JPH08109394A - Detergent composition - Google Patents

Abstract

PURPOSE: To obtain a detergent composition capable of preventing itch of body and scalp and providing deodorizing effect, having excellent cleaning power, foaming properties, low irritation and excellent sterilizing power, containing a specific polyoxyethylene-based nonionic surfactant, specific other nonionic and betaine type surfactants and a germicide. CONSTITUTION: This composition contains (A) 5-50wt.% surfactant of the formula R<1> O-(CH2 CH2 O)n H (R<1> is a 11-15C alkyl, etc.; (n) is 11-30), (B) 1-10wt.% betaine type surfactant, (C) 1-10wt.% surfactant which is a compound of formula I (R<2> is a 8-18C alkyl), a compound of the formula R<3> -(OR<4> )s -Gt (R<3> is a 6-18C alkyl, etc.; R<4> is a 2-4C alkylene; G is a residue derived from a 5-6C reducing saccharide; (s) is 0-10; (t) is 1-10), a compound of formula II [one of R<5> to R<7> is a group of the formula O=CR<8> (R<8> is R<3> ) and the others are H] or a compound of formula III (R<9> is a 8-16C alkyl, etc.; one of (u) and (Y) is 0-10 and the other is 1-10) and (D) 0.01-10wt.% cationic germicide in the weight ratio of the composition A/(B+C) of 1/1-10/1.

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a detergent composition, and more specifically, it has excellent detergency and foaming properties, is mild, and can contain a cationic germicide in a stable manner. The present invention relates to a detergent composition capable of imparting sufficient anti-dandruff properties to the scalp, antipruritic properties to the body and scalp, and deodorizing / deodorizing effects because of exerting a high bactericidal effect.

[0002]

2. Description of the Related Art Conventional cleaning agents, particularly hair cleaning agents,
Anionic surfactants are often used as the main base because of their excellent detergency and foaming power. However, since anionic surfactants are highly irritating, they are often used in combination with a hypoallergenic active agent when blended in a hair cleansing agent, and a milder hair cleansing agent is desired. ing.

Many cleaning agents having a bactericidal effect have been studied, and those using a cationic bactericide as a bactericide are known. However, when a cationic bactericidal agent is added to a detergent containing an anionic surfactant as a main base, a complex of the cationic bactericidal agent and the anionic surfactant is formed, so that the compounding is difficult. ,
There is a problem that the bactericidal effect is not sufficiently expressed.

For this reason, a cleaning agent based on a nonionic surfactant, which is less irritating than an anionic surfactant and is easy to mix with a cationic bactericide, has been studied. For example, a detergent composition (Japanese Patent Publication No. 6-23087) containing an alkyl saccharide-based nonionic surfactant and an antibacterial agent is known as an alkyl saccharide-based nonionic surfactant. .

However, since alkyl saccharide-based nonionic surfactants are relatively expensive, attempts have also been made to blend polyoxyethylene alkyl ether type nonionic surfactants, which are generally cheaper than these, into detergents. However, since polyoxyethylene alkyl ether type nonionic surfactants generally have poor foaming properties, they are rarely used in hair detergents, and amidoamine type amphoteric activators or alkylolamide type nonionic activators are the main active agents. Shampoo composition containing a polyoxyethylene type activator as an auxiliary ingredient (Japanese Patent Laid-Open No. 55-25
No. 436) is known.

[0006]

SUMMARY OF THE INVENTION Therefore, the object of the present invention is to obtain a high bactericidal effect, which is excellent in detergency and foamability, has low irritation, and can be stably blended with a cationic bactericide. An object of the present invention is to provide a cleaning composition that can be used.

[0007]

Under such circumstances, the inventors of the present invention have conducted diligent research and, as a result, have found that a specific polyoxyethylene alkyl ether type nonionic surfactant, a betaine type surfactant and a specific nonionic surfactant are used. By combining the agent with a specific ratio, and further combining this with a cationic bactericide, it has high detergency, high foaming property and low irritation.
Moreover, they have found that a detergent composition capable of imparting sufficient antidandruff properties, antipruritic properties, and deodorizing / deodorizing effects can be obtained, and completed the present invention.

That is, the present invention provides the following component (A),
(B), (C) and (D): (A) General formula (1);

[0009]

[Chemical Formula 8] R ¹ O- (CH ₂ CH ₂ O) _n -H (1)

(In the formula, R ¹ represents a linear or branched alkyl group or alkenyl group having 11 to 15 carbon atoms, and n is 1
5 to 50 wt% of a polyoxyethylene alkyl ether type nonionic surfactant represented by the formula (1 to 30), (B) betaine type surfactant
1 to 10% by weight, (C) general formulas (2) to (5);

[0011]

[Chemical 9]

(In the formula, R ² represents a linear or branched alkyl group or alkenyl group having 8 to 18 carbon atoms)

[0013]

[Chemical Formula 10] R ^3- (OR ⁴ ) _s -G _t (3)

(In the formula, R ³ represents a linear or branched alkyl or alkenyl group having 6 to 18 carbon atoms, R ⁴ represents an alkylene group having 2 to ⁴ carbon atoms, and G represents 5 or 5 carbon atoms. 6
Is a reducing sugar-derived residue, s is an integer of 0 to 10,
(t is a number from 1 to 10)

[0015]

[Chemical 11]

(In the formula, only one of R ⁵ , R ⁶ and R ⁷ is O = CR ⁸ (R ⁸ represents a linear or branched alkyl or alkenyl group having 6 to 18 carbon atoms) , And the other two represent hydrogen atoms.)

[0017]

[Chemical 12]

(In the formula, R ⁹ represents a linear or branched alkyl or alkenyl group having 8 to 16 carbon atoms, and u and v
Each represents an integer of 0 to 10, and at least one of u and v is 1 or more), 1 type or 2 or more types selected from the nonionic surfactants represented by 1 to 10% by weight, (D) cationic Fungicide
0.01 to 10% by weight, and the weight ratio of (A) / [(B) + (C)] is 1 /
The present invention provides a detergent composition which is 1 to 10/1.

The present invention also provides the above-mentioned components (A) to (D).
In addition, 0.5 parts of the component (D) cationic fungicide
The present invention provides a detergent composition containing a metal chelating agent in an amount equal to or more than twice the molar amount of the metal chelating agent.

The component (A) polyoxyethylene alkyl ether type nonionic surfactant used in the present invention is
It is represented by the general formula (1), wherein R ¹
Examples of the linear or branched alkyl group or alkenyl group having 11 to 15 carbon atoms represented by are undecyl groups,
Examples thereof include dodecyl group, tridecyl group, tetradecyl group, pentadecyl group, undecenyl group, dodecenyl group, tridecenyl group, tetradecenyl group and pentadecenyl group. As the component (A), the carbon number of R ¹ is 11 to ¹
5 and the number n of ethylene oxide added is 11 to 30
It is necessary to satisfy the following conditions, and sufficient detergency and foamability cannot be obtained outside this range. Of these, those in which R ¹ has 12 to 14 carbon atoms and n is 15 to 25 are preferable because higher foaming property can be obtained.

The polyoxyethylene alkyl ether type nonionic surfactant of the component (A) serves as the main base of the detergent composition of the present invention, and is contained in an amount of 5 to 50% by weight (hereinafter, simply %), Preferably 7 to 30%, particularly preferably 10 to 20%. If it is less than 5%, sufficient cleaning performance and foamability cannot be obtained, and if it exceeds 50%, the viscosity of the detergent becomes high and it becomes difficult to blend other components, which is not preferable.

The betaine-type surfactant of the component (B) used in the present invention may be any of carbobetaine-type, sulfobetaine-type, imidazolinium-betaine-type and the like, among which the general formula (8)

[0023]

[Chemical 13]

(Wherein R ¹³ is a linear or branched alkyl or alkenyl group having 8 to 20 carbon atoms or R ¹⁴ C
ONH (CH ₂ ) _z- (R ¹⁴ represents a linear or branched alkyl group or alkenyl group having 8 to 20 carbon atoms, z represents an integer of 1 to 5), and M represents A hydrogen atom, an alkali metal or triethanolamine, and y represents an integer of 1 to 5), a carbobetaine-type surfactant represented by the general formula (9)

[0025]

Embedded image

(In the formula, R ¹⁵ represents a linear or branched alkyl group or alkenyl group having 8 to 20 carbon atoms, and M and y
Represents the same meaning as described above) and is preferably a sulfobetaine-type surfactant. Further, a carbobetaine type surfactant represented by the general formula (8) is preferable, and among them, a fatty acid amide propyl betaine in which R ¹³ is R ¹⁴ CONH (CH ₂ ) ₃ — in the general formula (8) is preferable.

The betaine type surfactant as the component (B) is contained in the entire composition in an amount of 1 to 10%, preferably 1 to 5%, particularly preferably 1 to 3%. If it is less than 1%, sufficient detergency and foamability cannot be obtained, and if it exceeds 10%, it is not preferable in terms of irritation.

The nonionic surfactant as the component (C) used in the present invention is an alkyldimethylamine oxide represented by the general formula (2), an alkyl saccharide represented by the general formula (3), or a general formula (4). And a alkanolamide represented by the general formula (5). As the alkyldimethylamine oxide represented by the general formula (2),
In the formula, R ² is preferably an alkyl group having 10 to 16 carbon atoms, and particularly preferably a decyl group, a lauryl group or a myristyl group. In the alkyl saccharide represented by the general formula (3), in the formula, R ³ has 10 to 14 carbon atoms.
The alkyl group of is preferably a decyl group, a dodecyl group,
A tetradecyl group is preferable, and R ⁴ is preferably an ethylene group or a propylene group. The structure of G is determined by a monosaccharide or a saccharide having two or more sugars used as a raw material, and glucose, galactose and fructose are particularly preferable. s is preferably 0 to 2, and t is preferably 1 to 2. As the alkyl saccharide (3), s = 0
And an alkyl polyglucoside in which G is a residue derived from glucose is preferable. In the fatty acid monoglyceride represented by the general formula (4), R ^{8 in} the formula has 8 carbon atoms.
It is preferably -12. As the alkanolamide represented by the general formula (5), in the formula, R ⁹ has 10 carbon atoms.
-14 are preferable, and u and v are preferably 0-3.

Of these, the alkyldimethylamine oxide represented by the general formula (2) and the fatty acid monoglyceride represented by the general formula (4) are preferable because the foamability can be further enhanced, and the general formula (4) Among the fatty acid monoglycerides represented by), decanoic acid monoglyceride and lauric acid monoglyceride are preferable.

The nonionic surfactant as the component (C) can be used alone or in combination of two or more kinds, and it is particularly preferable to use in combination of two or more kinds because the foaming property can be further enhanced. . The nonionic surfactant as the component (C) is blended in an amount of 1 to 10%, preferably 1 to 5% in the total composition. If it is less than 1%, sufficient detergency and foamability cannot be obtained, and if it exceeds 10%, detergency may be impaired.

Further, in the detergent composition of the present invention,
The blending amount of the component (A) is a weight ratio (A) / [(B) + (C)] to the total blending amount of the components (B) and (C),
It is necessary to be in the range of 1/1 to 10/1, and if it is out of this range, the cleaning performance, the foaming property and the low irritation cannot be exhibited at the same time. This weight ratio is preferably 3/2 to 3/1 because the foaming property is further enhanced.

Examples of the cationic bactericide of the component (D) used in the present invention include, for example, the following general formula (6) or (7)
The thing represented by is mentioned.

[0033]

[Chemical 15]

An alkyl group represented by (at least one of R ¹¹ and R ¹² represents a linear or branched alkyl or alkenyl group having 6 to 20 carbon atoms, and the rest represents a hydrogen atom, a methyl group or an ethyl group) Indicates phosphoric acid]

Specific examples thereof include benzalkonium chloride, benzalkonium monoalkyl phosphate, benzethonium chloride, cetylpyridinium chloride, and the like, particularly those represented by the general formula (6), for example, benzalcochloride. , Benzalkonium monoalkyl phosphate and benzethonium chloride are preferred, and further, the compound represented by the general formula (6 ′)

[0036]

Embedded image

A benzalkonium type germicide represented by:
For example, benzalkonium chloride and benzalkonium monoalkylphosphoric acid are preferable.

The cationic bactericide of the component (D) can be used alone or in combination of two or more kinds, and is 0.01 to 10%, preferably 0.01 to 5%, and particularly preferably in the total composition. Is added in an amount of 0.1 to 5%. If it is less than 0.01%, a sufficient bactericidal effect cannot be obtained, and if it exceeds 10%, it is not preferable in terms of irritation.

The detergent composition of the present invention may further contain a metal chelating agent, whereby even if an anionic substance is present in the hair or the like, a cationic bactericidal agent is added. A more sufficient bactericidal effect can be obtained without lowering the activity. The metal chelating agent is not particularly limited as long as it has the ability to chelate metal ions, and examples thereof include ethylenediaminetetraacetic acid, hydroxyethylethylenediaminetriacetic acid, diethylenetriaminepentaacetic acid, nitrilotriacetic acid, triethylenetetraminehexaacetic acid, and phosphone. Acids, tripolyphosphoric acid, ethylene glycol bis (2-aminoethyl ether) tetraacetic acid, citric acid, maleic acid, polyacrylic acid, isoamylene-maleic acid copolymer, silicic acid, gluconic acid, hydroxybenzyliminodiacetic acid,
Examples include iminodiacetic acid and salts thereof. Of these, ethylenediaminetetraacetic acid, hydroxyethylethylenediaminetriacetic acid, citric acid, tripolyphosphoric acid or salts thereof are particularly preferable.

When compounding these metal chelating agents,
It is preferable to add 0.5 times or more, particularly 0.5 to 2 times, and further 1 to 2 times the mol of the cationic bactericide of the component (D). When the metal chelating agent is blended in an amount of 0.5 times the mole of the component (D) or more, even if an anionic substance is present in the hair, the reduction of the bactericidal effect can be sufficiently suppressed.

In addition, the detergent composition of the present invention may contain an anionic surfactant which is usually used in detergents, as long as the effect of the present invention is not impaired. Examples of such anionic surfactants include alkyl sulfates, alkyl ether sulfates, alkyl sulfonates, sulfosuccinates, α-sulfo fatty acid ester salts, α-olefin sulfonates, saturated or unsaturated fatty acid salts, and monophosphoric acid salts. Examples thereof include ester type surfactants and acylated amino acids.

Further, the cleaning composition of the present invention can contain a silicone derivative in a range that does not impair the effects of the present invention, and a good slippery feel and a smooth feel can be obtained. The silicone derivative is not particularly limited as long as it is usually blended in detergents and cosmetics, and examples thereof include dimethylpolysiloxane, methylphenylpolysiloxane, polyether-modified silicone, epoxy-modified silicone, alkoxy-modified silicone, amino-modified silicone. Etc.

Furthermore, in the detergent composition of the present invention, in addition to the above-mentioned components, if necessary, components usually added to cosmetics, pharmaceuticals, foods, etc., such as anti-dandruff agents, bactericides and anti-inflammatory agents. Agents, medicinal agents, preservatives; humectants such as propylene glycol, glycerin, diethylene glycol monoethyl ether, sorbitol, panthenol; coloring agents such as dyes and pigments; conditioning agents such as perfluoropolyether; pearling agents, hydroxypropyl Chitosan derivatives such as chitosan; various blended fragrances; other encyclopedia of shampoo ingredients [E
NCYCLOPEDIA OF SHAMPOO IN
GREDIENTS (MICELLE PRESS 1
985)] and the like can be appropriately blended within a range that does not impair the effects of the present invention.

The detergent composition of the present invention can be produced by a conventional method, and can be made into a paste, gel, liquid, or other dosage form. Further, it is suitable as a detergent for hair and body, and particularly suitable as a detergent for hair.

[0045]

The detergent composition of the present invention is excellent in detergency and foaming property, has low irritation, and can contain a cationic bactericide stably, and exhibits a high bactericidal effect. Therefore, sufficient anti-dandruff properties can be imparted to the scalp, and antipruritic properties and deodorant / deodorant effects can be imparted to the body and the scalp.

[0046]

The present invention will be described in more detail below with reference to examples, but the present invention is not limited to these examples.

Example 1 Shampoos having the compositions shown in Tables 1 to 4 were produced by a conventional method, and their cleaning properties, foaming properties and anti-dandruff properties were evaluated. The results are shown in Tables 1 to 4.

(Evaluation Method) Detergency: 20 g (15 cm) of hair of a healthy Japanese woman was coated with 1 g of shampoo liquid, washed for 1 minute, and the feeling after rinsing was evaluated by 20 professional panelists according to the following criteria. It was evaluated by. ⊚: Very good (90% or more of the people evaluated that the detergency was good). ◯: Good (80 to less than 90% of the people evaluated that the detergency was good). Δ: Slightly poor (70 to 80% or less of people evaluated that the detergency was good). X: Poor (less than 70% of people evaluated that the cleaning power was good).

Foaming property: 800 ml of a 20-fold diluted shampoo solution (liquid temperature: 20 ° C.) was poured into a cylinder, a stirring blade was placed in the solution and rotated for 5 minutes, then allowed to stand for 30 seconds and foamed. Was evaluated according to the following criteria. The rotation speed of the stirring blade was 1000 rpm and it was reversed every 5 seconds. A: Very good foaming. ○: Good foaming. Δ: Foaming, but felt insufficient. X: Almost no foaming.

Anti-dandruff property: Ten professional panelists evaluated the anti-dandruff effect when each shampoo was used once a day for 2 weeks, according to the following criteria. A: Nine or more people felt that dandruff had decreased. ○: 8 people felt that dandruff decreased. Δ: Seven people felt that dandruff decreased. X: Six or less people felt that dandruff decreased.

[0051]

[Table 1]

[0052]

[Table 2]

[0053]

[Table 3]

[0054]

[Table 4]

Example 2 (Shampoo) A shampoo having the following composition was produced by a conventional method. The obtained shampoo was excellent in detergency and foamability, and had a high anti-dandruff effect.

[0056]

[Table 5] (Components) (%) Polyoxyethylene (15) lauryl ether 10.0 Lauryl hydroxysulfobetaine 1.0 Alkyl glucoside ¹⁾ 4.0 Decanoic acid monoglyceride 3.0 Cationized cellulose ²⁾ 0.3 Hydroxy Ethyl cellulose ³⁾ 0.1 benzalkonium chloride ⁴⁾ 1.0 Perfume proper amount water balance 100.0 1): In the general formula (3), R ³ = C ₁₀ H ₂₁ , s = 0, G = glucose residue, t = 1.4 2): JR400 (manufactured by UCC) 3): HEC-SE850 (manufactured by Shin-Etsu Chemical Co., Ltd.) 4): Sanizole C (manufactured by Kao)

Example 3 (Shampoo) A shampoo having the following composition was produced by a conventional method. The obtained shampoo had excellent cleaning performance and foaming property, and also had a high anti-dandruff effect.

[0058]

(Table 6) (Components) (%) Polyoxyethylene (20) lauryl ether 10.0 Lauryl dimethylamine oxide 1.0 Lauric acid amidopropyl betaine 3.0 Lauric acid monoglyceride 2.0 Benzalkonium chloride ⁵⁾ 1. 0 Silicone emulsion ⁶⁾ 2.0 Fragrance, proper amount of water Balance 100.0 5): Sanizole C (manufactured by Kao) 6): BY22-029 (manufactured by Toray Dow Corning)

Example 4 (Body shampoo) A body shampoo having the following composition was produced by a conventional method. The obtained body shampoo had excellent cleaning performance and foaming performance, and also had excellent antipruritic effects and excellent deodorizing and deodorizing effects.

[0060]

[Table 7] (Components) (%) Polyoxyethylene (20) myristyl ether 15.0 Lauroyl diethanolamide 3.0 Lauric acid amide propyl betaine 2.0 Decanoic acid monoglyceride 2.0 Ethylenglycol distearate 1.0 Alkyl phosphorus Acid benzalkonium ⁷⁾ 1.5 Perfume proper amount water balance 100.0 7): Sanizole P (manufactured by Kao Corporation)

Example 5 (Shampoo) A shampoo having the composition shown below was produced by a conventional method. The obtained shampoo had excellent cleaning performance and foaming property, and also had a high anti-dandruff effect.

[0062]

Table 8 (Components) (%) Polyoxyethylene (20) lauryl ether 8.0 Lauric acid amidopropyl betaine 2.0 Alkyl glucoside ⁸⁾ 2.0 Polyoxyethylene (3) lauryl ether sulfate-sodium 4.0 Cationized cellulose ⁹⁾ 0.2 Benzalkonium chloride 1.0 1.0 Dipotassium ethylenediaminetetraacetate 1.0 Perfume water balance 100.0 8): In the general formula (3), R ³ = C ₁₀ H ₂₁ , S = 0, G = glucose residue, t = 1.49): JR400 (manufactured by UCC)

─────────────────────────────────────────────────── ─── Continuation of the front page (51) Int.Cl. ⁶ Identification code Internal reference number FI technical display location C11D 1/75 1/90 3/48

Claims (11)

[Claims] 1. The following components (A), (B), (C) and (D): (A) General formula (1); embedded image R ¹ O— (CH ₂ CH ₂ O) _n − Polyoxyethylene alkyl ether type represented by H (1) (wherein R ¹ represents a linear or branched alkyl group or alkenyl group having 11 to 15 carbon atoms, and n represents a number of 11 to 30) 5 to 50% by weight of nonionic surfactant, (B) betaine-type surfactant
1 to 10% by weight, (C) general formulas (2) to (5); (In the formula, R ² represents a linear or branched alkyl or alkenyl group having 8 to 18 carbon atoms) embedded image R ³ — (OR ⁴ ) _s —G _t (3) (wherein R 2 ³ represents a linear or branched alkyl or alkenyl group having 6 to 18 carbon atoms, R ⁴ represents an alkylene group having 2 to ⁴ carbon atoms, and G represents a residue derived from a reducing sugar having 5 or 6 carbon atoms. Represents a group, s is an integer of 0 to 10, and t is 1 to 10.
The number of) (In the formula, only one of R ⁵ , R ⁶ and R ⁷ is O = CR
⁸ (R ⁸ represents a linear or branched alkyl group or alkenyl group having 6 to 18 carbon atoms), and the remaining two represent hydrogen atoms. (In the formula, R ⁹ represents a linear or branched alkyl group or alkenyl group having 8 to 16 carbon atoms, and u and v are 0 respectively.
1 to 10% by weight, which is an integer of 10 to 10 and at least one of u and v is 1 or more) selected from nonionic surfactants represented by (D) a cationic bactericide.
0.01 to 10% by weight, and the weight ratio of (A) / [(B) + (C)] is 1 /
The cleaning composition which is 1 to 10/1. 2. In the general formula (1), R ¹ has ¹ carbon atom.
The cleaning composition according to claim 1, which is a linear or branched alkyl group or an alkenyl group of 2 to 14, and n is a number of 15 to 25. 3. The cleaning composition according to claim 1 or 2, wherein the component (B) is a carbobetaine-type amphoteric surfactant. 4. The component (C) is represented by the general formula (2) or (4).
4. A nonionic surfactant represented by
The cleaning composition according to any one of 1. 5. The cleaning composition according to claim 1, wherein the weight ratio of (A) / [(B) + (C)] is 3/2 to 3/1. 6. The component (D) is represented by the general formula (6) or (7): (At least one of R ¹¹ and R ¹² represents a linear or branched alkyl group or alkenyl group having 6 to 20 carbon atoms, and the rest represents a hydrogen atom, a methyl group or an ethyl group). The cleaning composition according to any one of claims 1 to 5, which is a cationic bactericide represented by the following formula. 7. The component (D) has the general formula (6 ′): A benzalkonium type bactericide represented by:
The cleaning composition according to claim 1. 8. The cleaning composition according to claim 1, which contains the component (D) in an amount of 0.01 to 5% by weight. 9. The composition further contains a metal chelating agent in an amount of at least 0.5 times the molar amount of the cationic bactericide as the component (D).
9. The cleaning composition according to any one of items 8 to 8. 10. The metal chelating agent is ethylenediaminetetraacetic acid, hydroxyethylethylenediaminetriacetic acid, diethylenetriaminepentaacetic acid, nitrilotriacetic acid, triethylenetetraminehexaacetic acid, phosphonic acids, tripolyphosphoric acid, ethyleneglycolbis (2-aminoethylether) tetra. The washing according to claim 9, which is selected from acetic acid, citric acid, maleic acid, polyacrylic acid, isoamylene-maleic acid copolymer, silicic acid, gluconic acid, hydroxybenzyliminodiacetic acid, iminodiacetic acid and salts thereof. Agent composition. 11. The detergent composition according to claim 9, wherein the metal chelating agent is selected from ethylenediaminetetraacetic acid, hydroxyethylethylenediaminetriacetic acid, tripolyphosphoric acid, citric acid and salts thereof.