JP5845538B2 - Liquid detergent composition - Google Patents

Description

  The present invention relates to a liquid detergent composition suitable for washing textiles such as clothes. More specifically, the present invention relates to a liquid detergent composition in which the fragrance of the fragrance lasts until the garment is worn or the textile product such as a towel is used.

  Recently, consumer interest in fragrance has increased, and liquid cleaning compositions excellent in fragrance stability have been proposed (see, for example, JP 2000-160192 A and JP 2007-314693 A). However, it has not been sufficient in that the flavor of the fragrance contained in the liquid detergent composition is imparted over a long period of time to a textile product such as clothes after washing and drying.

JP 2000-160192 A JP 2007-314693 A

  An object of this invention is to provide the liquid detergent composition which further improved the residual fragrance | flavor property of the fragrance | flavor provided to textiles, such as clothes after washing and drying.

［式中、Ｘ¹¹〜Ｘ¹⁴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し、Ｒは水素原子又は水酸基を表し、ｎ１は０又は１の整数を表す。］

…（ｂ２）
［式中、Ａはアルキル基、カルボキシ基、スルホ基、アミノ基、水酸基又は水素原子を表し、Ｘ²¹〜Ｘ²³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し、ｎ２は０〜５の整数を表す。］
（Ｃ）下記一般式（Ｃ１）又は（Ｃ２）で表される化合物、又はその塩

…（Ｃ１）
［式中、Ｒ₅は直鎖又は分岐したＣ_7~27炭化水素基を表し、ここでＲ₅はヒドロキシ基及びアミノ基からなる群より選ばれた置換基を有していてもよく、またＲ₅は炭素鎖中に連結基を有していてもよく、Ｒ₆は直鎖又は分岐したＣ_1~25炭化水素基を表し、ここでＲ₆はヒドロキシル基を有していてもよく、またＲ₆は炭素鎖中に連結基を有していてもよく、Ｒ₇は直鎖又は分岐したＣ_1~4アルキル基、直鎖又は分岐したＣ_1~4ヒドロキシアルキル基、又はエチレンオキサイド付加モル数１〜２５のポリオキシエチレン基を表す。］

…（Ｃ２）
［式中、Ｒ₁₆及びＲ₁₇は、それぞれ独立して、水素原子、又は直鎖又は分岐したＣ_1~25炭化水素基を表し、ここでＲ₁₆及びＲ₁₇は、それぞれ独立して、置換基を有していてもよく、またＲ₁₆及びＲ₁₇は、それぞれ独立して、炭素鎖中に連結基を有していてもよく、又はＲ₁₆及びＲ₁₇は、それぞれ独立して、エチレンオキサイド付加モル数１〜２５のポリオキシエチレン基を表し、Ｒ₁₈は直鎖又は分岐したＣ_8~25炭化水素基を表し、ここでＲ₁₈は置換基を有していてもよく、またＲ₁₈は炭素鎖中に連結基を有していてもよく、Ｒ₁₉は水素原子、直鎖又は分岐したＣ_1~3アルキル基、直鎖又は分岐したＣ_1~3ヒドロキシアルキル基、又はエチレンオキサイド付加モル数１〜２５のポリオキシエチレン基を表し、Ｚ^-は陰イオンを表す。］
（Ｄ）香料 The present invention provides a liquid detergent composition containing the following components (A) to (D).
(A) One or more water-soluble metal salts selected from the group consisting of a water-soluble salt of copper, a water-soluble salt of zinc or a water-soluble salt of silver (B) represented by the following general formula (b1) or (b2) Chelate compound

[Wherein, X ^{11 to} X ¹⁴ each independently represents a hydrogen atom, an alkali metal, an alkaline earth metal or cationic ammonium, R represents a hydrogen atom or a hydroxyl group, and n1 represents an integer of 0 or 1. . ]

... (b2)
[Wherein, A represents an alkyl group, a carboxy group, a sulfo group, an amino group, a hydroxyl group or a hydrogen atom, and X ^{21 to} X ²³ each independently represents a hydrogen atom, an alkali metal, an alkaline earth metal or a cationic ammonium. N2 represents an integer of 0 to 5. ]
(C) A compound represented by the following general formula (C1) or (C2), or a salt thereof

... (C1)
Wherein, R ₅ represents a linear or branched C _{7 ~ 27} hydrocarbon radicals, wherein R ₅ may have a substituent group selected from the group consisting of hydroxy group and amino group, also R ₅ may have a linking group in the carbon chain, R ₆ represents a linear or branched C _{1 ~ 25} hydrocarbon radicals, wherein R ₆ may have a hydroxyl group, R ₆ may have a linking group in the carbon chain, and R ₇ is a linear or branched C _1-4 alkyl group, a linear or branched C _1-4 hydroxyalkyl group, or an ethylene oxide addition. A polyoxyethylene group having 1 to 25 moles is represented. ]

... (C2)
Wherein, R ₁₆ and R ₁₇ each independently represent a hydrogen atom, or a linear or branched C _{1 ~ 25} hydrocarbon radicals, wherein R ₁₆ and R ₁₇ are each independently a substituted R ₁₆ and R ₁₇ may each independently have a linking group in the carbon chain, or R ₁₆ and R ₁₇ each independently represents ethylene. represents a polyoxyethylene group of oxide addition mole number 1 to 25, R ₁₈ represents a linear or branched C _{8 ~ 25} hydrocarbon radicals, wherein R ₁₈ may have a substituent, and R ₁₈ may have a linking group in the carbon chain, and R ₁₉ is a hydrogen atom, a linear or branched C _1-3 alkyl group, a linear or branched C _1-3 hydroxyalkyl group, or ethylene oxide. It represents a polyoxyethylene group having 1 to 25 addition moles, and Z ⁻ represents an anion. ]
(D) Fragrance

  By using the liquid detergent composition of the present invention, it is possible to improve the residual fragrance of the fragrance imparted to the textile product such as clothes after washing and drying.

［式中、Ｘ¹¹〜Ｘ¹⁴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し、Ｒは水素原子又は水酸基を表し、ｎ１は０又は１の整数を表す。］

…（ｂ２）
［式中、Ａはアルキル基、カルボキシ基、スルホ基、アミノ基、水酸基又は水素原子を表し、Ｘ²¹〜Ｘ²³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し、ｎ２は０〜５の整数を表す。］
（Ｃ）下記一般式（Ｃ１）又は（Ｃ２）で表される化合物、又はその塩

…（Ｃ１）
［式中、Ｒ₅は直鎖又は分岐したＣ_7~27炭化水素基を表し、ここでＲ₅はヒドロキシ基及びアミノ基からなる群より選ばれた置換基を有していてもよく、またＲ₅は炭素鎖中に連結基を有していてもよく、Ｒ₆は直鎖又は分岐したＣ_1~25炭化水素基を表し、ここでＲ₆はヒドロキシル基を有していてもよく、またＲ₆は炭素鎖中に連結基を有していてもよく、Ｒ₇は直鎖又は分岐したＣ_1~4アルキル基、直鎖又は分岐したＣ_1~4ヒドロキシアルキル基、又はエチレンオキサイド付加モル数１〜２５のポリオキシエチレン基を表す。］

…（Ｃ２）
［式中、Ｒ₁₆及びＲ₁₇は、それぞれ独立して、水素原子、又は直鎖又は分岐したＣ_1~25炭化水素基を表し、ここでＲ₁₆及びＲ₁₇は、それぞれ独立して、置換基を有していてもよく、又はＲ₁₆及びＲ₁₇は、それぞれ独立して、炭素鎖中に連結基を有していてもよく、又はＲ₁₆及びＲ₁₇は、それぞれ独立して、エチレンオキサイド付加モル数１〜２５のポリオキシエチレン基を表し、Ｒ₁₈は直鎖又は分岐したＣ_8~25炭化水素基を表し、ここでＲ₁₈は置換基を有していてもよく、又はＲ₁₈は炭素鎖中に連結基を有していてもよく、Ｒ₁₉は水素原子、直鎖又は分岐したＣ_1~3アルキル基、直鎖又は分岐したＣ_1~3ヒドロキシアルキル基、又はエチレンオキサイド付加モル数１〜２５のポリオキシエチレン基を表し、Ｚ^-は陰イオンを表す。］
（Ｄ）香料
また、本発明の液体洗浄剤組成物は、さらに（Ｅ）低ＥＯ非イオン性界面活性剤を含有しても良い。 The liquid detergent composition of the present invention contains the following components (A) to (D).
(A) One or more water-soluble metal salts selected from the group consisting of a water-soluble salt of copper, a water-soluble salt of zinc or a water-soluble salt of silver (B) represented by the following general formula (b1) or (b2) Chelate compound

[Wherein, X ^{11 to} X ¹⁴ each independently represents a hydrogen atom, an alkali metal, an alkaline earth metal or cationic ammonium, R represents a hydrogen atom or a hydroxyl group, and n1 represents an integer of 0 or 1. . ]

... (b2)
[Wherein, A represents an alkyl group, a carboxy group, a sulfo group, an amino group, a hydroxyl group or a hydrogen atom, and X ^{21 to} X ²³ each independently represents a hydrogen atom, an alkali metal, an alkaline earth metal or a cationic ammonium. N2 represents an integer of 0 to 5. ]
(C) A compound represented by the following general formula (C1) or (C2), or a salt thereof

... (C1)
Wherein, R ₅ represents a linear or branched C _{7 ~ 27} hydrocarbon radicals, wherein R ₅ may have a substituent group selected from the group consisting of hydroxy group and amino group, also R ₅ may have a linking group in the carbon chain, R ₆ represents a linear or branched C _{1 ~ 25} hydrocarbon radicals, wherein R ₆ may have a hydroxyl group, R ₆ may have a linking group in the carbon chain, and R ₇ is a linear or branched C _1-4 alkyl group, a linear or branched C _1-4 hydroxyalkyl group, or an ethylene oxide addition. A polyoxyethylene group having 1 to 25 moles is represented. ]

... (C2)
Wherein, R ₁₆ and R ₁₇ each independently represent a hydrogen atom, or a linear or branched C _{1 ~ 25} hydrocarbon radicals, wherein R ₁₆ and R ₁₇ are each independently a substituted R ₁₆ and R ₁₇ may each independently have a linking group in the carbon chain, or R ₁₆ and R ₁₇ each independently represents ethylene. represents a polyoxyethylene group of oxide addition mole number 1 to 25, R ₁₈ represents a linear or branched C _{8 ~ 25} hydrocarbon radicals, wherein R ₁₈ may have a substituent, or R ₁₈ may have a linking group in the carbon chain, and R ₁₉ is a hydrogen atom, a linear or branched C _1-3 alkyl group, a linear or branched C _1-3 hydroxyalkyl group, or ethylene oxide. It represents a polyoxyethylene group having 1 to 25 addition moles, and Z ⁻ represents an anion. ]
(D) Fragrance The liquid detergent composition of the present invention may further contain (E) a low EO nonionic surfactant.

(A) Water-soluble metal salt (A-1) Water-soluble salt of copper The water-soluble salt of copper is not particularly limited as long as it dissolves in water and releases zinc ions at that time. . Examples of water-soluble salts of copper include copper nitrate, copper sulfide, copper sulfate, copper chloride, copper acetate, copper perchlorate, copper cyanide, copper chloride ammonium, copper tartrate, copper gluconate, etc. The hydrate can also be used. Copper sulfate pentahydrate is preferable in terms of handling properties, cost, safety, and the like.
(A-2) Water-soluble salt of zinc The water-soluble salt of zinc is not particularly limited as long as it dissolves in water and releases zinc ions at that time. Examples of water-soluble salts of zinc include zinc nitrate, zinc sulfate, zinc sulfide, zinc chloride, zinc acetate, zinc cyanide, zinc chloride ammonium, zinc tartrate, zinc perchlorate, etc. Zinc sulfate is preferred in terms of raw material supply properties and the like.
(A-3) Water-soluble salt of silver The water-soluble salt of silver is not particularly limited as long as it is soluble in water and releases silver ions at that time. Examples of the water-soluble salt of silver include silver sulfate, silver nitrate, silver acetate, silver fluoride, and silver perchlorate. Silver sulfate is preferable from the viewpoint of handleability and odor.
The blending amount of the water-soluble metal salt in the liquid detergent composition is not particularly limited, but it is preferably blended so as to be 0.05% by mass or more, more preferably 0.1% by mass or more. , 0.3% by mass or more is particularly preferable. If the said water-soluble metal salt is mix | blended 0.05 mass% or more in cleaning composition, sufficient improvement effect of the residual scent performance of PE (polyester) clothing will be acquired. On the other hand, the upper limit of the amount of the water-soluble metal salt is not particularly limited, but is preferably 5% by mass or less, and more preferably 3% by mass or less. If the amount of the water-soluble metal salt is 5% by mass or less, a composition having good stability can be obtained. In addition, even if the blending amount of the water-soluble metal salt exceeds 5% by mass, it is difficult to obtain the effect of improving the residual scent performance of PE clothing corresponding thereto, which is economically disadvantageous.

…（ｂ１）
［式中、Ｘ¹¹〜Ｘ¹⁴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し、Ｒは水素原子又は水酸基を表し、ｎ₁は０又は１の整数を表す。］

…（ｂ２）
［式中、Ａはアルキル基、カルボキシ基、スルホ基、アミノ基、水酸基又は水素原子を表し、ここで該アルキル基は、その水素原子の一部が置換基にて置換されていてもよく、Ｘ²¹〜Ｘ²³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し、ｎ₂は０〜５の整数を表す。］ (B) Chelate compound The component (B) is a chelate compound represented by the following general formula (b1) or (b2). In the component (B), when dissolved in water, ionized by -COO ^- is produced. The -COO ^- part of it is believed to form complexes with metal ions released from the component (A).

... (b1)
[Wherein, X ^{11 to} X ¹⁴ each independently represents a hydrogen atom, an alkali metal, an alkaline earth metal or a cationic ammonium, R represents a hydrogen atom or a hydroxyl group, and n ₁ represents an integer of 0 or 1. Represent. ]

... (b2)
[In the formula, A represents an alkyl group, a carboxy group, a sulfo group, an amino group, a hydroxyl group or a hydrogen atom, wherein the alkyl group may have a part of the hydrogen atom substituted with a substituent; X ^{21 to} X ²³ each independently represent a hydrogen atom, an alkali metal, an alkaline earth metal, or cationic ammonium, and n ₂ represents an integer of 0 to 5. ]

In formula (b1), examples of the alkali metal in X ^{11 to} X ¹⁴ include sodium and potassium. Examples of the alkaline earth metal include calcium and magnesium. Incidentally, at least one of X ¹¹ to X ¹⁴ corresponds to 1/2 atomic if an alkaline earth metal. For example, if X ¹¹ is calcium, -COOX ¹¹ is ^"- 1/2 (Ca) ^- COO".
Examples of the cationic ammonium include alkanolamines such as monoethanolamine and diethanolamine, and specifically, those in which 1 to 3 hydrogen atoms of ammonium are substituted with alkanol groups. As for carbon number of an alkanol group, 1-3 are preferable.
Among the above, X ^{11 to} X ¹⁴ are preferably alkali metals.
X ^{11 to} X ¹⁴ in formula (b1) may be the same or different.
n ₁ is preferably 1.
Specific examples of the chelate compound represented by the formula (b1) include iminodisuccinic acid, 3-hydroxy-2,2′-iminodisuccinic acid or salts thereof. 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, and sodium salt or potassium salt is particularly preferable.

In formula (b2), the alkali metal, alkaline earth metal, and cationic ammonium in X ^{21 to} X ²³ are the same as the alkali metal, alkaline earth metal, and cationic ammonium in X ^{11 to} X ¹⁴ , respectively. Is mentioned.
Among the above, X ^{21 to} X ²³ are preferably alkali metals.
X ^{21 to} X ²³ in the formula (b2) may be the same or different from each other.
The alkyl group in A may be either linear or branched. 1-30 are preferable and, as for carbon number of an alkyl group, 1-18 are more preferable. In the alkyl group, a part of the hydrogen atoms may be substituted with a substituent. Examples of the substituent include a sulfo group (—SO ₃ H), an amino group (—NH ₂ ), a hydroxyl group, and a nitro group (—NO ₂ ).
A may be any of an alkyl group, a carboxy group, a sulfo group, an amino group, a hydroxyl group, and a hydrogen atom, and a hydrogen atom is particularly preferable.
n ₂ is preferably an integer of 0 to 2, and 1 is particularly preferable.

Specific examples of the chelate compound represented by the formula (b2) include, for example, nitrilotriacetic acid, methylglycine diacetic acid, dicarboxymethylglutamic acid, L-aspartic acid-N, N-diacetic acid, serine diacetic acid, or salts thereof In particular, methylglycine diacetate is preferable. 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, and sodium salt or potassium salt is particularly preferable.
A component (B) may be used individually by 1 type, and may use 2 or more types together. 0.1-10 mass% is preferable with respect to the total mass of a liquid detergent composition, the compounding quantity of a component (B) has more preferable 0.2-5 mass%, and 0.3-3 mass% is further. preferable. When the content is in the range of 0.1 to 10% by mass, a composition having a good residual scent performance of PE clothing can be obtained. On the other hand, when the content of the component (B) is less than 0.1% by mass, the residual scent performance of the PE clothing may be insufficient. Moreover, even if content exceeds 10 mass%, the improvement effect of the residual scent performance of PE clothing corresponding to it is difficult to be acquired, and it becomes economically disadvantageous.
Moreover, the ratio (B / A) of the mass of the component (B) to the mass of the component (A) is preferably 0.5 to 10.0, more preferably 0.8 to 1.8, Preferably it is about 1.5.

…（Ｃ１）
［式中、Ｒ₅は直鎖又は分岐したＣ_7~27炭化水素基を表し、ここでＲ₅はヒドロキシ基及びアミノ基からなる群より選ばれた置換基を有していてもよく、またＲ₅は炭素鎖中に連結基を有していてもよく、Ｒ₆は直鎖又は分岐したＣ_1~25炭化水素基を表し、ここでＲ₆はヒドロキシル基を有していてもよく、またＲ₆は炭素鎖中に連結基を有していてもよく、Ｒ₇は直鎖又は分岐したＣ_1~4アルキル基、直鎖又は分岐したＣ_1~4ヒドロキシアルキル基、又はエチレンオキサイド付加モル数１〜２５のポリオキシエチレン基を表す。］

…（Ｃ２）
［式中、Ｒ₁₆及びＲ₁₇は、それぞれ独立して、水素原子、又は直鎖又は分岐したＣ_1~25炭化水素基を表し、ここでＲ₁₆及びＲ₁₇は、それぞれ独立して、置換基を有していてもよく、またＲ₁₆及びＲ₁₇は、それぞれ独立して、炭素鎖中に連結基を有していてもよく、又はＲ₁₆及びＲ₁₇は、それぞれ独立して、エチレンオキサイド付加モル数１〜２５のポリオキシエチレン基を表し、Ｒ₁₈は直鎖又は分岐したＣ_8~25炭化水素基を表し、ここでＲ₁₈は置換基を有していてもよく、またＲ₁₈は炭素鎖中に連結基を有していてもよく、Ｒ₁₉は水素原子、直鎖又は分岐したＣ_1~3アルキル基、直鎖又は分岐したＣ_1~3ヒドロキシアルキル基、又はエチレンオキサイド付加モル数１〜２５のポリオキシエチレン基を表し、Ｚ^-は陰イオンを表す。］ (C) Component (C) is a compound represented by the following general formula (C1) or (C2), or a salt thereof.

... (C1)
Wherein, R ₅ represents a linear or branched C _{7 ~ 27} hydrocarbon radicals, wherein R ₅ may have a substituent group selected from the group consisting of hydroxy group and amino group, also R ₅ may have a linking group in the carbon chain, R ₆ represents a linear or branched C _{1 ~ 25} hydrocarbon radicals, wherein R ₆ may have a hydroxyl group, R ₆ may have a linking group in the carbon chain, and R ₇ is a linear or branched C _1-4 alkyl group, a linear or branched C _1-4 hydroxyalkyl group, or an ethylene oxide addition. A polyoxyethylene group having 1 to 25 moles is represented. ]

... (C2)
Wherein, R ₁₆ and R ₁₇ each independently represent a hydrogen atom, or a linear or branched C _{1 ~ 25} hydrocarbon radicals, wherein R ₁₆ and R ₁₇ are each independently a substituted R ₁₆ and R ₁₇ may each independently have a linking group in the carbon chain, or R ₁₆ and R ₁₇ each independently represents ethylene. represents a polyoxyethylene group of oxide addition mole number 1 to 25, R ₁₈ represents a linear or branched C _{8 ~ 25} hydrocarbon radicals, wherein R ₁₈ may have a substituent, and R ₁₈ may have a linking group in the carbon chain, and R ₁₉ is a hydrogen atom, a linear or branched C _1-3 alkyl group, a linear or branched C _1-3 hydroxyalkyl group, or ethylene oxide. It represents a polyoxyethylene group having 1 to 25 addition moles, and Z ⁻ represents an anion. ]

In the general formula (C1), R ₅ is a linear or branched C _{7 to 27} hydrocarbon group, preferably a linear or branched C _{7 to 25} hydrocarbon group. R ₅ may be saturated or unsaturated. R ₅ may be substituted with a hydroxy group or an amino group. Furthermore, R ₅ may have a linking group in the carbon chain. Examples of the linking group include an amide group, an ester group, and an ether group, and an amide group and an ester group are preferable. In addition, carbon number of a substituent or a coupling group is not included in carbon number 7-27 of the above-mentioned hydrocarbon group. Among them, R ₅ is —R ₈ —W (wherein R ₈ is a linear or branched C _1-4 alkylene group, W is —NHCO—R ₉ or —OOC—R ₁₀ , R ₉ C _{7 ~ 23} hydrocarbon group, preferably a C _{7 ~ 21} hydrocarbon group, R ₁₀ is C _{11 ~ 23} hydrocarbyl, preferably C _{12 ~ 20} hydrocarbon group, R ₉ and R ₁₀ May be linear or branched and may be saturated or unsaturated).
R ₆ is a linear or branched C _{1 ~ 25} hydrocarbon group, preferably a linear or branched C _{1 ~ 4} hydrocarbon group. R ₆ may be saturated or unsaturated. R ₆ may be substituted with a hydroxyl group. R ₆ may have a linking group in the carbon chain. Examples of the linking group include an amide group, an ester group, and an ether group. R ₆ is preferably a linear or branched C _1-4 alkyl group and a linear or branched C _1-4 hydroxyalkyl group.
R ₇ is a linear or branched C _1-4 alkyl group, a linear or branched C _1-4 hydroxyalkyl group, or a polyoxyethylene group having 1 to 25 moles of ethylene oxide added. A linear or branched C _1-4 alkyl group and a linear or branched C _1-4 hydroxyalkyl group are preferred.
The compound represented by the above general formula (C1) may be used alone or in combination with a plurality of types of compounds represented by the general formula (C1).

…（Ｃ１−２）
式（Ｃ１−２）中、Ｒ₁₁及びＲ₁₂は、それぞれ独立して直鎖又は分岐したＣ_1~4アルキル基、又は、直鎖又は分岐したＣ_1~4ヒドロキシアルキル基である。
Ｒ₁₃は直鎖又は分岐したＣ_1~4アルキレン基である。
Ｚは、下記一般式（Ｃ１−３）又は（Ｃ１−４）で表される基である。

…（Ｃ１−３）

…（Ｃ１−４）
一般式（Ｃ１−３）中、Ｒ₁₄は、直鎖又は分岐したＣ_7~23炭化水素基、好ましくは直鎖又は分岐したＣ_7~21炭化水素基であり、一般式（Ｃ１−４）中、Ｒ₁₅は、直鎖又は分岐したＣ_11~23炭化水素基、好ましくは直鎖又は分岐したＣ_12~20炭化水素基である。Ｒ₁₄及びＲ₁₅は、それぞれ独立して飽和していてもよく、不飽和であってもよい。
上記の一般式（Ｃ１−２）で表される化合物は、単独で用いてもよく、複数種類の一般式（Ｃ１−２）で表される化合物を組み合わせて使用してもよい。 Among the compounds represented by the general formula (C1), a compound represented by the following general formula (C1-2) is preferable.

... (C1-2)
In formula (C1-2), R ₁₁ and R ₁₂ are each independently a linear or branched C _1-4 alkyl group or a linear or branched C _1-4 hydroxyalkyl group.
R ₁₃ is a linear or branched C _1-4 alkylene group.
Z is a group represented by the following general formula (C1-3) or (C1-4).

... (C1-3)

... (C1-4)
In the general formula (C1-3), R ₁₄ represents a linear or branched C _{7 ~ 23} hydrocarbyl, preferably straight-chain or branched C _{7 ~ 21} hydrocarbon group, the general formula (C1-4) among, R ₁₅ is a linear or branched C _{11 ~ 23} hydrocarbon group, preferably a linear or branched C _{12 ~ 20} hydrocarbon group. R ₁₄ and R ₁₅ may be independently saturated or unsaturated.
The compound represented by the above general formula (C1-2) may be used alone or in combination of a plurality of types of compounds represented by the general formula (C1-2).

  The compound represented by the general formula (C1) (and (C1-2)) is a known substance and can be easily obtained in the market or can be prepared. Specific examples of the compound represented by the general formula (C1) include caprylic acid dimethylaminopropylamide, capric acid dimethylaminopropylamide, lauric acid dimethylaminopropylamide, myristic acid dimethylaminopropylamide, palmitic acid dimethylaminopropylamide. , Long chain aliphatic amide dialkyl tertiary amines such as stearic acid dimethylaminopropylamide, behenic acid dimethylaminopropylamide, oleic acid dimethylaminopropylamide; long chain such as palmitic acid diethanolaminopropylamide, stearic acid diethanolaminopropylamide Aliphatic amide dialkanol tertiary amine; aliphatic ester dialkyl 3 such as palmitate ester propyldimethylamine, stearate ester propyldimethylamine Amine: Lauryl dimethylamine, myristyl dimethylamine, palm alkyl dimethylamine, palmityl dimethylamine, beef tallow alkyl dimethylamine, hardened beef tallow alkyl dimethylamine, stearyl dimethylamine, stearyl diethanolamine, polyoxyethylene hardened tallow alkylamine (Lion Akzo Corporation) ), Product name: ETHOMEEN HT / 14, etc.). These are particularly preferably used alone or in combination of two or more. In particular, it is more preferable to use amidopropyldimethylamine palmitate and amidopropyldimethylamine stearate in combination. In this case, the mass ratio of amidopropyldimethylamine palmitate and amidopropyldimethylamine stearate is preferably 10:90 to 50:50, and more preferably 20:80 to 40:60. By using in such a ratio, a composition having excellent stability and a high effect of improving the remaining fragrance can be obtained.

Here, “aliphatic amide alkyl tertiary amine”, which is a specific example of the compound represented by the general formula (C1), includes a fatty acid or a fatty acid derivative (fatty acid lower alkyl ester or animal / vegetable oil or the like) and dialkyl ( Alternatively, it can be produced by a condensation reaction with an alkanol) aminoalkylamine and then distilling off the 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 Examples include oil fatty acids, beef tallow fatty acids, palm kernel fatty acids, soybean oil fatty acids, linseed oil fatty acids, castor oil fatty acids, olive oil fatty acids and other vegetable oils and animal oil fatty acids, and methyl esters, ethyl esters, glycerides, etc., among them caprylic acid Capric acid, lauric acid, myristic acid, palmitic acid, stearic acid, oleic acid and behenic acid are particularly preferred. 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, and diethylaminoethylamine. Among them, dimethylaminopropylamine is particularly preferable.
The amount of dialkyl (or alkanol) aminoalkylamine used is preferably 0.9 to 2.0 moles, particularly preferably 1.0 to 1.5 moles, based on the fatty acid or derivative thereof.
The reaction temperature 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 maintained moderately, and coloring of the tertiary amine compound obtained by setting the reaction temperature to 220 ° C. or lower can be prevented or reduced.

The “aliphatic ester alkyl tertiary amine” which is a specific example of the compound represented by the general formula (C1) is a fatty acid or a fatty acid derivative (fatty acid lower alkyl ester or animal / vegetable oil or fat) and a dialkylamino alcohol. It can be produced by performing a condensation reaction and then distilling off the unreacted dialkylamino alcohol by reducing the pressure or blowing with nitrogen.
The fatty acid or fatty acid derivative is the same as that described in the above-described method for producing “aliphatic amide alkyl tertiary amine”.
Examples of the dialkylamino alcohol 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 derivative thereof. Is more preferable, and 1.0 to 1.5 times mole is particularly preferable.
The reaction temperature is usually 100 to 220 ° C, preferably 120 to 180 ° C. Within the above range, it is possible to suppress coloring of the tertiary amine as a product while maintaining an appropriate reaction rate.

The production conditions of the compound represented by the general formula (C1) other than the above can be appropriately changed depending on the type of raw material used and the like. For example, the pressure during the reaction may be normal pressure or reduced pressure, such as nitrogen during the reaction. It can also be introduced by blowing an inert gas.
In addition, when using a fatty acid as a raw material, an acid catalyst such as sulfuric acid or p-toluenesulfonic acid is used. When a fatty acid derivative is used, an alkali catalyst such as sodium methylate, caustic potash or caustic soda is used. The reaction can proceed efficiently in a short time.
In addition, when the resulting tertiary amine compound is a compound having a high melting point, it is preferably molded 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, paratoluenesulfonic acid, cumenesulfonic acid, and the like. These may be used alone or in combination of two or more.
The salt of the compound represented by the general formula (C1) may be used alone, or a plurality of types of salt of the compound represented by the general formula (C1) may be used in combination.

In formula (C2), R ₁₆ and R ₁₇ are each independently hydrogen atom, or a linear or branched C _{1 ~ 25} hydrocarbon group. R ₁₆ and R ₁₇ may each independently be saturated or unsaturated. R ₁₆ and R ₁₇ may each independently contain a substituent such as a hydroxy group. R ₁₆ and R ₁₇ each independently have a linking group such as an amide group, an ester group (—C (O) —O—) or an ether group (—O—) in its carbon chain. There may be. Furthermore, R ₁₆ and R ₁₇ may each independently be a polyoxyethylene group having 1 to 25 ethylene oxide addition moles. Among these, as R ₁₆ and R ₁₇ , each independently is preferably a hydrogen atom, a linear or branched C _1-4 alkyl group, and a linear or branched C _1-4 hydroxyalkyl group. And a methyl group is more preferable. Also, C _{1 ~ 25} hydrocarbon group having an ester group in the carbon chain are also preferred.
In formula (C2), R ₁₈ is a linear or branched C _{8 ~ 25} hydrocarbon group, preferably a C _{16 ~ 22} hydrocarbon group. R ₁₈ may be saturated or unsaturated. R ₁₈ may contain a substituent such as a hydroxy group. Furthermore, R ₁₈ may have a linking group such as an amide group, an ester group or an ether group in its carbon chain. The linking group is preferably an ester group.
In the general formula (C2), R ₁₉ is a hydrogen atom, a linear or branched C _1-3 alkyl group, a linear or branched C _1-3 hydroxyalkyl group, or a polyoxy group having 1 to 25 moles of ethylene oxide added. Ethylene group. Among them, a hydrogen atom, a linear or branched C _{1 ~ 3} alkyl groups and linear or branched C _{1 ~ 3} hydroxyalkyl groups, more preferably a hydrogen atom or a methyl group.
In the general formula (C2), Z ⁻ is an anion. Specifically, halogen atom ions such as chlorine ion, bromine ion and iodine ion, and general formula R ₂₀ SO ⁴⁻ [wherein R ₂₀ is a C _1-3 alkyl group (for example, methyl group, ethyl group or propyl group). Group), and particularly preferably a methyl group. ] The ion etc. which are represented by] are mentioned. Of these, chlorine ions are preferred.

Specific examples of the compound represented by the general formula (C2) include monoalkylammonium salts such as cetyltrimethylammonium chloride, cetostearyltrimethylammonium chloride, stearyltrimethylammonium chloride, and behenyltrimethylammonium chloride; monoester ammonium salt; Examples include alkanolamine ester quaternary salts such as diester ammonium salts and triester ammonium salts, and mixtures thereof. Of these, stearyltrimethylammonium chloride, a mixture of behenyltrimethylammonium chloride and an alkanolamine ester quaternary salt is preferable.
The compound represented by the above general formula (C2) may be used alone or in combination with a plurality of types of compounds represented by the general formula (C2).
The compound represented by the general formula (C2) is a known substance, and can be easily obtained on the market or can be prepared.
Examples of the salt of the compound represented by the general formula (C2) 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, paratoluenesulfonic acid, cumenesulfonic acid, and the like. These may be used alone or in combination of two or more.
The salt of the compound represented by the general formula (C2) may be used alone, or a plurality of types of salt of the compound represented by the general formula (C2) may be used in combination.

As the component (C), the compound represented by the general formula (C1) and the salt thereof, and the compound represented by the general formula (C2) and the salt thereof are used alone or in combination of two or more. Can be used. The content of the component (C) is preferably 0.1 to 5% by mass in the liquid detergent composition, more preferably 0.2 to 4% by mass, and 1 to 4% by mass. More preferably. When the content of the component (C) is 0.1% by mass or more, a negative charge formed by the component (A) and the component (B) by adding the component (C) having a positive charge site in the washing liquid Since the formation of a complex with a complex having selenium is promoted, the residual scent performance of PE clothing is more easily obtained. On the other hand, when the content of the component (C) is 5% by mass or less, the liquid detergent composition does not gel on the liquid surface even at low temperatures, and a film is hardly formed. Moreover, it becomes easy to take a blending balance with other components.
Further, the ratio ((A + B) / C) of the total mass of the component (A) and the component (B) to the mass of the component (C) is preferably 0.2 to 15.0, more preferably 0.00. 5 to 5.0, most preferably about 0.5.

(D) Fragrance The fragrance used in the present invention preferably contains 4- (p-hydroxyphenyl) -2-butanone (D-1) and salicylic acid ester (D-2). 4- (p-Hydroxyphenyl) -2-butanone (D-1) is a fragrance having a structure represented by the following formula, and is a fragrance mainly used for floral fruity tones and flavors.

式中、Ｒ₂₀は炭素数３〜８の飽和炭化水素、不飽和炭化水素、分岐炭化水素、芳香環である。具体的な香料としては、サリチル酸ヘキシル、サリチル酸ベンジル、サリチル酸イソアミル、サリチル酸アミル、サリチル酸エチル、サリチル酸ブチル、サリチル酸イソブチル、サリチル酸フェニル、サリチル酸ｐ−クレジル、サリチル酸ｃｉｓ−３−ヘキセニル、サリチル酸フェニルエチル、サリチル酸イソブチル、サリチル酸シクロヘキシル、ラズベリーケトンなどがある。このうち、サリチル酸ヘキシル、サリチル酸ベンジル、サリチル酸イソアミル、サリチル酸アミル、ラズベリーケトンが好ましく、ラズベリーケトンが特に好ましい。 Salicylic acid ester (D-2) is a fragrance having a structure represented by the following formula.

In the formula, R ₂₀ is a C 3-8 saturated hydrocarbon, unsaturated hydrocarbon, branched hydrocarbon, or aromatic ring. Specific fragrances include: 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 and raspberry ketone. Among these, hexyl salicylate, benzyl salicylate, isoamyl salicylate, amyl salicylate, and raspberry ketone are preferable, and raspberry ketone is particularly preferable.

  (D-1) In the case of a fragrance alone, the remaining fragrance after washing has a sweet and spreading fragrance, so that the cognition is poor and the scent of the fragrance is rarely felt. On the other hand, (D-2) the fragrance alone scents refreshingly but is weak and lacks cognition. As a result of intensive research by the present inventors, (D-1) perfume is combined with (C-2) perfume, so that the sweetly spreading scent of (D-1) is refreshingly fragrant, thereby recognizing the scent. Has been found to increase dramatically. (D-1) + (D-2) is preferably contained in an amount of 10 to 60% by mass, more preferably 10 to 50% by mass, based on the total amount of the fragrance composition. When the total amount of (D-1) and (D-2) in the entire fragrance composition is less than 10% by mass, the feeling of residual fragrance becomes weak, and when it increases, it becomes difficult to adjust various fragrances. End up. The blending ratio is preferably (D-1) / [(D-1) + (D-2)] = 10 to 50% by mass, and more preferably 10 to 30% by mass. When the component (D-1) is larger than this ratio, the scent becomes sweet and the fresh feeling as a cleaning agent becomes weak. Moreover, if it decreases, it will stop feeling a scent.

  In an actual formulation system, the scent must match the palatability and product characteristics. Therefore, in the present invention, conventionally known perfume ingredients other than the above (D-1) and (D-2) perfume can be used freely. The typical perfume ingredients are described below. Hydrocarbons such as aliphatic hydrocarbons, terpene hydrocarbons, aromatic hydrocarbons, aliphatic alcohols, alcohols such as terpene alcohols, aromatic alcohols, aliphatic ethers, ethers such as aromatic ethers, aliphatic oxides, Oxides such as terpene oxides, aliphatic aldehydes, terpene aldehydes, alicyclic aldehydes, aldehydes such as thioaldehydes, aromatic aldehydes, aliphatic ketones, terpene ketones, alicyclic ketones, aliphatic cyclic ketones, Non-benzene aromatic ketones, ketones such as aromatic ketones, acetals, ketals, phenols, phenol ethers, fatty acids, terpene carboxylic acids, alicyclic carboxylic acids, acids such as aromatic carboxylic acids, acids Amides, aliphatic lactones, macrocyclic lactones, terpene lactones, fats Lactones such as formula lactones and aromatic lactones, aliphatic esters, furan carboxylic acid esters, aliphatic cyclic carboxylic acid esters, cyclohexyl carboxylic acid esters, terpene carboxylic acid esters, aromatic carboxylic acid esters and the like Nitromusks, nitriles, amines, pyridines, quinolines, pyrroles, nitrogen-containing compounds such as indoles, and the like, and natural fragrances from animals and plants, natural fragrances and / or blended fragrances containing synthetic fragrances or Two or more types can be mixed and used. For example, in 1996, Motoichi Into, published by Chemical Industry Daily, “Synthetic Fragrance Chemistry and Product Knowledge”, 1969 MONTCLAIR, N. J. et al. Fragrances described in “Perfume and Flavor Chemicals” by STEFEN Arctander can be used. In addition, diethyl phthalate, dipropylene glycol, benzyl benzoate, isopropyl myristate, rosin resin (trade name Hercorin) and the like can be arbitrarily blended in the fragrance composition as a solvent or a retaining agent. The blending amount of the fragrance composition containing (D-1) and (D-2) in the liquid detergent composition is preferably 0.01 to 5% by mass, and 0.10 to 3% by mass. More preferably. Furthermore, 0.30-1 mass% is preferable. If the blending amount of the fragrance composition in the liquid detergent composition is less than 0.01% by mass, sufficient PE clothing residual scent performance is not exhibited, and if it exceeds 5% by mass, the aroma at the time of washing is too strong. Not only does it give pleasure, it is also disadvantageous economically.

(E) Low EO nonionic surfactant A complex having a minus charge site formed by the component (A) and the component (B) in the washing liquid by adding a low EO nonionic surfactant And a component (C) having a positive charge site form a complex. This complex is adsorbed on the surface of PE clothing, and component (D) is adsorbed by hydrophobic interaction, and component (E) has a high hydrophobic property. (D) also improves the residual fragrance property of PE clothing because it is efficiently adsorbed to PE clothing, and component (E) improves the anti-recontamination performance of PE clothing because it effectively disperses the soil component in the washing liquid. . Although it does not specifically limit as a low EO nonionic surfactant used by this invention, For example, the polyoxyalkylene type nonionic surfactant represented by following formula (III) is used suitably.

R ^a -Y- (EO) _s (PO) _t -R ^b (III)

In the above formula (III), R ^a is a hydrophobic group having 8 to 22 carbon atoms, preferably 10 to 16 carbon atoms. Preferred examples of the hydrophobic group include an alkyl group or an alkenyl group, which may be linear or branched. A branched chain is particularly preferable. Examples of the raw material used for introducing the hydrophobic group include primary or secondary higher alcohols, higher fatty acids, higher fatty acid amides, and the like.
R ^b is a hydrogen atom or a linear or branched alkyl group or alkenyl group having 1 to 6 carbon atoms, preferably 1 to 3 carbon atoms, and more preferably a hydrogen atom.
-Y- is a linking group, preferably -O-, -COO-, or -CONH-, more preferably -O-.
EO is ethylene oxide and PO is propylene oxide.
s and t represent the average number of moles added. s is an integer of 3-9, preferably 4-8, more preferably 5-8. t is 0-6, preferably 0-3. By setting the average added mole number s of EO to 9 or less, the residual fragrance property of PE clothing and the performance of preventing re-contamination of PE clothing are improved. By setting the average added mole number s of EO to 3 or more, it is possible to suppress a decrease in storage stability of the composition at a high temperature. The added mole number distribution of EO or PO varies depending on the reaction method during the production of the nonionic surfactant (A), and is not particularly limited. For example, the addition mole number distribution of EO or PO is relatively wide when ethylene oxide or propylene oxide is added to a hydrophobic group raw material using a general alkali catalyst such as sodium hydroxide or potassium hydroxide. It becomes. On the other hand, metal ions such as Al ³⁺ , Ga ³⁺ , In ³⁺ , Tl ³⁺ , Co ³⁺ , Sc ³⁺ , La ³⁺ and Mn ²⁺ described in JP-B-615038 were added. When ethylene oxide or propylene oxide is added to a hydrophobic group raw material using a specific alkoxylation catalyst such as magnesium oxide, the distribution tends to be relatively narrow.

Specific examples of the low EO nonionic surfactant represented by the above formula (III) include: Nippon Nippon Rika Co., Ltd .: trade name Conol (ethylene oxide equivalent to 9 moles relative to natural alcohol such as C12) BASF, Inc .: trade names: Lutensol TO7, Lutensol TO10 (equivalent to 7 mol or 10 mol for 1 mol of C13 alcohol obtained by subjecting C12 alkene obtained by trimerizing butene to the oxo method) To which ethylene oxide is added).
Moreover, the following compound is mentioned as a component (E).
(E-13) Polyoxyethylene fatty acid methyl ester ( ₉ mol of MEE EO, C ₁₁ H ₂₃ CO— (OC ₂ H ₄ ) ₉ —OCH ₃ , narrow ratio 33% by mass)
(E-13) was manufactured by the method based on the method as described in Unexamined-Japanese-Patent No. 2002-144179. That is, alumina hydroxide / magnesium hydroxide (trade name Kyoward 300, manufactured by Kyowa Chemical Industry Co., Ltd.) having a chemical composition of 2.5 MgO.Al ₂ O ₃ .nH ₂ O is fired at 600 ° C. for 1 hour in a nitrogen atmosphere. 4 g of calcined alumina hydroxide / magnesium catalyst (unmodified) obtained as described above, 2.9 mL of 0.5N potassium hydroxide ethanol solution as a surface modifier, and 350 g of lauric acid methyl ester A liter autoclave was charged and the catalyst was reformed in the autoclave. Next, after replacing the inside of the autoclave with nitrogen, the temperature was raised, and while maintaining the temperature at 180 ° C. and the pressure of 3 × 10 5 Pa, 648 g of ethylene oxide was introduced and reacted while stirring. Next, 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 to obtain the target product (e-13).
A component (E) may be used individually by 1 type, or may use 2 or more types together. In the present invention, the blending amount of component (E) (when two or more are used in combination means the total amount. The same applies to the other components). % Is preferable, and 2 to 10% by mass is particularly preferable. When the blending amount of the component (E) is 2% by mass or more, the residual fragrance property of PE clothing and the performance of preventing re-contamination of PE clothing are improved. It will be easy to handle.

  The liquid detergent composition of the present invention may contain other nonionic surfactants in addition to the component (E). Examples of such other nonionic surfactants include polyoxyethylene (EO addition mole number 3 to 9) sorbitan fatty acid (C10-22) ester, polyoxyethylene (EO addition mole number 3 to 9) sorbite fatty acid. (C10-22) ester, polyoxyethylene (EO addition mole number 3-9) glycol fatty acid (C10-22) ester, glycerin fatty acid (C10-22) ester, alkyl (C10-22) glycoside and the like can be mentioned.

In addition to the above components, the liquid cleaning composition of the present invention may further contain the following optional components as necessary. Specific examples include alcohols such as ethanol and glycol solvents such as ethylene glycol, propylene glycol, and polypropylene glycol. Of these, ethanol is preferred.
Moreover, you may contain 0-1 mass% of C8-C22 fatty acid as a foam suppressor.
Furthermore, for the purpose of improving detergency, 0 to 1% by mass of enzymes such as lipase, cellulose, amylase and protease, boric acid, borax, formic acid or the like for the purpose of enzyme stabilization 0 to 3% by mass of calcium salts such as salts, calcium chloride and calcium sulfate, and 0 to 5 silicones such as dimethyl silicone, polyether-modified silicone and amino-modified silicone for the purpose of improving the texture. 0% to 1% by mass of a fluorescent agent such as a distyrylbiphenyl type for the purpose of improving the whiteness of white clothing, and 0.0001 to 0% of a pigment such as an acid dye for the purpose of coloring a liquid detergent composition 0.001% by mass, for the purpose of stabilizing the aroma, 0.0001 to 0.5% by mass of an antioxidant such as dibutylhydroxytoluene, and 0% of an antibacterial agent such as Kaesson CG / ICP for the purpose of antiseptic properties 0.05 It can be an amount% formulation. 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 0 in the liquid detergent composition of the present invention. 0.01 to 1% by mass can be blended.
Furthermore, as a pH adjuster, inorganic acids and inorganic bases such as sulfuric acid, sodium hydroxide, and potassium hydroxide can be blended. The pH of the liquid detergent composition of the present invention includes sebum dirt cleaning power, after storage From the viewpoint of maintaining the detergency, 6.0 to 11.0 is preferable.

The liquid detergent composition of the present invention is an aqueous composition and can be prepared by balancing the above components (A) to (E) and optional components with water as necessary. The balance water used is preferably purified water or ion exchange water.
The liquid detergent composition of the present invention can be used by directly applying to a soil, or it can be used by immersing clothes by dissolving in water. Further, it may be left as appropriate after application as a washing pretreatment agent and then washed with a washing liquid containing an anionic surfactant.

(Evaluation of residual fragrance of PE clothing)
<Laundry processing>
Three pieces of 10 cm × 10 cm PE cloth (polyester tropical: 100% polyester, Tanigami Shoten Co., Ltd.) was sewed per cotton towel (Toshin Co., Ltd., 220 piece border FT).
After putting the liquid detergent composition for clothes of each example shown in Table 1 into a concentration of 1333 mg / L (16 g of liquid detergent composition for clothes with respect to 12 L of tap water) and washing under the following washing conditions And dried in an environment of 25 ° C. and 65% RH for 18 hours. Thereafter, the following fragrance evaluation was performed.
Washing conditions: Using a fully automatic electric washing machine (product name: JW-Z23A, manufactured by Haier), the PE cloth with a bath ratio of 50 times (low water level: 12 L) according to the light course of the fully automatic electric washing machine Three cotton towels (total 240 g) sewn with were washed in the same bath.
<Rescent fragrance evaluation>
After drying, sensory evaluation was performed by a method in which ten professional panelists sniff the fragrance remaining on the PE cloth portion sewn on the cotton towel. The intensity of odor was scored based on the following evaluation criteria, and the average value of 10 persons was calculated. The results are shown in Table ○. In addition, the case where the said average value was 2.0 points or more was set as the pass (◎ :: 3.0 points or more, ◎: 2.5 points or more, less than 3.0 points, ○: 2.0 points or more, 2.5 Less than point, x: less than 2.0 point).
5 points: A very strong fragrance.
4 points: Strong fragrance.
3 points: Perfumes that can be easily detected.
2 points: A weak perfume fragrance that tells you what it is.
1 point: A faint fragrance.
0 point: There is no fragrance of the fragrance.

(Evaluation of re-contamination of PE clothing)
[Recontamination evaluation method]
Five sheets of polyester tropical (polyester tropical: 100% polyester, Tanigami Shoten Co., Ltd.) cut into 5 × 5 cm were prepared as re-contamination determination cloths.
<Washing>
Using a round tester (FI-301, manufactured by Tester Sangyo Co., Ltd.), 200 mL of a detergent solution with a concentration of 3000 mg / L adjusted with 3 ° DH hard water at 25 ° C. was placed in a stainless steel sample bottle (500 ± 50 mL). 5 re-contamination determination cloths, wet artificial contamination cloth (manufactured by Japan Association of Laundry Science, oleic acid 28.3 mass%, triolein 15.6 mass%, cholesterol oleate 12.2 mass%, liquid paraffin 2.5 20% by mass, 20% by mass, 2.5% by mass of squalene, 1.6% by mass of cholesterol, 7.0% by mass of gelatin, 29.8% by mass of mud, 0.5% by mass of carbon black, 5 cm × 5 cm / 1 sheet) Skin shirt skin shirt (BVD company skin shirt: 100% cotton, G0134TS) is cut finely (about 3 x 3 cm) and the bath ratio is adjusted to 10 times, 20 rpm And washed for 25 minutes at 25 ° C..
<Rinse>
The washed cloth was dehydrated for 1 minute and then returned to a sample bottle containing 200 mL of 25 ° C. 3 ° DH hard water and rinsed at 40 rpm at 25 ° C. for 3 minutes. This rinsing process was repeated twice.
<Drying>
The rinsed cloth was dehydrated for 1 minute, and then only the recontamination determination cloth was taken out and sandwiched between filter papers and dried with an iron.
This washing-rinsing-drying process is repeated three times, and the reflectance of the recontamination determination cloth is measured using a reflectance meter (Nippon Denshoku Industries Co., Ltd., spectral color difference meter SE2000) and calculated as a Z value. A value obtained by subtracting the Z value after washing from the Z value, ΔZ, was obtained, and the recontamination property was evaluated from the average value of five sheets.
[Evaluation criteria]
◎: ΔZ is 4 or less ◎: ΔZ is larger than 4 and 6 or less ○: ΔZ is larger than 6 and 8 or less ×: ΔZ is 8 or more

・硫酸亜鉛・７水和物：硫酸亜鉛（ＩＩ）七水和物、関東化学株式会社製
・硫酸銅・５水和物 ：硫酸銅（ＩＩ）五水和物、関東化学株式会社製
・硫酸銀 ：特級、和光純薬工業株式会社製
・ＭＧＤＡ・３Ｎａ ：メチルグリシン二酢酸三ナトリウム、トリロンＭ ｌｉｑｕｉｄ、ＢＡＳＦ社製
・Ｃ１６−１８アミドアミン：品名「カチナールＭＰＡＳ−Ｒ」、脂肪酸（Ｃ１６／Ｃ１８）ジメチルアミノプロピルアミド、ステアリン酸／パルミチン酸の質量比＝７／３）東邦化学社製
・Ｃ１０アミドアミン：ＲＣＯＮＨ（ＣＨ₂）₃Ｎ（ＣＨ₃）₂（Ｒはアルキル基（炭素数１０））、下記の方法により合成
還流冷却器を備えた１リットル四ツ口フラスコに、カプリン酸メチル２６０．９ｇ（ライオンケミカル社製、パステルＭ−１０、分子量１８６）を仕込み、６０℃にて窒素置換を２回行った後、１５０℃に昇温し、ジメチルアミノプロピルアミン（分子量１０２）１８６ｇ（混合脂肪酸に対するモル比：１．３０）を１．５時間かけて滴下した。滴下終了後、１８５〜１９０℃に保持し、７時間熟成した。
・Ｃ１６−１８カチオン：塩化アルキル（炭素数Ｃ１６〜Ｃ１８）トリメチルアンモニウム、品名「アーカードＴ−８００」、ライオンアクゾ社製 Table 1 (Examples 1-6)

・ Zinc sulfate ・ Heptahydrate: Zinc sulfate (II) heptahydrate, manufactured by Kanto Chemical Co., Ltd. ・ Copper sulfate pentahydrate: Copper sulfate (II) pentahydrate, manufactured by Kanto Chemical Co., Ltd. ・ Sulfuric acid Silver: Special grade, manufactured by Wako Pure Chemical Industries, Ltd. MGDA, 3Na: Trisodium methylglycine diacetate, Trilon M liquid, manufactured by BASF, C16-18 Amidoamine: Product name “Catinal MPAS-R”, fatty acid (C16 / C18) Dimethylaminopropylamide, mass ratio of stearic acid / palmitic acid = 7/3) manufactured by Toho Chemical Co., Ltd. C10 amidoamine: RCONH (CH ₂ ) ₃ N (CH ₃ ) ₂ (R is an alkyl group (carbon number 10)), Synthesis by the following method: In a 1-liter four-necked flask equipped with a reflux condenser, 260.9 g of methyl caprate (manufactured by Lion Chemical Co., Ltd., Pastel M-10, molecular weight 1) 6) was charged, and nitrogen substitution was performed twice at 60 ° C., then the temperature was raised to 150 ° C. and 186 g of dimethylaminopropylamine (molecular weight 102) (molar ratio to the mixed fatty acid: 1.30) was added for 1.5 hours. It was dripped over. After completion of dropping, the mixture was kept at 185 to 190 ° C. and aged for 7 hours.
C16-18 cation: alkyl chloride (carbon number C16 to C18) trimethylammonium, product name “Arcade T-800”, manufactured by Lion Akzo

-Fragrance A: as follows-Fragrance B: as follows-Fragrance C: as follows

Low EO (C12 · 7EO) nonion: “EMALEX 707”, polyoxyethylene lauryl ether (7EO), manufactured by Nippon Emulsion Co., Ltd. • C12-14 • 12EO: P & G product name “natural alcohol CO-1270” On the other hand, ethylene oxide equivalent to an average of 12 moles was added.
MA agent: acrylic acid / maleic anhydride copolymer sodium salt (product name “AQUALIC TL-400”, manufactured by Nippon Shokubai Co., Ltd .; pure 40% by weight aqueous solution).
・ Polyether-modified silicone: Polyether-modified silicone CF1188N, manufactured by Toray Dow Corning ・ Paratoluenesulfonic acid aqueous solution: Product name “PTS acid”, manufactured by Kyowa Hakko Kogyo Co., Ltd. ・ Sodium benzoate: Product name “Sodium benzoate”, Toa Gosei・ Citric acid: Liquid citric acid, manufactured by Otsuka Kogyo Co., Ltd. ・ Ethanol: Product name: “Specific alcohol 95-degree synthesis”, Japan alcohol sales company: • Dibutylhydroxytoluene: Product name: “SUMILZER BHT-R”, manufactured by Sumitomo Chemical Co., Ltd. -Isothiazolone solution: Product name "Caisson CG (5-chloro-2-methyl-4-isothiazolin-3-one / 2-methyl-4-isothiazolin-3-one / magnesium salt / water mixed solution)", Rohm and House-made, liquid caustic soda: Tsurumi Soda Co., dilute sulfuric acid: Toho Zinc Co., Ltd. Dye: Trade name “Green No. 3”, manufactured by Kasei Kasei Co., Ltd .: Water: Purified water

Table 2 (Examples 7 to 11)

Table 3 (Examples 12 to 17)

Table 4 (Examples 18 to 23)

Table 5 (Comparative Examples 1-4)

Claims (3)

A liquid detergent composition containing the following components (A) to (D).
(A) One or more water-soluble metal salts selected from the group consisting of a water-soluble salt of copper, a water-soluble salt of zinc or a water-soluble salt of silver (B) represented by the following general formula (b1) or (b2) Chelate compound

[Wherein, X ^{11 to} X ¹⁴ each independently represents a hydrogen atom, an alkali metal, an alkaline earth metal or cationic ammonium, R represents a hydrogen atom or a hydroxyl group, and n1 represents an integer of 0 or 1. . ]

... (b2)
[Wherein, A represents an alkyl group, a carboxy group, a sulfo group, an amino group, a hydroxyl group or a hydrogen atom, and X ^{21 to} X ²³ each independently represents a hydrogen atom, an alkali metal, an alkaline earth metal or a cationic ammonium. N2 represents an integer of 0 to 5. ]
(C) A compound represented by the following general formula (C1) or (C2), or a salt thereof

... (C1)
Wherein, R ₅ represents a linear or branched C _{7 ~ 27} hydrocarbon radicals, wherein R ₅ may have a substituent group selected from the group consisting of hydroxy group and amino group, also R ₅ may have a linking group in the carbon chain, R ₆ represents a linear or branched C _{1 ~ 25} hydrocarbon radicals, wherein R ₆ may have a hydroxyl group, R ₆ may have a linking group in the carbon chain, and R ₇ is a linear or branched C _1-4 alkyl group, a linear or branched C _1-4 hydroxyalkyl group, or an ethylene oxide addition. A polyoxyethylene group having 1 to 25 moles is represented. ]

... (C2)
Wherein, R ₁₆ and R ₁₇ each independently represent a hydrogen atom, or a linear or branched C _{1 ~ 25} hydrocarbon radicals, wherein R ₁₆ and R ₁₇ are each independently a substituted R ₁₆ and R ₁₇ may each independently have a linking group in the carbon chain, or R ₁₆ and R ₁₇ each independently represents ethylene. represents a polyoxyethylene group of oxide addition mole number 1 to 25, R ₁₈ represents a linear or branched C _{8 ~ 25} hydrocarbon radicals, wherein R ₁₈ may have a substituent, and R ₁₈ may have a linking group in the carbon chain, and R ₁₉ is a hydrogen atom, a linear or branched C _1-3 alkyl group, a linear or branched C _1-3 hydroxyalkyl group, or ethylene oxide. It represents a polyoxyethylene group having 1 to 25 addition moles, and Z ⁻ represents an anion. ]
(D) Fragrance   The liquid detergent composition according to claim 1, further comprising (E) a low EO nonionic surfactant. Component (A) is a water-soluble zinc salt,
Component (B) is trisodium methylglycine diacetate,
The component (D) is a fragrance composition containing 10 to 60% by mass of 4- (p-hydroxyphenyl) 2-butanone and a salicylic acid ester based on the total amount of the fragrance composition,
The liquid detergent composition of Claim 2 whose component (E) is a polyoxyalkylene type nonionic surfactant represented by the following general formula (III).
R ^a -Y- (EO) _s (PO) _t -R ^b (III)
Wherein R ^a is a hydrophobic group having 8 to 22 carbon atoms, R ^b is a hydrogen atom or a linear or branched alkyl group or alkenyl group having 1 to 6 carbon atoms, and —Y— is a linking group. EO is ethylene oxide, PO is propylene oxide, s and t represent the average number of added moles, s is an integer of 3 to 9, and t is 0 to 6.)