alkali metal silicate as corrosion inhibitors.
The following examples are given additionally to illustrate the nature of the invention and it will be understood that the invention is not limited thereto. All parts and percentages are by weight unless otherwise specified.
EXAMPLE I A series of heavy-duty laundry detergent compositions were formulated according to the following guide formula:
Percent Organic synthetic detergent 17.5 Sodium tripolyphosphate 50 Sodium silicate having SiO :Na O ratio of 1.6:1 6 Moisture 10 Sodium carboxymethylcellulose 0.3
Stilbene whitener (as herein before defined) as the sodium salt (disodium salt) 0.2 Sodium sulfate Balance A series of compositions, in sets of four each (described in greater detail below), were tested in a fourbucket miniature washer with paddle-arm agitators, designed as a simplified, scaled-down Washing machine (similar to a tergotometer but larger in capacity). Each bucket was filled with one gallon of water at 130 F. of 7 grains per gallon hardness. 0.2% by weight of each composition was added to each bucket and the resulting solution was agitated for one minute. Fabric loads of 12 inch by 12 inch unsoiled cloth swatches (3 terrycloth, 2 muslin and 2 nylon per load) were added to each washing solution. The fabrics were pretreated to remove any fiuorescers used in the cloth manufacture. The swatches were washed for ten minutes in the respective washer buckets. After washing, water was extracted from the swatches. The buckets were then emptied of wash water and filled with one gallon each of rinse water at 100 F. of 7 grains per gallon hardness. The swatches were rinsed for two minutes. After rinsing, water was again extracted from the swatches which were then dried in an automatic steam drier.
All the test compositions were rated as poorer or better in nylon fabric whiteness than each other on a relative basis. Comparisons were made in artificial north daylight by skilled graders who subjectively rated the nylon fabric swatches on the basis of (a) no difference, (b) slightly better or poorer, (c) markedly better or poorer or (d) very markedly better or poorer, with arbitrary positive numbers indicating better results and similar arbitrary negative numbers indicating poorer results, the numbers conforming to the subjective scale. The graders did not know which compositions were used to wash the fabrics being graded. The number of washings, evaluations and grades in the test, the design of the tests and the analysis thereof were such to make the results and the conclusions therefrom statistically significant.
In the series of detergents prepared and tested, the 17.5% active portion in the above guide formula was varied as to synthetic detergent type and proportions as follows; the corresponding results in nylon fabric whiteness as determined by panel score units are noted:
Nylon Anionic Zwitterionic or Semi Polar Weight Fabric Ratio whiteness Grade 17.5% TAS. 0% HAPS 1. 15 13.12% 'IAS 4.38% TAS 1. +1.00 0% TAS 65 17.5% ABS 25 13.12% ABS. 60 4.38% ABS 80 0% ABS 17.5% HAPS 1. 15
17.5% ABS 0% DDAO 25 13.12% ABS 3:1 10 4.33% ABS 1:3 80 0% ABS 17.5% DDAO 45 17.5% ABS- 0% DDPO 0.00 13.12% ABS. 0. 00 4.38% ABS 60 0% ABS 60 17.5% 'IAS 0 .15 13.12% TAS 25 4.38% 'IAS 13.12% HDMSO r 40 0% TAS 17.5% HDMSO 50 17.5% TAS 0% tallow betaine 05 4.38% tallow beta1ne 3:1 10 13.12% tallow betaine 1:3 75 17.5 tallow betaiue TAS=sodium tallow alkyl sulfate.
HAPS =3-(N,N-dimethyl-N-coconut alkyl ammonio). 2-hydroxypropane-l-sulionate (The coconut alkyl was approximately 65% dodecyl 25% tetradecyl 10% hexadecyl).
ABS =sodium dodecylbene sulfonate.
D D A0 dhnethyldodecylamine oxide.
D DP 0 dunethyldodecylphosphine oxide.
HD MSO =methyl-3-dodecoxy-Z-hydroxypropyl sulfoxide.
Tallow betaine=3(N, N,-dimethyl-N tallo\v alkyl ammonio) acetate,
These results show the surprisingly superior whiteness results achieve-d by the process and compositions of this invention. These data show superior results with a ratio of 3:1 to 1:3 anionic to switterionic or sulfoxide and with a ratio of 1:3 anionic to amine or phosphine oxide.
This detergent can be used to provide a product washing solution concentration of 0.5% in water at F. to launder and whiten nylon fabric.
The ternary mixtures of this invention can be used in the following detergent formulations of the type of copending application Serial No. 423,008 of January 4, 1965, which are especially useful in cleaning and whitening nylon, particularly under the washing conditions outlined in Example I:
Unbuilt liquid detergent Percent Sodium salt of sulfonated a tetradecene 5 3-(N,N-dimethyl-N-tetradecyl ammonio) propane-1- sulfonate Stilbene whitener (as defined above-diammonium salt) 0.2 Ethanol 10 Water Balance 7 Granular detergent Percent Sodium salt of sulfonated 1:1 mixture of a dodecene and a tetradecene l 3-(N,N-dimethyl-N-dodecyl am-monio) 2 hydroxy propane-l-sulfonate 10 Stilbene whitener (as defined abovedi potassium salt) 0.3 Sodium tripolyphosphate 20 Sodium nitrilotriacetate 10 Trisodium ethane-l-hydroxy 1,1-diphosphonate l0 Moisture 10 Sodium silicate 6 Sodium sulfate Balance Other modifications can be made in the invention without departing from the spirit of it. What is claimed is:
1. A detergent composition, especially suitable for cleaning and whitening nylon consisting essentially of (1) a mixture of (a) an anionic, non-soap, organic synthetic detergent having in its molecular structure an alkyl radical containing from 8 to 22 carbon atoms and a radical selected from the group consisting of sulfonic acid and sulfuric acid ester radicals and (b) a detergent selected from the group consisting of zwitterionic and semi-polar synthetic detergents and (2) 4,4'-bis[4,6-dianilino-s-triazin-2-yl)amino]-2,2'-stilbene disulfonate; wherein: the weight ratio of (a) to (b) ranges from about 3:1 to about 1:3 in the case of zwitterionic and sulfoxide semi-polar detergents and is about 1:3 in the case of amine oxide and phosphine oxide semi-polar detergents; the amount by weight of said disulfonate ranges from about 0.05% to about 2.0% of the said mixture of (a) and (b); said zwitterionic detergent has the formula wherein R is an alkyl radical having from 10 to 18 carbon atoms, R and R are each alkyl radicals having from 1 to 3 carbon atoms, R; is selected from the group consisting of alkylene and hydroxyalkylene radicals having from 1 to 4 carbon atoms and X is selected from the group consisting of 80 S0 and COO=; said semipolar detergent is selected from the group consisting of amine oxide, phosphine oxide and sulfoxide detergents, said amine oxide having the formula wherein R is selected from the group consisting of alkyl and hydroxyalkyl radicals having from to 18 carbon atoms and R and R7 are each selected from the group consisting of methyl, ethyl and hydroxyethyl radicals, said phosphine oxide having the formula R3R9RmP O wherein R is selected from the group consisting of alkyl,
alkenyl and hydroxyalkyl radicals having from 10 to 18 carbon atoms and R and R are selected from the group consisting of alkyl and monohydroxyalkyl radicals having 1 to 3 carbon atoms, and said sulfoxide having the formula wherein R is selected from the group consisting of methyl and ethyl and R is selected from the group consisting of alkyl, hydroxyalkyl and alkoxy radicals having from 10 to 18 carbon atoms.
2. The composition of claim 2 wherein component (b) is a zwitterionic detergent and component (2) is the disodium salt.
3. The composition of claim 2 wherein component (a) is selected from the group consisting of C -C alkyl benzene sulfonates, C C alkyl sulfates and sulfonated C C a olefin salts.
4. The composition of claim 3 wherein component (b) is 3(N,N-dimethyl-N-coconut alkyl ammonio) Z-hydroxypropane-l-sulfonate.
5. The composition of claim 4 wherein component (a) is selected from the group consisting of sodium tallow alkyl sulfate, sodium dodecyl benzene sulfonate and sodium tetradecene sulfonate.
6. A built detergent consisting essentially of the composition of claim 1 and a water-soluble detergency builder salt in a weight ratio of composition to builder ranging from 1:05 to 1:10, said water soluble builder salt being selected from the group consisting of inorganic alkaline detergency builder salts and organic alkaline sequestrant builder salts.
7. The built detergent of claim 6 wherein the said composition is that of claim 2.
8. The built detergent of claim 6 wherein the said composition is that of claim 5.
9. A method of cleaning and whitening nylon com prising the steps of preparing an aqueous washing solution of about 0.05% to about 2.0% by weight of the composition of claim 1 and washing nylon fabric therein.
10. The method of claim 9 wherein said composition is that of claim 2 and the washing solution temperature ranges from about F. to about F.
References Cited by the Examiner UNITED STATES PATENTS 2,787,595 4/1957 Webb 252138 3,213,030 10/1965 Diehl 252152 3,222,287 12/ 1965 Laughlin 252152 XR 3,223,647 12/1965 Drew 252--137 FOREIGN PATENTS 1,100,583 1/1958 Germany.
LEON D. ROSDOL, Primary Examiner.
S. E. DARDEN, Assistant Examiner.