FI89721C - FLYTANDE TVAETTMEDELKOMPOSITION INNEHAOLLANDE FAST PEROXIBLEKNINGSMEDEL - Google Patents

Abstract

Solid peroxygen bleach containing aqueous liquid detergent compositions having a pH of at least 8 are disclosed. The peroxygen bleach is water-soluble. The liquid detergent composition comprises a solvent system comprising water and a water-miscible solvent. The solvent system provides sufficient solubility of anionic surfactants, while keeping the solubility of the peroxygen bleach compound within defined limits.

Description

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The present invention relates to liquid detergent compositions containing a solid, water-soluble peroxygen bleach compound. The present compositions comprise a solvent system consisting of water and a water-miscible organic solvent. The solvent system is designed to keep the amount of active oxygen in the solution below 0.5%, preferably below 0.1%. The amount of active oxygen in the liquid phase is at most one-fifth of the total amount of peroxygen bleach contained in the composition, preferably at most one-tenth.

15 The so-called liquid high performance detergent compositions typically contain organic surfactants, enzymes and perfumes. These components are generally incompatible with peroxygen bleaches. For this reason, liquid detergent compositions containing peroxygen bleach are not commercially available today.

EP 0 037 184, issued January 23, 1985 to Interox Chemicals Ltd. , describes liquid detergent compositions comprising organic surfactants, a builder system, at least 2% hydrogen peroxide and a stabilizer system consisting of aminoethylene phosphonate or hydroxyalkyl diphosphonate aliphatic polyhydroxy and aliphatonate aliphatic polyhydroxycarboxylate or carboxylate carboxylate.

EP Patent 0 086 511, issued July 2, 1986 to Procter & Gamble Company, describes aqueous liquid detergent compositions having a pH below y and. containing organic surfactants, oxygen bleach, fatty acid and water-soluble calcium salt.

DE-A-35 11 515, published 35 October 17, 1985, describes anhydrous liquid detergent compositions containing 2,83721 sodium perborate monohydrate and perborate activator. FR Patent 2,579,615, issued October 3, 1986, describes similar anhydrous compositions which additionally contain catalase inhi-5 bits. Exemplary compositions of these two patents do not contain anionic surfactants.

It is an object of the present invention to provide aqueous liquid detergent compositions containing substantial amounts of a solid, water-soluble peroxygen bleach. It is a further object of the present invention to provide such bleach-containing liquid detergent compositions containing substantial amounts of anionic surfactant.

The liquid detergent compositions of the present invention have a pH of at least 8, contain organic surfactants and further a certain amount, based on the weight of the composition, of a solid, water-soluble peroxy compound dispersed in a liquid phase of a water system comprising water and at least one water-miscible organic solvent. the amount of active oxygen dissolved in the liquid phase (AVO) is at most 0.5% by weight, preferably at most 0.1% by weight, based on the liquid phase. The amount of oxygen dissolved in the active liquid phase is at most one-fifth to 25 parts of the amount of peroxy compound contained in the composition, preferably at most one-tenth.

In this context, detergent compositions having a pH of at least 9, more preferably at least 9.5, are preferred.

Preferred solid, water-soluble peroxy compounds are perborates. Preferred water-miscible organic solvents are low molecular weight monohydric alcohols, and of these, ethanol is the most preferred.

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Also preferred are liquid detergent compositions which additionally contain detergent enzymes.

The present invention relates to the problem of formulating a stable liquid detergent composition containing significant amounts of an organic surfactant, e.g. anionic surfactants, and a solid, water-soluble peroxy bleach. It has now been found that the problem is solved by a solvent system consisting of water and a water-miscible organic solvent. This allows a significant amount of peroxy compound to be added to the liquid detergent composition and at the same time that the amount of active oxygen in solution can be kept below 0.5% by weight, preferably below 0.1% based on the solvent system. Less than 1/5, preferably less than 1/10 of the peroxy compound is soluble in the liquid phase.

The presence of water in the solvent system is necessary, e.g. for anionic surfactants. It has been found that the low concentration of active oxygen in the solution causes the bleaching system to withstand storage under typical storage conditions.

Liquid detergent compositions are formulated to have a pH of at least 8, preferably at least 9, and more preferably at least 9.5. Alkaline pH promotes the bleaching effect of the peroxy compound, especially when the peroxy compound is perborate. The stability of the bleaching system in alkaline water is in any case surprising. It is assumed that at least some of the active oxygen is in the form of hydrogen peroxide. hydrogen peroxide is not sufficiently stable in the solvent systems of the liquid detergent compositions of the present invention, however, it has been found that solid, water-soluble peroxygen bleaches are stable in these solvent systems.It is apparent that the concentration of active oxygen in solution is low. in terms of system stability.

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Examples of suitable water-soluble solid peroxy compounds are perborates, persulphates, peroxide sulphates, perphosphates and crystalline peroxyhydrates formed by the reaction of hydrogen peroxide with sodium carbonate or urea. Preferred peroxygen bleaching compounds are sodium perborate monohydrate and sodium perborate tetrahydrate.

The active oxygen (AVO) content of the composition can be determined by a standard iodometric method (e.g., described in Houben-Weyl, Methoden der Organischen Chemie, 1953, Vol. 2, p. 562).

In order for the liquid phase and the solid phase to be fully equilibrated, the compositions must be kept at room temperature for 3 days after mixing before opening the AVO-tit-15. The products must be shaken thoroughly before carrying out the analyzes to ensure reliable sampling.

To determine the active oxygen (AVO) in the liquid phase, samples of the composition were centrifuged at 10,000 rpm for 10 minutes. The liquid was then separated from the solid and assayed for active oxygen by titration.

It is not necessary that the organic solvent be completely miscible with water if the solvent is miscible with the water of the composition to such an extent that the solubility of the peroxy compound is adequate. Completely water-soluble solvents are then preferred.

The water-miscible organic solvent must, of course, be compatible with the peroxygen bleach compound 30 at the pH used. Thus, polyalcohols having adjacent hydroxy groups (e.g., 1,2-propanediol and glycerol) are less desirable when the peroxy bleach component is perborate.

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Examples of suitable water-miscible organic solvents are lower aliphatic monoalcohols, ethers of diethylene glycol and lower monoaliphatic monoalcohols, especially ethanol, n-propanol, isopropanol, butanol, polyethylene glycol (e.g.

PEG 1 50, 200, 300, 400), dipropylene glycol, hexylene glycol, methoxyethanol, ethoxyethanol, butoxyethanol, ethyl diglycol ether, benzyl alcohol, butoxypropanol, butoxypropoxypropanol and mixtures thereof. Preferred solvents are ethanol, isopropanol, 1-methoxy-2-propanol and butyl diglycol ether. The preferred solvent system consists of ethanol and a co-solvent having a higher flash point than ethanol.

Although the presence or absence of other ingredients is important, the ratio of water to organic solvent largely determines the amount of active oxygen in solution. The lower this ratio (i.e., the more organic solvent there is in the solvent system), the less active oxygen is in solution. Although this is an advantage for the stability of the bleaching system, it is less desirable for good solubility of other components (e.g., electrolyte, anionic surfactants). In any case, it is not necessary to use more organic solvent than is necessary to keep the amount of active oxygen in the solution below 0.5%, preferably below 0.1%.

In practice, this means that the ratio of water to organic solvent is in most systems: in the range 8: 1 to 1: 3, preferably 5: 1 to 1: 2.

The liquid detergent compositions discussed herein contain 5-60%, preferably 15-40% of an organic surfactant from the group of nonionic, anionic and zwitterionic surfactants and mixtures thereof, based on the liquid detergent composition.

Synthetic anionic surfactants can be represented by the general formula rT50 ^ M, wherein R1 is a hydrocarbon group 6 89721 selected from the group consisting of straight or branched alkyl radicals having from about 8 to about 24 carbon atoms and alkylphenyl radicals having from about 9 to about 15 carbon atoms in the alkyl group. . M is a salt-forming cation, typically selected from the group consisting of sodium, potassium, ammonium, and mixtures thereof.

The preferred synthetic anionic surfactant is a water-soluble salt of alkylbenzenesulfonic acid having 9 to 15 carbon atoms in its alkyl group. Another preferred synthetic anionic surfactant is an alkyl sulfate or alkyl polyethoxylate ether sulfate having from about 8 to about 24, preferably from about 10 to about 18 carbon atoms in the alkyl group, and from about 1 to about 20, preferably from about 1 to about 12 ethoxy group, water-soluble salt. Other suitable anionic ten-15 bonds are described in U.S. Patent 4,170,565 to Flesher et al., Issued October 9, 1979.

Nonionic surfactants are usually prepared by condensing ethylene oxide with a hydrocarbon having a reactive hydrogen atom, e.g., a hydroxyl, carboxyl group or amido group, in the presence of an acidic or basic catalyst. Such compounds have the general formula RA (CH 0 CH 2) H, wherein R is a hydrophobic moiety, A is a group containing a reactive hydrogen atom, and n is the average number of ethylene oxide moieties. R typically contains about 25 to 8 to 22 carbon atoms. The compounds can also be prepared by condensing propylene oxide with a small molecule compound. n is usually about 2 to about 24.

The hydrophobic portion of the non-ionic compound is preferably a primary or secondary, straight or branched, aliphatic alcohol having from about 8 to about 24, preferably from about 12 to about 20 carbon atoms. Suitable nonionic surfactants are described in more detail in U.S. Patent 4,111,855. Mixtures of nonionic surfactants may be desirable.

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Zwitterionic surfactants are derivatives of aliphatic quaternary ammonium, phosphonium and sulfonium compounds, the aliphatic moiety of which may be straight-chain or branched and one aliphatic substituent containing from about 8 to about 24 carbon atoms and the other substituent containing at least one an anionic, water-soluble group. Particularly preferred zwitterionic materials are the ethoxylated ammonium sulfonates and sulfates described in U.S. Patents 3,925,262, Laughlin et al., Issued December 9, 1975, and 3,929,678, Laughlin et al., Issued December 30, 1975.

Semipolar nonionic surfactants include water-soluble amine oxides having one alkyl or hydroxyalkyl moiety of about 8 to about 28 carbon atoms and two moieties of alkyl groups and hydroxyalkyl groups having 1 to about 3 carbon atoms, which may optionally be attached to ring structures.

Suitable anionic synthetic surfactant salts are selected from the group consisting of sulfonates and sulfates. Such anionic detergents are known in the detergent industry and are widely used in commercial detergents. Preferred anionic synthetic water-soluble sulfonate or sulfate salts have an alkyl radical in the molecular structure containing from about 8 to about 22 carbon atoms.

. Examples of such preferred anionic surfactant salts are the reaction products obtained from C8-C18 fatty alcohols derived from sulfated tallow and coconut oil, alkylbenzenesulfonates having from about 9 to 15 carbon atoms in the alkyl group, sodium alkylglycene. 30 ethyl ether sulfonates, ether sulfates of fatty alcohols derived from tallow and coconut oil, coconut fatty acid pomonoglyceride sulfates and sulfonates, and paraffin sulfonates having from about 8 to about 22 alkyl chains. liatom, water-soluble salts. Sulfonated olefins. The dressings described in more detail in, e.g., U.S. Patent No. 8,397,221 to 3,332,880 are also useful. The neutralizing cations of the anionic synthetic sulfonates and / or sulfates can be conventional cations widely used in detergent technology, e.g. sodium and potassium.

In this connection, a particularly preferred anionic synthetic surfactant component consists of water-soluble salts of alkylbenzenesulfonic acid, preferably sodium alkylbenzenesulfonates having from about 10 to 13 carbon atoms in the alkyl group.

A preferred group of non-ionized ethoxylates is represented by a condensation product consisting of a fatty alcohol having 12 to 15 carbon atoms and about 4 to 10 moles of ethylene oxide per mole of fatty alcohol. Suitable varieties of this ethoxylate group 15 are the condensation product consisting of C Oxoalcohols and 7 moles of ethylene oxide per mole of alcohol, condensation product consisting of narrow-chain ^-C10 alcohols and 7 or 9 moles of ethylene oxide per fatty (oxo) alcohol-20 moles, condensation product of narrow-chain 2_-oxo-alcohols ) alcohol and 6.5 moles of ethylene oxide per mole of fatty alcohol, and condensation products; formed by a β-coconut fatty alcohol having a degree of ethoxylation (moles of ethylene oxide / 25 moles of fatty alcohol) in the range of 5 to 8. Fatty oxoalcohols are generally linear, but may have some content due to the processing conditions and the olefins used as feedstock. branches, especially short-chain ones such as methyl branches.

30 The degree of branching of commercial oxoalcohols is often 15-50% by weight.

Preferred non-ionized ethoxylated components may also be represented by a mixture of two separately ethoxylated non-ionized surfactants with different degrees of ethoxylation. An example is 9,897,221 nonionic ethoxylated surfactants having 3 to 7 moles of ethylene oxide per mole of hydrophobic moiety, and another ethoxylated variety having 8 to 14 moles of ethylene oxide per mole of hydrophobic moiety. The preferred ionized-5 mat ethoxylated mixture contains a lower ethoxylate, which is a condensation product formed by 2- to 3-oxo alcohol, a degree of branching of up to 50% by weight, and approx.

3-7 moles of ethylene oxide per mole of fatty oxoalcohol, and the higher ethoxylate, which is a condensation product formed by β-oxol alcohol, has a degree of decomposition of more than 50% by weight, and about 8 to 14 moles of ethylene. oxide per mole of branched oxoalcohol.

The liquid detergent compositions discussed herein optionally contain a cationic surfactant, preferably in a concentration of 0.1 to 4% by weight based on the composition.

Examples of suitable cationic surfactants are quaternary ammonium compounds of the formula R.j, in which R.j is C1-4-20 or hydroxy-alkyl, R2 is C1-4alkyl or C1-6alkyl. 2-20-3-C1-4-hydroxyalkyl or -4-hydroxyalkyl, R3 and R2 are each C1-6-alkyl or hydroxyalkyl or C1-8-aryl or alkylaryl and X is halogen. Single long chain quaternary amino acids are preferred. 25 compounds (i.e., compounds of the above formula, wherein R 2 is C 1-6 alkyl or hydroxyalkyl).

The liquid detergent compositions discussed herein. . optionally contain a fatty acid component as an enhancer. However, the amount of fatty acid is preferably '! Less than 5% by weight of the composition, more preferably less than 4%. Preferred saturated fatty acids have 10 to 16, more preferably 12 or 14 carbon atoms. Preferred unsaturated fatty acids are oleic acid and palmitic oleic acid.

Detergent enzymes may be used in the liquid detergent compositions of this invention. Indeed, one desirable feature of the present compositions is that they are compatible with such detergent enzymes. Suitable enzymes include detergent proteases, amylases, lipases and cellulases. Enzyme stabilizers are also known for use in aqueous liquid detergents. In this connection, a formic acid salt, e.g. sodium formate, is preferred. The amount of this stabilizer is typically in the range of 0.5 to 2%.

Preferred compositions contain an inorganic or organic enhancer. Examples of inorganic builders are phosphorus-based builders, e.g. sodium tripolyphosphate, sodium pyrophosphate and aluminosilicates (Zeolites).

Examples of organic enhancers are polyacids such as citric acid, nitrilotriacetic acid and mixtures of tartrate monosuccinate and tartrate disuccinate. Preferred enhancers useful herein include citric acid and alk (en) yl-substituted succinic acid compounds in which the alk (en) yl contains 10 to 16 carbon atoms. An example of this group of compounds is dodecenyl succinic acid. Polymeric carboxylate enhancers can also be used, e.g. polyacrylates, polyhydroxyacrylates and polyacrylate-poly-maleate copolymers.

The compositions discussed herein may contain a number of other optional ingredients, most often in an amount of "30" at the additive level, usually less than about 5%.

Examples of such additives are polyacids, enzymes and enzymatic stabilizers, foam control agents, opacifiers, agents which improve compatibility with the enamelled surfaces of the washing machine, bactericides, colorants, perfumes, brighteners and the like.

11 8 9 721 The liquid compositions discussed herein may contain other additives in a concentration of 0.05 to 2%.

These additives include polyaminocarboxylates such as ethylenediaminetetraacetic acid, diethylenetria-5-aminopentaacetic acid, ethylenediaminodisuccinic acid or their water-soluble alkali metal salts. Other additives include organophosphonic acids; particularly preferred are ethylenediaminotetramethylenephosphonic acid, hexamethylenediaminotetramethylenephosphonic acid, diethylenetriaminopentamethylenephosphonic acid and aminotrimethylenephosphonic acid.

Bleach stabilizers such as ascorbic acid, dipicolinic acid, sodium stannates and 8-hydroxyquinolin can also be added to these compositions at a concentration of 0.01-1%.

Advantageous use of the compositions of the invention under varying conditions of use may require the addition of a suds controlling agent. Although all foam control agents used in detergents can generally be used, alkylated polysiloxanes such as dimethylpolysiloxane, often referred to as silicones, are preferred herein. The amount of silicones used is often at most 1.5%, most preferably in the range 0.1 to 1.0%.

It may also be desirable to use opacifiers, especially because they contribute to the homogeneous appearance of concentrated liquid detergent compositions. Examples of suitable opacifiers are • j-polystyrene, sold under the trade name LYTRON 621. : Monsanto Chemical Corporation. The usual application rate of opacifiers is 0.3 to 1.5%.

The liquid detergent compositions of this invention may further contain an agent to improve compatibility with the washing machine, especially its enamelled surfaces.

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In addition, it may be desirable to add 0.1 to 1% of known anti-redeposition agents and / or compatibility enhancers. Examples of such additives are sodium carboxymethylcellulose, 5-hydroxy-C 1 -C 6 alkylcellulose, homopolymeric or copolymeric ingredients based on polycarboxylic acids such as polymaleic acid, maleic anhydride and mole 2 ethylenically unsaturated monocarboxylic acid monomer having up to 5, preferred! 3 or 4 carbon atoms, e.g. (meth) acrylic acid, and an ethylenically unsaturated dicarboxylic acid monomer having up to 6, preferably 4 carbon atoms, the molar ratio of monomers being in the range 1: 4 to 4: 1. Said copolymer is described in more detail in EP patent application 0 066 915, filed on 17 May 1982.

The physical stability of liquid detergent compositions can be improved by the addition of small amounts of saturated g_22 ~ fatty acid soaps or derivatives of such fatty acids such as esters or amides. Alkali metal soaps of g_22 fatty acids are preferred, typically in an amount of 0.1 to 2%. A suitable example is sodium stearate.

The following examples illustrate the invention and facilitate its understanding.

Liquid detergent compositions were prepared: · by mixing the listed ingredients in the indicated ratios: 13 8 9 721

Ingredient Composition (% by weight) I 11 lii II 1

Water 33 32 26 23 34

Ethanol 14 15 18 22 11 5 Linear dodecylbenzenesulphonic acid 12 10 8 8 12 Condensation product of 1 mole of C 1 -C 4 oxoalcohol and 7 moles of ethylene oxide 7 9 10 8 7

Sodium cocoyl sulphate 23 42 2

Dodecenylsuccinic acid 13 10 12 15 13 10 Citric acid 0.8 1 1 0.8 0.8 Oleic acid 3.3 4 3 2 3.3

Protease 0.3 0.5 - 0.5

Diethylenetriamine pentamethylenephosphobic acid 0.05 0.85 0.05 0.05 0.05

Sodium formate 0.9 1-1 15 Sodium perborate monohydrate 10 10 12 10 10 *)

Sodium hydroxide (to adjust pH) to pH 9 10 9 11 8.2

Perfume, · minor constituents ------ remaining —— - - - - *) sodium perborate tetrahydrate 14 89721

Ingredient Composition (% by weight) vi_ vn vjm ix x xi xn

Water 31 28 27 32 23 28 22

Ethanol 6.5 - 7 567 8 5 1-methoxy-2-propanol-14 3.5 - - 7 7

Isopropanol 6.5 --- 6--

Butyldiglycolether '.' - - 4.0 5

Linear dodecylbenzenesulfonic acid 11.4 12 7 13 12 10 9

Non-ionizing surfactant 7.2 7 11 3.5 58 7 10 Sodium cocooyl sulphate 3.1 2.5 2.5 3.0 4.0 3.0 2.0 TMS / TDS * - - - 6.5 3.5

Dodecenyl succinic acid 13.4 9 - - 7 8.5 9.5

Tetradecenyl succinic acid - 4 - - - - 1.0

Coconut fatty acid - - 16 1.0 1.0 15 Oleic acid 3.5 3.6 4.0 2.0 3.0 2.0 2.5

Citric acid 0.8 0.9 0.5 - 3.5 - 0.5 DTPMPA ** 0.9 0.5 0.5 - 0.4 0.8 1.5

Ethylenediaminetetraacetic acid - - - 1,0 0,4

Sodium tripolyphosphate - 15.0 - 20 Sodium perborate tetrahydrate - - 17

Sodium perborate monohydrate 9.0 10.4 9 13 - 13 19

Sodium formate 0.9 0.8 1.0 1.0 1.5 0.5 1.0

Protease 0.7 0.6 0.8 0.5 1.0 0.5 0.6! Sodium hydroxide ad to pH 9 10 11 11 9.5 10.5 10.5 25 Fragrance, minor constituents ------- rest -----—---- * mixture of tartrate monosuccinate and tartrate disuccinate 80:20 * * diethylenetriaminopentamethylenephosphonic acid is 89721

Ingredient Composition (% by weight) xiii xiv xv m_ xm xvm

Water 27 27 27 24 23.5 25

Ethanol 13 8 10 13 13 10

Co-solvent 1) -53--3 5 Linear dodecylbenzenesulfonic acid Condensation product consisting of 1 mol of C13-C15 oxoalcohol and 7 mol of ethylene oxide 7 7 777 7

Sodium cocoyl sulphate 1 1 111 1 10 Dodecenyl succinic acid 13 13 13 13 13 13

Citric acid 0.8 0.8 0.8 0.8 0.8 0.8 Oleic acid 333333

Protease 0.8 0.5 0.5 0.5 0.5 0.5

Diethylenetriamine inipentamethylene - 5 phosphonic acid 0.7 0.7 0.7 0.7 0.7 0.7

Sodium stearate

Sodium formate 1.0 1.0 1.0 1.0 1.0 1.0 1.0

Sodium perborate monohydrate 14.0 14.0 14.0 14.0 14.0 14.0 C12-C14-Nimethyl ammonium oride - - - 2.0 - 20 C12-C14- (2-hydroxyethyl) dimethylammonium chloride - 2.0

Cj- (2-hydroxyethyl) dimethylammonium chloride - - - - - 2,0 ** · "Sodium hydroxide ad to pH 10 10 10 10 10 10 • ** 25 Perfume, minor constituents -----— rest - - - - - - - 1) selected from the group consisting of PEG 150, 200, 300, 400 / dipropylene glycol, hexylene glycol, n-ptopanol, isopropanol, methoxyethanol, ethoxyethanol, butoxyethanol, ethyldiol glycol, butyldiglycol ether, butoxyalcohol, benzoxyalcohol, benzyl - propanol

Claims (12)

A liquid bleach-containing detergent composition which contains anionic surfactants and has a pH of at least 8, wherein said composition contains, based on the weight of the composition, a predetermined amount of a solid, water-soluble peroxy compound in the form of a suspension. liquid phase, which consists of a solvent system comprising water and at least one water-miscible organic solvent, characterized in that the amount of the oxygen dissolved in the liquid phase is not more than 0.5% by weight, calculated on the liquid phase, and corresponds to a maximum of one-fifth of the amount of the peroxy compound in the composition. Liquid detergent composition according to claim 1, characterized in that the amount of active oxygen present in the liquid phase is not more than 0.1% by weight, calculated on the liquid phase. Liquid detergent composition according to claim 1 or 2, characterized in that the amount of the active dissolved oxygen in the liquid phase corresponds to at most one tenth of the amount of the peroxy compound. Liquid detergent composition according to claim 1, 2 or 3, characterized in that the water-miscible organic solvent is an aliphatic monoalcohol. Liquid detergent composition according to claim 4, characterized in that the water-miscible organic solvent is ethanol. Liquid detergent composition according to claim 5, characterized in that the solvent contains water and ethanol in a ratio of 8: 1 to 1: 3 ethanol water. Liquid detergent composition according to claim 6, characterized in that the poured water into ethanol is 5: 1 - 1: 2. 19 S 9 721 Liquid detergent composition according to any one of the preceding claims, characterized in that the solid, water-soluble peroxy compound is perborated. Liquid detergent composition according to any one of the preceding claims, characterized in that it has a pH of at least 9. Liquid detergent composition according to claim 9, characterized in that it has a pH of at least 9.5. Liquid detergent composition according to any of the preceding claims, characterized in that it contains less than 4% of fatty acid. Liquid detergent composition according to any one of the preceding claims, characterized in that the composition contains 5 - 40% of a builder substance selected from the group of dodecyl succinic acid, tetradecyl succinic acid, dodecyl succinic acid, 80:20 mixture of tartrate monosodate and tartrate monosodate. citric acid and mixtures thereof.