JP2016035059A - Liquid detergent for fiber product - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a liquid detergent for a fiber product that can give a fragrance of the detergent to a fiber product while keeping the fragrance thereof, and also has improved detergency.SOLUTION: A liquid detergent for a fiber product comprises at least one selected from compounds represented by formula (A1) and formula (A2), an anion surfactant, at least one selected from a specific amine compound or a specific quaternary ammonium compound, and a flavor. The liquid detergent for a fiber product may further comprise a silicone compound and a flavor precursor. (Xto Xand Xto Xeach independently represent H, alkali metal, alkaline earth metal or cationic ammonium; Ris H or a hydroxy group; m is 0 or 1; Ris an alkyl group, a carboxy group, a sulfo group, an amino group, a hydroxy group or H; n is an integer of 0-5).SELECTED DRAWING: None

Description

  The present invention relates to a liquid detergent for textile products.

In recent years, consumer interest in fragrance has increased. For example, at the time of washing, a scent is imparted (perfumed) to a textile product such as clothing using a detergent containing a fragrance.
Patent Document 1 discloses at least one water-soluble metal salt selected from the group consisting of a water-soluble salt of copper, a water-soluble salt of zinc, and a water-soluble salt of silver, a specific chelating agent, and a specific amine compound. Or the liquid detergent containing a specific quaternary ammonium compound and a fragrance | flavor is disclosed. In this liquid detergent, improvement of the residual fragrance of the scent added to the textile product (polyester (PE) garment) after washing and improvement of the anti-recontamination performance in PE garment are achieved.

JP 2013-177512 A

However, when the liquid detergent described in Patent Document 1 is used, the scent of the textile product after washing is not the same as the scent of the liquid detergent. Thus, conventionally, it has been difficult for fiber products to be scented while maintaining the fragrance of the cleaning agent during cleaning.
In addition, the liquid cleaning agent described in Patent Document 1 is prone to re-contamination, particularly in cotton fiber products, and the cleaning effect is insufficient.
This invention is made | formed in view of the said situation, and makes it a subject the liquid cleaning agent for textiles which can perfume textiles, maintaining the aroma of a cleaning agent, and the cleaning effect was improved.

As a result of intensive studies, the present inventors provide the following means in order to solve the above problems.
That is, the liquid detergent for textiles of the present invention is at least selected from the group consisting of component (A): a compound represented by the following general formula (A1) and a compound represented by the following general formula (A2). 1 type, (B) component: Anionic surfactant, (C) component: The compound represented by the following general formula (C1), the salt of the compound represented by the following general formula (C1), and the following general formula It contains at least one selected from the group consisting of the compound represented by (C2) and (D) component: a fragrance.

［式（Ａ１）中、Ｘ^１１〜Ｘ^１４は、それぞれ独立に、水素原子、アルカリ金属、アルカリ土類金属又はカチオン性アンモニウムを表す。Ｒ^１０は、水素原子又はヒドロキシ基を表す。ｍは、０又は１を表す。式（Ａ２）中、Ｘ^２１〜Ｘ^２３は、それぞれ独立に、水素原子、アルカリ金属、アルカリ土類金属又はカチオン性アンモニウムを表す。Ｒ^２０は、アルキル基、カルボキシ基、スルホ基、アミノ基、ヒドロキシ基又は水素原子を表す。ｎは、０〜５の整数を表す。］

[In Formula (A1), X ^{11 to} X ¹⁴ each independently represents a hydrogen atom, an alkali metal, an alkaline earth metal, or cationic ammonium. R ¹⁰ represents a hydrogen atom or a hydroxy group. m represents 0 or 1. In formula (A2), X ^{21 to} X ²³ each independently represent a hydrogen atom, an alkali metal, an alkaline earth metal, or cationic ammonium. R ²⁰ represents an alkyl group, a carboxy group, a sulfo group, an amino group, a hydroxy group, or a hydrogen atom. n represents an integer of 0 to 5. ]

［式（Ｃ１）中、Ｒ^１は、炭素数７〜２７の直鎖状又は分岐鎖状の炭化水素基を表す。Ｒ^１における炭化水素基は、ヒドロキシ基及びアミノ基からなる群より選択される少なくとも１種の置換基を有していてもよく、炭素鎖中に連結基を有していてもよい。Ｒ^２は、炭素数１〜２５の直鎖状又は分岐鎖状の炭化水素基を表す。Ｒ^２における炭化水素基は、置換基としてヒドロキシ基を有していてもよく、炭素鎖中に連結基を有していてもよい。Ｒ^３は、炭素数１〜４の直鎖状もしくは分岐鎖状のアルキル基、炭素数１〜４の直鎖状もしくは分岐鎖状のヒドロキシアルキル基、又は、−（ＣＨ_２ＣＨ_２Ｏ）_ｐ−Ｈで表される基（ｐは、１〜２５の整数を表す。）を表す。式（Ｃ２）中、Ｒ^１１及びＲ^１２は、それぞれ独立に、水素原子、炭素数１〜２５の直鎖状もしくは分岐鎖状の炭化水素基、又は、−（ＣＨ_２ＣＨ_２Ｏ）_ｑ−Ｈで表される基（ｑは、１〜２５の整数を表す。）を表す。Ｒ^１１及びＲ^１２における炭化水素基は、それぞれ独立に、置換基を有していてもよく、炭素鎖中に連結基を有していてもよい。Ｒ^１３は、炭素数８〜２５の直鎖状又は分岐鎖状の炭化水素基を表す。Ｒ^１３における炭化水素基は、置換基を有していてもよく、炭素鎖中に連結基を有していてもよい。Ｒ^１４は、水素原子、炭素数１〜３の直鎖状もしくは分岐鎖状のアルキル基、炭素数１〜３の直鎖状もしくは分岐鎖状のヒドロキシアルキル基、又は、−（ＣＨ_２ＣＨ_２Ｏ）_ｒ−Ｈで表される基（ｒは、１〜２５の整数を表す。）を表す。Ｚ⁻は、対アニオンを表す。］

[In Formula (C1), R ¹ represents a linear or branched hydrocarbon group having 7 to 27 carbon atoms. The hydrocarbon group for R ¹ may have at least one substituent selected from the group consisting of a hydroxy group and an amino group, and may have a linking group in the carbon chain. R ² represents a linear or branched hydrocarbon group having 1 to 25 carbon atoms. The hydrocarbon group in R ² may have a hydroxy group as a substituent and may have a linking group in the carbon chain. R ³ is a linear or branched alkyl group having 1 to 4 carbon atoms, a linear or branched hydroxyalkyl group having 1 to 4 carbon atoms, or — (CH ₂ CH ₂ O) _p. Represents a group represented by —H (p represents an integer of 1 to 25). In formula (C2), R ¹¹ and R ¹² are each independently a hydrogen atom, a linear or branched hydrocarbon group having 1 to 25 carbon atoms, or — (CH ₂ CH ₂ O) _q —. A group represented by H (q represents an integer of 1 to 25). The hydrocarbon groups in R ¹¹ and R ¹² may each independently have a substituent and may have a linking group in the carbon chain. R ¹³ represents a linear or branched hydrocarbon group having 8 to 25 carbon atoms. The hydrocarbon group for R ¹³ may have a substituent and may have a linking group in the carbon chain. R ¹⁴ represents a hydrogen atom, a linear or branched alkyl group having 1 to 3 carbon atoms, a linear or branched hydroxyalkyl group having 1 to 3 carbon atoms, or — (CH ₂ CH ₂ O) A group represented by _r- H (r represents an integer of 1 to 25). Z ⁻ represents a counter anion. ]

  In the liquid detergent for textiles of this invention, it is preferable to further contain (E) component: silicone compound.

  Moreover, in the liquid detergent for textiles of this invention, it is preferable to further contain (F) component: a fragrance | flavor precursor.

  The liquid detergent for textiles of the present invention can perfume textiles while maintaining the fragrance of the detergent, and can enhance the cleaning effect.

The liquid detergent for textiles of the present invention (hereinafter also simply referred to as “liquid detergent”) is composed of (A) component: a compound represented by the general formula (A1) and a compound represented by the general formula (A2). At least one selected from the group consisting of: (B) component: an anionic surfactant; (C) component: a compound represented by general formula (C1); a compound represented by general formula (C1) It contains at least one selected from the group consisting of a salt and a compound represented by the general formula (C2), and component (D): a fragrance.
The liquid detergent of the present invention can be used for both household use and industrial use, and is particularly suitable for home use.
Examples of the types of objects to be cleaned include those similar to those to be cleaned by washing at home, and examples thereof include textiles such as clothes, cloths, towels, and sheets.

<(A) component>
The component (A) is a compound represented by the following general formula (A1) (hereinafter also referred to as “(A1) component”) and a compound represented by the following general formula (A2) (hereinafter “(A2) component”). Or at least one selected from the group consisting of: The component (A), when dissolved in water, -COO within the molecule dissociation ^- produce.
In the liquid cleaning agent of the present invention, by containing the component (A), the effect (fragrance maintenance performance) that the fiber product can be scented while maintaining the fragrance of the cleaning agent is further enhanced.

［式（Ａ１）中、Ｘ^１１〜Ｘ^１４は、それぞれ独立に、水素原子、アルカリ金属、アルカリ土類金属又はカチオン性アンモニウムを表す。Ｒ^１０は、水素原子又はヒドロキシ基を表す。ｍは、０又は１を表す。式（Ａ２）中、Ｘ^２１〜Ｘ^２３は、それぞれ独立に、水素原子、アルカリ金属、アルカリ土類金属又はカチオン性アンモニウムを表す。Ｒ^２０は、アルキル基、カルボキシ基、スルホ基、アミノ基、ヒドロキシ基又は水素原子を表す。ｎは、０〜５の整数を表す。］

[In Formula (A1), X ^{11 to} X ¹⁴ each independently represents a hydrogen atom, an alkali metal, an alkaline earth metal, or cationic ammonium. R ¹⁰ represents a hydrogen atom or a hydroxy group. m represents 0 or 1. In formula (A2), X ^{21 to} X ²³ each independently represent a hydrogen atom, an alkali metal, an alkaline earth metal, or cationic ammonium. R ²⁰ represents an alkyl group, a carboxy group, a sulfo group, an amino group, a hydroxy group, or a hydrogen atom. n represents an integer of 0 to 5. ]

≪ (A1) component≫
In the formula (A1), X ^{11 to} X ¹⁴ each independently represent a hydrogen atom, an alkali metal, an alkaline earth metal, or cationic ammonium.
Examples of preferred alkali metals in X ^{11 to} X ¹⁴ include sodium and potassium.
In the present invention, the “alkaline earth metal” includes beryllium and magnesium (Group 2 element) in addition to calcium, strontium, barium and radium. Preferable alkaline earth metals in X ^{11 to} X ¹⁴ include magnesium, calcium and the like. For example, if ^{X 11} is calcium, ^-COOX 11 forms a -COO · 1 / 2Ca.
As preferred cationic ammonium in X ^{11 to} X ¹⁴ , ammonium (NH ₄ ), 1 to 3 hydrogen atoms of the ammonium are alkanol groups (— (CH ₂ ) _k —OH; k is the number of repeating methylene groups And the like (this is referred to as “alkanol ammonium”). k is preferably 1, 2 or 3. Preferable alkanol ammonium includes monoethanol ammonium, diethanol ammonium, triethanol ammonium and the like.
Among these, X ^{11 to} X ¹⁴ are preferably alkali metals and cationic ammonium, and more preferably alkali metals, since the fragrance maintenance performance is more likely to be improved.
X ^{11 to} X ¹⁴ may be the same as or different from each other.

In the formula (A1), R ¹⁰ represents a hydrogen atom or a hydroxy group.
In the formula (A1), m represents 0 or 1, and 1 is preferable because the fragrance maintenance performance is more easily improved.

Specific examples of the component (A1) include iminodisuccinic acid, 3-hydroxy-2,2′-iminodisuccinic acid or salts thereof.
Examples of the salt form include alkali metal salts such as sodium salt and potassium salt; alkanol ammonium salts such as monoethanolammonium salt, diethanolammonium salt and triethanolammonium salt. Alkali metal salts are preferred.

≪ (A2) component≫
In the formula (A2), X ^{21 to} X ²³ each independently represent a hydrogen atom, an alkali metal, an alkaline earth metal, or cationic ammonium. Examples of X ^{21 to} X ²³ include the same as X ^{11 to} X ¹⁴ in the formula (A1).
Among these, X ^{21 to} X ²³ are preferably an alkali metal and cationic ammonium, and more preferably an alkali metal, since the fragrance maintenance performance is easily improved.
X ^{21 to} X ²³ may be the same as or different from each other.

In the formula (A2), R ²⁰ represents an alkyl group, a carboxy group, a sulfo group (—SO ₂ (OH)), an amino group (—NH ₂ ), a hydroxy group, or a hydrogen atom.
The alkyl group for R ²⁰ may be linear or branched. 1-30 are preferable and, as for carbon number of this alkyl group, 1-18 are more preferable. In the alkyl group for R ²⁰ , part of the hydrogen atoms may be substituted with a substituent. Examples of the substituent include a sulfo group (—SO ₂ (OH)), an amino group (—NH ₂ ), a hydroxy group, a nitro group (—NO ₂ ), and the like.
Among these, R ²⁰ is preferably a carboxy group, a hydroxy group, or a hydrogen atom, and more preferably a hydrogen atom, since the fragrance maintenance performance is more easily improved.

  In said formula (A2), n represents the integer of 0-5, and since fragrance maintenance performance improves more easily, 0, 1 or 2 is preferable and 1 is especially preferable.

Specific examples of the component (A2) include nitrilotriacetic acid, methyl glycine diacetic acid, dicarboxymethyl glutamic acid, L-aspartic acid-N, N-diacetic acid, serine diacetic acid, and salts thereof, among these. Methyl glycine diacetic acid or a salt thereof is preferred.
Examples of the salt form include alkali metal salts such as sodium salt and potassium salt; alkanol ammonium salts such as monoethanolammonium salt, diethanolammonium salt and triethanolammonium salt. Alkali metal salts are preferred.

As the component (A), one type may be used alone, or two or more types may be used in appropriate combination.
Among these, the component (A) is preferably the component (A2) because the fragrance maintenance performance is particularly easily improved.
The content of the component (A) in the liquid detergent for textiles is preferably 0.1 to 10% by mass, more preferably 0.2 to 5% by mass with respect to the total mass of the liquid detergent, Preferably it is 0.3-3 mass%.
When the content of the component (A) is equal to or more than the preferable lower limit value, the fragrance maintenance performance is further improved. On the other hand, even if it exceeds the preferable upper limit value, it is difficult to obtain an effect of improving the fragrance maintenance performance, which is disadvantageous economically.

<(B) component>
(B) component is an anionic surfactant and can use the well-known thing conventionally used for detergents for clothes.
In the liquid cleaning agent of this invention, by containing (B) component, a cleaning effect is exhibited and in addition, aroma maintenance performance is improved more. In addition, recontamination, especially on cotton fibers, is suppressed.

Examples of the component (B) include linear alkylbenzene sulfonates, α-olefin sulfonates, linear or branched alkyl sulfates, alkyl ether sulfates, alkenyl ether sulfates, and alkyl groups. Alkane sulfonic acid salt having α-sulfo fatty acid ester salt; higher fatty acid salt (soap), alkyl ether carboxylate, polyoxyalkylene ether carboxylate, alkyl amide ether carboxylate, alkenyl amide ether carboxylate, acyl Carboxylic acid type anionic surfactants such as aminocarboxylates; alkyl phosphate ester salts, polyoxyalkylene alkyl phosphate ester salts, polyoxyalkylene alkyl phenyl phosphate ester salts, glycerin fatty acid ester monophosphate ester salts, etc. And phosphoric acid ester type anionic surfactants.
Examples of these salts include alkali metal salts such as sodium and potassium; alkaline earth metal salts such as magnesium; alkanol ammonium salts such as monoethanolammonium salt, diethanolammonium salt and triethanolammonium salt.

(B) A component may be used individually by 1 type and may be used in combination of 2 or more types as appropriate.
As the component (B), among the above, since the effects of the present invention (fragrance maintenance performance, cleaning effect) are more easily exhibited, linear alkylbenzene sulfonate, α-olefin sulfonate, linear or branched Chain alkyl sulfates, alkyl ether sulfates, alkenyl ether sulfates, alkane sulfonates having an alkyl group, α-sulfo fatty acid ester salts, and higher fatty acid salts (soaps) are preferred.

As the linear alkylbenzene sulfonate, a linear alkyl group having 8 to 16 carbon atoms is preferable, and a linear alkyl group having 10 to 14 carbon atoms is more 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 group having 10 to 20 carbon atoms, or a linear or branched alkenyl group having 10 to 20 carbon atoms. A polyoxyethylene alkyl ether sulfate ester salt or a polyoxyethylene alkenyl ether sulfate ester salt added with an average of 1 to 10 moles of ethylene oxide 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 preferable.
As the α-sulfo fatty acid ester salt, an α-sulfo fatty acid ester salt having 10 to 20 carbon atoms is preferable.
As the higher fatty acid salt, a fatty acid salt having 10 to 20 carbon atoms is preferable.
Among these, the component (B) is composed of a linear alkylbenzene sulfonate, alkane sulfonate, alkyl ether sulfate ester salt, α-olefin sulfonate salt and higher fatty acid salt because of its high anti-recontamination effect. At least one anionic surfactant selected from the group is preferred, at least one anionic surfactant selected from the group consisting of linear alkylbenzene sulfonates and higher fatty acid salts is more preferred, linear alkylbenzene sulfonic acids A combination of a salt and a higher fatty acid salt is particularly preferred.

The content of the component (B) in the liquid detergent for textile products is preferably 1 to 30% by mass, more preferably 3 to 25% by mass, and further preferably 6 to 4%, based on the total mass of the liquid detergent. 20% by mass.
When the content of the component (B) is equal to or more than the preferable lower limit, the fragrance maintenance performance and the cleaning effect are further improved. On the other hand, even if the above preferable upper limit is exceeded, it is difficult to obtain the effect of improving the fragrance maintenance performance and the cleaning effect, which is economically disadvantageous.

<(C) component>
The component (C) includes a compound represented by the following general formula (C1), a salt of a compound represented by the following general formula (C1) (hereinafter collectively referred to as “component (C1)”), and the following. Selected from the group consisting of the compound represented by the general formula (C2) (excluding those corresponding to the salt of the compound represented by the general formula (C1)) (hereinafter also referred to as “component (C2)”). Is at least one kind.
In the liquid detergent of this invention, a fragrance maintenance performance is exhibited mainly by containing (C) component.

［式（Ｃ１）中、Ｒ^１は、炭素数７〜２７の直鎖状又は分岐鎖状の炭化水素基を表す。Ｒ^１における炭化水素基は、ヒドロキシ基及びアミノ基からなる群より選択される少なくとも１種の置換基を有していてもよく、炭素鎖中に連結基を有していてもよい。Ｒ^２は、炭素数１〜２５の直鎖状又は分岐鎖状の炭化水素基を表す。Ｒ^２における炭化水素基は、置換基としてヒドロキシ基を有していてもよく、炭素鎖中に連結基を有していてもよい。Ｒ^３は、炭素数１〜４の直鎖状もしくは分岐鎖状のアルキル基、炭素数１〜４の直鎖状もしくは分岐鎖状のヒドロキシアルキル基、又は、−（ＣＨ_２ＣＨ_２Ｏ）_ｐ−Ｈで表される基（ｐは、１〜２５の整数を表す。）を表す。式（Ｃ２）中、Ｒ^１１及びＲ^１２は、それぞれ独立に、水素原子、炭素数１〜２５の直鎖状もしくは分岐鎖状の炭化水素基、又は、−（ＣＨ_２ＣＨ_２Ｏ）_ｑ−Ｈで表される基（ｑは、１〜２５の整数を表す。）を表す。Ｒ^１１及びＲ^１２における炭化水素基は、それぞれ独立に、置換基を有していてもよく、炭素鎖中に連結基を有していてもよい。Ｒ^１３は、炭素数８〜２５の直鎖状又は分岐鎖状の炭化水素基を表す。Ｒ^１３における炭化水素基は、置換基を有していてもよく、炭素鎖中に連結基を有していてもよい。Ｒ^１４は、水素原子、炭素数１〜３の直鎖状もしくは分岐鎖状のアルキル基、炭素数１〜３の直鎖状もしくは分岐鎖状のヒドロキシアルキル基、又は、−（ＣＨ_２ＣＨ_２Ｏ）_ｒ−Ｈで表される基（ｒは、１〜２５の整数を表す。）を表す。Ｚ⁻は、対アニオンを表す。］

[In Formula (C1), R ¹ represents a linear or branched hydrocarbon group having 7 to 27 carbon atoms. The hydrocarbon group for R ¹ may have at least one substituent selected from the group consisting of a hydroxy group and an amino group, and may have a linking group in the carbon chain. R ² represents a linear or branched hydrocarbon group having 1 to 25 carbon atoms. The hydrocarbon group in R ² may have a hydroxy group as a substituent and may have a linking group in the carbon chain. R ³ is a linear or branched alkyl group having 1 to 4 carbon atoms, a linear or branched hydroxyalkyl group having 1 to 4 carbon atoms, or — (CH ₂ CH ₂ O) _p. Represents a group represented by —H (p represents an integer of 1 to 25). In formula (C2), R ¹¹ and R ¹² are each independently a hydrogen atom, a linear or branched hydrocarbon group having 1 to 25 carbon atoms, or — (CH ₂ CH ₂ O) _q —. A group represented by H (q represents an integer of 1 to 25). The hydrocarbon groups in R ¹¹ and R ¹² may each independently have a substituent and may have a linking group in the carbon chain. R ¹³ represents a linear or branched hydrocarbon group having 8 to 25 carbon atoms. The hydrocarbon group for R ¹³ may have a substituent and may have a linking group in the carbon chain. R ¹⁴ represents a hydrogen atom, a linear or branched alkyl group having 1 to 3 carbon atoms, a linear or branched hydroxyalkyl group having 1 to 3 carbon atoms, or — (CH ₂ CH ₂ O) A group represented by _r- H (r represents an integer of 1 to 25). Z ⁻ represents a counter anion. ]

≪ (C1) component≫
In the formula (C1), R ¹ represents a linear or branched hydrocarbon group having 7 to 27 carbon atoms. The hydrocarbon group for R ¹ may be a saturated hydrocarbon group or an unsaturated hydrocarbon group. The number of carbon atoms of the hydrocarbon group for R ¹ is preferably 7-25.
The hydrocarbon group in R ¹ may have at least one substituent selected from the group consisting of a hydroxy group and an amino group (—NH ₂ ), and has a linking group in the carbon chain. Also good. Note that the carbon number of the substituent or the linking group that R ¹ may have is not included in the carbon number of 7 to 27 of the hydrocarbon group in R ¹ .
Examples of the linking group that may be present in the carbon chain in R ¹ include an amide group (—C (═O) —NH—), an ester group (—C (═O) —O—), and an ether group. (-O-) is mentioned, and an amide group and an ester group are preferable.

Among the above, R ¹ is preferably a linear or branched hydrocarbon group having 7 to 27 carbon atoms and having a linking group in the carbon chain.
Preferable R ¹ includes, for example, a group represented by —R ⁶ —R ⁷ .
R ⁶ represents a linear or branched alkylene group having 1 to 4 carbon atoms. Among these, a linear alkylene group having 1 to 4 carbon atoms is preferable, and a linear alkylene group having 1 to 3 carbon atoms is more preferable.
R ⁷ represents a group represented by —NH—C (═O) —R ⁸ or —O—C (═O) —R ⁹ .
R ⁸ represents a hydrocarbon group having 7 to 23 carbon atoms, preferably a hydrocarbon group having 7 to 21 carbon atoms. The hydrocarbon group for R ⁸ may be linear or branched, and may be a saturated hydrocarbon group or an unsaturated hydrocarbon group.
R ⁹ represents a hydrocarbon group having 11 to 23 carbon atoms, preferably a hydrocarbon group having 12 to 20 carbon atoms. The hydrocarbon group for R ⁹ may be linear or branched, and may be a saturated hydrocarbon group or an unsaturated hydrocarbon group.

In the formula (C1), ^{R 2} represents a linear or branched hydrocarbon group having 1 to 25 carbon atoms. The hydrocarbon group for R ² may be a saturated hydrocarbon group or an unsaturated hydrocarbon group. The number of carbon atoms of the hydrocarbon group for R ² is preferably 1 to 20, 1 to 4 carbon atoms is more preferred.
The hydrocarbon group in R ² may have a hydroxy group as a substituent and may have a linking group in the carbon chain. In addition, the carbon number of the connecting group that R ² may have is not included in the carbon number 1 to 25 of the hydrocarbon group in R ² .
Examples of the linking group that may be present in the carbon chain in R ² include an amide group (—C (═O) —NH—), an ester group (—C (═O) —O—), and an ether group. (-O-) is mentioned.
Among the above, R ² is preferably a linear or branched hydrocarbon group having 1 to 25 carbon atoms, which may have a hydroxy group as a substituent. Among these, a linear or branched alkyl group having 1 to 4 carbon atoms and a linear or branched hydroxyalkyl group having 1 to 4 carbon atoms are more preferable, and a linear chain having 1 to 4 carbon atoms. Or a branched alkyl group is more preferable.

In the formula (C1), R ³ represents a linear or branched alkyl group having 1 to 4 carbon atoms, a linear or branched hydroxyalkyl group having 1 to 4 carbon atoms, or-( CH ₂ CH ₂ O) A group represented by _p— H (p represents an integer of 1 to 25).
Among these, a linear or branched alkyl group having 1 to 4 carbon atoms and a linear or branched hydroxyalkyl group having 1 to 4 carbon atoms are preferable, and a linear chain having 1 to 4 carbon atoms. Alternatively, a branched alkyl group is more preferable.

As the component (C1), one type may be used alone, or two or more types may be used in appropriate combination.
Among the components (C1), a compound represented by the following general formula (C1-1) or a salt thereof is preferable.

［式（Ｃ１−１）中、Ｒ^４及びＲ^５は、それぞれ独立に、炭素数１〜４の直鎖状もしくは分岐鎖状のアルキル基、又は、炭素数１〜４の直鎖状もしくは分岐鎖状のヒドロキシアルキル基を表す。Ｒ^６は、炭素数１〜４の直鎖状又は分岐鎖状のアルキレン基を表す。Ｒ^７は、−ＮＨ−Ｃ（＝Ｏ）−Ｒ^８、又は、−Ｏ−Ｃ（＝Ｏ）−Ｒ^９で表される基を表す。Ｒ^８は、炭素数７〜２３の炭化水素基を表す。Ｒ^９は、炭素数１１〜２３の炭化水素基を表す。］

[In Formula (C1-1), R ⁴ and R ⁵ are each independently a linear or branched alkyl group having 1 to 4 carbon atoms, or a linear or branched group having 1 to 4 carbon atoms. Represents a chained hydroxyalkyl group. R ⁶ represents a linear or branched alkylene group having 1 to 4 carbon atoms. R ⁷ represents a group represented by —NH—C (═O) —R ⁸ or —O—C (═O) —R ⁹ . R ⁸ represents a hydrocarbon group having 7 to 23 carbon atoms. R ⁹ represents a hydrocarbon group having 11 to 23 carbon atoms. ]

In the formula (C1-1), R ⁴ and R ⁵ are each preferably a linear or branched alkyl group having 1 to 4 carbon atoms, and a linear alkyl group having 1 to 4 carbon atoms. More preferably, a linear alkyl group having 1 to 3 carbon atoms is more preferable, and a methyl group is particularly preferable.
In formula (C1-1), R ⁶ , R ⁷ , R ⁸ , and R ⁹ are the same as described above.

Specific examples of the component (C1) include caprylic acid dimethylaminopropylamide, capric acid dimethylaminopropylamide, lauric acid dimethylaminopropylamide, myristic acid dimethylaminopropylamide, palmitic acid dimethylaminopropylamide, stearic acid dimethylaminopropyl. Long chain aliphatic amide dialkyl tertiary amines such as amides, behenic acid dimethylaminopropylamide, oleic acid dimethylaminopropylamide; long chain aliphatic amide dialkanols such as palmitic acid diethanolaminopropylamide, stearic acid diethanolaminopropylamide 3 Tertiary amines; aliphatic ester dialkyl tertiary amines such as palmitate ester propyldimethylamine and stearate ester propyldimethylamine; lauryl Methylamine, myristyl dimethylamine, coconut alkyl dimethylamine, palmityl dimethyl amine, tallow alkyl dimethylamine, hydrogenated tallow alkyl dimethyl amine, stearyl dimethylamine, stearyl diethanolamine, polyoxyethylene hardened beef tallow alkyl amine.
Among these, long-chain aliphatic amide dialkyl tertiary amines are preferable, and among them, it is more preferable to use palmitic acid dimethylaminopropylamide and stearic acid dimethylaminopropylamide in combination.
In the case of such combined use, the mass ratio of palmitic acid dimethylaminopropylamide / stearic acid dimethylaminopropylamide is preferably 10/90 to 50/50, more preferably 20/80 to 40/60. When this mass ratio is within the above-mentioned preferable range, the aroma maintenance performance is more easily exhibited, and the liquid stability is enhanced.

  The above-mentioned “long-chain aliphatic amidodialkyl tertiary amine” is a condensation reaction between a fatty acid or a fatty acid derivative (fatty acid lower alkyl ester or animal / vegetable oil or fat) and a dialkyl (or alkanol) aminoalkylamine, It can be produced by distilling off unreacted dialkyl (or alkanol) aminoalkylamine under reduced pressure or nitrogen blowing.

  Examples of the fatty acid or fatty acid derivative include caprylic acid, capric acid, lauric acid, myristic acid, palmitic acid, stearic acid, oleic acid, behenic acid, erucic acid, 12-hydroxystearic acid, coconut oil fatty acid, cottonseed oil fatty acid Corn oil fatty acid, beef tallow fatty acid, palm kernel oil fatty acid, soybean oil fatty acid, flaxseed oil fatty acid, castor oil fatty acid, olive oil fatty acid and other vegetable oil or animal oil fatty acid, or methyl ester, ethyl ester or glyceride thereof. Among these, caprylic acid, capric acid, lauric acid, myristic acid, palmitic acid, stearic acid, oleic acid, and behenic acid are particularly preferable. These fatty acids and fatty acid derivatives may be used alone or in combination of two or more.

Examples of the dialkyl (or alkanol) aminoalkylamine include dimethylaminopropylamine, dimethylaminoethylamine, diethylaminopropylamine, diethylaminoethylamine, and among them, dimethylaminopropylamine is particularly preferable.
The amount of dialkyl (or alkanol) aminoalkylamine used is preferably 0.9 to 2.0 moles, more preferably 1.0 to 1.5 moles, based on the fatty acid or fatty acid derivative.
The temperature condition of the condensation reaction is usually 100 to 220 ° C, preferably 150 to 200 ° C. By setting the reaction temperature to 100 ° C. or higher, the reaction rate can be kept moderate, and by setting it to 220 ° C. or lower, coloring of the resulting tertiary amine compound can be prevented or reduced.

The above “aliphatic ester dialkyl tertiary amine” is a fatty acid or a fatty acid derivative (fatty acid lower alkyl ester or animal / vegetable oil or the like) and a dialkylamino alcohol, followed by an unreacted dialkylamino alcohol. Can be produced by distilling it off under reduced pressure or nitrogen blowing.
Examples of the fatty acid or fatty acid derivative herein include the same fatty acids or fatty acid derivatives as those exemplified in the description of the above-mentioned “long-chain aliphatic amide dialkyl tertiary amine”.
Examples of dialkylamino alcohols here include distearyl amino alcohol, dimyristyl amino alcohol, and dioleyl amino alcohol.
The amount of dialkylamino alcohol used is preferably 0.1 to 5.0 times mol, more preferably 0.3 to 3.0 times mol, and 0.9 to 2.0 times mol for the fatty acid or fatty acid derivative. Is more preferable, and 1.0 to 1.5 times mole is particularly preferable.
The temperature condition of the condensation reaction is usually 100 to 220 ° C, preferably 120 to 180 ° C. When the temperature condition is within the above range, coloring of the resulting tertiary amine compound can be prevented or reduced while maintaining an appropriate reaction rate.

What is necessary is just to change suitably the manufacturing conditions other than the above about (C1) component with the kind etc. of the raw material to be used. For example, the pressure during the reaction may be normal pressure or reduced pressure. An inert gas such as nitrogen may be blown during the reaction.
Also, when using fatty acid as a raw material, by using an acid catalyst such as sulfuric acid or p-toluenesulfonic acid; when using a fatty acid derivative, it is low by using an alkali catalyst such as sodium methylate, caustic potash or caustic soda. The reaction can proceed more efficiently in a short time at the reaction temperature.
In addition, when the resulting tertiary amine compound is a compound having a high melting point, it is preferably formed into a flake shape or a pellet shape after the reaction in order to improve handling properties, or in an organic solvent such as ethanol. It is preferable to dissolve and make it liquid.

  Examples of the salt of the compound represented by the general formula (C1) include an acid salt obtained by neutralizing the compound with an acid. Examples of the acid used for neutralization include hydrochloric acid, sulfuric acid, nitric acid, phosphoric acid, glycolic acid, lactic acid, citric acid, polyacrylic acid, p-toluenesulfonic acid, cumenesulfonic acid and the like. These acids may be used individually by 1 type, and may use 2 or more types together.

≪ (C2) component≫
In the formula (C2), R ¹¹ and R ¹² are each independently a hydrogen atom, a linear or branched hydrocarbon group having 1 to 25 carbon atoms, or — (CH ₂ CH ₂ O) _q. The group represented by -H (q represents an integer of 1 to 25).
The hydrocarbon groups in R ¹¹ and R ¹² may each be a saturated hydrocarbon group or an unsaturated hydrocarbon group. The number of carbon atoms in the hydrocarbon group in R ¹¹ and ^{R 12,} preferably from 1 to 20, 1 to 4 carbon atoms is more preferred.
The hydrocarbon groups in R ¹¹ and R ¹² may each independently have a substituent and may have a linking group in the carbon chain. The carbon number of the substituent or the linking group that R ¹¹ and R ¹² may have is not included in the carbon number 1 to 25 of the hydrocarbon group in R ¹¹ and R ¹² . Examples of the substituent that the hydrocarbon group may have include a hydroxy group. Examples of the linking group that may be present in the carbon chain include an amide group (—C (═O) —NH—), an ester group (—C (═O) —O—), or an ether group (—O—). ) And the like.
Among the above, R ¹¹ and R ¹² are each preferably a hydrogen atom or a linear or branched hydrocarbon group which may have a substituent. Among these, a hydrogen atom, a linear or branched alkyl group having 1 to 4 carbon atoms, or a linear or branched hydroxyalkyl group having 1 to 4 carbon atoms is preferable, and a hydrogen atom or a carbon number having 1 to 4 carbon atoms is preferable. 4 linear or branched alkyl groups are more preferable, and a hydrogen atom and a methyl group are more preferable.
R ¹¹ and R ¹² are each preferably a linear or branched hydrocarbon group having an ester group in the carbon chain.

In the formula (C2), R ¹³ represents a linear or branched hydrocarbon group having 8 to 25 carbon atoms. The hydrocarbon group for R ¹³ may be a saturated hydrocarbon group or an unsaturated hydrocarbon group. The number of carbon atoms of the hydrocarbon group for R ¹³ is preferably 16 to 22.
The hydrocarbon group for R ¹³ may have a substituent and may have a linking group in the carbon chain. The carbon number of the substituent or the linking group that R ¹³ may have is not included in the carbon number of 8 to 25 of the hydrocarbon group in R ¹³ . Examples of the substituent that the hydrocarbon group may have include a hydroxy group. Examples of the linking group that may be present in the carbon chain include an amide group (—C (═O) —NH—), an ester group (—C (═O) —O—), or an ether group (—O—). ) And the like. Among them, an ester group is preferable.

In the formula (C2), R ¹⁴ represents a hydrogen atom, a linear or branched alkyl group having 1 to 3 carbon atoms, a linear or branched hydroxyalkyl group having 1 to 3 carbon atoms, or _{, - (CH 2 CH 2 O} ) groups represented by r -H (r represents an integer of 1 to 25.) represents the.
Among these, R ¹⁴ is preferably a hydrogen atom, a linear or branched alkyl group having 1 to 3 carbon atoms, or a linear or branched hydroxyalkyl group having 1 to 3 carbon atoms, and hydrogen. A linear or branched alkyl group having 1 to 3 carbon atoms is more preferred, and a hydrogen atom and a methyl group are more preferred.

In the formula (C2), Z ⁻ represents a counter anion. Specific examples of Z ⁻ include halogen atom ions such as chlorine ion, bromine ion and iodine ion; general formula R ¹⁵ SO ⁴⁻ , wherein R ¹⁵ is an alkyl group having 1 to 3 carbon atoms (for example, methyl group, Ethyl group, propyl group, etc.), particularly preferably a methyl group. And the like. Among these, halogen atom ions are preferable, and chlorine ions are more preferable.

As the component (C2), one type may be used alone, or two or more types may be used in appropriate combination.
Specific examples of the component (C2) include mono long chain alkyl quaternary ammonium salts such as cetyltrimethylammonium chloride, cetostearyltrimethylammonium chloride, stearyltrimethylammonium chloride, and behenyltrimethylammonium chloride; monoester ammonium salt, diester ammonium salt , Ester ammonium salts such as triester ammonium salts, or mixtures thereof. Of these, mono long-chain alkyl quaternary ammonium salts are preferred.

As the component (C), one type may be used alone, or two or more types may be used in appropriate combination.
Among these, the component (C) is preferably the component (C1) because of its higher fragrance maintenance performance.
The content of the component (C) in the liquid detergent for textiles is preferably 0.1 to 5% by mass, more preferably 0.2 to 3% by mass with respect to the total mass of the liquid detergent, Preferably it is 0.5-2 mass%.
When the content of the component (C) is equal to or more than the preferable lower limit value, the fragrance maintenance performance is further improved. On the other hand, even if the preferable upper limit value is exceeded, the fragrance maintenance performance commensurate with it is difficult to be exhibited, which is economically disadvantageous.

In the present invention, “mass ratio represented by component (B) / component (C)” means component (B) relative to the content (mass%) of component (C) contained in the liquid detergent for textiles. It means the ratio of the content (mass%).
The mass ratio represented by the component (B) / (C) (hereinafter referred to as “(B) / (C) mass ratio”) is preferably 1 to 100, more preferably 5 to 50, and 15 ~ 30 is more preferred.
If (B) / (C) mass ratio is more than the said preferable lower limit, aroma maintenance performance and a cleaning effect will improve more. On the other hand, if it is below the preferable upper limit value, the aroma maintaining performance is further improved.

<(D) component>
(D) A component is a fragrance | flavor and can use the well-known thing conventionally used for cleaning agents for clothes.
(D) As a component, the fragrance | flavor composition containing a fragrance | flavor component is mentioned, for example.

As a fragrance component, published in 1996 by Chemical Industry Daily, Motoichi Into, “Synthetic fragrance chemistry and product knowledge”; 1969 MONCLAIR, N. J. et al. And those described in “Perfume and Flavor Chemicals” by Steffen Arccander. More specifically, synthetic fragrances, natural fragrances from animals or plants, natural fragrances and / or blended fragrances containing synthetic fragrances can be mentioned.
Examples of the fragrance component include hydrocarbons such as aliphatic hydrocarbons, terpene hydrocarbons and aromatic hydrocarbons; alcohols such as aliphatic alcohols, terpene alcohols and aromatic alcohols; aliphatic ethers and aromatic ethers. Ethers; oxides such as aliphatic oxides and terpene oxides; aldehydes such as aliphatic aldehydes, terpene aldehydes, alicyclic aldehydes, thioaldehydes, aromatic aldehydes; aliphatic ketones, terpene ketones, alicyclics Ketones such as ketones, aliphatic cyclic ketones, non-benzene aromatic ketones, aromatic ketones; acetals, ketals, phenols, phenol ethers; fatty acids, terpene carboxylic acids, alicyclic carboxylic acids, aromatics Acids such as carboxylic acids; acid amides; aliphatic lactones, macrocyclic lactones, Lactones such as pen lactones, alicyclic lactones, aromatic lactones; aliphatic esters, furan carboxylic acid esters, aliphatic cyclic carboxylic acid esters, cyclohexyl carboxylic acid esters, terpene carboxylic acid esters, aromatic carboxylic acids Examples include esters such as acid esters; nitrogen-containing compounds such as nitromusks, nitriles, amines, pyridines, quinolines, pyrroles, and indoles.

Among the above, as the fragrance component, since it has a high scent recognition, it is preferable to include at least one selected from the group consisting of ketones and esters. Aromatic ketones and aromatic carboxylic acid esters Those containing at least one selected from the group consisting of are more preferred, those containing an aromatic ketone, and those containing a combination of an aromatic ketone and an aromatic carboxylic acid ester are more preferred.
Among them, those containing a combination of an aromatic ketone and an aromatic carboxylic acid ester are particularly preferred because the fragrance is likely to remain for a long time (good fragrance properties).

Preferred aromatic ketones include 4- (p-hydroxyphenyl) -2-butanone (raspberry ketone) (hereinafter also referred to as “(d1) component”). The component (d1) is mainly used for floral fruity tone, flavor, and the like, and after washing, the fragrance component alone gives a sweet and spreading scent.
Preferred aromatic carboxylic acid esters include salicylic acid esters (hereinafter also referred to as “(d2) component”). As component (d2), hexyl salicylate, benzyl salicylate, isoamyl salicylate, amyl salicylate, ethyl salicylate, butyl salicylate, isobutyl salicylate, phenyl salicylate, p-cresyl salicylate, cis-3-hexenyl salicylate, phenylethyl salicylate, isobutyl salicylate, Examples include cyclohexyl salicylate. Among these, hexyl salicylate, benzyl salicylate, isoamyl salicylate, and amyl salicylate are preferable. Salicylate alone gives a refreshing scent after washing.
The fragrance component combining the component (d1) and the component (d2) has a refreshing scent that spreads sweetly, and the fragrance is easily recognized.

A fragrance | flavor component may be used individually by 1 type, and may be used in combination of 2 or more type as appropriate.
(D) When using a fragrance | flavor composition as a component, 50 mass% or more is preferable with respect to the total mass of a fragrance | flavor composition, and 70 mass% or more is more preferable, and 80 mass% is preferable. % Or more is more preferable, and may be 100% by mass.
The content of the fragrance component in the liquid detergent for textiles is preferably 0.01 to 5% by mass, more preferably 0.1 to 3% by mass, and still more preferably relative to the total mass of the liquid detergent. 0.4-2 mass%.

  The fragrance composition may contain an optional component for fragrance other than the fragrance component, if necessary. Examples of the perfume ingredients include perfume solvents, perfume stabilizers, and the like, for example, diethyl phthalate, dipropylene glycol, benzyl benzoate, isopropyl myristate, rosin resin (for example, trade name Hercorin), etc. Can be used.

As the component (D), one type may be used alone, or two or more types may be used in appropriate combination.
The content of the component (D) in the liquid detergent for textiles is preferably 0.01 to 5% by mass, more preferably 0.1 to 3% by mass with respect to the total mass of the liquid detergent, Preferably it is 0.5-2 mass%.
When the content of the component (D) is equal to or more than the preferable lower limit value, the scent is sufficiently perfumed into the fiber product. On the other hand, if the above preferable upper limit is exceeded, the fragrance may remain too strong.

When a fragrance composition containing a combination of the component (d1) and the component (d2) is used as the component (D), the total content of the component (d1) and the component (d2) in the fragrance composition is 10-60 mass% is preferable with respect to the total mass of a fragrance | flavor composition, More preferably, it is 10-50 mass%. When the total content is less than the preferable lower limit value, the residual fragrance becomes weak. On the other hand, when the total content exceeds the preferable upper limit value, it becomes difficult to prepare various fragrances.
Further, the mass ratio represented by (d1) component / ((d1) component + (d2) component) is preferably 10-50, more preferably 10-30. If this mass ratio is less than the above-mentioned preferred lower limit value, the residual fragrance becomes weak. On the other hand, if it exceeds the preferred upper-limit value, the sweetness of the scent becomes strong, and there is a possibility that the fragrance tone has a weak fresh feeling.
“Mass ratio represented by (d1) component / ((d1) component + (d2) component)” is (d1) relative to the total mass of the (d1) component and the (d2) component in the fragrance composition. ) Means the proportion of the mass of the component.

In the present invention, the mass ratio represented by [{(A) component + (C) component} × (B) component] / (D) component (hereinafter referred to as “[{(A) + (C)} × (B) ] / (D) mass ratio ") is preferably 10-100, more preferably 15-75, and still more preferably 20-50.
If the [{(A) + (C)} × (B)] / (D) mass ratio is equal to or greater than the above-mentioned preferred lower limit value, the aroma maintenance performance is further improved, and in addition, the cleaning effect is further improved. On the other hand, if it is below the preferable upper limit value, the aroma maintaining performance is further improved.

<Solvent>
The liquid detergent of the present invention preferably contains water as a solvent from the viewpoint of ease of preparation of the preparation, solubility in water when used, and the like.
The content of water in the liquid detergent for textile products is preferably 80% by mass or less, more preferably 40 to 75% by mass, and further preferably 40 to 65% by mass with respect to the total mass of the liquid detergent. is there.
If water content is below the said preferable upper limit, liquid viscosity will become low moderately and it becomes favorable from a viewpoint of usability.

<Optional component>
The liquid cleaning agent of the present invention may contain other components other than the above-described components as necessary as long as the effects of the present invention are not impaired.

≪ (E) ingredient≫
In the liquid cleaning agent of this invention, it is preferable to further contain (E) component: silicone compound in addition to said (A)-(D) component. (E) By further containing a component, aroma maintenance performance is improved more.
In the present invention, the “silicone compound” refers to a compound having a repeating structure of a siloxane bond in which a silicon atom and an oxygen atom are bonded.
The component (E) may be a modified silicone compound or an unmodified silicone compound.
Examples of the component (E) include dimethyl silicone, amino-modified silicone, amino-polyether-modified silicone, amide-modified silicone, amide-polyether-modified silicone, alkyl-modified silicone, alkyl-polyether-modified silicone, and polyether-modified silicone. Is mentioned. Among these, polyether modified silicone and amino modified silicone are preferable, and polyether modified silicone is more preferable because it is easy to ensure the appearance stability of the liquid detergent in addition to the aroma maintaining performance.

 As the component (E), commercially available products can be used. For example, SF8417, SF8418, SH3772, SH3775, DC2501, DC2502, DC2503, DC580, AMS-C30, SF8417 manufactured by Toray Dow Corning Co., Ltd. can be used. , BY16-837, BY16-878, BY16-891, BY16-906, FZ-2203, FZ-3789, ABN SILWET FZ-F1-009-54, ABN SILWET FZ-2222 (all are trade names), etc. Can be used.

As the component (E), one type may be used alone, or two or more types may be used in appropriate combination.
When the liquid detergent of this invention further contains (E) component, content of (E) component in the liquid detergent for textiles is 0.01-5 mass% with respect to the total mass of a liquid detergent. Is more preferable, 0.01-3 mass% is more preferable, More preferably, it is 0.2-2 mass%.
(E) Aroma maintenance performance improves more as content of a component is more than the said preferable lower limit. On the other hand, when the above preferable upper limit is exceeded, it is difficult to obtain an effect of improving the aroma maintenance performance commensurate with it, and this is economically disadvantageous.

In the present invention, a mass ratio represented by [{(A) component + (C) component + (E) component} × (B) component] / (D) component (hereinafter referred to as “[{(A) + (C) + (E)} × (B)] / (D) mass ratio ”) is preferably from 10 to 100, more preferably from 25 to 80, and even more preferably from 30 to 60.
If the [{(A) + (C) + (E)} × (B)] / (D) mass ratio is equal to or greater than the above-mentioned preferred lower limit value, the fragrance maintenance performance is further enhanced, and in addition, the cleaning effect is improved. More improved. On the other hand, if it is below the preferable upper limit value, the aroma maintaining performance is further improved.

≪ (F) component≫
In the liquid detergent of this invention, in addition to said (A)-(D) component or in addition to said (A)-(E) component, (F) component: The fragrance | flavor precursor is further contained. It is preferable to do. By further containing (F) component, the intensity | strength (fragrance intensity | strength) of the fragrance felt from the to-be-washed | cleaned material after a washing process and drying is raised more. In addition, the aroma maintenance performance is further improved.
The “perfume precursor” means that the compound itself is odorless or nearly odorless, and generates a fragrance in a liquid detergent or by an oxidation reaction on a fiber.

As the component (F), those generally used for liquid detergents can be used without particular limitation.
In the present invention, the component (F) may be appropriately selected according to the type of the component (D), and examples thereof include a sulfur-containing fragrance precursor, preferably a compound represented by the following general formula (F1). Can be mentioned. In particular, when a fragrance composition containing a combination of the component (d1) and the component (d2) is used as the component (D), it is preferable to use the compound represented by the general formula (F1) in combination. By such combined use, the fragrance peculiar to the fragrance composition containing the combination is easily added to the fiber product, and the residual fragrance of the fragrance is enhanced.

［式（Ｆ１）中、Ｓは硫黄原子である。Ｊは、下記の化学式（Ｊ−１）〜（Ｊ−７）でそれぞれ表される基、及びこれらの異性体からなる群より選択される少なくとも１種の基を表す。化学式（Ｊ−４）中、ｊは、５〜２０の整数を表す。化学式（Ｊ−１）〜（Ｊ−７）中、波線は、Ｓと結合する結合手を表す。化学式（Ｊ−１）〜（Ｊ−２）中、点線は、点線が設けられている炭素原子間の結合の１つ以上が二重結合であることを意味する。Ｇは、置換基を有していてもよい炭素数２〜１５の直鎖状又は分岐鎖状の炭化水素基を表す。Ｑは、−Ｓ−Ｊで表される基、−ＮＲ^１７−Ｊで表される基又は水素原子（Ｓは硫黄原子である。Ｎは窒素原子である。Ｊは、下記の化学式（Ｊ−１）〜（Ｊ−７）でそれぞれ表される基、及びこれらの異性体からなる群より選択される少なくとも１種の基を表す。Ｒ^１７は、水素原子又はメチル基を表す。）を表す。］

[In Formula (F1), S is a sulfur atom. J represents at least one group selected from the group consisting of groups represented by the following chemical formulas (J-1) to (J-7) and isomers thereof. In chemical formula (J-4), j represents an integer of 5 to 20. In chemical formulas (J-1) to (J-7), a wavy line represents a bond that bonds to S. In chemical formulas (J-1) to (J-2), a dotted line means that one or more of bonds between carbon atoms provided with a dotted line are double bonds. G represents a linear or branched hydrocarbon group having 2 to 15 carbon atoms which may have a substituent. Q is a group represented by -S-J, a group represented by -NR < ¹⁷ > -J, or a hydrogen atom (S is a sulfur atom. N is a nitrogen atom. J is represented by the following chemical formula (J- 1) to (J-7), and at least one group selected from the group consisting of isomers thereof, and R ¹⁷ represents a hydrogen atom or a methyl group. . ]

“These isomers” in J in the formula (F1) are isomers that the groups represented by chemical formulas (J-1) to (J-7) can take in terms of chemical structure, for example, stereoisomerism. Refers to the body.
Among these, as J, a group represented by the chemical formula (J-1) and a group represented by the chemical formula (J-2) are more preferable.
In said chemical formula (J-4), j represents the integer of 5-20, Preferably the integer of 5-15 is represented.

In the formula (F1), the hydrocarbon group in G may be a saturated hydrocarbon group or an unsaturated hydrocarbon group, that is, an alkyl group or an alkenyl group. Especially, as a hydrocarbon group in G, a linear alkyl group is preferable.
As for carbon number of the hydrocarbon group in G, 10-14 are preferable.
The hydrocarbon group for G may have a substituent. As this substituent, for example, —OR ¹⁶ , —N (R ¹⁶ ) ₂ , —COOR ¹⁶ (R ¹⁶ is an alkyl group having 1 to 6 carbon atoms, an alkenyl group having 1 to 6 carbon atoms, or a hydrogen atom. For example).

Preferred examples of the component (F) include methyl or ethyl 2- (4-oxo-4- (2,6,6-trimethylcyclohex-3-en-1-yl) butan-2-ylamino) -3- (4-Oxo-4- (2,6,6-trimethylcyclohex-3-en-1-yl) butan-2-ylthio) propanate, methyl or ethyl 2- (4-oxo-4- (2,6 , 6-Trimethylcyclohex-2-en-1-yl) butan-2-ylamino) -3- (4-oxo-4- (2,6,6-trimethylcyclohex-2-en-1-yl) Butan-2-ylthio) propanate, methyl or ethyl 2- (2-oxo-4- (2,6,6-trimethylcyclohex-1-en-1-yl) butan-4-ylamino) -3- (2 -Oxo-4- (2,6, -Trimethylcyclohex-1-en-1-yl) butan-4-ylthio) propanate, methyl or ethyl 2- (2-oxo-4- (2,6,6-trimethylcyclohex-2-ene-1-) Yl) butan-4-ylamino) -3- (2-oxo-4- (2,6,6-trimethylcyclohex-2-en-1-yl) butan-4-ylthio) propanate, 3- (dodecylthio) -1- (2,6,6-trimethylcyclohex-3-en-1-yl) -1-butanone, 3- (dodecylthio) -1- (2,6,6-trimethylcyclohex-2-ene- 1-yl) -1-butanone, 4- (dodecylthio) -4- (2,6,6-trimethylcyclohex-2-en-1-yl) -2-butanone, 4- (dodecylthio) -4- ( 2,6,6-tri Tilcyclohex-1-en-1-yl) -2-butanone, 2-dodecylsulfanyl-5-methyl-heptane-4-one, 2-cyclohexyl-1-dodecylsulfanyl-hept-6-en-3-one , 3- (dodecylthio) -5-isopropenyl-2-methylcyclohexanone and the like.
Among these, from the viewpoint of enhancing scent sustainability, 3- (dodecylthio) -1- (2,6,6-trimethylcyclohex-3-en-1-yl) -1-butanone, 4- (dodecylthio) -4- (2,6,6-trimethylcyclohex-2-en-1-yl) -2-butanone, 4- (dodecylthio) -4- (2,6,6-trimethylcyclohex-1-ene- Preference is given to at least one compound selected from the group consisting of 1-yl) -2-butanone and 3- (dodecylthio) -5-isopropenyl-2-methylcyclohexanone.
Among them, 3- (dodecylthio) -1- (2,6,6-trimethylcyclohex-3-en-1-yl) -1-butanone and 4- (dodecylthio) -4- (2,6,6- Particularly preferred is at least one compound selected from the group consisting of trimethylcyclohex-2-en-1-yl) -2-butanone.

The component (F) can be easily obtained on the market and can be synthesized by a known method.
As the component (F), one type may be used alone, or two or more types may be used in appropriate combination.
When the liquid detergent of the present invention further contains the component (F), the content of the component (F) in the liquid detergent for textile products is 0.0001 to 1% by mass with respect to the total mass of the liquid detergent. Is more preferably 0.001 to 0.1% by mass, still more preferably 0.006 to 0.04% by mass, and particularly preferably 0.01 to 0.04% by mass.
(F) When content of a component is more than the said preferable lower limit, while aroma intensity | strength is raised more, aroma maintenance performance improves more. On the other hand, if the above preferable upper limit is exceeded, the fragrance may remain too strong.

In the present invention, “mass ratio represented by component (D) / component (F)” means component (D) relative to the content (mass%) of component (F) contained in the liquid detergent for textiles. It means the ratio of the content (mass%).
The mass ratio represented by component (D) / component (F) (hereinafter referred to as “(D) / (F) mass ratio”) is preferably 1000 or less, more preferably 20 to 200, and more preferably 25 to 25. 100 is more preferable.
If (D) / (F) mass ratio is below the said preferable upper limit, while fragrance intensity | strength will be raised more, fragrance maintenance performance will improve more. On the other hand, if it is more than the preferable lower limit value, the scent is easily maintained.

  In addition, in the liquid detergent of the present invention, components that are usually blended into detergents for clothing, for example, surfactants other than the component (B), water-miscible organic solvents, preservatives, if necessary. (A) Chelating agents other than component, enzymes, enzyme stabilizers, fluorescent brighteners, foam control agents, thickeners or solubilizers, colorants, emulsifiers, extracts, pH adjusters, etc. You may contain.

Examples of the surfactant other than the component (B) include nonionic surfactants and amphoteric surfactants.
Nonionic surfactants include, for example, alkylene oxide adducts of fatty acid alkyl esters, alkylene oxide adducts of higher alcohols, alkylene oxide adducts of alkylphenols, alkylene oxide adducts of higher fatty acids, alkylene oxide adducts of higher amines, Oxyethylene polyoxypropylene block copolymer, fatty acid alkanolamine, fatty acid alkanolamide, polyhydric alcohol fatty acid ester or its alkylene oxide adduct, polyhydric alcohol fatty acid ether, alkylamine oxide, alkenylamine oxide, alkylene oxide adduct of hydrogenated castor oil , Sugar fatty acid ester, N-alkyl polyhydroxy fatty acid amide, alkyl glucoside and the like. Among these, alkylene oxide adducts of fatty acid alkyl esters and alkylene oxide adducts of higher alcohols are preferred.
Examples of amphoteric surfactants include alkyl betaine type, alkyl amide betaine type, imidazoline type, alkyl amino sulfone type, alkyl amino carboxylic acid type, alkyl amide carboxylic acid type, amide amino acid type or phosphoric acid type amphoteric surfactant. Etc.
(B) Surfactant other than a component may be used individually by 1 type, and may use 2 or more types together. As the surfactant other than the component (B), a nonionic surfactant is preferable because the cleaning effect is further enhanced.

  When the liquid cleaning agent of the present invention further contains a surfactant other than the component (B), the total surfactant content of the component (B) and the other surfactant is the total amount of the liquid cleaning agent. 15 mass% or more is preferable with respect to mass, 20-50 mass% is more preferable, More preferably, it is 20-45 mass%.

  Moreover, 20 mass% or more is preferable, as for the ratio of (B) component to the content of total surfactant, More preferably, it is 20-60 mass%, More preferably, it is 25-55 mass%. (B) When the ratio of a component is more than the said preferable lower limit, the recontamination with respect to especially a cotton fiber is suppressed and the cleaning effect increases more. In addition, the fragrance maintenance performance is further enhanced. On the other hand, the cleaning power with respect to various stain | pollution | contamination increases more that it is below the said preferable upper limit.

  In addition, when the component (B) contains a linear alkylbenzene sulfonate, the proportion of the linear alkylbenzene sulfonate in the total surfactant content is preferably 20% by mass or more, more preferably 20 to 20%. 60% by mass. When the linear alkylbenzene sulfonate is at least the above-mentioned preferred lower limit, the fragrance maintenance performance is further enhanced. Moreover, the re-contamination with respect to a cotton fiber is suppressed and the cleaning effect increases more. On the other hand, even if it exceeds the above-mentioned preferable upper limit value, it is difficult to obtain a blending effect commensurate with it, which is disadvantageous economically.

When (B) component (anionic surfactant) and nonionic surfactant are used together, the mass ratio represented by nonionic surfactant / (B) component is preferably 0.5 to 4, more preferably 0. .6 to 3.5, and more preferably 0.7 to 3. When this mass ratio is not less than the above-mentioned preferable lower limit value, re-contamination on cotton fibers in particular is suppressed, and the cleaning effect is further enhanced. On the other hand, the cleaning power with respect to various stain | pollution | contamination increases more that it is below the said preferable upper limit.
“Nonionic surfactant / mass ratio represented by component (B)” means the content of nonionic surfactant relative to the content (mass%) of component (B) contained in the liquid detergent for textiles ( % By mass).

In the liquid detergent of the present invention, a water-miscible organic solvent may be used as a solvent other than water from the viewpoint of improving the stability of the liquid appearance.
“Water-miscible organic solvent” refers to an organic solvent that dissolves 50 g or more in 1 L of ion-exchanged water at 25 ° C.
Examples of water-miscible organic solvents include alcohols such as ethanol, 1-propanol, 2-propanol, and 1-butanol; glycols such as propylene glycol, butylene glycol, and hexylene glycol; diethylene glycol, triethylene glycol, tetraethylene glycol, Polyethylene glycol having a weight average molecular weight of about 200, polyethylene glycol having a weight average molecular weight of about 400, polyethylene glycol having a weight average molecular weight of about 1000, polyglycols such as dipropylene glycol; alkyl ethers such as diethylene glycol monomethyl ether and diethylene glycol dimethyl ether Etc.
A water-miscible organic solvent may be used individually by 1 type, and may use 2 or more types together.

The pH of the liquid detergent of the present invention can be adjusted by adding a pH adjuster as necessary.
Examples of the pH adjuster include inorganic acids such as hydrochloric acid, sulfuric acid and phosphoric acid; organic acids such as p-toluenesulfonic acid and citric acid; sodium hydroxide, potassium hydroxide and alkanolamine. From the above aspect, hydrochloric acid, sulfuric acid, sodium hydroxide, potassium hydroxide, and alkanolamine are preferable. A pH adjuster may be used individually by 1 type, and may use 2 or more types together.

The liquid detergent of the present invention preferably has a pH of 4 to 10 at 25 ° C., more preferably 6 to 8, and even more preferably 6.5 to 7.5. If pH is in the said preferable range, the effect of this invention will become more easy to be acquired.
The pH (25 ° C.) of the liquid detergent for textile products is a value measured with a pH meter after adjusting the sample to 25 ° C.

  The liquid cleaning agent of the present invention is prepared by mixing a solvent, a component (A), a component (B), a component (C), a component (D), and other optional components as necessary. Manufactured by doing.

According to the liquid detergent for textiles of the present invention described above, the textile can be fragranced while maintaining the fragrance of the detergent during washing, and the washing effect can be enhanced. The reason why such an effect is obtained is not clear, but is presumed as follows.
The liquid detergent for textiles of the present invention comprises (A) and (B) components that generate negative ions in water, (C) components that generate positive ions in water, and (D) components that are perfumes. contains. In the cleaning liquid prepared by adding this liquid detergent for textiles to water, a complex of (A) component, (B) component, and (C) component is formed by electrostatic interaction. The And various fragrance | flavor components in (D) component adsorb | suck to this composite_body | complex by hydrophobic interaction. Thereby, in washing | cleaning, since the composite_body | complex to which various fragrance | flavor components adsorb | sucked adheres to a textiles, it is thought that the scent of the textiles after washing maintains the aroma of a liquid detergent.
Moreover, since the said composite_body | complex is formed by the electrostatic interaction, the cation intensity | strength is low. For this reason, during washing | cleaning, a composite_body | complex does not adhere to a textile product excessively, but adheres in a moderate quantity. This effect is significant in the case of cotton fibers that tend to have a negative surface. Thereby, it is thought that the cleaning effect is enhanced by suppressing recontamination during cleaning.
As described above, the liquid cleaning agent of the present invention in which the (A) component, the (B) component, the (C) component, and the (D) component are combined is particularly used as a cleaning agent for textile products. Is suitable.

  Moreover, in addition to the components (A) to (D), in the liquid detergent of the present invention that further contains a component (E) that is a silicone compound, the complex is subjected to hydrophobic interaction (E). The component also adsorbs. Accordingly, the hydrophobic interaction between the complex and the various fragrance components in the component (D) is strengthened, and the various fragrance components in the component (D) are more easily adsorbed to the complex. Become. Thereby, the liquid cleaning agent of this invention is thought that aroma maintenance performance is improved more.

  Further, in addition to the components (A) to (D), the liquid detergent of the present invention containing the component (F) which is a fragrance precursor further comprises the component (F) and other compounding components (composite, Due to the interaction with the various fragrance components (D), the strength (fragrance strength) of the scent felt from the washed article after washing / drying is further increased, and the remaining fragrance property is excellent.

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

The compositions of the liquid detergents in each example are shown in Tables 2-4.
The raw materials used in this example are as follows.

-(A) component A-1: Methyl glycine diacetate trisodium, a brand name "Trilon M liquid", the product made from BASF. In the general formula (A2), X ²¹ = sodium, X ²² = sodium, X ²³ = sodium, R ²⁰ = hydrogen atom, n = 1.

-(B) component B-1: Sodium linear alkylbenzenesulfonate. As a raw material, linear alkyl (carbon number 10 to 14) benzenesulfonic acid (trade name “Lypon LH-200”, manufactured by Lion Co., Ltd., pure content 96 so that the neutralized product has the content shown in the table. % By weight) and neutralized with sodium hydroxide.
B-2: Sodium coconut fatty acid. A coconut fatty acid (manufactured by NOF Corporation) is used as a raw material and neutralized with sodium hydroxide so that the neutralized product has a content shown in the table.

-(C) component C-1: C16-18 amidoamine, brand name "Catinal MPAS-R", the Toho Chemical Co., Ltd. make. In General Formula (C1), R ¹ = R—C (═O) —NH— (CH ₂ ) ₃ —, R is C ₁₇ H ₃₅ / C ₁₅ H ₃₁ = 7/3 (mass ratio). R ² = methyl group, R ³ = methyl group.
C-2: Alkyl chloride (16 to 18 carbon atoms) trimethylammonium, trade name “Arcade T-800”, manufactured by Lion Akzo Corporation.

-(D) component D-1: The fragrance | flavor composition (a) shown in Table 1.
D-2: A fragrance composition (b) shown in Table 1.
D-3: A fragrance composition (c) shown in Table 1.

-Optional component-(E) component E-1: Polyether modified silicone, brand name "Polyether modified silicone CF1188N", Toray Dow Corning Co., Ltd. make.

.. (F) component F-1: 3- (dodecylthio) -1- (2,6,6-trimethylcyclohex-3-en-1-yl) -1-butanone. The compound described in Example 4 of JP-T-2005-511710. In the above general formula (F1), a compound in which J is a group represented by the chemical formula (J-1) (having a double bond between the 3 and 4 positions), G is a dodecyl group, and Q is a hydrogen atom.
F-2: 4- (dodecylthio) -4- (2,6,6-trimethylcyclohex-2-en-1-yl) -2-butanone. A compound synthesized using dodecanethiol (manufactured by Tokyo Chemical Industry Co., Ltd.) and β-nonone (manufactured by Ve Manfis Fragrance Co., Ltd.) as raw materials in the same manner as the synthesis method described in Example 4 of JP-T-2005-511710. . In the above general formula (F1), a compound in which J is a group represented by the chemical formula (J-2) (having a double bond between the 1 and 2 positions), G is a dodecyl group, and Q is a hydrogen atom.

  Citric acid: Manufactured by Yushi Co., Ltd. (A) Comparative component.

.. Common component AE: Ethylene oxide equivalent to 15 moles was added to natural alcohol (trade name “CO-1214”, manufactured by Procter & Gamble Co., Ltd .; a mixture of a C12 alcohol and a C14 alcohol). thing. Synthesized by the following synthesis method.
[Method of synthesizing AE]
861.2 g of natural alcohol (trade name “CO-1214”) and 2.0 g of NaOH 30% by mass aqueous solution were placed 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. Next, while stirring the reaction solution, 760.6 g of ethylene oxide (gaseous) was gradually added to the reaction solution. At this time, using the blowing tube, it added, adjusting the addition rate so that reaction temperature might not exceed 180 degreeC. 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. Thereafter, 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, the temperature was cooled to 100 ° C. or lower, and then neutralized by adding 70% by mass p-toluenesulfonic acid so that the pH of the 1% by mass aqueous solution of the reaction product was about 7, thereby obtaining AE. .

MEE: A coconut fatty acid methyl (a mixture of methyl laurate / methyl myristate = 8/2 in mass ratio) added with 15 moles of ethylene oxide using an alkoxylation catalyst. Synthesized by the following synthesis method.
[Method of synthesizing MEE]
MEE was synthesized according to the synthesis method described in JP 2000-144179 A (corresponding to sample D).
Alumina-magnesium hydroxide (trade name “KYOWARD 330”, manufactured by Kyowa Chemical Industry Co., Ltd.) having a composition of 2.5 MgO.Al ₂ O ₃ .wH ₂ O was fired at 600 ° C. for 1 hour in a nitrogen atmosphere. The calcined alumina / magnesium hydroxide (unmodified) catalyst 2.2 g obtained, 2.9 mL of 0.5 N potassium hydroxide ethanol solution, 280 g of lauric acid methyl ester, and 70 g of myristic acid methyl ester were obtained. A 4 L autoclave was charged 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 × 10 ⁵ Pa, 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 the catalyst was filtered off to obtain MEE.

PEG: Polyethylene glycol, trade name “# 1000”, manufactured by Lion Corporation.
Ethanol: trade name “specific alcohol 95 degree synthesis”, manufactured by Nippon Alcohol Sales Co., Ltd.
Sodium benzoate: trade name “Sodium benzoate”, manufactured by Toagosei Co., Ltd.
Isothiazolone liquid: 5-chloro-2-methyl-4-isothiazolin-3-one / 2-methyl-4-isothiazolin-3-one / magnesium salt / water mixture, trade name “Caisson CG”, Rohm and Made by Haas.
Colorant: Trade name “Green No. 3”, manufactured by Hatake Kasei Co., Ltd.
pH adjuster: sodium hydroxide (manufactured by Tsurumi Soda Co., Ltd.), sulfuric acid (manufactured by Kanto Chemical Co., Ltd.).
Water: Purified water.

<Preparation of liquid detergent>
According to the composition shown in Tables 2 to 4 (formulation components, content (mass%)), liquid detergents of respective examples were prepared by the following production methods. The content shown in the table indicates the content of the compounding component (pure equivalent amount). In the table, a blank means that the blending component is not blended.

In the table, “(B) / (C) mass ratio” is synonymous with the mass ratio represented by (B) component / (C) component, and the content of component (C) contained in the liquid detergent. It means the ratio of the content (mass%) of the component (B) to (mass%).
“(D) / (F) mass ratio” is synonymous with the mass ratio represented by (D) component / (F) component, and the content (mass%) of (F) component contained in the liquid detergent. ) To the content (mass%) of the component (D).
“[{(A) + (C)} × (B)] / (D) mass ratio” is expressed by [{(A) component + (C) component} × (B) component] / (D) component. The mass ratio is synonymous with.
“[{(A) + (C) + (E)} × (B)] / (D) mass ratio” is expressed by [{(A) component + (C) component + (E) component} × (B). Component] / (D) The mass ratio represented by the component is synonymous.

The composition of the common components contained in the liquid detergent of each example is shown below. Content (mass%) of each compounding component shows the ratio in a liquid cleaning agent.
The “appropriate amount” indicating the content of the pH adjuster is the total amount of sodium hydroxide and sulfuric acid required to adjust the pH of the liquid detergent to 7.0.
The “balance” indicating the water content is an amount required to make the entire liquid cleaning agent 100% by mass.

Common component (S):
AE 15% by mass, PEG 5% by mass, ethanol 5% by mass, sodium benzoate 0.5% by mass, isothiazolone solution 0.01% by mass, colorant 0.0001% by mass, pH adjuster appropriate amount, water balance.

Common component (T):
MEE 30% by mass, PEG 5% by mass, ethanol 5% by mass, sodium benzoate 0.5% by mass, isothiazolone solution 0.01% by mass, colorant 0.0001% by mass, pH adjuster appropriate amount, water balance.

Common component (U):
MEE 20% by mass, PEG 5% by mass, ethanol 5% by mass, sodium benzoate 0.5% by mass, isothiazolone solution 0.01% by mass, colorant 0.0001% by mass, pH adjuster appropriate amount, water balance.

(Examples 1-17, Comparative Examples 1-5)
The liquid detergent for each example was prepared by the following procedure.
Water and the component (B) were added to a 500 mL beaker, a stir bar was added, and the mixture was stirred using a stirrer (MAGNETIC STIRRR SW-RS077 NISSIN) until uniform. Next, component (A), an ethanol solution of component (C) (concentration 50 mass%), and citric acid were added while confirming that they were uniformly dissolved. Next, an ethanol solution of component (E) (concentration: 50% by mass) and a common component excluding water were added in order and stirred until uniform. Finally, component (D) was added and stirred until uniform to prepare each of the liquid cleaning agents in each example. The pH of the liquid detergent was adjusted to 7.0.
The stirring operation was performed at room temperature without particularly controlling the temperature condition, and the stirring speed was controlled by controlling the rotation speed of the stirring bar.

(Examples 18 to 31)
The (D) component added last is changed to the ethanol solution which (D) component and (F) component melt | dissolved in ethanol similarly to the said (Examples 1-17, Comparative Examples 1-5). In each case, the liquid cleaning agent of each example was prepared. The pH of the liquid detergent was adjusted to 7.0.

  The pH of the liquid detergent was measured with a pH meter (HM-30G, manufactured by Toa Denpa Kogyo Co., Ltd.) after leaving the liquid detergent as a sample in a water bath set at 25 ° C. for 30 minutes.

<Evaluation of liquid detergent>
About the liquid cleaning agent of each example, evaluation of "fragrance maintenance degree", "fragrance intensity | strength", and "cleaning effect" was performed by the evaluation method shown below, respectively. The results are also shown in Tables 2-4.

[Evaluation of degree of fragrance maintenance]
1) Washing treatment Using a fully automatic electric washing machine (product name “JW-Z23A”, manufactured by Haier), in this washing machine, eight cotton towels (220-piece border FT, Toshin Co., Ltd.) and tap water 12L The liquid cleaning agents of each example were added so that the concentrations shown in the table were obtained. For example, the concentration of the liquid cleaning agent in the cleaning liquid can be adjusted to 667 mg / L by setting the usage amount of the liquid cleaning agent to 8 g with respect to 12 L of tap water. By setting the usage amount of the liquid cleaning agent to 4 g with respect to 12 L of tap water, the concentration of the liquid cleaning agent in the cleaning liquid can be adjusted to 333 mg / L.
Next, the washing process was performed at a bath ratio of 20 times (low water level: 12 L) according to the standard course of the fully automatic electric washing machine.
After the washing treatment, the substrate was dried for 18 hours in an environment of a temperature of 25 ° C. and a relative humidity of 65% RH.

2) Evaluation of fragrance maintenance degree The sensory evaluation of the fragrance of the liquid cleaning agent used in the washing process and the fragrance of the cotton towel after the washing process and drying were performed. Sensory evaluation was performed by a method in which 10 expert panelists sniff directly.
The fragrance of the liquid detergent used for the washing treatment was evaluated by sniffing the odor that was scented when 1 g of the liquid detergent of each example was dropped on the petri dish.
The aroma of the cotton towel after washing / drying was evaluated by smelling the cotton towel after washing / drying.
And the degree of the difference of both fragrances was scored based on the following evaluation criteria (1), and the average value of 10 professional panelists was calculated.

Evaluation criteria (1)
3 points: The aroma of the liquid detergent on the petri dish and the aroma of the cotton towel after washing and drying are felt exactly the same.
2 points: The aroma of the liquid detergent on the petri dish and the aroma of the cotton towel after washing and drying seem to be slightly different.
1 point: The aroma of the liquid detergent on the petri dish and the aroma of the cotton towel after washing and drying seem to be quite different.
0 point: The fragrance of the liquid detergent on the petri dish and the fragrance of the cotton towel after washing / drying seem to be completely different.

Using the average value of 10 professional panelists as an index, the degree of fragrance maintenance was evaluated based on the following evaluation criteria (2). The case where this average value was 2.0 points or more was regarded as acceptable.
Evaluation criteria (2)
◎◎: 2.5 points or more.
A: 2.0 or more and less than 2.5.
○: 1.5 points or more and less than 2.0 points.
X: Less than 1.5 points.
The higher the average value, the higher the fragrance maintenance degree, that is, it means that the fiber product can be fragranced while maintaining the fragrance of the liquid cleaning agent.

[Evaluation of aroma intensity]
The cotton towel aroma after washing and drying was stored for 7 days under conditions of a temperature of 25 ° C. and a relative humidity of 50 RH, and then sensory evaluation was performed. The sensory evaluation was performed by a method in which 10 expert panelists sniff directly.
And the difference in the aroma intensity | strength of a cotton towel was scored based on the following evaluation criteria (3), and the average value of 10 professional panelists was computed.

Evaluation criteria (3)
5 points: Strong smell.
4 points: Strong smell.
3 points: Smell that can be easily detected.
2 points: A weak smell that can sense what smell it is.
1 point: The smell that can finally be detected.
0 point: odorless.

Using the average value of 10 professional panelists as an index, the aroma intensity was evaluated based on the following evaluation criteria (4). The case where this average value was 2.5 points or more was regarded as acceptable.
Evaluation criteria (4)
A: 3.5 or more points.
A: 3.0 or more and less than 3.5.
○: 2.5 points or more and less than 3.0 points.
X: Less than 2.5 points.
The higher the average value, the higher the fragrance intensity, that is, the fragrance intensity is maintained even after a certain period of time.

[Evaluation of cleaning effect]
A cotton skin shirt (BVD skin shirt: G0134TS, 100% cotton) cut into 5 cm × 5 cm was prepared as a cloth (re-contamination determination cloth) for determining re-contamination during cleaning. .
As the wet artificial contamination cloth, a 5 cm × 5 cm size fabric manufactured by the Laundry Science Association was used. The composition of the soil was 28.3 mass% oleic acid, 15.6 mass% triolein, 12.2 mass% cholesterol oleate, 2.5 mass% liquid paraffin, 2.5 mass% squalene, 1.6 mass% cholesterol. Gelatin 7.0% by mass, mud 29.8% by mass, carbon black 0.5% by mass.
Moreover, the liquid cleaning agent of each example was melt | dissolved in 25 degreeC 3 degree DH hard water so that it might become the density | concentration shown in a table | surface, and the washing | cleaning liquid was prepared.

Cleaning operation:
Using a round tester (FI-301, manufactured by Tester Sangyo Co., Ltd.), in a stainless steel sample bottle (500 ± 50 mL), 200 mL of the cleaning liquid, the five recontamination cloths, and the wet artificial contamination Twenty pieces of cloth and those obtained by finely cutting the cotton shirt (about 3 cm × 3 cm) were added, the bath ratio was adjusted to 10 times, and a washing operation was performed at 20 rpm and 25 ° C. for 25 minutes.

Rinse operation:
After the washing operation, all the objects to be washed were taken out and dehydrated for 1 minute. Thereafter, 200 mL of 3 ° DH hard water at 25 ° C. was placed in the stainless steel sample bottle, and the dehydrated article was added thereto, followed by rinsing operation at 40 rpm and 25 ° C. for 3 minutes. This rinsing operation was repeated twice.
Drying operation:
The object to be washed after the second rinsing operation was dehydrated for 1 minute. Thereafter, only the recontamination determination cloth was taken out, sandwiched between filter papers, and dried with an iron.

The above washing operation-rinsing operation-drying operation was repeated three times.
Next, using a reflectance meter (spectral color difference meter SE2000, manufactured by Nippon Denshoku Industries Co., Ltd.), the reflectance of each of the five recontamination determination cloths is measured and calculated as a Z value (Z value after cleaning). did. Next, a value (difference) obtained by subtracting the Z value after washing from the Z value before washing that was measured and calculated in advance was obtained, and an average value of five sheets was calculated for this value (difference), which was taken as ΔZ.
And based on the following evaluation criteria (5), the recontamination property was evaluated.
Evaluation criteria (5)
A: ΔZ is 8 or less.
A: ΔZ is greater than 8 and 12 or less.
○: ΔZ is larger than 12 and 16 or less.
X: ΔZ is 16 or more.
A smaller ΔZ means that recontamination is less likely to occur and the cleaning effect is enhanced.

  From the evaluation results shown in Tables 2 and 3, the liquid detergents of Examples 1 to 17 to which the present invention is applied can be fragranced to the fiber product while maintaining the fragrance of the detergent, and the cleaning effect is enhanced. I was able to confirm that.

All of the liquid detergents of Comparative Example 1 lacking the component (A) and Comparative Example 5 containing no component (A) and having an increased amount of citric acid had a good cleaning effect but low fragrance maintenance performance.
The liquid cleaning agent of Comparative Example 2 lacking the component (B) had low fragrance maintenance performance and cleaning effect.
The liquid detergents of Comparative Example 3 lacking the component (C) and Comparative Example 4 lacking the component (D) all had good cleaning effects but low fragrance maintenance performance.

  From the evaluation results shown in Table 4, the liquid cleaning agents of Examples 18 to 31 to which the present invention was applied can be fragranced to the textile product while maintaining the fragrance of the cleaning agent, and the cleaning effect is enhanced. Was confirmed. In addition, the liquid detergents of Examples 18 to 31 further include the component (F), so that the strength of the fragrance (fragrance strength) felt from the washed object after washing / drying is further increased. I was able to confirm.

Claims (3)

(A) component: at least one selected from the group consisting of a compound represented by the following general formula (A1) and a compound represented by the following general formula (A2);
(B) component: an anionic surfactant;
Component (C): selected from the group consisting of a compound represented by the following general formula (C1), a salt of a compound represented by the following general formula (C1), and a compound represented by the following general formula (C2) At least one,
(D) component: perfume,
A liquid detergent for textiles containing

[In Formula (A1), X ^{11 to} X ¹⁴ each independently represents a hydrogen atom, an alkali metal, an alkaline earth metal, or cationic ammonium. R ¹⁰ represents a hydrogen atom or a hydroxy group. m represents 0 or 1. In formula (A2), X ^{21 to} X ²³ each independently represent a hydrogen atom, an alkali metal, an alkaline earth metal, or cationic ammonium. R ²⁰ represents an alkyl group, a carboxy group, a sulfo group, an amino group, a hydroxy group, or a hydrogen atom. n represents an integer of 0 to 5. ]

[In Formula (C1), R ¹ represents a linear or branched hydrocarbon group having 7 to 27 carbon atoms. The hydrocarbon group for R ¹ may have at least one substituent selected from the group consisting of a hydroxy group and an amino group, and may have a linking group in the carbon chain. R ² represents a linear or branched hydrocarbon group having 1 to 25 carbon atoms. The hydrocarbon group in R ² may have a hydroxy group as a substituent and may have a linking group in the carbon chain. R ³ is a linear or branched alkyl group having 1 to 4 carbon atoms, a linear or branched hydroxyalkyl group having 1 to 4 carbon atoms, or — (CH ₂ CH ₂ O) _p. Represents a group represented by —H (p represents an integer of 1 to 25). In formula (C2), R ¹¹ and R ¹² are each independently a hydrogen atom, a linear or branched hydrocarbon group having 1 to 25 carbon atoms, or — (CH ₂ CH ₂ O) _q —. A group represented by H (q represents an integer of 1 to 25). The hydrocarbon groups in R ¹¹ and R ¹² may each independently have a substituent and may have a linking group in the carbon chain. R ¹³ represents a linear or branched hydrocarbon group having 8 to 25 carbon atoms. The hydrocarbon group for R ¹³ may have a substituent and may have a linking group in the carbon chain. R ¹⁴ represents a hydrogen atom, a linear or branched alkyl group having 1 to 3 carbon atoms, a linear or branched hydroxyalkyl group having 1 to 3 carbon atoms, or — (CH ₂ CH ₂ O) A group represented by _r- H (r represents an integer of 1 to 25). Z ⁻ represents a counter anion. ]   (E) component: The liquid cleaning agent for textiles of Claim 1 which further contains a silicone compound.   (F) Component: The liquid cleaning agent for textiles of Claim 1 or 2 which further contains a fragrance | flavor precursor.