MXPA96004478A - Detergent bars of washing with inhibition of transfer of colorante and blancura improvement - Google Patents

Abstract

The laundry detergent bar of the present invention comprises a detergent surfactant, builder, an effective amount of a dye transfer inhibitor, and an effective amount of an optical brightener to improve whiteness and inhibition of dye transfer. clothes washed with the bars, preferably, the bars comprise from about 10 to 60% by weight of anionic surfactant, from about 5 to 60% builder, from about 0.10 to 2.0% of a dye transfer inhibitor, and from about 0.05 to 1.0% of an optical brightener, non-limiting examples of dye transfer inhibitors include polyvinylpyrrolidone N-oxide, polyvinylpyrrolidone, (PVP), PVP-polyvinylimidazole copolymer, and mixtures thereof; N-vinylpyrrolidone copolymers and N-vinylimidazole polymers (PVPI) are also preferred for use herein. Preferred optical brighteners are diaminostilbene, optical brighteners of the di-styrylbiphenyl type, and mixtures thereof.

Description

.flRRRS WASH DETERGENTS WITH INHIBITION OF IMPROVED COLORING AND BLANCURE TRANSFER BACKGROUND OF THE INVENTION The invention relates to improved laundry detergent bars. In particular, it relates to laundry detergent bars comprising an ammonium detergent agent, a detergent enhancer, an effective amount of a dye transfer inhibitor for improved clarity and inhibition of dye transfer, and a effective amount of an optical brightener for whiteness and improved dye transfer inhibition. Detergent compositions in the form of synthetic detergent granules and liquids are used in many laundry-washing societies, particularly in those societies where mechanical washing machines are common. End portions of those societies, and more often in societies where mechanical washing machines are not common, laundry detergent bars consisting of synthetic organic surfactants and detergent builders are used to wash clothes. Technical developments in the field of detergent bars for laundry have been interested in formulating detergent bars that are effective in cleaning clothes; that they have acceptable foaming characteristics in water and cold and in hard and not hard water, that they have wear and tear during use, hardness, duraty and sensation acceptable, that they have low dipping, and that have a pleasing odor and appearance Examples of laundry bars include those described in the following patents and publications: US Patent No. 3,178,370 (issued to Okenfuss on April 13, 1965 and incorporated herein by reference) discloses detergent sticks for laundry consisting of sodium alkylbenzenesulfate (Oily), sodium ripolium phosphate, sodium bicarbonate, tri-hate orthophosphate, and water, and procedures for making these; Philippine Patent 13,778 (issued to Anderson on September 23, 1980 ) describes synthetic detergent bars for laundry containing surfactant, alkali metal pyrophosphate, from about 18% to about 60% alkali metal carbonate. soil, from about 1% to about 20% water; U.S. Patent 4,543,204 (issued to Gervasio on September 24, 1985) discloses laundry detergent bars containing from 10 to 35% higher alkyl sulphate, and from 1 to 10% higher fatty acid - which makes the bars more resistant to rupture during handling and storage; U.S. Patent 5,089,174, issued to Ka? and others, on February 18, 1992, discloses an improved laundry bar consisting of a mixture of ammonium surfactants which consist of a sulphurous and alkyl benzensulphonate, where fatty alcohol is added to advantageously reduce the speed. of l < bar wear and improve soluty.The surfactant proportions of 90/10 to 10/90 by weight alkyl sulfate / alkylbenzensulfonate are described, and Philippine Patent 26,860 (issued November 16, 1982 to Unilever ) discloses a laundry bar containing surfactant which is at least one third primary alkyl sulfate and 12-60% builder consisting of at least two alkali metal phosphates selected from orthophosphate, pyrophosphate and phosphorus. for making laundry detergent bars are well known in the art Examples of method of making laundry bars include those described in the art. The following patents and publications: Philippine Patent 23,689 (issued September 27, 1989 to Umlever) describes a method for making a bar containing 7-45% detergent surfactant, consisting of the steps of neutralizing with alkaline material (such as carbonate). ) the acid precursor of the detergent surfactant, in the presence of a desiccant / absorbent material, such as oleum, sulfuric acid and anhydrous sulfate, followed by the addition of other ingredients, prior to the formation in bars; and Philippine Patent 24,551 (issued August 3, 1990 to Unilever) discloses a process for making a bar containing 7-45% detergent surfactant and 0-50% detergent builder, consisting of ") s steps to neutralize with alkaline material (such as carbonate) the acid precursor of detergent surfactant, in the presence of 0.25-50% on eo of silica-containing material, such as crystalline alkylinosilicate, silica gels, and amorphous silica, followed of the addition of other ingredients, prior to the formation in bar-ras One of the most persistent and annoying problems that arise during conventional washing operations is the tendency of some colored fabrics to release dyes towards washing solutions. so-called fugitive dyes are then transferred to other fabrics often having different colors of fugitive colors.This problem is commonly known in the art as "transfere" ncia de colorantes ". For white fabrics, this is usually perceived as increased tarnish. Within the meaning of dye transfer the dye material is conveniently included in "dirt" in the fabrics to be washed which can similarly be transferred to other fabrics in the wash solution. As is known, one way of solving the dye transfer problem is to complex or otherwise absorb fugitive dyes before they have the opportunity to join other fabric articles in the wash solution. For that purpose, various polymers have been included in detergent compositions to inhibit dye transfer. For example, European application No. 372 291, "" ico s and others, describes a process for washing discoloration sensitive fabrics in which the wash solution contains several water-soluble polymers including N-vi nilimidazole, N-vini loxazolidon, N-vmilpirrolidone and copolymers thereof to inhibit color-ante transfer. Optical brighteners are fluorescent whitening agents that show benefits of inhibition of dye transfer by a mechanism of modification of the surface of the fabric. The brighteners can displace dyes from the surface of the fabric due to their greater affinity to the fabric. The polish then gives the surface of the fabric a more ammonic character which is expected to repel fugitive dyes from the inlet, decreasing the kinetics of desorption of the dyes. However, none of the dye transfer inhibitors or optical brighteners alone are completely satisfactory in their performance. Therefore, there remains a need to improve bleaching and inhibition of dye transfer from washed fabrics using wash bars while maintaining good removal and cleaning of dirt and other physical bar properties. It is an object of the present invention to improve the bleaching and the inhibition of dye transfer of fabrics washed with wash bars containing an amount of a dye transfer inhibitor in combination with an effective titer of an optical brightener, same time as providing good surfactant performance, good cleaning, good use value, good solubility and other bar systems.

BRIEF DESCRIPTION OF THE INVENTION The laundry detergent bars of the present invention comprise detergent surfactant, builder, an effective amount of a dye transfer inhibitor, and an effective amount of an optical brightener to improve the whiteness and inhibition of clothes dye transfer. washed with the bars. Preferably, the bars comprise from about 10% to 60% by weight of ammonium surfactant, from about 5 to 60% by weight of detergency builder, from about 0.10 to 2.0% of a dye transfer inhibitor, and from 0.05 to 1.0% approximately of a pt i co brightener. Examples of non-polymerizing dye transfer inhibitors include polyoxymethylpyrrolidone, polyvinylpyrrolidone (PVP), PVP-polyvinylnitridazole copolymer and mixtures thereof. They are also preferred for use as dye transfer inhibitors in the present N-vimlpyrrolidone copolymer and N-viml nmdazole (PVPI) polymers.

Preferred optical brighteners are stilben-diamine, optical brighteners of the di-styrylbiphenyl type and mixtures thereof.

DETAILED DESCRIPTION OF THE INVENTION Although this specification concludes with the claims clearly stating and particularly claiming what is considered co or the invention, it is believed that the invention can be better understood by a careful reading of the following detailed description of the invention. In this specification, all percentages are by weight, all temperatures are expressed in degrees Celeius, molecular weights are by average weight, and decimal is represented by point (.), Unless otherwise specified.

Detergent Surfactant The laundry bars of the present invention typically consist of 10% to about 60% of an anionic surfactant. A preferred anionic surfactant to be used is an alkyl sulfate (AS) having an alkyl chain of 10 to 20 carbon atoms, a branched chain alkylbenzene sulfonate (OSB) having an alkyl chain of 10 to 22 carbon atoms, a straight chain alkyl benzene sulphonate (ASL) having an alkyl chain of from 10 to 22 carbon atoms, and ineqlas of them.The preferred bar-ras consist of about L5% about 40%, most preferably from about 18% to about 32% of said ammonium surfactant 5 The alkyl portion of said surfactant of RSTÍ or RSL preferably contains from 10 to 16 carbon atoms, most preferably from 10 to 14 carbon atoms. Most preferably still, the alkylbenzene fonate surfactant and R L. The alkyl portion of a surfactant RS preferably contains from 10 to 18 carbon atoms, most preferably from 12 to 16 carbon atoms. The surfactant RS may include a longer chain AS mixture, such as one having 16 to 18 carbons, and a shorter chain alkyl as one that has 11 to .13 carbons. Preferred surfactants RS include coconut alkyl sulfate, tallow sulfate, and mixtures thereof; most preferably, coconut alkyl sulfate. The cation pair-to RSB, ASL and RS is preferably Sodium, although other useful cations include tpotanola ina, potassium, ammonium, magnesium, and calcium, or mixtures thereof. A preferred anionic surfactant includes a mixture of RS and alkylbenzenesulfonate. A mixture of RS and '? ": alkylbenzenesulfonate surfactant consists of a ratio of surfactant RS: alkylbenzene, fonate from 10:90 to 95: 5, most preferably from 40:60 to 95: 5, and most preferably still from 75:25 to approximately 90:10 In a preferred embodiment, the laundry bar consists of an ammonium surfactant consisting of a mixture of molar ratio of RS and ASI from 80:20 to about 90: LO, preferably from about 82:18 to about 88:12, and most preferably from about 84:16 to about 87:13, said detergent bars are described in the co-pending Philippine patent application 47165-R, filed on 9 October 1993 by Rodney M. Uise and Belal U. S ddique, assigned to The Procter-R Gamble Company. Other optional surfactants include zwitterionic nonionic amphoteric surfactants alone or in conjunction with ammonium surfactants.

Detergency Enhancer The laundry bars of the present invention consist of from about 5% to about 60% by weight of detergency improvement. Preferred laundry bars consist of from about 5% to about 30% builder, most preferably from about 5% to about 20%, by weight of the bar. These detergency builders can be, for example, water-soluble alkali metal salts of phosphates, pyrophosphates, orthophosphates, polyphosphates, higher polyphosphates and mixtures of the same. A preferred builder is a water-soluble salt of polyphosphate, and a mixture of polyphosphate and pyrophosphate. The detergoncia enhancer can also be a non-phosphate builder. Specific examples of a non-phosphorus inorganic builder include water-soluble inorganic carbonate and bicarbonate salts. Carbonates, bicarbonates and alkali metal silicates (e.g., sodium and potassium) are particularly useful herein. Sodium carbonate is a particularly preferred ingredient in laundry bars, V? that in addition to its use as a builder, can also provide alkalinity to laundry bar for improved detergency, and can also serve as a neutralizing agent for acid components added to bar processing. Sodium carbonate is particularly preferred as an inorganic neutralization salt for an acid precursor for an ammonium surfactant used in such laundry bars, such as alkylsulfuric acid and chl-benzene sulfonic acid. The aluminosilicate ion exchange materials are also useful. These aluminosilicates can be crystalline or amorphous in structure and can occur naturally or be derived synthetically. Preferred synthetic crystalline alumino-ion exchange materials useful herein are available under the "R, zeolite B, and zeolite X" resignations. In an especially preferred embodiment, the exchange material of Crystalline aluminosilicate ions is zeolite R and has the formula: Nai2 CÍR102) l2 - (SÍO2) l2 ^ .XH2O where x is from about 20 to about 30, especially about 27. Water-soluble organic detergents, for example alkali metal, ammonium and substituted ammonium polycarboxylates, are also useful herein Specific examples of polycarboxylate builder salts include sodium, potassium, ammonium and substituted ammonium salts of ethylenediaminetetraacetic acid, nitrilotriacetic acid, oxydisuccinic acid, Rhinitic acid, benzenepolycarboxylic acid, polyacrylic acid, polyalene acid, acrylic acid copolymer Ionic - maleic acid, polyacephalic acid and citric acid, or such acids per se. These polymers typically have an average molecular weight of less than about 100,000, most preferred 1,000-10,000. Other useful polycarboxylate detergent builders are the materials discussed in US Pat. No. 3,308,067 issued to Diehl on March 7, 1967, incorporated herein by reference. Mixtures of builders can be used in the present invention. The copolymers of acrylic acid and maleic acid are preferred as auxiliary detergency builders, since "it has been observed that their use in combination with fabric softening clay and clay flocculating agent also stabilizes and improves clay deposition and softening action of the fabrics Preferred specific examples of detergency builders include t-poly L sodium phosphates (STPP) and sodium pyrophosphates (TSPP), and mixtures thereof Other examples of specifically preferred builders include zeolite and poly carboxylates .

Dye transfer inhibitors The preferred polya-N-oxide polymers for use herein, contain units with the following structural formula: R-R? -P; where P is a polimerizable unit to which a group of N-0 can be added or the group N-0 can form part of a polyrneable unit of group M-0 can be added to both units: a is one of the following structures; -MC (O) -, C (0) 0-, -S-, -0-, N =; x is 0 or l; and R is an aliphatic, ethoxylated, aromatic, heterocyclic or cyclic aliphatic group or any combination thereof for which the nitrogen of the N-0 group may be added or the N-0 group is part of these groups Preferred polyarynin N-oxides are those in which R is a heterocyclic group, such as pirpdine, pyrrole, imidazole, pyrrolidine, pipen dine and derivatives thereof. The group N-0 can be represented by the following general structures: where Ri, R2 and R3. they are aliphatic, ar-ornat, helocyclic or alicyclic groups or combinations thereof; x, y and z are 0 or 1; and the nitrogen of group N-0 may be added to or form part of any of the aforementioned groups. The amine oxide unit of the polyarnine-N-oxides has a? Ka < 10, preferably pKa < 7, very preferably pKa < 6. Any polymer base structure can be used as long as the polymer formed from amine oxide is water soluble and has dye tolerance properties. Examples of a suitable polyvinyl base structure are polyvinyl, polyalkylene, polyester, polyether, polyarynide, polyester, polyacrylate and mixtures thereof. The polymer can include block or random copolymers where one type of atom is an N-oxide of amine and the other type rnonomer is an N-oxide. The amine N-oxide polymers typically have a ratio of amine to amine N-oxide from 10: 1 to 1: 1.00. However, the number of amine oxide groups presents a polymer of polyarynn oxide that can be varied by appropriate copolymeation or by an N-oxidation L4. ^ appropriate grade. Polyarnine oxides can be obtained in any degree of polymerization. Typically, < - 1 average moLccuLar weight is within the range of 500 to 1,000,000; most preferably from 1,000 to 500,000, most preferably even from 5,000 to 100,000. The dye transfer inhibitor is advantageously used at levels in the bar of up to 10%, preferably from 0.1 to 2% approximately, preferably from 0.1 to 0.25% approximately. Alternative dye transfer inhibitor can be used. Copolymers of polymers of M-vimlpyrrolidone and N-vmilipudazole (referred to as "PVPI") are also preferred for use herein. Preferably, the PVPI has an average molecular weight of 500 to 1,000,000, most preferred of 5,000 to 200,000 and most preferred of 10,000 to ,000. (The average molecular weight scale is determined by Light scattering as described in Barth et al.

Chemical Rnalysis, Vol 113. "Modern Methods of Polymer Oharactepzat ion ", the descriptions of which are incorporated herein by reference.) PVPT copolymers typically have a molar ratio of vinyl irnidazole to vim Ipyrrolidone-N from 1: 1 to 0.2: 1, most preferably from 0.8: 1 to 0.3: 1, very preferably even from 0.6: 1 to 0.4: 1. These copolymers can be both linear and branched The compositions of the present invention can also contain a polyvinylpyrrolidone ("PVP") having an L5.

The molecular average of about 5000 to about 400,000, preferably from about 5,000 to about 200,000, most preferred from about 5,000 to about 50,000 Examples of PVP are described in, for example, EP-fl-262,897 and EP-R-256, 696, incorporated herein by reference, The compositions containing PVP may also include polyethylene glycol ("PEG") having an average molecular weight of from about 500 to about 100,000, preferably from about 1000 to about 10,000.Preferably the weight ratio of PEG to PVP is from about 2: 1 to about 50: 1, and most preferably from about 3: 1 to about 10: 1.

Optical brightener Optical brighteners are fluorescent whitening agents that show benefits of inhibition of dye transfer through a modi ication mechanism of the fabric surface. The brighteners can displace the dyes from the surface of the fabric due to their greater affinity for the fabric. The brightener then gives the surface of the cloth an ammonic character which is expected to repel incoming fugitive dyes, decreasing the kinetics of desorption of color-before. The preferred optical brighteners are dianinoesfiblose, optical brighteners of the sestiplbifemlo type. Preferred as examples of said < tl > p rippers are acid 4, 4 '-b? s. { T4 -ani l-na-6-bs (2-hydr-oxyethyl). Arnmo-1,3, 5-tpz? Na-2-? L Ham? No.}. Est-lben-2, 2 '- disulfonic disodium salt, 4-4 '-b? e (2-sulfortril) bi femlo and disodium salt of acid 4,4'-bis (4-an? lmo-6-morphol? no-1, 3,5-tαa-2 γ) ammonium-2, 2'-di-sulphonic These optical brighteners, or mixtures thereof, can be used at levels in the bar around 0.05% -1.0%, preferably ü.05% ~ 0.5%.

OPTIONAL COMPONENTS The detergent bars of the present invention may contain up to about 70% by weight of optional ingredients commonly used in detergent products. A typical list of the optional classes and species of surfactants, optional detergency builders and other useful ingredients herein appears in U.S. Patent No. 3,664,961, issued to Norps on May 23, 1972, and EP 550,652 published on April 16, 1992, incorporated herein by reference. The following are representative of said materials, but are not intended to be limiting.

Optional surfactant detergent agent: Optional detergent surfactants may include up to about 1% of about 10%, most preferably about 0.01% to about 5%, by weight of the composition. The types of detergent surfactants which can be used as optional surfactants include ammonium, cationic, nonionic, anophotopic and zwitterionic surfactants. The optional ammonium surfactants used herein as auxiliary surfactants include: alkyl glyceryl sodium ether sulfates, especially those ethers of higher alcohols derived from coconut oil and tallow; sulfonates and sulphates of fatty acid monoglycides of coconut oil and sodium; sodium or potassium salts of alkyl phenol-ethylene oxide ether sulfates, and sodium or potassium methyl ether salts R-CH (SO 3) -COORi, wherein R is C 8 -C 22 alkyl or alkenyl, R 1 is Ci-alkyl C4, and M is a counterion, preferably Na or K, as described in UO-93-05013, published March 18, 1992; sulphates; there are secondary salts having an alkyl chain of 10 to 20 carbon atoms; larger fatty acids (ie, "soaps") such as sodium, potassium, ammonium and alkaline salts or higher fatty acids. Its soaps can be made by direct saponification of fats and oils or by the freezing of free fatty acids Particularly useful are the sodium and potassium salts of fatty acid mixtures derived from coconut oil and tallow. say, coconut soap and sodium or potassium tallow; alkylalkoxysul ate consisting of an alkyl portion of 6 to 18 carbon atoms and an alkoxy portion consisting of, on average, about 0.5 to about 20 moles of units alkoxy, preferably ethoxy, very I) preferably from about 0.5 to about 5 ethoxy units, and alkylethoxycarboxylates of the formula RO (CH2CH2O) x CH2COO- +, where R is an alkyl Ce to C; x ranges from 0 to 10 , and the ethoxylate distribution is such that, on a weight basis, the amount of material where x is 0 and less than 20%, the amount of material where x is greater than 7 and less than 25%, and where the average x is 2-4 when the average R is 0i3 or less, and s 3-6 when R is greater than C13; and M is an alkali metal, alkaline earth metal, ammonium, mono, di- and ethanolamome. Other optional surfactants may be non-ionic, and may include: alkyl polysaccharides, alkyl polyglucosides, as described in US Pat. No. 4,565,647, Filling; polyhydroxy fatty acid amides, of the formula R-CtO-NÍR1) -Z, where R is hydrocarbyl CS-C31, preferably aC alkyl or C11-C17 alkemyl, R1 is hydrocarbyl H, Ci-C4, 2- udroxyethyl, 2-h ? roxy propyl, or a mixture thereof, preferably methyl, and Z is (linear) polyhydroxy hydrocarbyl chain having at least 1 hydroxyl directly connected to the chain, preferably -CH2- (CHOH4) -CH2? H, as they are described in EP 550,652; non-ionic surfactants are ipolar, such as water-soluble amine oxides, water-soluble phosphine oxide surfactants, and water-soluble sulfoxide surfactants; and water-soluble synthetic nonionic surfactants broadly defined as compounds produced by the condensation of ethylene oxide groups (essentially hydrophilic) with an organic hydrophobic compound, which may be essentially alkyl or aliphatic aromatic. The length of the polyoxyethylene group which is condensed with a particular hydrophobic group can be adjusted to aid a water-soluble compound having the desired degree of balance between the hydrophilic and hydrophobic elements. The cationic surfactants can also be used in the detergent compositions herein and suitable quaternary ammonium surfactants are selected from monoalkyl or alkenmlarnomary surfactants of Oß-Ciß preferably from Ce-Cio, wherein the Remaining positions of N are replaced by methyl, hydroxyethyl or hydroxypropyl groups. Optional surfactants can also include ampholytic surfactants including aliphatic derivatives of heterocyclic secondary and tertiary amines; z-etheric surfactants which include derivatives of aliphatic quaternary ammonium compounds, phosphine and sulfonam; water-soluble salts of ethers of aliphatic acid fatty acids; ether sulfates; water-soluble salts of olefin sulphonates; betaalcoxialcansul phonates; Betaines having the formula R (R1) 2N + R2C00-, wherein R is a hydrocarbyl group or Cß-Ciß, preferably a do-Cie alkyl group or a Cy-Ciß acylaryl alkyl group, each R * is typically Ci-alkyl C3, preferably methyl, and 2 is a group of C 1 -C 7 hydrocarbyl, preferably a C 1 -C 3 alkylene group, most preferably a C 1 -C 2 alkylene group. Examples of suitable betaines include coconut acrylamide dopropyldimethylbetaine; hexadecildi ethylbetaine; acylcaridopropyl beta of C12-Cn; acyl C8-C14 idohexyldietilbetaine; 1-carboxybutan- [acirnet ia idodietiiamomo of Ci4-? E3; acrylamidodimethyl betaine of Ciß-Ciß; acila idopentanediet ilbetaine of C12-C16; and Lací Imetila idodimetiibetaí na of Ci2-Ci6l. Preferred betaines are dimethylamine or C12-C18 hexonoate and acyl lamidopropane ethane) d? Met? L (or diethyl) betaines of Cio-Ci?; and The sultaines having the formula (R (Ri) 2_ + R2S03- wherein R is a Cß-Cis hydrocarbyl group, preferably a C 10 -C 16 alkyl group, most preferably an C22 ~ i3 alkyl group, each R1 is typically Ci-C3 alkyl, preferably methyl, and R2 is a hydrocarbyl group, preferably an alkylene group or preferably a C1-C3 hydroxyalkylene group, Examples of suitable sultames include 2-hydroxy. C2-C dimethylammonium propylene sulfonate, arn? doprop? lamon? o-2-hydroxyl pro? lish of C12-C14, di-12-C14 dihydroxyethylammonium propionate, and hexanesulfonate Dimethyl-Ciß-Ciß, with the preferred use being C12-C14 arn? dopro? monmon-o-2-hydroxy propyl ester. In addition to the auxiliary surfactants mentioned above, a hydrotrope, or mixture of hydrotropes , they can be present in the laundry detergent bar.

Preferred hydrotropes include alkali metal, preferably sodium, toluenesulfonate, xi lensul fonate, cumensul fonate, sulfosuccmate salts and mixtures thereof. I preferred blernente, the hydrotrope, either in the acid form or in the salt form, being substantially anhydrous, is added to the linear alkylbenzene-phonic acid before its neutralization. The hydrotrope will preferably be present in about 0.5% to about 5% of the laundry detergent bar.

Fabric Softening Clay Fabric softening clay is preferably a smectite-like clay. Srnectite clay clays can be described as expandable three-layer clays; for example, aluminum silicates and magnesium silicates, which have an exchange capacity) ~ Lones «Je for at least about 50 rneq / LOO g. of clay. Preferably the clay particles are of a size that can not be perceived palpably, so as not to have a gritty feel in the treated fabric of the clothes. The softening clay of fabrics can be added to the bar to provide approximately 1 to 30% in weight of the bar, more specifically of about 20%, and most preferably about 8 to 14%. Although some of the clays of the srnectite type described herein are useful in the present invention, certain clays are preferred. For example, Gelwhite GP is an ex-white clay form of the smectite type and is therefore preferred when formulating white granular detergent compositions. Volclay BC, which is a clay type mineral is ectite contains at least 3% iron (expressed as Fß2? 3) in the crystalline lattice, and which has a very high ion exchange capacity, is one of the most efficient and Effective clay for use in these compositions from the point of view of product performance. On the other hand, certain clays of the esinectata type are sufficiently contaminated by other silicate minerals that their ion exchange capacities fall below the required scale; such clays are not to be used in the present compositions.

Clay flocculation people The polymer clay flocculation agent is selected to provide improved deposition of fabric softening clay. Typically said materials have a high molecular weight, greater than about 100,000. Examples of such materials may include long chain polymers and copolymers derived from onorneros such as ethylene oxide, acplarnide, acrylic acid, ethylene diamine-methacrylate, vinyl alcohol, vinyl pyrrolidone and ethyleneamine. Gums, like guar gums, are also suitable. A clay flocculating agent is preferably selected from a high molecular weight polyether oxide, polyacrylic amide, and polyacrylate having a molecular weight of from about 100,000 to about 10 million. It has been found that the use of a clay fl occulation agent in a laundry bar containing softening clay surprisingly provides an improved softening clay deposition in the clothes and softening action in the clothes, compared to that in the barrels. -a laundry consisting of softening clay. The amount of clay flocculating agent that will be used in the laundry bar is preferably an appreciably improved fabric softening effective amount. The amount of clay flocculating agent that is used may vary depending on the type of clay flocculation agent employed, the type of fabric softening clay, and the types and ranges of other detergent adjuvants in the laundry bar. The level of clay flocculation agent is conveniently referred to in terms of its percentage by weight of the amount of softening clay the fabrics in the bar. The bar will be constituted, by weight of the fabric softening clay, from about 0.001% to about 30% clay flocculating agent, most preferably from about 0.01% to about 15%, and most preferably still from 0.5% to about 5%. The effectiveness of the clay flocculating agent is generally increased by increasing the molecular weight of the flocculating agent. The polymers typically have an average molecular weight of about 100,000 to about 10 million, most preferred of about 150,000 to about 5 million. As for the level of the clay flocculating agent, the selection of an appropriate polymer molecular weight will depend on the type of clay and the type of flocculating agent, as well as other components of the composition. The preferred clay flocculating agent is a polymer (oxide) of poly (and wood).

Detergent chelator: A particularly preferred optional component of the present invention is a detergent chelator. Such chelators can separate and chelate alkali cations (such as sodium, lithium and potassium), alkaline earth metal ions (magnesium and calcium), and most preferably, heavy metal cations such as iron, manganese, zinc and aluminum. . Preferred cations include sodium, magnesium, zinc and mixtures of the same. The detergent latent is particularly beneficial to maintain a good cleaning action and improve the performance of the surfactant, despite the presence of the softening clay and clay flocculating agent. Without having to be limited to any theory, it is believed that the smoothing structure contains fier-ro (Fe) and other transition metal ions. In the washing process, substitution by calcium and magnesium in the wash water and in the soils of iron or other transition metal ions may occur, dislodging the transition metal ion in the wash solution. It is known that these metal ions contribute to the suckling and percudido the fabrics. The detergent chelator can significantly reduce these effects. The detergent chelator is preferably a phosphonate chelator, in particular one chosen from the group consisting of diethyltinparninopentarnet and lyphosphoid acid, ilenfosfome ethylendia motet ramet acid, and mixtures and salts and complexes thereof, and an acetate chelator, -similarly one selected from the group consisting of dietetic acid - ammonia, entarnet, and lyphosphonic acid (acid), acid, and phosphoric acid, and mixtures and salts and complexes thereof. Particularly preferred are the ales and complexes of sodium, zinc, magnesium and aluminum of d? Et i lenet ri arninopentamet iolenphosphonate, diethylene glycol inopenta-aceto and mixtures thereof. Preferably said salts or complexes have a molar ratio of metal ion to chelator molecule of at least 1: 1, preferably at least 2: 1. The detergent chelator may be included in the laundry bar at a level of up to about 5%, preferably from about 0.1% to about 3%, most preferably from about 0.2% to about 2%, most preferably from about 0.5% to approximately 1.0%. Said component of the detergent chelator can be beneficially used to improve the performance of the surfactant of the present laundry bar, which means that for a given level of the unique surfactant and level of the detergent chelator, performance and action of the detergent can be achieved. equivalent cleaning compared to a similar bar containing a higher level of ammonium surfactant but without the detergent chelator. The detergent chelators can be used in a particulate or granular form, or in a solvent or aqueous solution. Methods for preparing said salts and compounds are well known and US Pat. No. 4,259,200, issued March 31, 1981, is described whose description is incorporated by reference. A preferred form is a particular or granular shape. Said forms of particles or ranks of the detergent chelator can be formed with inorganic or organic binder material. An organic suitable binding material is, for example, a nonionic surfactant. Such suitable inorganic binder materials include sodium tripolyphosphate, sodium carbonate, magnesium sulfate and the like. Any granulation technique known in the art may be employed, for example, by spraying a molten nonionic surfactant onto a moving bed of the dry metal complex, fluid bed drying, etc. Enzyme: Another particularly preferred component is a detergent enzyme. Non-limiting types of enzymes include cellulase, lipase, amylase, lipolase, malease, protease, catalase, rnaltase and phosphatase. Parculularly preferred are cellulase, lipase, protease, amylase and mixtures thereof. Conveniently, the enzymes are used at levels of up to 5%. A particularly cellulase enzyme that provides care and softness benefits to fabrics by means of amorphous and non-crystalline cellulase hydrolysis, which is associated with damaged cellulose fibers. A particularly preferred cellulase is the Carezyme® cellulase, stocked by Novo Nordisk. Another useful optional component of the laundry detergent bars of this invention is silicate, especially sodium or magnesium icate. The sodium silicate can be used up to about 15% solids of licates having a weight ratio of 1O2 to Na2? between about 1.0: 1 and about 3.4: L. Another preferred additional component is a crystalline alkali silicate with layers. A preferred silicate with commercially available layers is known as "SKS-6" (Na2 i2? S), is available from Hoechst, and is described in U.S. Patent 4,654,839, issued May 12, 1987. Another preferred layered silicate is described in EP 550,048, July 7, 1993 (Kao), which describes a synthesized crystalline material having a chain structure and having a composition represented by the following formula in anhydrous form: wherein M represents Na and / or K; M 'represents Ca and / or Mg: y / x is 0.5 to 2.0; and z / x is 0.005 to 1.0, said chain structure looking like a main dispersion tip in the Rarnan spectrum of at least 1970 ± 30 cm_1 on the scale of 900 to 1200 crn-1. Said stratified silicate material is particularly preferred because it can provide both alkalinity and calcium sequestration functionality or detergency builder. Another preferred additional component of the bar for laundry is fatty alcohol having an alkyl chain of 8 to 22 carbon atoms, most preferably 12 to 18 carbon atoms. Fatty alcohol is effective in reducing the rate of wear and tear (pulpy appearance) of the '> arra of the present bar-ras for laundry. A preferred fatty alcohol has an alkyl chain predominantly containing 16 to 18 carbon atoms, the so-called "high-cut fatty alcohol", which may exhibit less odor of fatty alcohol base relative to broad-cut fatty alcohols . Typically, the fatty alcohol is contained in the laundry bar to a level of 10%, most preferably from about 0.75% to about 6%, more preferably from about 2% to about 5%. The fatty alcohol is generally added to the formulation of the present invention as free fatty alcohol. However, low levels of fatty alcohol can be introduced into the bars as impurities or as a starting material without reaction. For example, laundry bars based on coconut fatty alkyl sulfate can contain, as unreacted starting material, from 0.1% to 3.5%, more typically from 2% to 3%, by weight of coconut-free fatty alcohol in a base of coconut fatty alkyl sulfate. Free fatty alcohol can also serve as a foam enhancer, to reinforce and extend foam generation and duration. For the foam increase, a preferred fatty alcohol has an alkyl chain which predominantly contains from 12 to 14 carbon atoms, used in the composition at a level of about 0.5% to 3%. Preferably, a narrow-cut C12 alkyl alcohol is used at a level, from 0.5% to 2%. Another preferred laundry component may include a soil release polymer. Such soil release polymers can be used at levels up to 5%, preferably from about 0.0.5% to about 3%, most preferably from about 0.2% to about 1.0%. A dirt-releasing polymer can improve the cleanliness of laundry laundry items with the laundry bar. Preferred dirt-releasing polymer materials include those described in U.S. Patent 4,877,896, issued October 31, 1989, and U.S. Patent No. 5,182,043, issued January 26, L993, which are described herein by reference. A preferred soil release polymer is an ether blocked at the ends with substantially linear sulfoaroyl having a molecular weight of from about 500 to about 20,000, wherein said ether consists, on a molar basis, of (i) about 1 about 2 moles of units blocked at the ends with sulphobenzoyl of the formula (MO3 S) (CeFU) -C (0) ~, where M is a cation form or salt: (JI ) from about 2 to about 50 moles of units of ox? -1, 2-? rop? lenox? or mixtures thereof with oxyethyleneoxy units provided that the molar ratio of ox? -1, -? rop ienoxy: oxyethyleneoxy is on the scale of about 1:10 to about 1: 1; and 1L (m) of about 1 to about 40 moles of terephthaloyl units provided that the molar ratio of said units identified by (n) and (111) is from about 2: 1 to about 1:24; and optionally further comprising, per mole of said ether, dv) from 0 to about 30 moles of 5-suL phisophthaloyl units of the formula (0) C (CßH3) (S? 3M) C (0) (Jonde M is a form or salt cation; or (v) from 0 to about 25 moles of the poly (ox? et? leno) ox? units of the formula (0CH CH2) n0- where the average degree of ethoxylation n varies from 2 to about 100; or (vi) from 0 to about 30 moles of a mixture of said units (v) and (v) at a molar ratio of (? V) :( v) from about 29: 1 to about 1 : 29. Preferably, said substantially linear sulfoaroyl-coated end ester consists of, on a molded base, (i) about 2 moles of sulfobenzoyl end capped units of the formula (MO3S) (C6H1) -C (0) - where M is sodium; (11) about 14 moles of ox? -1,2-propyleneoxy units or mixtures thereof with oxyethylene units having a molar ratio of oxy-1, 2-? Rop? Le noxi: ox? et? lenox? on a scale of about 1: 0 to about 1: 7; and (m) about 11 moles of tereotolol units; and (iv) about 2 moles of 5- sulfoisophtalol units of the formula (0) C (C6H3) (S? 3M) C (0) - where M is sodium, and where at least 20% of the ester has a molecular weight of around 800-20,000. Another preferred soil release polymer is an end-blocked ester oligomeric polymer with polyethoxy / sulfonated propoxy, which consists of: (i) from about 1 to about 2 moles of end blocked units with poly-ethoxy / sulphonated propoxy of the formula ((M03S) CH2) m (CH2) m (CH2CH2?) (RO) "-, wherein M is a cation formed from salt selected from a group consisting of sodium and tet raalkylamino, m is 0 or 1, R is ethylene, propylene or a mixture thereof, and n is from 0 to 2; di) from about 0.5 to about 66 moles of units chosen from a group consisting of: a) oxyethiienoxy; b) a mixture of units of oxietiienoxi and oxy -1, 2-? rop? lenox? wherein said oxyethyleneoxy units are present in a molar ratio of oxyethyleneoxy to ox i -1, 2-? rop? lenox? which ranges from 0.5: 1 to approximately 10: 1; and e) a rnezcLa of a) or b) with units • e? ol? (ox? et? ieno) ox? wherein said units of pol i (oxyetj len) ox? have a degree of polymerization of 2 a; provided that when said units of poly (oxyethylene) ox? have a degree of polymerization of 2, the molar ratio of poly (ox? et? leno) ox units? the units of the total group n) will vary from 0: 1 to approximately 0.33: 1; and when said poly (ox? et? leno) oxi units have a degree of polymerization of 3, the molar ratio of poly (ox? et? leno) ox units. the units of the total group n) will vary from 0: 1 to approximately 0.22: 1; and when said units of poly (ox? et? leno) ox? having a degree of polymerization of 4, the mole ratio of poly (ox? et? leno) units to the units of the total group n) will range from 0: 1 to about 0.14: 1; (iii) from about 1.5 to about 40 moles of terephthaloyl units; and dv) from 0 to about 26 moles of 5-sul foSophthaloyl units of the formula - (0) C (CßH3) (S? 3M) C (0) - Where M is a salt or form cation. Preferably, said ether glycols have a molecular weight of from about 500 to about 20,000 very preferred from 500 to about 5000. An especially preferred ester ether polymer has the formula: NaO3 S (CH2CH2O) 2-C ( O) - (C6 F) -C (0) 0- C -CH CRH-OC (0) - (C6 H *) -C (0) 0- - - i: -OH2 CRH-OC (0) - ( Ce HA) SO3 Na-C (0) O- Ti -CH2 CH2 0CH2 CH2 SO3 Na where R is H or CH3 on a scale of the rededo r- of 1. 0: 1 The soil release polymer can be added to the stick composition during the forming process in a liquid or granular form. In a preferred embodiment, the soil release polymer is in a particular porous, low density form. Said porous form of soil release polymer can be made by spray drying a solution of the soil release polymer in liquid form, alone or with one or more carrier materials, to remove substantially all free water or other solvent liquid, by spray drying well known in the art. Another optional optional component in the laundry bar is a secondary fabric softening component in addition to the softening clay. Such materials can be used at levels of up to about 0.1% to 5%, most preferably from 0.3% to 3%, and can include: amines of the formula R4R5R6N, where R * is C5 to C22 to hydrocarbyl, Rs and Re are independently hydrocarbyl Ci a Cío - A preferred amine is di-benzylbenthyl amine; compounds of said amines with fatty acid of the formula R7COOH, wherein R7 is hydrocarbyl O9 to C22, as described in EP No. 0,133,804; compounds of said amines with phosphate ethers of the formula R 10 O-P (Q) (OH) -OR 9 and HO-P (O) (OH) -ORg, where Re and R 9 are independently C 1 to C 20 alkyl of alkyl ethoxylate of the formula -alkyl- (OCH2CH2); cyclic amines such as irnidazole 1 ace, of the general formula l- (higher alk) to mo (lower alkyl) -2- (alkyl) uroidazole (higher), wherein alkyl upepor is 12 < 22 carbons and in alkyl alkyl of 1 p 4 carbons, as described in the application of U.S. Patent No. 2,173,827; and ammonium compounds - a ternary of the formula Rio R1 and R12 R13 N + X- where Rio is alkyl having from 8 to 20 carbons, R11 is alkyl having from 1 to 10 car-bonds, R12 and R13 with the alkyl having from 1 to carbons, preferably methyl, and X is an anion, preferably CL- or B? -, such as alkylotropionammonium chloride Lo C12-13 - Another optional component in the laundry bar is a bleaching component The whitening component can be a source of the group -00H, t Les co or perbora or of sodium monohydrate, per-borate sodium tetrahydrate and sodium percarbonate.Sodium percarbonate (Na2 ?? 3 • 3H2O2) It is pr-eferred since it has a double function of both HOOH source and sodium carbonate source.Another optional bleaching component is a per-acid per se, with the formula: OH3 (CH2_) w -NH- C (0) - (0H2) ZC03H where Z is from 2 to 4 and w from 4 to 10. (The component of the last formula where z is 4 and w is 0 is later on r efferred as IIRPRR). The whitening component may contain, as a stabilizer, the bleaching component, a chelating agent for polyacrylate, nocarboxylic acids, polycarboxylates, as well as acid or nitrate acetate, acid di et al. co, and < - »Ethylene-diaminodiscimic acid and its salts with! e * al ', s of ^ Lquilo' -olubles ¡r? Water. The components I) 1 can be added to the Larra to a level of '' ()%, easily from 1% to 10%, very pronounced from around-% to approx imadainent%. The sulfur salt is a well-known filler which is compatible with the compositions of this invention, it can be a derivative of the sulphation and sulphonation procedures of surfactant, or it can be added sep radarnont or calcium carbonate. (also known as horn Oalcarb) is also a well-known and often used component of laundry bars. Such materials are typically used at levels of up to 40%, preferably from about 5% to about 25%. Agglutination agents to hold the bar together in a soluble cohesive form can also be used, and include starches, gums, natural thickeners and synthetics and mixtures thereof. Dirt suspension agents can be used.

In the invention, its use is balanced with the softening clay combination of * elas / agen t < = of flocculation of clay to provide the piece and optimal softening action of fabrics. The soil suspension agents may also include < - soluble in water of < > ') carboxirnetij cellulose and earhoxihi droxirnet íieel ulos. A preferred tire agent < a copero imero '] < ' er i 1 i co / inaleí co, '-o i ia lly available < orno oLol ^ ", de i) RSF Corp. Ot eos (suspension codes for 'sucded? n <, polyen pol? et il ngl L oles that have a molecular weight? d' =» - »1 of 4 (10 -.i 10,000, and mono and poloxas otoxylated, and salo ?, Quaternary of the same. Color-before, pigments, germicides and perfumes can also be added - the composition of the bar .

PROCEDURE: The laundry detergent bars of the present invention can be processed in conventional conventional soap bar or detergent bar manufacturing equipment - with part or all of the following important equipment: combiner / mixer, mill or extruder refining, two-stage vacuum extruder, Je logo printer / cutter, cooling tunnel and wrapper. In a typical procedure the cellulase over, the fabric softening clay, and optionally the clay flocculation are mixed, only with other starting materials, in the mixer. Laughing alk i Ibencensul f on i co (when used) is added to a mixture of non-metallic salts of metal (preferably including sodium carbonate) and the partially neutralized mixing mixture is my meat used for provoke homogeneity and complete the neutralization of the mixture. Once the inaction of - > In addition, the algering surfactant is added, < eguided by the other ingredient ingredients rcsi ii-t-f • ,, The mixture can be bored from one minute to one hor: *, < on the common mixing time being from 2 to 20 minutes. L cl is discharged to a wave tank. The product is transferred from the wave tank to the refining mill or extruder by means of a multi-purpose transfer conveyor belt. Alkyl 1 benzene sulphonic acid (HLRS) can be made by well-known procedures, such as with c? 3 or oil. I preferred Blernente to be able to include extra inorganic sulfuric acid (H O4) in the storage of HI S, which, at the time of neutralization, helps to increase the temperature of the product due to the heat of the neutralization of the acid. inorganic sulfuric Alternatively, the cellulose enzyme, to re il The fabric softener and clay flocculating agent can - Become independent at other times or places in the procedure, depending on the IP of the equipment and the type of formulation that is made. After preliminary grinding or extrusion, the product is then transferred to a double-stage vacuum extruder. operating at a high vacuum, for example 600 to 740 millimeters of mercury vacuum, so that the enclosed air is eliminated. The product is extruded and cut to the desired bar length, and printed with the product's trade name. I? printed bar can be cooled, for example in a tunnel of q r »f ria f, before being wrapped, ubier + ay sent for« ilmacenami c * nt e .. Examples of b rra of the present invention are found below enlistados by way of illustration, and not to mane r ^ of 11 rn itaoion.

EXAMPLES Vanilla bar compositions can be made using the method described above.

Example number 1 2 2 i 5 2 I 2 9 (By weight and weight) - ^ NaOFRs. (012 CIO) 2550 1575 1913 1120 2250 1350 I Na (012 -ClHJLnS 500 675 338 tha 19.00 1500 21.00 Lla2 CO3 2320 500 15.00 1500 1000 300 1300 ßoo 10.00 DTPP1 0.70 0.70 070 070 070 070 060 060 PFO- 'IO? 2 030 0.30 ITO-bO t 020 0.20 PEO- 1.2MM 0.15 rcí 11 a de ben em + o 10.0 10.0 5.00 So L o 1.1 n OP 1.3 040 070 0.40 0.70 0.40 100 0.20 7 SPP 5.00 5.00 5.00 5.00 500 15 « , 1 PP 5.00 1000 500 10.00 10.00 15.00 / eo Li a 1.25 1.25 125 1.25 1.25 125 Sodium Laurate 9.00 SRP-R4 0.30 0.30 0.30 0.30 0.30 0.30 0.22 0.22 Pol i er'o5 0.70 0.20 0.70 0.20 0.14 0.70 0.20 0.14 0.7 20 Rbrí 1 Lant ado? <; 0.20 0.20 017 070 020 0.20 0.70 0.17 0.20 znna pro easa? O.Oß 0.12 0.08 0.08 I n a amiiasaß 0.80 0.80 L nzi ina 1 i passes 0.10 0.10 Enzi a c o 1 u 1 a s 9 0.15 0.15 Balance 10 1. . - Diet and sodium lenetpaminopentafosfonato. 2. - PEO is (oxide) of pol i (et i leño) having a molecular weight as indicated. '! () 3.- SoLolan OP-5 is an independent operator. k. SRP-fl is Na03 (CH2CH20) 2-0 (0) - (Ce -HA) -CYO) 0-L ~ -CH2 CRH-OC (O) - (C6 -H «) - O (O) O - - r -CH2 CRH-OC (0) - (C6 HA) S03 Na-0 (0) 0 Ti - '! l? 01-1201 -12 OCH2 CH2 SO3 Na, where R is H or OH 3 in a ratio of approximately 1.0: 1. S. ~ The polymer is a polymer of N-oxide of pol lamina. 40 fi - The ab illnador esdiami noes 11 bonus, diest L? 1 b i feni 1 o or mixtures of the mis o'- ,. r '. - I a protease activity to the Ru / g of abast oci ?? i ente. 0. I a a < t? vidad ainilasa 100,000 a u / gm of a Lmaeonami ent .. '•). - Oeiulasa Carezy? NeR, supplied by Novo Nordisk, activity at 5000 Cevu / g supply. LO-- 1-1 r'esto consists of water (approximately 2% to 8%, including water of hydration), sodium sulfate, calcium carbonate and other minor ingredients.

Claims (4)

NOVELTY OF THE INVENTION CLAIMS

1. A laundry detergent bar comprising: a) from 10% to about 50% by weight of ammonium tonsioactive, (b) from about 5 to about 0% by weight of builder, (c) from 0.01 to 2% approximately of a dye transfer inhibitor, and) an effective amount of an optical brightener to improve the whiteness and 1A inhibition of color transfer-ante of the tel s.

2. A detergent laundry bar according to claim 1 further characterized in that the dye transfer inhibitor is a polymer of N-oxi io of pol lamina.

3. A detergent bar for laundry according to claim 2, further characterized in that the optical brightener is selected from the group consisting of styrofoam, distillate, or mixtures thereof.

4. A detergent laundry bar according to claim 2, further characterized in that the polymer N-oxide of polyarynin is selected from the group consisting of pirpdine, pyrrole, inuda / ol, pyrro 1 id na, pipepdine and derivatives thereof. -i '. - I. Detergent detergent for laundry according to claim 2, characterized ad > Further, said ammonium surfactant is selected from the group consisting of the quilsulfate having an alkyl chain of 10 to 20 carbon atoms, a linear chain alkyl (LES) benzene sulphonate (LAS) having a alkyl chain of 10 to 22 carbon atoms, a branched chain alkyl benzene sulfonate (RUS) which has an alkyl chain of 10 to 22 carbon atoms, and a mixture of the smi but. LO 6.- The bar The washing composition of claim 2, characterized in that the surfactant comprises a mixture of alkylation (RS) and linear alkylbenzenesulfonate (LRS) in a molar ratio of RS: LRS of 70:30 to 100: 0.7. - The wash bar of the rei indication 2, L5 further characterized in that the detorgency enhancer comprises sodium polyphosphate, tetrasodium pyrophosphate, or mixtures (ie the same, 0. - the wash bar of claim 1), further characterized by the detergency builder being " 5 20 to 20% of sodium polyphosphate. (-l "- A laundry detergent bar comprising: (a) from about 13 to 12% of ammonium surfactant, selected from alkyl sulfate, to the Ibencensul t onat or, and mixtures thereof, ib) from ci to 20% Approximately '-)!' phosphate detergent builder selected from p p? Li osphate, pyrophosphate, and mixtures thereof, (c) from \ Lv .10 Approximately 2.0% N-oxide of polvv i l? p dina, id) from approximately 0.5 to 1.0% of stylon di ino, dist ir i 11 »i fem lo, or mixtures thereof. 10. A laundry detergent bar according to claim 9, further characterized in that it comprises from 0.05 to 0.5% approximately stilben d lami or, di sti ri Lbi femlo, or mixtures thereof. 1L.- A laundry detergent bar comprising (a) from about 18 to 12% surfactant to ionic, selected from alkyl sulfate, alkylbenzenesulfonate, and ezclas thereof, (b) from about 5 to 20% builder of phosphate selected from tppoli pyrophosphate phosphate, and mixtures thereof, (c) from about 0.10 to 0.25% of N-oxide of polyvinyl-1-pyridine, (d) from about 0.05 to about 0.5% of the diarrhein stilbenze.