JP2015000894A - Liquid detergent composition - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a liquid detergent with little yellow discoloration without using sodium sulfite having an influence on a dye.SOLUTION: This invention provides a liquid detergent composition comprising (A) component: nonionic surfactant, (B) component: fatty acid and or salt thereof, (C) component: specific nonionic compound, (D) component: at least one or more selected from metal oxide or metal salt, and (E) component: aminocarboxylic acid and or salt thereof.

Description

  The present invention relates to a liquid detergent composition.

Liquid detergents tend to color when stored. Causes include surfactants, fragrances, alkali agents and the like. Therefore, it is known that a reducing compound such as sodium sulfite is blended as a hue stabilizer (yellowing inhibitor) (for example, Patent Document 1). On the other hand, it is known that a liquid cleaning agent is colored for the purpose of being easily measured when filling a transparent container or when weighing. However, when a reducing agent such as sulfite is blended to prevent coloring, there is a problem that the hue changes in a system blended with a pigment.
In recent years, so-called "compact type" cleaning agents, which contain a high concentration of surfactant and have a small amount of one-time use, have become mainstream in consideration of environmental factors and convenience at the time of purchase. . In these “compact” liquid detergents, liquid detergents containing a high concentration of nonionic surfactant have been actively developed. However, sufficient research has been conducted on the stabilization of the hue of liquid detergents. No (for example, Patent Documents 2 to 5).

JP 2009-173700 A JP2009-155594A JP 2009-84479 A JP2011-168730A JP2011-132331A

  An object of the present invention is to provide a liquid cleaning agent that does not use sodium sulfite that affects the pigment and causes little yellowing.

  As a result of intensive studies, the present inventors have found that the component (A) which is a nonionic surfactant, the fatty acid represented by the following general formula (1) and / or the salt thereof (B) component, and the following general formula The compound (C) represented by (2), at least one (D) component selected from metal oxides or metal salts, and an aminocarboxylic acid and / or a salt thereof (E) A liquid detergent composition is proposed.

R ⁵ COOH (1)
(In the formula, R ⁵ is a linear or branched alkyl or alkenyl group having 7 to 17 carbon atoms.)
_{^{R 4 O- (C 2 H 4}} O) n2 -H (2)
(In the formula, R ⁴ is H or an alkyl group having 1 to 3 carbon atoms, and n2 represents the average number of moles of ethylene oxide added and is 1 to 30000.)

    According to the liquid detergent composition of the present invention, discoloration due to storage is suppressed.

The liquid cleaning composition of the present invention comprises a component (A) which is a nonionic surfactant, a fatty acid represented by the following general formula (1) and / or a salt (B) component thereof, and the following general formula ( 2) The compound (C) component represented by 2), at least one (D) component selected from metal oxides or metal salts, and an aminocarboxylic acid and / or a salt thereof (E) Is.
<(A) component>
Any nonionic surfactant may be used as long as it is conventionally used in a liquid detergent. Examples thereof include polyoxyalkylene type nonionic surfactants, alkylene oxide adducts such as alkylphenols and higher amines, polyoxyethylene polyoxy Propylene block copolymer, fatty acid alkanolamine, fatty acid alkanolamide, polyhydric alcohol fatty acid ester or its alkylene oxide adduct, polyhydric alcohol fatty acid ether, alkyl (or alkenyl) amine oxide, alkylene oxide adduct of hydrogenated castor oil, sugar fatty acid ester N-alkyl polyhydroxy fatty acid amides, alkyl glycosides and the like. These nonionic surfactants may be used individually by 1 type, and may be used in combination of 2 or more type.

Among the above, the nonionic surfactant is preferably a polyoxyalkylene type nonionic surfactant in terms of viscosity and liquid stability.
Examples of the polyoxyalkylene type nonionic surfactant include a compound represented by the following general formula (3) (hereinafter sometimes referred to as compound (3)).
R ¹ -X- (EO) _s (PO) _t -R ² (3)
[In the formula (3), R ¹ is a hydrocarbon group having 8 to 22 carbon atoms, -X- is a divalent linking group, R ² is a hydrogen atom, an alkyl group having 1 to 6 carbon atoms, or carbon. It is an alkenyl group of formula 2-6. EO is an oxyethylene group, and s is a number from 3 to 20 representing the average number of repetitions of EO. PO is an oxypropylene group, and t is a number from 0 to 6 representing the average number of repetitions of PO. ]
In formula (I), the carbon number of the hydrocarbon group ^{R 1} is preferably 10 to 18. The hydrocarbon group for R ¹ may be linear or branched, and may or may not have an unsaturated bond.
Examples of —X— include —O—, —COO—, —CONH— and the like.
The number of carbon atoms in the alkyl group in R ² is 1-6, 1-3 are preferred.
The number of carbon atoms of the alkenyl group in R ² is 2-6, preferably 2-3.
Compound (I) in which —X— is —O—, —COO— or —CONH— is a primary or secondary higher alcohol (R ¹ —OH), higher fatty acid (R ¹ —COOH) or higher fatty acid amide (R ¹ -CONH) is obtained as a raw material. Higher grades have 6 or more carbon atoms.
s is the number of 3-20 showing the average number of repetitions of EO (namely, the average addition mole number of ethylene oxide), and 5-18 are preferable. If it exceeds the above upper limit value, the HLB value may become too high and the detergency against sebum may be reduced, and if it is less than the above lower limit value, odor may be deteriorated.
t is a number from 0 to 6 that represents the average number of repeating POs (that is, the average number of moles of propylene oxide added), and preferably 0 to 3. Above the upper limit, the liquid stability of the liquid detergent at high temperatures tends to be reduced.
When t is 1 or more, that is, when compound (3) has EO and PO, the addition method of ethylene oxide and propylene oxide is not particularly limited, and may be, for example, a random addition method or a block addition method. Block addition methods include, for example, a method of adding propylene oxide after adding ethylene oxide, a method of adding propylene oxide after adding propylene oxide, an ethylene oxide addition, adding propylene oxide, and further adding ethylene oxide. The method of adding etc. is mentioned.
The addition mole number distribution of ethylene oxide or propylene oxide is not particularly limited.
The added mole number distribution is likely to vary depending on the reaction method in producing the nonionic surfactant. For example, when ethylene oxide or propylene oxide is added to a hydrophobic raw material using a general alkali catalyst such as sodium hydroxide or potassium hydroxide, the distribution of the number of moles of ethylene oxide or propylene oxide added is relatively wide. It tends to be. Also, specific alkoxylation such as magnesium oxide to which metal ions such as Al ³⁺ , Ga ³⁺ , In ³⁺ , Tl ³⁺ , Co ³⁺ , Sc ³⁺ , La ³⁺ , Mn ^{2+ and the} like described in Japanese Patent Publication No. 6-15038 are added. When ethylene oxide or propylene oxide is added to a hydrophobic group raw material using a catalyst, the distribution of the number of moles of ethylene oxide or propylene oxide tends to be relatively narrow.
As the compound (3), in particular, a compound in which —X— is —O— (alcohol-type nonionic surfactant), or —X— is —COO—, and R ² is an alkyl having 1 to 6 carbon atoms. And a compound (fatty acid alkyl (alkenyl) ester) which is a group or an alkenyl group having 2 to 6 carbon atoms is preferred.
When -X- is -O-, the carbon number of R ¹ is preferably 10-22, more preferably 10-20, and still more preferably 10-18.
When -X- is -O-, R ² is preferably a hydrogen atom.
When -X- is -COO-, the carbon number of R ¹ is preferably 9-21, more preferably 11-21.
When -X- is -COO-, R ² is preferably an alkyl group having 1 to 6 carbon atoms or an alkenyl group having 2 to 6 carbon atoms, and more preferably an alkyl group having 1 to 3 carbon atoms.
As the compound (3) in which —X— is —O— or —COO—, for example, Diadol (trade name, C13 (C represents the number of carbon atoms; hereinafter the same)) manufactured by Mitsubishi Chemical Corporation, Shell Add 12 mole equivalent or 15 mole equivalent of ethylene oxide to alcohol such as Neodol (trade name, mixture of C12 and C13), Sasol 23 (trade name, mixture of C12 and C13) manufactured by Sasol. A product obtained by adding 12 mol or 15 mol of ethylene oxide to a natural alcohol such as CO-1214 or CO-1270 (trade name) manufactured by Procter & Gamble Co .; 7 mol equivalent of ethylene oxide was added to C13 alcohol obtained by subjecting the obtained C12 alkene to the oxo process. (Trade name: Lutensol TO7, manufactured by BASF); 9 mol equivalent of ethylene oxide added to C10 alcohol obtained by subjecting pentanol to garvet reaction (trade name: Lutensol XP90, manufactured by BASF); 7 mol equivalent of ethylene oxide added to C10 alcohol obtained by subjecting pentanol to garvet reaction (trade name: Lutensol XL70, manufactured by BASF); C10 alcohol obtained by subjecting pentanol to garvet reaction In contrast, 6 mol equivalent ethylene oxide added (trade name: Lutensol XA60, manufactured by BASF); 9 mol equivalent or 15 mol equivalent ethylene oxide was added to a secondary alcohol having 12 to 14 carbon atoms. Things (Product name: Softa 90, Softanol 150, manufactured by Nippon Shokubai Co., Ltd .; palm fatty acid methyl (lauric acid / myristic acid = 8/2) added with 15 mole equivalent of ethylene oxide using an alkoxylation catalyst (poly And oxyethylene coconut fatty acid methyl ester (EO 15 mol)).
As the compound (3), among the above, -X- is -COO-, R ² is an alkyl group having 1 to 6 carbon atoms, and t is 0, that is, a polyoxyethylene fatty acid alkyl ester. Preferably, polyoxyethylene fatty acid methyl ester (hereinafter sometimes referred to as MEE) in which R ² is a methyl group is more preferable.
By using polyoxyethylene fatty acid alkyl ester as the nonionic surfactant, the solubility of the liquid cleaning agent in water can be increased and the cleaning power can be increased. In addition, even if the content of the component (B) in the liquid detergent is increased, a significant increase in viscosity (gelation) hardly occurs, and a concentrated liquid detergent having good fluidity can be obtained.
Polyoxyethylene fatty acid alkyl esters, especially MEE, are nonionic surfactants having weak molecular orientation and unstable micelles in an aqueous solution system. For this reason, polyoxyethylene fatty acid alkyl ester does not cause gelation or the like at a high concentration, and it is presumed that the solubility in water can be improved even if one kind alone is blended in a large amount in a liquid detergent. Therefore, when the liquid cleaning agent containing polyoxyethylene fatty acid alkyl ester is dispersed in water, the concentration of polyoxyethylene fatty acid alkyl ester in the cleaning liquid becomes uniform quickly and comes into contact with the object to be washed at an arbitrary concentration from the initial stage of cleaning. It is thought that it exhibits high cleaning power.
In the polyoxyethylene fatty acid alkyl ester, the narrow ratio indicating the distribution ratio of compounds having different numbers of added moles of ethylene oxide is preferably 20% by mass or more. The upper limit of the narrow ratio is preferably substantially 80% by mass or less. As for a narrow rate, 20-60 mass% is more preferable. The higher the narrow ratio, the better the detergency can be obtained, but if it is too high, the liquid stability at low temperatures may be lowered, so 30 to 45% by mass is more preferable.
The narrow rate of polyoxyalkylene type nonionic surfactants such as polyoxyethylene fatty acid alkyl esters is a value determined by the following mathematical formula (S).

In the formula (S), S _max represents the number of added moles of alkylene oxide (value of s + t) in the alkylene oxide adduct most present in the polyoxyalkylene type nonionic surfactant.
i represents the number of added moles of alkylene oxide.
Yi represents the proportion (% by mass) of an alkylene oxide adduct having an added mole number of alkylene oxide present in the entire component represented by the formula (S).
The narrow rate can be controlled by, for example, a method for producing a polyoxyethylene fatty acid alkyl ester.
The production method of the polyoxyethylene fatty acid alkyl ester is not particularly limited. For example, a method of adding ethylene oxide to a fatty acid alkyl ester using a surface-modified composite metal oxide catalyst (special feature). Open 2000-144179).
Suitable examples of the surface-modified composite metal oxide catalyst include metal ions (Al ³⁺ , Ga ³⁺ , In ³⁺ , Tl ³⁺ , Co ³⁺⁾ that have been surface-modified with a metal hydroxide or the like. , Sc ³⁺ , La ³⁺ , Mn ^2+, etc.) and a mixed metal oxide catalyst such as magnesium oxide, a hydrotalcite calcined catalyst whose surface is modified with a metal hydroxide and / or a metal alkoxide, etc. Is mentioned.
In the surface modification of the composite metal oxide catalyst, the ratio of the metal hydroxide and / or metal alkoxide is preferably 0.5 to 10 parts by mass with respect to 100 parts by mass of the composite metal oxide. It is more preferable to set it as -5 mass parts.
As another method for producing the component (A), there is a method of adding an alkylene oxide to a fatty acid alkyl ester with an alkoxylation catalyst prepared from a mixture of an alkaline earth metal compound and oxyacid. The above alkoxylation catalyst is disclosed in Japanese Patent No. 04977609, WO1993004030, WO2002028269, WO201220435, and the like, for example, an alkaline earth metal salt of carboxylic acid and / or an alkaline earth metal salt of hydroxycarboxylic acid and sulfuric acid. Examples include an alkoxylation catalyst prepared from a mixture.
By increasing the content of the component (A) in the liquid detergent, it is possible to obtain an advantage that the object to be washed can be washed with a small amount of the liquid detergent, and the liquid detergent container can be made compact. In the case where the content of the component (A) in the liquid detergent is increased, the gelation region is small even at a high concentration, and it is easy to mix, and as the component (A), a secondary alcohol in which ethylene oxide is added to a secondary alcohol is used. Grade alcohol ethoxylate (for example, Softanol series manufactured by Nippon Shokubai Co., Ltd.) and MEE are preferable. Since these gelation regions are small even at high concentrations, gelation hardly occurs even if the content in the liquid detergent is increased.
A nonionic surfactant may be used individually by 1 type, and may be used in combination of 2 or more type.
For example, as the nonionic surfactant, a secondary alcohol ethoxylate or MEE and a primary alcohol ethoxylate obtained by adding ethylene oxide to a primary alcohol may be used in combination.
When the secondary alcohol ethoxylate or MEE is used in combination with the primary alcohol ethoxylate, the component (B) is represented by (secondary alcohol ethoxylate or MEE) / (primary alcohol ethoxylate). The mass ratio is preferably 3/7 to 10/0, more preferably 5/5 to 10/0, and still more preferably 7/3 to 10/0.
The content of the nonionic surfactant in the liquid detergent is preferably 0.1% by mass or more, more preferably 0.1 to 70% by mass, further preferably 5 to 65% by mass, and particularly preferably 10 to 60% by mass. . If it is more than the said lower limit, the compounding effect of nonionic surfactant will be easy to be acquired, and if it is below the said upper limit, the increase in the viscosity of the liquid detergent in low temperature can be suppressed more.
<(B) component>
In the present invention, the component (B) is a fatty acid represented by the following general formula (1) or a salt thereof. In the present invention, the component (B) is particularly useful for improving the foaming property during rinsing.

R ⁵ COOH (1)
(In the formula, R ⁵ is a linear or branched alkyl or alkenyl group having 7 to 17 carbon atoms.)
The component (B) is not particularly limited. In general formula (1), R ⁵ is a linear or branched alkyl group or alkenyl group having 7 to 17 carbon atoms, and preferably has a carbon number. Alkyl groups derived from 11 to 17 or coconut oil are preferred. Salts include sodium, potassium, ammonium and alkanolamine.

(B) A component can be used 1 type or in mixture of 2 or more types. (B) Content of a component is 0.1-10 mass% in a liquid detergent composition, Preferably it is 0.1-5 mass%. By being more than the lower limit of the range, the foaming property at the time of rinsing of the liquid detergent composition is easily improved. On the other hand, when the amount is not more than the upper limit, a sufficient effect of improving the foaming property at the time of rinsing can be obtained, which is economically advantageous.
<(C) component>
Component (C) is a compound represented by the following general formula (2). By containing the component (C), discoloration during storage can be suppressed. In addition, improvement in liquid stability of the liquid detergent composition can be expected.

^{_{R 4 O- (C 2 H 4}} O) n2 -H (2)
(In the formula, R ⁴ is H or an alkyl group having 1 to 3 carbon atoms, and n2 represents the average number of moles of ethylene oxide added and is 1 to 30000.)
As a specific example, when R ⁴ is H in the general formula (2), it is polyethylene glycol. Generally, n is 5 or more, and this weight average molecular weight is 200 to 1320000. Among them, PEG1000 having n of around 23 is preferable.

R ⁴ is an alkyl group having 1 to 3 carbon atoms, and when n is 1 to 30000, glycol monoether, diglycol monoether, polyethylene glycol monoether and the like can be mentioned. Among them, R ⁴ is a methyl group having 1 carbon atom, and n is methoxy PEG1000 having a vicinity of 23.

(C) component can be used 1 type or in mixture of 2 or more types. (C) Content of a component is 0.00001-20 mass% in a liquid detergent composition, Preferably it is 0.0001-15 mass%. When it is in the range of 0.00001 to 20% by mass, yellowing during storage can be suppressed, and a liquid stability effect can be obtained, which is economically advantageous.
<(D) component>
The component (D) is at least one component selected from metal oxides or metal salts. It does not specifically limit as a metal, You may combine 2 or more types individually. Of these, composite metal oxides are preferred. The composite metal oxide is an oxide having two or more metal species. The composite metal oxide is a solid catalyst for producing an alkylene oxide adduct, and is not particularly limited, but a metal ion such as aluminum described in JP-A-1-164437 is added. Magnesium oxide, calcined hydrotalcite described in JP-A-2-71841, magnesium oxide containing zinc, antimony, tin, etc. described in JP-A-7-227540, JP-A-8-268919 And magnesium-based composite metal oxides such as aluminum-magnesium composite oxides obtained by calcination activation of aluminum hydroxide-magnesium described in Japanese Patent Publication No. WO 2007/113985 are preferred. Activated aluminum / magnesium composite gold Oxide is more preferable. Of these, composite metal oxides surface-modified with metal hydroxides or metal alkoxides as described in JP-A-8-169860 and JP-A-8-169661 are preferable.
(D) component can be used 1 type or in mixture of 2 or more types. (D) Content of a component is 0.00001-0.01 mass% in a liquid detergent composition, Preferably it is 0.00003-0.005 mass%. By being more than the lower limit of the range, yellowing of the liquid detergent composition can be suppressed. On the other hand, by being below the upper limit, a sufficient yellowing suppression effect can be obtained, which is economically advantageous.
<(E) component>
(E) A component shows aminocarboxylic acid and its salt.

  The aminocarboxylic acid is preferably a polycarboxylic acid containing a plurality of carboxy groups. 2-5 are preferable and, as for the number of the carboxy group in one molecule, 2 or 3 is more preferable.

  Examples of aminocarboxylic acid salts include sodium salts, potassium salts, ammonium salts, and alkanolamine salts such as ethanolamine.

  As the aminocarboxylic acid (salt), a compound represented by the following general formula (b1) is particularly preferable.

... (b1)

[Wherein R ³ is — (CH ₂ ) _n —A, A is H, OH or COOM, M is H, Na, K, NH ₄ or alkanolamine, and n is 0-5. It is an integer. ]
Specific examples of aminocarboxylic acid (salt) include methyl glycine diacetate (salt) such as methyl glycine diacetate trisodium (MGDA), ethyl glycine diacetate (salt) such as ethyl glycine diacetate trisodium, nitrilotriacetic acid (Salt), iminodisuccinic acid (salt), aspartic acid-N, N-tetrasodium diacetate, trisodium serine diacetate, tetrasodium glutamate diacetate and the like. Among these, methyl glycine diacetate (salt) and ethyl glycine diacetate (salt) are preferable, and trisodium methyl glycine diacetate (MGDA) is particularly preferable.
There is no restriction | limiting in particular as content of the said (E) component in the said liquid cleaning composition, Although it can select suitably according to the objective, 0.01 mass%-3 mass% are preferable, and 0.02 A mass% to 2 mass% is more preferable. If the content of the component (E) is less than 0.01% by mass, the yellowing suppression effect may be reduced, and if it exceeds 3% by mass, precipitation or the like may occur.
[Other ingredients]
The liquid detergent composition of the present invention, if necessary, within the range not impairing the effects of the present invention, the above component (A), component (B), component (C), component (D) and component (E) You may contain other components other than. As this other component, the component normally used for a liquid detergent can be mix | blended, For example, what is shown below is mentioned.

  The water-miscible organic solvent is not particularly limited, and examples thereof include alcohols such as ethanol, 1-propanol, 2-propanol and 1-butanol, and alkyl ethers such as diethylene glycol dimethyl ether and diethylene glycol monobutyl ether (butyl carbitol). Can be mentioned.

  As for the compounding quantity of a water-miscible organic solvent, 0.1-15 mass% is preferable with respect to the total mass of a liquid detergent composition.

  As the anionic surfactant, known anionic surfactants other than the component (B) can be used and can be easily obtained in the market.

  Examples of the anionic surfactant include a linear alkylbenzene sulfonic acid or a salt thereof; an α-olefin sulfonate; a linear or branched alkyl sulfate ester salt; an alkyl ether sulfate ester salt or an alkenyl ether sulfate ester salt; Examples include alkane sulfonates having an α-sulfo fatty acid ester salt.

  Examples of these salts include alkali metal salts such as sodium and potassium, alkaline earth metal salts such as magnesium, and alkanolamine salts such as monoethanolamine and diethanolamine.

  Among these, as the linear alkylbenzene sulfonic acid or a salt thereof, one having 8 to 16 carbon atoms in the linear alkyl group is preferable, and one having 10 to 14 carbon atoms is particularly preferable.

  The α-olefin sulfonate is preferably one having 10 to 20 carbon atoms.

  As the alkyl sulfate ester salt, those having 10 to 20 carbon atoms are preferable.

  The alkyl ether sulfate ester salt or alkenyl ether sulfate ester salt has a linear or branched alkyl or alkenyl group having 10 to 20 carbon atoms, and an average of 1 to 10 moles of ethylene oxide added (that is, Polyoxyethylene alkyl ether sulfate ester salt or polyoxyethylene alkenyl ether sulfate ester salt) is preferable.

  As the alkanesulfonate, a secondary alkanesulfonate having an alkyl group having 10 to 20 carbon atoms, preferably 14 to 17 carbon atoms, is particularly preferable.

  The α-sulfo fatty acid ester salt is preferably one having 10 to 20 carbon atoms.

  Among these, linear alkylbenzene sulfonic acid or a salt thereof, alkane sulfonate, polyoxyethylene alkyl ether sulfate, and α-olefin sulfonate are particularly preferable.

  Other anionic surfactants include, for example, carboxylic acid types such as alkyl ether carboxylates, polyoxyalkylene ether carboxylates, alkyl (or alkenyl) amide ether carboxylates, acylaminocarboxylates, and alkyl phosphate esters. And phosphoric acid ester type anionic surfactants such as salts, polyoxyalkylene alkyl phosphoric acid ester salts, polyoxyalkylene alkyl phenyl phosphoric acid ester salts and glycerin fatty acid ester monophosphoric acid ester salts.

  Examples of these salts include alkali metal salts such as sodium and potassium, alkaline earth metal salts such as magnesium, and alkanolamine salts such as monoethanolamine and diethanolamine.

  As the anionic surfactant, a single type of anionic surfactant may be used alone, or a plurality of types of anionic surfactants may be used in combination.

  It is preferable that the compounding quantity of an anionic surfactant is 0-20 mass% with respect to the total mass of a liquid detergent composition.

  Examples of the cationic surfactant include an alkyltrimethylammonium salt, a dialkyldimethylammonium salt, an alkylbenzyldimethylammonium salt, and an alkylpyridinium salt cationic surfactant.

  Examples of these salts include alkali metal salts such as sodium and potassium, alkaline earth metal salts such as magnesium, and alkanolamine salts such as monoethanolamine and diethanolamine.

  Examples of amphoteric surfactants include alkylbetaine type, alkylamide betaine type, imidazoline type, alkylaminosulfone type, alkylaminocarboxylic acid type, alkylamidecarboxylic acid type, amide amino acid type, and phosphoric acid type amphoteric surfactant. Can be mentioned.

  As a thickener and solubilizer, aromatic sulfonic acid or a salt thereof, for example, toluene sulfonic acid, xylene sulfonic acid, cumene sulfonic acid, substituted or unsubstituted naphthalene sulfonic acid, toluene sulfonate, xylene sulfonate, Examples include cumene sulfonate and substituted or unsubstituted naphthalene sulfonate.

  Examples of the salt include sodium salt, potassium salt, calcium salt, magnesium salt, ammonium salt, alkanolamine salt and the like.

  These acids or salts thereof can be used alone or in combination.

  The blending amount of the thinning agent and the solubilizing agent is preferably 0.01 to 15% by mass with respect to the total mass of the liquid detergent composition. Within this range, the effect of suppressing the formation of a film formed by gelation of the liquid detergent composition on the liquid surface of the liquid detergent composition is improved.

  Examples of the alkaline agent include monoethanolamine, diethanolamine, and triethanolamine. Alkaline agents can be used alone or in combination.

  As a compounding quantity of an alkaline agent, 0.5-5 mass% is preferable with respect to the total mass of a liquid detergent composition.

Examples of the metal ion scavenger (chelating agent) other than the component (E) include citric acid, malonic acid, succinic acid, malic acid, diglycolic acid, tartaric acid, aminocarboxylic acid (salt), and phosphonic acid (salt). It is done.
(E) As for the compounding quantity of metal ion scavengers other than a component, 0.01-20 mass% is preferable with respect to the total mass of a liquid detergent composition.

  The antioxidant is not particularly limited, but is preferably a phenolic antioxidant because of its good detergency and liquid stability, and monophenolic antioxidants such as dibutylhydroxytoluene and butylhydroxyanisole, 2 , 2′-methylenebis (bisphenol-based antioxidants such as 4-methyl-6-t-butylphenol, phenol-based antioxidants such as dl-α-tocopherol are more preferable, monophenolic antioxidants, polymer type oxidation An inhibitor is more preferred.

  Of the monophenol antioxidants, dibutylhydroxytoluene is particularly preferred. Among the polymer type phenol antioxidants, dl-α-tocopherol is particularly preferable.

  An antioxidant can be used 1 type or in mixture of 2 or more types.

  As for the compounding quantity of antioxidant, 0.01-2 mass% is preferable with respect to the total mass of a liquid detergent composition.

  As an antiseptic | preservative, you may contain 0.001-1 mass%, for example by Rohm & Haas: Brand name Kaison CG etc.

  Benzoic acid or a salt thereof (also effective as a preservative) may be contained for the purpose of improving storage stability. Examples of the salt include sodium salt, potassium salt, calcium salt, magnesium salt, ammonium salt, alkanolamine salt and the like. 0.1-5 mass% is preferable with respect to the total mass of a liquid cleaning composition, and, as for the compounding quantity of benzoic acid (salt), 0.15-2 mass% is more preferable.

  You may contain 0-2 mass% of calcium salts, such as boric acid, borax, formic acid or its salt, calcium chloride, and calcium sulfate for the purpose of enzyme stabilization.

  You may contain 0-5 mass% of silicones, such as a dimethyl silicone, a polyether modified silicone, an amino modified silicone, for the purpose of a feeling improvement.

  You may contain 0-1 mass% of fluorescent whitening agents, such as a distyryl biphenyl type, for the purpose of the whiteness improvement of white clothing.

  For the purpose of preventing migration and recontamination, 0 to 2% by mass of a recontamination inhibitor such as polyvinylpyrrolidone and carboxymethylcellulose may be contained.

  You may contain a pearl agent, a soil release agent, etc.

  Hydrogen peroxide may be contained.

  For the purpose of improving the added value of products, flavoring agents, coloring agents, emulsifying agents, natural products and the like may be contained.

  As a flavoring agent, the fragrance | flavor composition A, B, C, D etc. of Table 11-18 of Unexamined-Japanese-Patent No. 2002-146399 can be used as a typical example. The blending amount of the flavoring agent is preferably 0.1 to 1% by mass with respect to the total mass of the liquid detergent composition.

  General-purpose dyes and pigments such as Acid Red 138, Polar Red RLS, Acid Yellow 203, Acid Blue 9, Blue No. 1, Blue No. 205, Green No. 3, Turquoise P-GR (all trade names) Is mentioned. The blending amount of the colorant is preferably about 0.00005 to 0.005% by mass with respect to the total mass of the liquid detergent composition.

  Examples of the emulsion include polystyrene emulsion and polyvinyl acetate emulsion, and usually an emulsion having a solid content of 30 to 50% by mass is suitably used. Specific examples include polystyrene emulsion (manufactured by Syden Chemical Co., Ltd .: trade name Cybinol RPX-196 PE-3, solid content 40% by mass) and the like. As for the compounding quantity of an emulsion, 0.01-0.5 mass% is preferable with respect to the total mass of a liquid detergent composition.

  Examples of extracts such as natural products include Inuenju, Uwaurushi, Echinacea, Koganebana, Yellowfin, Ouren, Allspice, Oregano, Enju, Chamomile, Honeysuckle, Clara, Keigai, Kay, Bay bay, Honoki, Burdock, Comfrey, Jasho, Waremokou, Peonies, Ginger, Solidago, Elderberry, Sage, Mistletoe, Prunus, Thyme, Prunus, Clove, Satsuma Mandarin, Tea Tree, Barberry, Dokudami, Nanten, Nyuko, Yorigusa, Shirogaya, Bow Fu, Dutch Hyu, Mountain, Gray , Murasakitagayasan, yamahakka, cypress, yamajiso, eucalyptus, lavender, rose, rosemary, balun, cedar, gilead balsamno , Ringworm, kochia, Polygonum aviculare, Jingyou, sealed and Adenophortriphylla, Yamabishi, cayratia japonica, licorice, plant extracts, such as St. John's Wort.

  The blending amount of extracts such as natural products is preferably about 0 to 0.5% by mass relative to the total mass of the liquid detergent composition.

  The liquid detergent composition of the present invention preferably has a pH at 25 ° C. of 4 to 9, more preferably pH 6 to 9. When the pH is in such a range, the storage stability of the liquid detergent composition can be maintained well.

  The pH of the liquid detergent composition can be adjusted by blending a pH adjuster as necessary. The pH adjuster is optional as long as the effects of the present invention are not impaired, but sulfuric acid, sodium hydroxide, potassium hydroxide, alkanolamine and the like are preferable from the viewpoint of the stability of the component (A).

  The liquid detergent composition of the present invention is prepared by mixing the above components (A) to (E) and other components as necessary with water.

  The mixing conditions are not particularly limited, and examples of water include purified water, distilled water, ion exchange water, pure water, and ultrapure water.

  The amount of water is not particularly limited as long as the total amount is 100% by mass, but is preferably 30 to 45% by mass with respect to the total mass of the liquid detergent composition, and 25 to 55% by mass is used.

  The method for using the liquid detergent composition of the present invention may be the same as the method for using a normal liquid detergent composition. That is, the liquid detergent composition of the present invention (the product of the present invention) is poured into water together with the laundry at the time of washing, the method of directly applying the product of the present invention to mud and sebum soil, and the product of the present invention in advance. For example, a method of immersing clothing by dissolving it in Also preferred is a method in which the product of the present invention is applied to the laundry and then allowed to stand as appropriate, followed by normal washing using a normal laundry solution. In that case, the usage-amount of this invention product can be less less than the usage-amount of the conventional liquid detergent composition.

Hereinafter, the present invention will be described in detail using examples, but the present invention is not limited to these examples. “%” Means “% by mass” unless otherwise specified.
<Manufacture of liquid detergent composition>
Using the following blending components, a liquid detergent composition having the composition shown in Table O is produced according to a conventional method. Purified water is added so that the total amount of each component (the total amount is 100 parts by mass) is 95 parts by mass. After stirring and mixing, the pH is adjusted, and the total amount is 100% by mass. Is added to produce a liquid detergent composition.
[Raw materials]
As the component (A), the following reagents were used.

(A-1): a mixture of C ₁₁ H ₂₃ CO (OCH ₂ CH ₂ ) _m OCH ₃ and C ₁₃ H ₂₇ CO (OCH ₂ CH ₂ ) _m OCH ₃ in a mass ratio of 8/2, m = average 15 , Narrow ratio 33% by mass, synthetic product.
(A-2): An average of 15 moles of ethylene oxide added to natural alcohol CO-1217 (trade name) manufactured by P & G.
The narrow ratio of the component (A-1) was measured by the following procedure.

Under the following measurement conditions, the distribution of ethylene oxide adducts having different numbers of moles of ethylene oxide added was measured, and the narrow ratio (% by mass) was calculated from the above formula (S).
[Conditions for measuring distribution of ethylene oxide adducts by HPLC]
Apparatus: LC-6A (manufactured by Shimadzu Corporation),
Detector: SPD-10A,
Measurement wavelength: 220 nm
Column: Zorbax C8 (manufactured by Du Pont)
Mobile phase: acetonitrile / water = 60/40 (volume ratio),
Flow rate: 1 mL / min,
Temperature: 20 ° C
Said (A-1) and (A-2) were each synthesize | combined in the following procedures.

Synthesis of (A-1):
Synthesis was performed according to Production Example 1 in Examples described in JP-A No. 2000-144179.

That is, alumina hydroxide / magnesium hydroxide (product name: Kyoward 300, manufactured by Kyowa Chemical Industry Co., Ltd.) having a chemical composition of 2.5 MgO.Al ₂ O ₃ .nH ₂ O, at 600 ° C. for 1 hour in a nitrogen atmosphere Calcined alumina hydroxide / magnesium (unmodified) catalyst 2.2 g obtained by calcining under pressure, 2.9 mL of 0.5 N potassium hydroxide ethanol solution, 280 g of lauric acid methyl ester and myristic acid methyl ester 70 g was charged into a 4 liter autoclave and the catalyst was reformed in the autoclave. Next, after the inside of the autoclave was replaced with nitrogen, the temperature was raised, and while maintaining the temperature at 180 ° C. and the pressure at 3 atm, 1052 g of ethylene oxide was introduced and reacted while stirring. Further, the reaction solution was cooled to 80 ° C., 159 g of water and 5 g of activated clay and diatomaceous earth as filter aids were added respectively, and then the catalyst was filtered off to obtain (A-1).

The amount of alkali added to the catalyst was adjusted so that the narrow ratio of (A-1) was 33% by mass.
Synthesis of (A-2):
224.4 g of natural alcohol CO-1270 manufactured by P & G, and 2.0 g of 30% NaOH aqueous solution were collected in a pressure-resistant reaction vessel, and the inside of the vessel was purged with nitrogen. Next, after dehydrating for 30 minutes at a temperature of 100 ° C. and a pressure of 2.0 kPa or less, the temperature was raised to 160 ° C. While stirring the alcohol, 760.4 g of ethylene oxide (gaseous) was gradually added to the alcohol liquid using a blowing tube while adjusting the addition rate so that the reaction temperature did not exceed 180 ° C.

  After completion of the addition of ethylene oxide, aging was performed at a temperature of 180 ° C. and a pressure of 0.3 MPa or less for 30 minutes, and unreacted ethylene oxide was distilled off at a temperature of 180 ° C. and a pressure of 6.0 kPa or less for 10 minutes.

Next, after cooling the temperature to 100 ° C. or lower, 70% p-toluenesulfonic acid was added to neutralize so that the pH of the 1% aqueous solution of the reaction was about 7, to obtain (A-2). .
As the component (B), the following reagents were used.
Zushi fatty acid: As a component of NOF Corporation (C), the following reagents were used.
(C-1): Methoxypolyethylene glycol, manufactured by Toho Chemical Industry Co., Ltd., trade name: MethoxyPEG-1000
(C-2): Polyethylene glycol (weight average molecular weight 1000), manufactured by NOF Corporation, trade name: PEG # 1000
(C-3): Polyethylene glycol (weight average molecular weight 6000), Wako Pure Chemical Industries, Ltd., trade name: PEG # 6000
(C-4): Polyethylene glycol (weight average molecular weight 20000), Wako Pure Chemical Industries, Ltd., trade name: PEG # 20000
(C-5): Polyethylene glycol (weight average molecular weight 100,000), Wako Pure Chemical Industries, Ltd., trade name: PEG # 100000
As the component (D), the following reagents were used.

Alumina / magnesium hydroxide: Kyowa Chemical Industry Co., Ltd., trade name: KYOWARD 300
As the component (E), the following reagents were used.

  Methyl glycine diacetate trisodium (MGDA): BASF Corporation, trade name “Trilon M”.

  As other components, the following reagents were used.

  LAS-H: linear alkylbenzene sulfonic acid, trade name, Rypon LH-200, manufactured by Lion Corporation.

  Monoethanolamine (MEA): manufactured by Nippon Shokubai Co., Ltd.

  Dibutylhydroxytoluene (BHT): manufactured by Sumitomo Chemical Co., Ltd., trade name “SUMILZER BHT-R”.

  Ethanol: manufactured by Nippon Alcohol Sales Co., Ltd., trade name “specific alcohol 95 degree synthesis”.

  C12 cation: Lion Akzo Co., Ltd., trade name “ARCARD 12-37w”.

  Amidoamine: Toho Chemical Co., Ltd., trade name “Catinal MPAS-R”.

SR agent: Clariant Japan, trade name “TexCare SRN-170C”
Hydrogen peroxide: Mitsubishi Gas Chemical Company, trade name “hydrogen peroxide”
Sodium benzoate: manufactured by Toagosei Co., Ltd., trade name “Sodium benzoate”.

  Sodium lactate: manufactured by Kanto Chemical Co., Ltd., trade name “sodium lactate”.

  Protease: Product name “Coronase 48L” manufactured by Novozymes.

  Cellulase: Product name “Carezyme Premium 4500L” manufactured by Novozymes.

Mannanase: Product name “Manaway 4.0L” manufactured by Novozymes.
Green No. 3 (pigment): Product name “Green No. 3” manufactured by Sakai Kasei Co., Ltd.

  Fragrance | flavor: The fragrance | flavor composition A of Tables 11-18 of Unexamined-Japanese-Patent No. 2002-146399.

  Sodium hydroxide: manufactured by Tsurumi Soda Co., Ltd.

Sulfuric acid: Toho Zinc Co., Ltd.
<Evaluation method of storage stability of color tone>
50 mL of the liquid detergent composition shown in Table 1 is stored and sealed in a glass bottle with a screw cap of 50 mL, and stored in a thermostatic chamber at 50 ° C. for 1 month. The color tone of the liquid detergent composition after storage and immediately after blending is visually compared, and the storage stability of the color tone is evaluated according to the following criteria.

○: No difference in color tone is observed Δ: Some difference in color tone is observed ×: Difference in color tone is clearly recognized

Claims (1)

The liquid detergent composition containing the following (A)-(E).
(A) a nonionic surfactant,
(B) a fatty acid represented by the following general formula (2) or a salt thereof,
R ⁵ COOH (2)
(In the formula, R ⁵ is a linear or branched alkyl or alkenyl group having 7 to 17 carbon atoms.)
(C) a compound represented by the following general formula (3);
_{^{R 4 O- (C 2 H 4}} O) n2 -H (3)
(In the formula, R ⁴ is H or an alkyl group having 1 to 3 carbon atoms, and n2 represents the average number of moles of ethylene oxide added and is 1 to 30000.)
(D) At least one compound selected from metal oxides or metal salts (E) At least one compound selected from aminocarboxylic acids and salts thereof