JP2008024753A - Liquid detergent composition for clothing - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To obtain a detergent composition for clothing, having excellent water absorption properties of material to be washed after washing and drying and excellent pH storage stability. <P>SOLUTION: The detergent composition for clothing comprises a nonionic surfactant (A) represented by general formula R<SP>1</SP>-X-(CH<SB>2</SB>CH<SB>2</SB>O)n-R<SP>2</SP>(R<SP>1</SP>is a straight-chain or branched-chain alkyl group or alkenyl group; -X- is -O- or -COO-, when -X- is -O-, R<SP>1</SP>is a 10-20C alkyl group and R<SP>2</SP>is a hydrogen atom and when -X- is -COO-, R<SP>1</SP>is a 7-13C alkyl group and R<SP>2</SP>is a methyl group or an ethyl group; n is an integer of 10-20), an antioxidant (B), at least one kind (C) selected from the group consisting of a polycarboxylic acid, a hydroxycarboxylic acid, a polycarboxylic acid salt and a hydroxycarboxylic acid salt and 0-<0.05 mass% of an anionic surfactant and/or cationic surfactant (D). <P>COPYRIGHT: (C)2008,JPO&INPIT

Description

  The present invention relates to a liquid cleaning composition for clothing.

Conventionally, the cleaning composition has been used in the form of powder or liquid. Among these, liquid detergent compositions have recently been used worldwide for reasons such as no concerns about undissolved residue in water and direct application to objects to be cleaned (objects to be cleaned). The proportion of use is increasing.
Various studies have been made on liquid detergent compositions so far, and many compositions such as liquid detergent compositions for clothing have been disclosed. For example, an acidic liquid detergent composition containing a specific nonionic surfactant, a specific cationic surfactant, an amphoteric surfactant and water has been proposed (see Patent Document 1).
Further, a weakly acidic liquid detergent composition containing an anionic surfactant and a nonionic surfactant, a terpene hydrocarbon, an organic acid and a salt thereof, and an alcohol solvent and having a pH adjusted to 3 to 6. Has been proposed (see Patent Document 2).
A liquid detergent composition for clothing containing a nonionic surfactant as a main detergent component has also been proposed.
JP 2005-97432 A JP 2003-138300 A

By the way, among the articles to be washed, fiber products having good water absorption, such as cotton and linen, have a problem that the water absorption inherent in the fiber product is easily damaged by repeated washing.
This is considered to be due to the fact that the anionic surfactant and the cationic surfactant contained in the liquid detergent composition for clothing remain in the textile product during washing.
When washing is performed using the compositions described in Patent Documents 1 and 2, the water absorption of the washing object after washing and drying is not sufficiently satisfactory. This is because, for example, the liquid detergent composition described in the Examples of Patent Document 1 contains a total of 0.5% by mass or more of a cationic surfactant and an anionic surfactant (bleach activator). It is considered that the weakly acidic liquid detergent composition described in the examples contains 30% by mass or more of anionic surfactant, and these components remain in the textile after washing and drying.
In addition, in a liquid cleaning composition for clothing containing a nonionic surfactant as a main cleaning component, for example, an anionic surfactant has been conventionally used to improve cleaning power, and convenience has been improved. From the viewpoint, a composition to which a cationic surfactant is added for imparting flexibility has been proposed. However, when these compositions are used for washing, the water absorption of the washing object after washing and drying is not fully satisfactory.

  On the other hand, in a liquid cleaning composition for clothing containing a nonionic surfactant as a main cleaning component, the pH change of the composition over time should be suppressed (the storage stability of the pH is good). However, it is important from the viewpoint of liquid stability (for example, stable blending of a nonionic surfactant).

  The present invention has been made in view of the above circumstances, and it is an object to provide a liquid detergent composition for clothing that is excellent in water absorption of an object to be washed after washing and drying and has good storage stability of pH. To do.

  In order to solve the above problems, in the present invention, a nonionic surfactant (A) represented by the following general formula (1), an antioxidant (B), a polyvalent carboxylic acid, a hydroxycarboxylic acid, At least one selected from the group consisting of polyvalent carboxylates and hydroxycarboxylates (C), and an anionic surfactant and / or a cationic surfactant (D) content of 0 to 0. A liquid detergent composition for clothing, which is less than 5% by mass, is proposed.

［式中、Ｒ^１は直鎖もしくは分岐鎖状のアルキル基またはアルケニル基であり；−Ｘ−は−Ｏ−または−ＣＯＯ−であり、−Ｘ−が−Ｏ−のとき、Ｒ^１の炭素数は１０〜２０であり、かつＲ^２は水素原子であり、−Ｘ−が−ＣＯＯ−のとき、Ｒ^１の炭素数は７〜１３であり、かつＲ^２はメチル基またはエチル基であり；ｎはエチレンオキサイドの平均付加モル数を示し、１０〜２０の数である。］

[Wherein, R ¹ is a linear or branched alkyl group or alkenyl group; —X— is —O— or —COO—, and when —X— is —O—, the carbon of R ¹ The number is 10 to 20, and R ² is a hydrogen atom. When —X— is —COO—, R ¹ has 7 to 13 carbon atoms and R ² is a methyl group or an ethyl group. N represents the average number of moles of ethylene oxide added, and is a number from 10 to 20. ]

Further, in the liquid detergent composition for clothing of the present invention, a plant belonging to the genus Melaleuca (Meraleuca), a plant belonging to the Rosa family, a plant belonging to the Rosaceae family, a plant belonging to the genus Mosla (mosla), and a plant belonging to the family Ginger family. It is preferable to further contain at least one plant extract (E) selected from the group.
Moreover, in the liquid detergent composition for clothes of this invention, it is preferable that the pH in 25 degreeC is 3-10.

  ADVANTAGE OF THE INVENTION According to this invention, the liquid detergent composition for clothing which is excellent in the water absorption of the to-be-washed object after washing and drying, and has favorable storage stability of pH can be provided.

The liquid detergent composition for clothing of the present invention comprises a nonionic surfactant (A) represented by the general formula (1) (hereinafter referred to as component (A)) and an antioxidant (B) (hereinafter referred to as “component”). , (B) component) and at least one (C) selected from the group of polyvalent carboxylic acid, hydroxycarboxylic acid, polyvalent carboxylate and hydroxycarboxylate (hereinafter referred to as component (C)). ) And an anionic surfactant and / or a cationic surfactant (D) (hereinafter referred to as component (D)) of 0 to less than 0.5% by mass.
In addition, the liquid detergent composition for clothing of the present invention preferably further contains a specific plant extract (E) (hereinafter referred to as (E) component).
Moreover, the liquid detergent composition for clothes of the present invention preferably has a pH of 3 to 10 at 25 ° C.

<(A) component>
In the present invention, the component (A) is a nonionic surfactant represented by the general formula (1). By containing the component (A), a liquid detergent composition for clothing having a cleaning effect on, for example, sebum stains can be obtained.
Moreover, it contributes to the improvement of the water absorption of the washing object after washing and drying. The reason for this is not clear, but it is presumed that the component (A) is less likely to remain in the object to be washed after washing than the nonionic surfactants other than the components (D) and (A) described later. Is done.

In the general formula (1), R ¹ is a linear or branched alkyl group, or a linear or branched alkenyl group, and is preferably a linear or branched alkyl group.
—X— is —O— or —COO—.
When -X- is -O-, the component (A) represented by the general formula (1) is an alcohol ethoxylate. At this time, the number of carbon atoms of ^{R 1} is 10 to 20, preferably from 10 to 16.
When -X- is -COO-, the component (A) represented by the general formula (1) is a fatty acid ester type nonionic surfactant. At this time, the number of carbon atoms in ^{R 1} is 7 to 13, preferably 11 to 13, more preferably 11.
In the general formula (1), R ¹ has a carbon number of 10 or more when —X— is —O—, or 7 or more when —X— is —COO—. Detergency as an agent composition is improved.
On the other hand, the carbon number of R ¹ is 20 or less when -X- is -O-, or 13 or less when -X- is -COO-. Control becomes even easier. For example, an increase in viscosity of the liquid detergent composition for clothing is suppressed, and good liquidity is easily obtained.
In the general formula (1), R ² is a hydrogen atom when —X— is —O—. When -X- is -COO-, R ² is a methyl group or an ethyl group, preferably a methyl group.

In formula (1), n shows the average addition mole number of ethylene oxide.
n is a number of 10 to 20, preferably 12 to 18. Within this range, the cleaning power is further improved. Moreover, the liquid stability (for example, stability with time at low temperature, etc.) of the liquid detergent composition for clothing is improved.

The addition mole number distribution of ethylene oxide varies depending on the reaction method when ethylene oxide is added, but the addition mole number distribution may be wide or narrow. For example, a relatively wide distribution in which ethylene oxide is added to a hydrophobic group raw material using a general alkali catalyst such as sodium hydroxide or potassium hydroxide may be used, or Al described in Japanese Patent Publication No. 6-15038. Ethylene oxide is added to a hydrophobic group raw material using a specific alkoxylation catalyst such as magnesium oxide to which metal ions such as ³⁺ , Ga ³⁺ , In ³⁺ , Tl ³⁺ , Co ³⁺ , Sc ³⁺ , La ³⁺ , Mn ²⁺ are added. A narrow distribution may be used.

In the present invention, the component (A), that is, the alcohol ethoxylate or fatty acid ester type nonionic surfactant may be used alone or in combination of two or more, or both may be used in combination. May be.
The content of the component (A) is preferably 15 to 45% by mass, more preferably 25 to 45% by mass in the liquid cleaning composition for clothing. By being above the lower limit of the range, the detergency against sebum stains and the like is improved. On the other hand, if it is below the upper limit, the remaining amount in the article to be washed is reduced and the water absorption is further improved. In addition, an increase in viscosity of the liquid detergent composition is suppressed, and usability is improved. In addition, aging (low temperature) stability is also improved.

<(B) component>
In the present invention, the component (B) is an antioxidant. By containing the component (B), the component (A) can be blended more stably. Moreover, it contributes to the improvement of the effect of the present invention.

(B) It does not specifically limit as a component, Usually, the antioxidant which can be used for a liquid detergent composition can be used. Of these, radical scavengers that break the chain of radical reaction are preferred. Of these, phenolic antioxidants are preferred because of the good effects obtained by containing component (B), and monophenolic antioxidants such as dibutylhydroxytoluene and butylhydroxyanisole; '-Methylenebis (bisphenol-based antioxidants such as 4-methyl-6-t-butylphenol; polymer type antioxidants such as dl-α-tocopherol are more preferred, monophenolic antioxidants, polymer types More preferred are phenolic antioxidants.
Of the monophenol antioxidants, dibutylhydroxytoluene is particularly preferred. Among the polymer type phenolic antioxidants, dl-α-tocopherol is particularly preferable.

(B) A component can be used 1 type or in mixture of 2 or more types.
(B) It is preferable that content of a component is 0.01-5 mass% in the liquid cleaning composition for garments, More preferably, it is 0.02-3 mass%. By being more than the lower limit of this range, the effect by containing (B) ingredient becomes easy to be acquired. On the other hand, when it is at most the upper limit value, the effect of containing the component (B) is sufficiently obtained, which is economically advantageous.

<(C) component>
In the present invention, the component (C) is at least one selected from the group consisting of polycarboxylic acids, hydroxycarboxylic acids, polyvalent carboxylates and hydroxycarboxylates. By containing the component (C), the storage stability of the pH of the liquid cleaning composition for clothing is improved. Moreover, the said (A) component can be mix | blended more stably.

(C) As a component, what has the buffer effect which suppresses a pH change is mentioned as a suitable thing. Preferred examples of the polyvalent carboxylic acid include succinic acid, maleic acid, fumaric acid and the like.
Preferred examples of the hydroxycarboxylic acid include citric acid, malic acid, glycolic acid, p-hydroxybenzoic acid, and the like.
Of these, citric acid and malic acid are more preferable, and citric acid is particularly preferable because the pH buffering effect is good.
Examples of the salt include alkali metal salts such as sodium salt and potassium salt; alkaline earth metal salts such as magnesium salt and calcium salt; ammonium salt; alkanolamine salts such as monoethanolamine salt, diethanolamine salt and triethanolamine salt. Can be mentioned. Of these, alkali metal salts are preferable, and sodium salts are more preferable.

(C) component can be used 1 type or in mixture of 2 or more types.
(C) It is preferable that content of a component is 0.05-3 mass% in the liquid cleaning composition for garments, Preferably it is 0.1-1.5 mass%. By being more than the lower limit of this range, the effect (pH storage stability) which suppresses the change with time of pH of the liquid detergent composition for clothes improves. On the other hand, by being below the upper limit value, the effect of suppressing the pH change with time can be sufficiently obtained, which is economically advantageous.

<(D) component>
In the present invention, the component (D) is an anionic surfactant and / or a cationic surfactant. Content of this (D) component is 0-0.5 mass% in the liquid cleaning composition for clothes of this invention. By being in this range, the liquid detergent composition for clothes of the present invention is excellent in the water absorption of the washing object after washing and drying.

In the component (D), the anionic surfactant is not particularly limited, and conventionally known anionic surfactants can be used as those used in the liquid detergent composition for clothing.
For example, a soap and a non-soap anionic surfactant are mentioned, and a non-soap anionic surfactant is preferable. Specific examples of non-soap anionic surfactants include α-olefin sulfonates, α-sulfo fatty acid methyl ester salts, alkane sulfonates, linear alkylbenzene sulfonates, and polyoxyethylene alkyl ether sulfates. It is done.
As an alpha olefin sulfonate, carbon number of an alkyl group becomes like this. Preferably it is 14-18, More preferably, it is 14.
As alpha-sulfo fatty acid methyl ester salt, carbon number of a fatty acid becomes like this. Preferably it is 8-18, More preferably, it is 12-16.
The alkane sulfonate is preferably a secondary alkane sulfonate. Carbon number of an alkyl group becomes like this. Preferably it is 10-21, More preferably, it is 10-14.
As linear alkylbenzene sulfonate, carbon number of an alkyl group becomes like this. Preferably it is 8-16, More preferably, it is 10-14.
As polyoxyethylene alkyl ether sulfate, carbon number of an alkyl group becomes like this. Preferably it is 10-20, More preferably, it is 10-16. Moreover, the average addition mole number of ethylene oxide becomes like this. Preferably it is 0.5-8.
Examples of the salt include alkali metal salts such as sodium salt and potassium salt, and alkanolamine salts such as monoethanolamine salt and diethanolamine salt. Of these, sodium salts are preferred.
Among the above, linear alkylbenzene sulfonate is more preferable, and sodium alkylbenzene sulfonate having 10 to 14 carbon atoms in the alkyl group is particularly preferable.

In the component (D), the cationic surfactant is not particularly limited, and conventionally known cationic surfactants can be used as those used for liquid cleaning compositions for clothing.
Examples thereof include amine salt type cationic surfactants and quaternary ammonium salt type cationic surfactants, and among them, quaternary ammonium salt type cationic surfactants represented by the following general formula (2) are preferable.
Here, the “amine salt type” includes a primary amine salt, a secondary amine salt, and a tertiary amine salt.

［式中、Ｒ^３〜Ｒ^６のうち、２つ以上はそれぞれ独立して炭素数１〜３のアルキル基またはヒドロキシアルキル基であり；それ以外は炭素数８〜２２の直鎖もしくは分岐鎖状のアルキル基またはアルケニル基である。Ｚ⁻はハロゲンイオンまたはアルキル硫酸イオンである。］

[In the formula, two or more of R ^{3 to} R ⁶ are each independently an alkyl group having 1 to 3 carbon atoms or a hydroxyalkyl group; the others are linear or branched having 8 to 22 carbon atoms. An alkyl group or an alkenyl group. Z ⁻ is a halogen ion or an alkyl sulfate ion. ]

In the general formula (2), two or more of R ^{3 to} R ⁶ are each independently an alkyl group having 1 to 3 carbon atoms or a hydroxyalkyl group, and the others are straight chain having 8 to 22 carbon atoms. Or it is a branched alkyl group or alkenyl group.
Preferred examples of the component (D) represented by the general formula (2) include, for example, R ^{3 to} R ⁵ are each independently an alkyl group having 1 to 3 carbon atoms or 1 to 3 carbon atoms. Compound (D-1) wherein R ⁶ is a linear or branched alkyl group having 8 to 22 carbon atoms or a linear or branched alkenyl group having 8 to 22 carbon atoms Hereinafter, it is referred to as component (D-1).); R ³ and R ⁴ are each independently an alkyl group having 1 to 3 carbon atoms or a hydroxyalkyl group having 1 to 3 carbon atoms, and R ⁵ and R ⁶ are each , Each independently a compound having a linear or branched alkyl group having 8 to 22 carbon atoms or a linear or branched alkenyl group having 8 to 22 carbon atoms (hereinafter referred to as (D- 2) “component”).

In the component (D-1), R ^{3 to} R ⁵ are each preferably an alkyl group having 1 to 3 carbon atoms, more preferably a methyl group, and particularly preferably a methyl group. preferable.
In the alkyl group or alkenyl group of R ⁶ , the carbon number is 8 to 22, preferably 10 to 22, and more preferably 16 to 18. R ⁶ is preferably a linear or branched alkyl group, and more preferably a linear alkyl group.

In the component (D-2), each of R ³ and R ⁴ is preferably an alkyl group having 1 to 3 carbon atoms, more preferably a methyl group, and particularly preferably a methyl group. preferable.
In the alkyl group or alkenyl group of R ⁵ and R ⁶ , the carbon number is 8 to 22, preferably 8 to 12, and more preferably 8 to 10. R ⁵ and R ⁶ are each preferably a linear or branched alkyl group, more preferably a linear alkyl group, and both are linear alkyl groups. Is particularly preferred.

Z ⁻ is a halogen ion or an alkyl sulfate ion.
Examples of Z constituting the halogen ion include a fluorine atom, a chlorine atom, a bromine atom, and an iodine atom, and a chlorine atom is preferable.
As Z which comprises an alkyl sulfate ion, what has a C1-C3 alkyl group is preferable.
Among these, Z ⁻ is preferably a halogen ion.

Specific examples of the cationic surfactant include (D-1) such as alkyl chloride (preferably having 16 to 18 carbon atoms) trimethylammonium (for example, trade name “Arcard T-800”, manufactured by Lion Akzo, etc.). component;
Examples thereof include (D-2) component such as didecyldimethylammonium chloride (for example, trade name “Arcard 210”, manufactured by Lion Akzo, etc.).

(D) component can be used 1 type or in mixture of 2 or more types.
(D) Content of a component is 0-0.5 mass% in the liquid cleaning composition for clothes, and it is preferable that it is 0-0.2 mass%. In this invention, it is so preferable that there are few (D) components, and it is especially preferable not to contain (0 mass%). By being in this range, the water absorption of the washing object after washing and drying is improved.

<(E) component>
In the present invention, the component (E) is selected from the group consisting of a plant belonging to the genus Melaleuca (Meraleuca), a plant belonging to the Rosa family, a plant belonging to the moss family Mosla, and a plant belonging to the genus Amoum. At least one plant extract.
In the liquid cleaning composition for clothing of the present invention, it is preferable to further contain the component (E). By containing the component (E), the deodorizing effect is remarkably obtained.

Examples of the plant belonging to the genus Melaleuca (Melaleuca) include Melaleuca alternifolia, M. quinquenervia, and the like.
Examples of plants belonging to the genus Rosa (Rosa) include Rosa damascena, Rosa gallica, and Rana rugosa.
Examples of plants belonging to the genus Mosla (Mosula) include Yamasiso (Mosla japonica), M. chinensis, M. scabra and the like.
Examples of plants belonging to the genus Amoum (Amomum) include, for example, Amomum xanthioides, A. tsao-ko and A. chinense.

  The plant part is not particularly limited, and it is particularly preferable to use the above-ground part. In the present invention, the Melaleuca (Melaleuca) genus plant is a leaf part, the Rosaceae Rosa plant is a flower part, the Lamiaceae Mosla (Mosula) genus fruit part, and the Ginger family Amomum is It is particularly preferable to use each fruit part.

A plant extract can be obtained as a liquid (extract) by performing an extraction process from a plant that is directly or directly dried or cut into an appropriate size or pulverized. it can.
Examples of the solvent that can be used for obtaining the plant extract include generally used organic solvents such as methanol, ethanol, butanol, hexane, heptane, cyclohexane, ethyl acetate, acetone, monoterpenes; glycerin, 1, 3 -Glycols such as butylene glycol, dipropylene glycol, propylene glycol; water and the like. Among these, ethanol, water, 1,3-butylene glycol, monoterpenes, or a mixed solvent thereof is preferable, and ethanol is particularly preferable.
The said solvent can be used individually by 1 type or in mixture of 2 or more types.
In the present invention, if the solvent for extraction is harmless in use, the extract can be used as it is for the production of a liquid detergent composition for clothing. Moreover, you may use the dilution liquid which diluted the extract with the appropriate solvent for manufacture of the liquid cleaning composition for clothes. Alternatively, a concentrated extract obtained by concentrating the extract, a dry powder by freeze drying, a paste prepared, or the like can be used.

The extraction treatment can be performed by a conventional method such as cold immersion, digestion, heated reflux, or a percolation method. In the present invention, in addition to the plant extract obtained by solvent extraction, plant extraction obtained by a method that is usually used industrially, such as steam distillation, supercritical extraction performed with carbon dioxide gas in a supercritical state, etc. Products can be used as well, and steam distillation is a particularly preferable extraction method. In supercritical extraction, hexane, ethanol, or the like can be used as an extraction aid.
The plant extract may be purified. Purification of the plant extract can be performed by treating the plant extract with activated carbon, liquid-liquid distribution, column chromatography, liquid chromatography, or the like.
The conditions for obtaining the above plant extract, such as extraction temperature and extraction pH, are not particularly limited.

Moreover, as a plant extract, the commercial product extracted using the method of the above-mentioned extraction process can also be utilized suitably.
As a suitable product of a plant extract, for example, tea tree oil is used as a plant extract of the genus Melaleuca (Meraleuca), rose oil is used as a plant extract of the Rosaceae Rosa, ) Yamajiso oil etc. can be used as the genus plant extract.
Moreover, as a ginger family Amoum (Amomumu) genus plant extract, shrunk sand is preferable.

(E) A component can be used 1 type or in mixture of 2 or more types.
(E) It is preferable that content of a component is 0.005-10 mass% in conversion of solid content in the liquid cleaning composition for garments, More preferably, it is 0.3-3 mass%. By being more than the lower limit of the range, the deodorizing effect is easily obtained. On the other hand, by being below the upper limit value, it is possible to balance with other components.

<Optional component>
In addition to the components (A) to (E), other optional components can be blended in the liquid cleaning composition for clothing of the present invention as necessary.
Specifically, examples of the hydrotrope include glycol solvents such as ethylene glycol, propylene glycol, polyethylene glycol, and polypropylene glycol, and alcohols such as ethanol. Among these, polyethylene glycol having a weight average molecular weight of 400 to 5000 (preferably about 1000) is preferable because the liquid stability is further improved. Further, ethanol is also preferable because liquid stability and antiseptic power are further improved.
A hydrotrope agent can be used 1 type or in mixture of 2 or more types.
It is preferable that content of a hydrotrope agent is 0.5-15 mass% in the liquid cleaning composition for garments.

Moreover, the liquid detergent composition for clothes of this invention can mix | blend nonionic surfactant and / or amphoteric surfactant other than the said (A) component.
Examples of the nonionic surfactant other than the component (A) include an alkyl polyglucoside having an alkyl group having 8 to 18 carbon atoms and having an average addition mole number of 1 to 10 glucose units; an alkyl having 8 to 18 carbon atoms. An alkyl glycerol ether having an average addition mole number of 1 to 3 glycerol units; a fatty acid diethanolamide having 10 to 20 carbon atoms; an alkyl group having 10 to 18 carbon atoms and an average addition mole number of ethylene oxide being 1 to 30 polyoxyethylene alkanoates and the like.
Said nonionic surfactant can be used 1 type or in mixture of 2 or more types.
Content of nonionic surfactant other than these (A) components is preferably 0-10 mass% in the liquid cleaning composition for clothes.

Examples of amphoteric surfactants include N-alkyl or alkenyl amino acids or salts thereof, betaine, and the like, and N-alkyl or alkenyl amino acids or salts thereof are preferred.
In the N-alkyl or alkenyl amino acid, an alkyl group or an alkenyl group is bonded to a nitrogen atom, and one or two “—R—COOH” (wherein R represents a divalent hydrocarbon group, preferably An alkylene group, particularly preferably having 1 to 2 carbon atoms.). In a compound in which one “—R—COOH” is bonded, a hydrogen atom is further bonded to the nitrogen atom. One “—R—COOH” is called a mono form, and two are called a di form. In the present invention, any of these mono- and di-forms can be used.
In the N-alkyl or alkenyl amino acid, the alkyl group or alkenyl group preferably has 10 to 20 carbon atoms, and these may be linear or branched.
The salt is preferably an alkali metal salt such as a sodium salt or a potassium salt, and more preferably a sodium salt.
As the N-alkyl or alkenyl amino acid or a salt thereof, alkyl or alkenylaminopropionic acid or a salt thereof is preferable, and laurylaminopropionic acid or a sodium salt thereof is more preferable.
Examples of commercially available products include Naurylaminopropionic acid Na (manufactured by Yushi Kogyo Co., Ltd.). This is a 90% by mass: 10% by mass mixture of mono and di.

Examples of betaines include alkyl betaines, carbobetaines, amide betaines, sulfobetaines, amide sulfobetaines, imidazolinium betaines, phosphobetaines, and the like. Specifically, fatty acid amidopropyl betaine such as lauric acid amidopropyl betaine, 2-alkyl-N-carboxymethyl-N-hydroxyethylimidazolinium betaine, alkyldimethylaminoacetic acid betaine, alkylhydroxysulfobetaine, lauryldimethylbetaine, etc. And alkyldimethylbetaine. Of these, alkylbetaines, amidobetaines, and sulfobetaines are preferable, and amidepropylbetaine laurate and lauryldimethylbetaine are particularly preferable.
Examples of commercially available products include lauric acid amidopropyl betaine (trade name “Softazoline LPB”, manufactured by Kawaken Fine Chemical Co., Ltd.), lauryl dimethyl betaine (trade name “Amphithol 24B”, manufactured by Kao Corporation), and the like.
Said amphoteric surfactant can be used 1 type or in mixture of 2 or more types.
The content of these amphoteric surfactants is preferably 0 to 3% by mass in the liquid detergent composition for clothing.

Moreover, the liquid cleaning composition for clothes of this invention can mix | blend a metal ion trapping agent.
Examples of the metal ion scavenger include citric acid; organic phosphonic acid derivatives such as 1-hydroxyethane-1,1-diphosphonic acid, nitrilotrimethylenephosphonic acid, ethylenediaminetetrakismethylenephosphonic acid; nitrilotriacetic acid, ethylenediaminetetraacetic acid, hydroxyethyl Examples include aminopolyacetic acids such as ethylenediaminetriacetic acid, diethylenetriaminepentaacetic acid, and triethylenetetraminehexaacetic acid; organic acids such as dicarboxymethylglutamic acid, and polymer chelating agents such as polyacrylic acid. Among these, organic phosphonic acid derivatives are preferable, and 1-hydroxyethane-1,1-diphosphonic acid is more preferable, from the viewpoint of good effect of improving the storage stability of the liquid detergent composition for clothing.
The metal ion scavenger can be used alone or in combination.
The content of the metal ion scavenger is preferably 0.1 to 5% by mass in the liquid cleaning composition for clothing.

Moreover, an alkaline agent can be mix | blended with the liquid cleaning composition of this invention.
Examples of the alkali agent include alkanolamine, and monoethanolamine, diethanolamine, and triethanolamine are preferable.
Alkaline agents can be used alone or in combination.
The content of these alkaline agents is preferably 0.5 to 15% by mass in the liquid cleaning composition for clothing.

Moreover, 1 or more types chosen from benzenesulfonic acid, an alkylbenzenesulfonic acid, a benzenesulfonate, and an alkylbenzenesulfonate can be mix | blended with the liquid cleaning composition for clothes of this invention.
In the alkylbenzene sulfonic acid and the alkylbenzene sulfonate, the number of alkyl groups (substituents) is preferably 1 to 3, and more preferably 1 to 2. The alkyl group preferably has 1 to 3 carbon atoms, more preferably a methyl group or an isopropyl group, and still more preferably a methyl group.
Examples of the salt include alkali metal salts such as sodium salt and potassium salt; alkaline earth metal salts such as magnesium salt and calcium salt; ammonium salt; alkanolamine salts such as monoethanolamine salt, diethanolamine salt and triethanolamine salt. Can be mentioned. Of these, sodium salt, monoethalamine salt, and diethanolamine salt are preferable.
Especially, the compound represented by the following general formula (3) is mentioned as a suitable thing.

［式中、Ｘ”、Ｙ”、Ｚ”は、それぞれ独立して水素原子、Ｃ_ｎ”Ｈ_{２ｎ”＋１}（ｎ”は１〜３の整数である。）または（ＣＨ_３）_２ＣＨであり；Ｍは、水素原子、アルカリ金属原子、アルカリ土類金属原子、ＮＨ_４ ^＋またはアルカノールアミン類を示す。］

[Wherein, X ″, Y ″ and Z ″ each independently represent a hydrogen atom, C _{n ″} H _{2n ″ +1} (n ″ is an integer of 1 to 3) or (CH ₃ ) ₂ CH. M represents a hydrogen atom, an alkali metal atom, an alkaline earth metal atom, NH ₄ ⁺ or an alkanolamine. ]

In the general formula (3), X ″, Y ″, and Z ″ each independently represent a hydrogen atom, C _{n ″} H _{2n ″ +1} (n ″ is an integer of 1 to 3) or (CH ₃ ). ₂ CH, preferably CH ₃ , (CH ₃ ) ₂ CH, and more preferably CH ₃ .
M represents a hydrogen atom; an alkali metal atom such as sodium or potassium; an alkaline earth metal atom such as magnesium or calcium; NH ₄ ⁺ ; or an alkanolamine such as monoethanolamine, diethanolamine or triethanolamine, preferably Sodium, monoethalamine and diethanolamine.

Examples of specific compounds include benzene sulfonic acid, benzene sulfonic acid sodium salt, benzene sulfonic acid potassium salt, benzene sulfonic acid ammonium salt, benzene sulfonic acid magnesium salt, benzene sulfonic acid calcium salt, and benzene sulfonic acid monoethanolamine salt. Benzenesulfonic acid diethanolamine salt, benzenesulfonic acid triethanolamine salt, p-toluenesulfonic acid, p-toluenesulfonic acid sodium salt, p-toluenesulfonic acid potassium salt, p-toluenesulfonic acid ammonium salt, p-toluenesulfonic acid Magnesium salt, p-toluenesulfonic acid calcium salt, p-toluenesulfonic acid monoethanolamine salt, p-toluenesulfonic acid diethanolamine salt, p-toluenesulfonic acid triethanol Min salt, o- or m- or p-xylene sulfonic acid, o- or m- or p-xylene sulfonic acid sodium salt, o- or m- or p-xylene sulfonic acid potassium salt, o- or m- or p Xylenesulfonic acid ammonium salt, o- or m- or p-xylenesulfonic acid magnesium salt, o- or m- or p-xylenesulfonic acid calcium salt, o- or m- or p-xylenesulfonic acid monoethanolamine salt O- or m- or p-xylenesulfonic acid diethanolamine salt, o- or m- or p-xylenesulfonic acid triethanolamine salt, cumenesulfonic acid, cumenesulfonic acid sodium salt, cumenesulfonic acid potassium salt, cumenesulfonic acid Ammonium salt, cumene sulfonic acid Magnesium salts, particulate members sulfonic acid calcium salt, particulate members acid monoethanolamine salt, particulate members acid diethanolamine salt, particulate members acid triethanolamine salt and the like.
Of these, p-toluenesulfonic acid, m-xylenesulfonic acid, cumenesulfonic acid or monoethanolamine salts thereof are preferable, and p-toluenesulfonic acid, cumenesulfonic acid, and m-xylenesulfonic acid are more preferable.
These can be used alone or in combination.
These contents are preferably 0.1 to 15% by mass, more preferably 0.5 to 10% by mass in the liquid detergent composition for clothing. Within this range, the effect of suppressing the formation of a film formed by gelling of the liquid cleaning composition for clothing on the liquid surface of the liquid cleaning composition for clothing is improved.

Furthermore, the liquid detergent composition for clothing according to the present invention comprises 0-2 mass% of a recontamination inhibitor such as polyvinylpyrrolidone or carboxymethylcellulose for the purpose of preventing recontamination; lipase, cellulase, amylase for the purpose of improving detergency. 0 to 1% by mass of enzymes such as protease; 0 to 3% by mass of calcium salts such as boric acid, borax, formic acid or salts thereof, calcium chloride, calcium sulfate for the purpose of enzyme stabilization; 0-5% by mass of silicone such as dimethyl silicone, polyether-modified silicone, amino-modified silicone; 0-1% by mass of fluorescent whitening agent such as distyrylbiphenyl type for the purpose of improving whiteness of white clothing; liquid detergent 0.0001 to 0.001% by mass of pigment such as acid dye for the purpose of coloring the composition; liquid stability and antiseptic properties Sodium benzoate, a preservative such as caisson CG (trade name) may be blended with 0.001 wt% such as manner.
Examples of the fragrance for aroma include a fragrance composition containing a fragrance component, a solvent and a stabilizer described in JP-A No. 2002-146399, and the like in the liquid cleaning composition for clothing of the present invention. 0.01-1 mass% can be mix | blended with this.

Furthermore, examples of the pH adjuster include inorganic acids such as hydrochloric acid, sulfuric acid, and phosphoric acid; sodium hydroxide, potassium hydroxide, ammonia, and the like.
A pH adjuster can be used 1 type or in mixture of 2 or more types.

In the liquid cleaning composition for clothing of the present invention, the pH at 25 ° C. is preferably 3 to 10, and more preferably 3 to 6. When the pH is in the above range, it can be used for washing a wide range of fiber products from natural fibers to synthetic fibers. Furthermore, when the pH is in the range of weakly acidic to neutral, a liquid detergent composition suitable for washing a wider range of textile products is obtained.
In the present invention, the pH of the liquid detergent composition for clothing (controlled at 25 ° C.) indicates a value measured by a pH meter (product name: HM-30G, manufactured by Toa DKK Co., Ltd.) or the like.

The liquid detergent composition for clothing of the present invention can be produced based on a conventional method, preferably using water as a solvent.
The usage method is a normal usage method, that is, a method of pouring the liquid detergent composition for clothing of the present invention (the product of the present invention) into the water together with the laundry at the time of washing, and the product of the present invention for mud and sebum soil. Examples thereof include a method of directly applying, and a method of immersing clothing by dissolving the product of the present invention in water in advance. 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.

ADVANTAGE OF THE INVENTION According to this invention, the liquid detergent composition for clothing which is excellent in the water absorption of the to-be-washed | cleaned object after washing and drying, and has favorable storage stability of pH can be provided.
Moreover, according to this invention, the liquid detergent composition for clothing excellent in the deodorizing effect with the water absorption of the to-be-washed object after washing-drying and the storage stability of pH can be provided.
In addition, the liquid detergent composition for clothes of the present invention is less susceptible to oxidative deterioration over time and has good detergency.
Moreover, according to the liquid detergent composition for clothes of this invention, the water absorption which a to-be-washed | cleaned material originally has is easy to be maintained by repetition of washing.
Moreover, the liquid detergent composition for clothing of the present invention can be used for washing a wide range of textile products from natural fibers to synthetic fibers.

  Hereinafter, the present invention will be described in more detail with reference to examples, but the present invention is not limited to these examples. “%” Means “% by mass” unless otherwise specified.

<< Manufacture of Liquid Cleaning Composition for Clothing: Examples 1 to 5, Comparative Examples 1 to 3 >>
A liquid detergent composition for clothing having the composition shown in Table 1 was produced as follows according to a conventional method.
First, the component (A) and polyethylene glycol were stirred and dissolved at 50 ° C. or lower, and then cooled to 40 ° C. or lower. All subsequent steps were performed between room temperature and 40 ° C.
Next, a mixed solution of component (B) and ethanol prepared in advance was added and stirred. Next, purified water was added so that the total amount (the total amount was 100 parts by mass) was 90 parts by mass, and then a fragrance was added and stirred.
Then, after adding (C) component, (D) component, (E) component, and other arbitrary components and stirring, pH was adjusted and the remaining purified water was added and the liquid cleaning composition for garments was manufactured. .
The pH is adjusted by appropriately adding a pH adjuster (sodium hydroxide or sulfuric acid) so that the pH at 25 ° C. immediately after the production of the liquid detergent composition for clothing is the pH shown in Table 1. It was.
In addition, the unit of the compounding quantity in Table 1 is mass%, and shows the pure amount conversion amount. Further, the amount of water was adjusted so that the total amount was 100% by mass. Below, the component shown in the table | surface is demonstrated.

<Description of ingredients shown in the table>
(A) Component A-1: Alcohol ethoxylate, C _{n ′} H _{2n ′ + 1} O (EO) ₁₅ H (71/29 in mass ratio of the compound of n ′ = 12 and the compound of n ′ = 14) Mixture); synthetic product.
(Synthesis method of A-1)
224.4 g of a C _12,14 alcohol manufactured by P & G (mixture of 71/29 in mass ratio of 12 carbon alcohol to 14 carbon alcohol; trade name: CO-1214, branching rate ^{* 10} mass%) 2.0 g of 30 mass% NaOH aqueous solution was extract | collected in the pressure | voltage resistant reaction container, and the inside of a container was substituted 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, 759.5 g of ethylene oxide (gaseous) was gradually added to the alcohol solution using a blowing tube while adjusting the addition rate so that the reaction temperature did not exceed 180 ° C. It was.
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, p-toluenesulfonic acid (70% by mass) was added to neutralize so that the pH of the 1% by mass aqueous solution of the reaction product was about 7, and A-1 Got.
* 1 Branching rate: The branching rate refers to the ratio of the number of moles of alcohol having a branched alkyl group to the number of moles of alcohol in the raw material alcohol.

A-2: Alcohol ethoxylate, C _{n ′} H _{2n ′ + 1} O (EO) ₁₅ H (mixture of 55/45 by mass ratio of the compound of n ′ = 12 and the compound of n ′ = 13); synthetic product .
(Synthesis method of A-2)
In the synthesis method of A-1, “Safol 23 alcohol” (trade name; mixture of 55/45 by mass ratio of alcohol having 12 carbon atoms and alcohol having 13 carbon atoms, branching ratio ^{* 1} 50 mass% ) Synthesize | combined by the method similar to the synthesis method of A-1, except having used 224.4g and ethylene oxide (gaseous form) 763.4g.

A-3: fatty acid methyl ester ethoxylate, C ₁₁ H ₂₃ CO (OC ₂ H ₄ ) ₁₅ OCH ₃ , narrow ratio 65% by mass; synthetic product.
(Synthesis method of A-3)
Manufactured according to the synthesis method described in JP-A-2000-144179 (note that A-3 corresponds to sample D described in JP-A-2000-144179).
Here, the “narrow ratio” indicates a distribution ratio of ethylene oxide adducts having different addition moles of ethylene oxide, and is represented by the following formula (S).

［式中、ｎ_ｍａｘは全体のエチレンオキサイド付加体中に最も多く存在するエチレンオキサイド付加体のエチレンオキサイドの付加モル数を示す。ｉはエチレンオキサイドの付加モル数を示す。Ｙｉは全体のエチレンオキサイド付加体中に存在するエチレンオキサイドの付加モル数がｉであるエチレンオキサイド付加体の割合（質量％）を示す。］

[ _Wherein n _max represents the number of moles of ethylene oxide added in the ethylene oxide adduct most present in the entire ethylene oxide adduct. i represents the number of moles of ethylene oxide added. Yi represents the ratio (% by mass) of the ethylene oxide adduct having an added mole number of ethylene oxide present in the entire ethylene oxide adduct. ]

-(B) component B-1: Dibutylhydroxytoluene, the Degussa company make, brand name "K-NOX BHT".
B-2: dl-α-tocopherol, manufactured by Junsei Chemical Co., Ltd., trade name “DL-α-Tocopherol”, reagent.

-Component (C): C-1: Trisodium citrate dihydrate, manufactured by Miles (USA), trade name "soda citrate".
C-2: Malic acid, manufactured by Roche, trade name “DL-malic acid”.

-(D) component D-1: Sodium linear alkylbenzenesulfonate (C10-C14 of alkyl group), manufactured by Lion Corporation.
D-2: Didecyldimethylammonium chloride, manufactured by Lion Akzo Co., Ltd., trade name “Arcade 210”.
D-3: Stearyltrimethylammonium chloride, manufactured by Lion Akzo, trade name “ARCARD T-800”.

-(E) component E-1: Myrtaceae Melaleuca (Meraleuca) genus plant (tea tree oil).
E-2: Rosa family (Rosa) genus plant (rose oil).
E-3: Labiatae Mosla (Mothra) plant (Yamajiso oil).
E-4: Ginger family Amoum (Amomumu) genus plant (condensed sand).
(Method for preparing E-1 to E-3)
The leaves of the genus Melaleuca plant (M. alternifolia: tea tree), the rose plant (R. damascena: rose), the plant part of the moss family (M. japonica) are dried. Each plant extract was obtained by steam-distilling 1 kg of each dried product.
(Method for preparing E-4)
The above-ground part and seeds of the ginger family Ammomaides genus (A. xanthioides: shredded sand) were dried and pulverized to obtain a crude powder. 10 g of each crude powder was immersed in 70% by mass of ethanol and extracted at room temperature for 5 days. Thereafter, the extract obtained by filtering the residue was concentrated under reduced pressure to obtain a plant extract.

-Arbitrary component Ethanol: The product name "95 vol% synthetic ethanol" made from NEDO.
Polyethylene glycol: manufactured by NOF Corporation, trade name “PEG # 1000”, weight average molecular weight 1000.
Alkyl amino acid: laurylaminopropionic acid Na;
HEDP: 1-hydroxyethane-1,1-diphosphonic acid, manufactured by ALBRITE & WILSON, trade name “BRIQUEST ADPA-A”.
Monoethanolamine: manufactured by Nippon Shokubai Co., Ltd.
p-Toluenesulfonic acid: manufactured by Kyowa Hakko Kogyo Co., Ltd.
Fragrance | flavor: The fragrance | flavor composition of Tables 11-18 of Unexamined-Japanese-Patent No. 2002-146399.
Sulfuric acid: Toho Zinc Co., Ltd.
Sodium hydroxide: manufactured by Tsurumi Soda Co., Ltd.

≪Evaluation≫
The obtained liquid detergent composition for clothing was evaluated by the following methods and evaluation criteria, and the results are also shown in Table 1.

<Evaluation of water absorption>
(Cleaning method)
30 L of water (15 ° C., 4 ° DH) is put into a tank of a two-layer washing machine (Mitsubishi Electric Co., Ltd., product number: CW-30A1-H1), and the liquid cleaning composition for clothing of each example is used. It added so that a density | concentration might be 0.066 mass%.
Next, 10 commercially available cotton towels were placed in the bath, washed for 10 minutes, and dehydrated for 1 minute. Thereafter, it was rinsed with running water for 1 minute, dehydrated for 1 minute, air-dried indoors, and left in a constant temperature and humidity room at 20 ° C. and 50% RH for 24 hours.
(Determination method of water absorption)
Five pieces of cloth cut into a size of 2.5 cm × 20 cm were prepared from the washed cotton towel. Next, the cloth piece is suspended vertically, and the cloth piece up to 1 cm at the lower end side is dipped in tap water stored in a stainless steel water tank of 8 cm in length, 28 cm in width, and 3 cm in height, and tap water is drawn from the lower end of the cloth piece. Was raised using capillary action. And the water absorption height (mm) 10 minutes after the time of making the lower end of this cloth piece contact tap water was measured, and the water absorption of the cloth piece after washing and drying was evaluated based on the following reference | standard.
However, the higher the water absorption height, the better the water absorption (according to JIS L1907, Bayrec method).
(Evaluation criteria for water absorption height)
A: 140 mm or more.
○: 120 mm or more and less than 140 mm.
Δ: 100 mm or more and less than 120 mm
X: Less than 100 mm.

<Evaluation of storage stability of pH>
About the liquid cleaning composition for clothes of each example, pH before and after storage for 1 month was each measured at 50 degreeC, and the storage stability of pH was evaluated based on the following evaluation criteria.
A: The difference between the pH before storage and the pH after storage was less than 0.2.
A: The difference between the pH before storage and the pH after storage was 0.2 or more and less than 0.4.
X: The difference between the pH before storage and the pH after storage was 0.4 or more.

<Evaluation of deodorizing effect>
With the liquid cleaning composition for clothing of each example, after washing and drying the fibers according to the following washing method, the smell of the fibers was sniffed, and the deodorizing effect of malodor was evaluated based on the following evaluation criteria.
(Washing method)
A hand towel used for half a year at home was further used for about 3 days in the kitchen, and then cut into a test cloth. (However, the test cloth is a hand towel with an intense smell of 5 levels according to the following evaluation criteria. .)
The test cloth is put in a fully automatic washing machine (product number: NA-F70SD1) together with 3 kg of other clothing for bath ratio adjustment, and tap water with a temperature of about 20 ° C. and a hardness of about 3 ° DH is injected. And I did laundry on the Omakase Course.
The input amount of the liquid detergent composition for clothing in each example was in accordance with the detergent amount display of the fully automatic washing machine. In addition, a new 100% cotton skin shirt (manufactured by BVD) is used for 3 kg of clothing for bath ratio matching, and the next washing process, that is, a fully automatic washing machine (manufactured by Matsushita Electric Industrial Co., Ltd., product number: NA) -F70SD1), a commercial synthetic detergent top (manufactured by Lion Co., Ltd.) is introduced, tap water with a hardness of about 3 ° DH at a temperature of about 20 ° C is poured, and washing is performed three times on the Omakase Course. It was.
(Drying method)
After the washing was completed, it was dried in a room at room temperature (about 25 ° C.) and a humidity of 90% RH and dried for 5 hours.
(Evaluation criteria)
Sensory evaluation of odor was performed by six panelists on the hand towels treated by the above washing and drying methods, respectively, and scored based on the following evaluation criteria.
5 points: Strong smell.
4 points: Strong odor.
3 points: A smell that can be easily detected.
2 points: A weak odor that tells what smell it is.
1 point: Smell felt faintly.
0 points: No smell.
As a result of sensory evaluation, an average score of 6 persons was calculated, and if it was less than 3 points (Δ, ○, ◎), it was determined that the deodorizing effect was good.
A: 0 or more and less than 1 point.
○: 1 point or more and less than 2 points.
Δ: 2 or more and less than 3 points.
X: 3 or more points.

From the results of Table 1, Examples 1 to 5 according to the present invention are superior to Comparative Examples 1 to 3 in terms of water absorption after washing and drying, and have good pH storage stability. did it.
Moreover, Examples 3-5 containing (E) component have confirmed that the deodorizing effect was also favorable in addition to the water absorption of the wash thing after washing and drying, and the storage stability of pH.

Claims (3)

From the group of the nonionic surfactant (A) represented by the following general formula (1), the antioxidant (B), polyvalent carboxylic acid, hydroxycarboxylic acid, polyvalent carboxylate and hydroxycarboxylate For clothing comprising at least one selected from (C) and having an anionic surfactant and / or a cationic surfactant (D) content of less than 0 to less than 0.5% by mass Liquid detergent composition.

[Wherein, R ¹ is a linear or branched alkyl group or alkenyl group; —X— is —O— or —COO—, and when —X— is —O—, the carbon of R ¹ The number is 10 to 20, and R ² is a hydrogen atom. When —X— is —COO—, R ¹ has 7 to 13 carbon atoms and R ² is a methyl group or an ethyl group. N represents the average number of moles of ethylene oxide added, and is a number from 10 to 20. ]   At least one plant extract (E) selected from the group of the genus Melaleuca, Rosa, Rosa, Mosla, and Ginger Amoum The liquid cleaning composition for clothing according to claim 1, further comprising: The liquid detergent composition for clothes according to claim 1 or 2, which has a pH of 3 to 10 at 25 ° C.