JP5986887B2 - Liquid detergent for textile products - Google Patents

Description

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

In recent years, liquid cleaning agents for textile products have been used to remove dirt adhering to textile products (cleaning effect), and to remove unpleasant odors generated from textile products (deodorization). (Effect), preventing the generation of unpleasant odors from textile products (deodorizing effect) is required (hereinafter, deodorizing effect and deodorizing effect are collectively referred to as deodorizing effect).
The unpleasant odor emitted from the textile product is often caused by the growth of microorganisms attached to the textile product during drying or storage of the textile product.
Generally, since a cationic surfactant has a bactericidal effect, an attempt has been made to remove microorganisms adhering to a textile product by blending a cationic surfactant. However, when an anionic surfactant is used in combination to enhance the cleaning effect of the liquid detergent, there is a problem that the bactericidal effect of the cationic surfactant is not sufficiently exhibited. In addition, although the detergent containing the cationic surfactant is effective in suppressing the odor derived from microorganisms, it cannot satisfy the deodorizing effect on various odor components.

In order to solve these problems, conventionally, liquid detergents for textiles that have been improved in deodorizing effect or deodorizing effect have been proposed.
For example, a liquid bleach composition for clothing containing hydrogen peroxide, cyclodextrin, and a specific nonionic surfactant has been proposed (for example, Patent Document 1). According to the invention of Patent Document 1, the deodorizing function and the coating cleaning power are improved.

JP 2011-225743 A

However, liquid detergents for textile products are required to further improve the deodorizing effect.
Then, this invention aims at the liquid cleaning agent for textiles which has favorable detergency and can improve a deodorizing effect more.

  As a result of intensive studies, the present inventors have obtained a good detergency and a deodorizing effect by combining a nonionic surfactant, a cyclic dextrin, and a specific amine compound or a specific ammonium compound. The present inventors have found that a liquid cleaning agent having excellent resistance can be obtained, and have reached the present invention.

That is, the liquid detergent for textiles of the present invention comprises (A) component: a nonionic surfactant and (B) component: one or more selected from tertiary amine compounds and quaternary ammonium compounds, Component (C) is characterized by containing a cyclic dextrin.
The component (C) is preferably a highly branched cyclic dextrin.

  According to the liquid detergent for textiles of the present invention, it has a good detergency and can further enhance the deodorizing effect.

(Liquid detergent for textile products)
The liquid detergent for textile products of the present invention (hereinafter sometimes simply referred to as “liquid detergent”) includes (A) component: nonionic surfactant, and (B) component: tertiary amine compound and quaternary ammonium. 1 or more types selected from a compound, and (C) component: Cyclic dextrin is contained.

Although the viscosity (25 degreeC) of a liquid detergent is not specifically limited, 10-150 mPa * s is preferable. When the viscosity is not less than the above lower limit value, the handleability is good. When the viscosity is not more than the above upper limit value, the permeability to the textile product, which is the object to be washed, is increased during the application cleaning.
The viscosity of the liquid detergent is a value (measurement condition: rotor No. 2, rotation speed 30 rpm, viscosity after 10 rotations) measured by a B-type viscometer (manufactured by TOKIMEC).

 The pH of the liquid detergent is preferably 4-9, and more preferably 4-8. When the pH is within the above range, the liquid stability can be further improved. The pH (25 ° C.) is a value measured by a pH meter (HM-30G, manufactured by Toa DKK Corporation) or the like.

<(A) component: nonionic surfactant>
The component (A) is a nonionic surfactant. The liquid detergent can exhibit good detergency by containing the component (A).

 The component (A) is not particularly limited, and examples thereof include alkylene oxide adducts such as fatty acid alkyl esters, higher alcohols, alkylphenols, higher fatty acids, higher fatty acid alkyl esters or higher amines; polyoxyethylene polyoxypropylene block copolymers, fatty acids 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 poly Examples thereof include hydroxy fatty acid amides and alkyl glucosides. Among these, a polyoxyalkylene type nonionic surfactant represented by the following general formula (a1) (hereinafter sometimes referred to as component (a1)) is preferable.

^{_{R 1 -X- (EO) n (}} PO) m -R 2 ··· (a1)

(A1) In the formula, R ¹ is a hydrocarbon group.
R ¹ has 8 to 22 carbon atoms, preferably 10 to 18 carbon atoms. If carbon number is in the said range, detergency can be raised more.
R ¹ may or may not have an unsaturated bond.
R ¹ is preferably an alkyl group or an alkenyl group.
R ¹ may be linear or branched.
Examples of R ¹ include hydrocarbon groups derived from primary or secondary higher alcohols, higher fatty acids, higher fatty acid amides, and the like.

R ² is a hydrogen atom, an alkyl group having 1 to 6 carbon atoms, or an alkenyl group having 2 to 6 carbon atoms.
When R ² is an alkyl group, the carbon number of ^{R 2} is from 1 to 3 are preferred.
When R ² is an alkenyl group, R ² has preferably 2 to 3 carbon atoms.

X is a functional group such as O, COO, or CONH.
In the formula (a1), when X is O, the component (a1) is an alkyl ether type nonionic surfactant.
When X is O, from the viewpoint of improving detergency, R ¹ is preferably a linear or branched alkyl group having 10 to 20 carbon atoms, or a linear or branched alkyl group having 10 to 20 carbon atoms, A linear or branched alkyl group having 10 to 18 carbon atoms or a linear or branched chain alkenyl group having 10 to 18 carbon atoms is more preferable. When X is O, R ² is preferably a hydrogen atom.

In the formula (a1), when X is COO, the component (a1) is a fatty acid ester type nonionic surfactant. When X is COO, from the viewpoint of improving detergency, R ¹ is preferably a linear or branched alkyl group having 9 to 21 carbon atoms, or a linear or branched alkyl group having 9 to 21 carbon atoms, A linear or branched alkyl group having 11 to 17 carbon atoms or a linear or branched alkyl group having 11 to 17 carbon atoms is more preferable. When X is COO, R ² is preferably an alkyl group having 1 to 3 carbon atoms.

In the formula (a1), EO represents an oxyethylene group, and PO represents an oxypropylene group.
n is a number of 3 to 20 representing the average number of EO repeats (that is, the average number of moles of ethylene oxide added), and a number of 5 to 18 is preferred. If n exceeds the above upper limit value, the HLB value becomes too high and the cleaning power tends to decrease. When n is less than the lower limit, the raw material odor of the component (a1) itself tends to deteriorate.
m is a number from 0 to 6 representing the average number of repeating POs (that is, the average number of moles of propylene oxide added), and a number from 0 to 3 is preferred. If m exceeds the above upper limit value, the storage stability of the liquid detergent at a high temperature tends to decrease.
EO and PO may be mixed and arranged, and EO and PO may be added randomly or may be added in blocks.

In the component (a1), the distribution of the number of repetitions of EO or PO is not particularly limited, and is likely to vary depending on the reaction method when the component (a1) is produced.
The distribution of the number of repetitions of EO or PO is, for example, ethylene oxide or propylene oxide as a raw material (primary or secondary higher alcohol, higher fatty acid, higher fatty acid, using a common alkali catalyst such as sodium hydroxide or potassium hydroxide. When added to a fatty acid amide or the like, the distribution tends to be relatively wide.
The distribution of the number of repetitions of EO or PO is, for example, 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. When ethylene oxide or propylene oxide is added to a raw material using a specific alkoxylation catalyst such as added magnesium oxide, the distribution tends to be relatively narrow.

As the component (a1), for example, Diadol (trade name, C13 (C represents the number of carbon atoms; hereinafter the same)) manufactured by Mitsubishi Chemical Corporation, Neodol (trade name, mixture of C12 and C13 manufactured by Shell) ), An alcohol such as Safol 23 (trade name, a mixture of C12 and C13) manufactured by Sasol, or the like, with 12 mol equivalent or 15 mol equivalent ethylene oxide added; CO-produced by Procter & Gamble Co. 1213 or CO-1270 (trade name) or other natural alcohol added with 12 or 15 moles of ethylene oxide; C13 obtained by subjecting C12 alkene obtained by trimerizing butene to the oxo process 7 mole equivalent ethylene oxide added to the alcohol (trade name: Lutensol TO 7, manufactured by BASF); a product obtained by adding 9 moles of ethylene oxide to C10 alcohol obtained by subjecting pentanol to gerbet reaction (trade name: Lutensol XP90, manufactured by BASF); 7 mol equivalent of ethylene oxide added to the C10 alcohol obtained (commercial name: Lutensol XL70, manufactured by BASF); 6 mol equivalent to the C10 alcohol obtained by subjecting pentanol to the garbed reaction Of ethylene oxide (trade name: Lutensol XA60, manufactured by BASF); 9 mole equivalent or 15 mole equivalent of ethylene oxide added to secondary alcohol having 12 to 14 carbon atoms (trade name: Softanol) 90, Softanol 150, stock Company Nippon Shokubai Co., Ltd.) Palm fatty acid methyl (lauric acid / myristic acid = 8/2) added with 15 moles of ethylene oxide using an alkoxylation catalyst (polyoxyethylene palm fatty acid methyl ester (EO15) Mol)) and the like.
These (A) components may be used individually by 1 type, and may be used in combination of 2 or more type.

 10-60 mass% is preferable and, as for content of (A) component in a liquid detergent, 10-50 mass% is more preferable. If it is more than the said lower limit, a higher detergency can be exhibited, and if it is below the said upper limit, liquid stability can be improved.

<Component (B): one or more selected from tertiary amine compounds and quaternary ammonium compounds>
Component (B) is at least one selected from tertiary amine compounds and quaternary ammonium compounds. By containing the component (B), the liquid cleaning agent can increase the adsorption amount of the component (C) to the object to be cleaned, and can further enhance the deodorizing effect.

≪Tertiary amine compound≫
Examples of the tertiary amine compound include compounds represented by the following general formula (b1) (hereinafter sometimes referred to as the component (b1)).

(In the formula (b1), R ¹⁰ represents a linear or branched hydrocarbon group having 7 to 27 carbon atoms, and has one substituent selected from the group consisting of a hydroxyl group and an amino group. The carbon chain may have a linking group, and R ¹¹ represents a linear or branched hydrocarbon group having 1 to 25 carbon atoms, and may have a hydroxyl group. R ¹² 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 oxyethylene. (Represents a (poly) oxyethylene group having an average number of repeating groups of 1 to 25.)

The number of carbon atoms in R ¹⁰ is preferably 16 to 22. R ¹⁰ may have an unsaturated bond.
Examples of the linking group that R ¹⁰ may have include an amide group, an ester group, and an ether group, and among them, an amide group and an ester group are preferable. In addition, the carbon number of a substituent or a linking group is not included in the carbon number of R ¹⁰ described above (the same applies hereinafter). Among them, as R ¹⁰ , —R ¹³ —W (wherein R ¹³ is a linear or branched alkylene group having 1 to 4 carbon atoms, and W is —NHCO—R ¹⁴ or —OOC—R ¹⁵ . And R ¹⁴ is a hydrocarbon group having 7 to 23 carbon atoms, and R ¹⁵ is a hydrocarbon group having 11 to 23 carbon atoms).
R ¹⁴ is preferably a hydrocarbon group having 7 to 21 carbon atoms. R ¹⁴ may be a straight chain, a branched chain, or may have an unsaturated bond.
R ¹⁵ is preferably a hydrocarbon group having 12 to 20 carbon atoms. R ¹⁵ may be linear, branched, or may have an unsaturated bond.

The number of carbon atoms of R ¹¹ is 1 to 4 is preferred.
R ¹¹ may have an unsaturated bond.
Examples of the linking group that R ¹¹ may have include an amide group, an ester group, and an ether group.
R ¹¹ is preferably 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.

R ¹² is preferably 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.

 Among the components (b1), compounds represented by the following general formula (b1-1) are preferable. This is because the compound represented by the formula (b1-1) has excellent adsorptivity to the fiber product.

(B1-1) In the formula, R ¹⁶ and R ¹⁷ are each independently a linear or branched alkyl group having 1 to 4 carbon atoms, or a linear or branched hydroxy group having 1 to 4 carbon atoms. It is an alkyl group.
R ¹⁸ is a linear or branched alkylene group having 1 to 4 carbon atoms.
X ¹⁰ is a group represented by the following general formula (b1-10) or (b1-11).

In the formula (b1-10), R ¹⁹ is a linear or branched hydrocarbon group having 7 to 23 carbon atoms, preferably a linear or branched hydrocarbon group having 16 to 22 carbon atoms.
In the formula (b1-11), R ²⁰ is a linear or branched hydrocarbon group having 11 to 23 carbon atoms, preferably a linear or branched hydrocarbon group having 16 to 22 carbon atoms.
R ¹⁹ and R ²⁰ may each independently be a saturated hydrocarbon group or an unsaturated hydrocarbon group.

 Examples of the component (b1) include caprylic acid dimethylaminopropylamide, capric acid dimethylaminopropylamide, lauric acid dimethylaminopropylamide, myristic acid dimethylaminopropylamide, palmitic acid dimethylaminopropylamide, and stearic acid dimethylaminopropylamide. , Long-chain aliphatic amide dialkyl tertiary amines such as behenic acid dimethylaminopropylamide and oleic acid dimethylaminopropylamide; long-chain aliphatic amide dialkanol tertiary such as palmitic acid diethanolaminopropylamide and stearic acid diethanolaminopropylamide Amines; Aliphatic ester dialkyl tertiary amines such as palmitate ester propyldimethylamine and stearate ester propyldimethylamine; Lauryl Methylamine, myristyldimethylamine, palm alkyldimethylamine, palmityldimethylamine, beef tallow alkyldimethylamine, cured beef tallow alkyldimethylamine, stearyl dimethylamine, stearyl diethanolamine, polyoxyethylene cured beef tallow alkylamine (manufactured by Lion Akzo Co., Ltd., product) Name: ETHOMEEN HT / 14, etc.). Among these, it is more preferable to have both amidopropyldimethylamine palmitate and amidopropyldimethylamine stearate. In this case, the mass ratio represented by palmitic acid amidopropyldimethylamine / stearic acid amidopropyldimethylamine is preferably 1/9 to 5/5, and more preferably 2/8 to 4/6.

The component (b1) may be a commercially available product or a product produced by the following method.
For example, an aliphatic amide alkyl tertiary amine such as a long-chain aliphatic amide dialkyl tertiary amine is produced by the following method. Fatty acid or fatty acid derivative (fatty acid lower alkyl ester, animal fat or vegetable oil or the like) is condensed with dialkyl (or alkanol) aminoalkylamine, and then unreacted dialkyl (or alkanol) aminoalkylamine is reduced in pressure. Alternatively, an aliphatic amidoalkyl tertiary amine can be produced by distilling off by 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 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 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, relative to the fatty acid or derivative thereof.
The reaction temperature is preferably 100 to 220 ° C, more preferably 150 to 200 ° C. By setting the reaction temperature to 100 ° C. or higher, the reaction rate can be kept moderate.

 An aliphatic ester alkyl tertiary amine such as a long-chain aliphatic ester dialkyl tertiary amine is obtained by condensation reaction of a fatty acid or a fatty acid derivative (fatty acid lower alkyl ester, animal oil or vegetable oil or the like) and a dialkylamino alcohol, Then, it can manufacture by distilling off unreacted dialkylamino alcohol by pressure reduction or nitrogen blow.

The fatty acid or fatty acid derivative is the same as the fatty acid or fatty acid derivative used in the above “aliphatic amidoalkyl 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 preferably from 100 to 220 ° C, more preferably from 120 to 180 ° C. Within the above range, coloring of the tertiary amine compound as a product can be suppressed while maintaining an appropriate reaction rate.

The production conditions for the component (b1) other than the above are appropriately determined depending on the type of raw material used, for example, the pressure during the reaction may be normal pressure or reduced pressure, and by blowing an inert gas such as nitrogen during the reaction. It may be introduced.
In the case of using a fatty acid as a raw material, the reaction can proceed efficiently in a short time at a low reaction temperature by using an acid catalyst such as sulfuric acid or p-toluenesulfonic acid. In the case of using a fatty acid derivative, the reaction can proceed efficiently in a short time at a low reaction temperature by using an alkali catalyst such as sodium methylate, potassium hydroxide or sodium hydroxide.
When the melting point of the component (b1) to be obtained is high, in order to improve handling properties, the product may be formed into flakes or pellets, or the product may be dissolved in an organic solvent such as ethanol to form a liquid. preferable.

 The tertiary amine compound may be a salt of the component (b1). Examples of the salt of the component (b1) include an acid salt obtained by neutralizing the component (b1) 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 tertiary amine compounds may be used alone or in combination of two or more.

≪Quaternary ammonium compound≫
Examples of the quaternary ammonium compound include a compound represented by the following general formula (b2) (hereinafter sometimes referred to as component (b2)).

(In the formula (b2), R ²² and R ²⁴ are each independently a hydrogen atom, a linear or branched hydrocarbon group having 1 to 25 carbon atoms, or an average number of repeating oxyethylene groups of 1 to 25. Represents a (poly) oxyethylene group, R ²² or R ²⁴ may have a substituent or a linking group, and R ²¹ has a straight or branched carbon number of 8; It is a hydrocarbon group having ˜25 and may have a substituent or a linking group, and R ²³ is a hydrogen atom, a linear or branched alkyl group having 1 to 3 carbon atoms. group, .Z representing a linear or hydroxyalkyl group having 1 to 3 carbon atoms branched, or oxyethylene groups average repeating number 1-25 (poly) oxyethylene group ^- represents a counter ion).

R ²² and R ²⁴ may each independently have an unsaturated bond.
Examples of the substituent that R ²² and R ²⁴ may have include a hydroxyl group, an amino group, and a carbonyl group.
Examples of the linking group that R ²² and R ²⁴ may have include an amide group, an ester group, and an ether group, and among them, an ester group is preferable.
R ²² and R ²⁴ include a hydrogen atom, a linear or branched alkyl group having 1 to 4 carbon atoms, a linear or branched hydroxy alkyl group having 1 to 4 carbon atoms, and a carbon having an ester group as a linking group. A C1-C25 alkyl group is preferable, and a hydrogen atom and a methyl group are more preferable.

R ²¹ may have an unsaturated bond.
The number of carbon atoms in R ²¹ is preferably 10 to 22, 16 to 22 is more preferable.
The substituent that R ²¹ may have is the same as the substituent that R ²² may have.
The linking group that R ²¹ may have is the same as the linking group that R ²² may have. As the linking group, an ester group is preferable.

R ²³ 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 more preferably a hydrogen atom or a methyl group.

Examples of the counter ion represented by Z ⁻ include halogen atom ions such as chlorine ion, bromine ion and iodine ion, RSO ₄ ⁻ (wherein R is an alkyl group having 1 to 3 carbon atoms, and more preferably A methyl group.), And the like. Among them, a chlorine ion is preferable.

 Examples of the component (b2) include monoalkylammonium salts such as cetyltrimethylammonium chloride, cetostearyltrimethylammonium chloride, stearyltrimethylammonium chloride, and behenyltrimethylammonium chloride; monoester ammonium salt, diester ammonium salt, triester ammonium salt And alkanolamine ester quaternary salts or mixtures thereof. Among these, a mixture of stearyl trimethyl ammonium chloride, behenyl trimethyl ammonium chloride and alkanolamine ester quaternary salt is preferable.

 A quaternary ammonium compound may be used individually by 1 type, and may be used in combination of 2 or more type.

These (B) components may be used individually by 1 type, and may be used in combination of 2 or more type.
As the component (B), the component (b1) or a salt thereof is preferable. The component (b2) tends to reduce storage stability.

 0.1-10 mass% is preferable and, as for content of (B) component in a liquid detergent, 0.5-5 mass% is more preferable. If it is more than the said lower limit, the adsorption amount of (C) component to the to-be-washed object after washing | cleaning can be raised, and the deodorizing effect with respect to an to-be-washed object can be improved more. Even if it exceeds the above upper limit value, an improvement in the adsorption amount of the component (C) commensurate with it is not seen, which is economically disadvantageous.

 In the liquid detergent, the mass ratio represented by component (A) / component (B) (hereinafter sometimes referred to as A / B ratio) is preferably 1/1 to 300/1, and 3/1 to 200 /. 1 is more preferable. If the A / B ratio is less than the lower limit, the amount of the (B) component adsorbed to the fiber product may be reduced. If the A / B ratio exceeds the upper limit, the dispersibility of the (B) component in the cleaning liquid to be described later decreases. There is a fear.

<(C) component: cyclic dextrin>
Component (C) is a cyclic dextrin. A liquid detergent can exhibit the deodorizing effect with respect to a to-be-washed object by containing (C) component.

 The component (C) may be any dextrin having one or more cyclic structures in the molecule, and examples thereof include cyclodextrins and highly branched cyclic dextrins. Among them, highly branched cyclic dextrins are preferable.

 Examples of the cyclodextrin include α-cyclodextrin, β-cyclodextrin, γ-cyclodextrin and the like. These cyclodextrins have a large internal volume per molecular weight in the order of γ, β, α. The larger the internal volume per molecular weight, the higher the ability to capture, so it is easier to capture dirt, and it is thought that the cleaning power and deodorizing effect can be enhanced. Accordingly, β-cyclodextrin and γ-cyclodextrin are preferable as the cyclodextrin. Β-cyclodextrin is preferable in that it can be obtained at low cost and the production cost of the liquid detergent can be suppressed.

 As α-cyclodextrin, Celdex A-100 (trade name, manufactured by Nippon Food Chemical Co., Ltd.) and the like, as β-cyclodextrin, Celldex B-100 (trade name, manufactured by Nippon Food Chemical Co., Ltd.), etc. Examples of γ-cyclodextrin include CAVAMAX (R) W8 Food (trade name, manufactured by Cyclochem).

A highly branched cyclic dextrin is a glucan having an inner branched cyclic structure portion and an outer branched structure portion. The inner branched cyclic structure portion is a cyclic glucan chain formed by an α-1,4-glucoside bond and an α-1,6-glucoside bond, and the outer branched structure portion is bonded to the inner branched cyclic structure portion. It is composed of acyclic glucan chains. Such highly branched cyclic dextrins are also called cluster dextrins.
The highly branched cyclic dextrin mainly includes one having an inner branched cyclic structure portion in the molecule, and having a weight average polymerization degree of about 2500 in which a large number of acyclic glucan chains are bonded to the inner branched cyclic structure portion.

The degree of polymerization of the highly branched cyclic dextrin is preferably 50 to 10,000, and more preferably 50 to 5,000.
The molecular weight of the highly branched cyclic dextrin is preferably 30,000 to 1,000,000, for example.
The degree of polymerization of the inner branched cyclic structure portion of the highly branched cyclic dextrin is preferably 10 to 100, for example.
For example, the degree of polymerization of the outer branched structure portion of the highly branched cyclic dextrin is preferably 40 or more.
For example, the average degree of polymerization of each glucan chain constituting the outer branched structure portion of the highly branched cyclic dextrin is preferably 10 to 20.

A highly branched cyclic dextrin is produced, for example, by using starch as a raw material and acting on an enzyme called a branching enzyme.
Starch, which is a raw material, is composed of amylose in which glucose is linearly bound by α-1,4-glucoside bonds and amylopectin having a structure branched by α-1,6-glucoside bonds. Amylopectin is a macromolecule in which many cluster structures are linked.
A branching enzyme is a glucan chain transferase widely distributed in animals, plants, and microorganisms, and acts on the seam portion of the cluster structure of amylopectin to catalyze the reaction of cyclizing it.
Examples of the highly branched cyclic dextrin include a glucan having an inner branched cyclic structure portion and an outer branched structure portion described in JP-A-8-134104 and having a polymerization degree in the range of 50 to 10,000. The highly branched cyclic dextrin has a specific structure as described above and has a high degree of polymerization (molecular weight), α-cyclodextrin (glucose unit = 6), β-cyclodextrin (glucose unit = 7), It differs from general cyclodextrins in which 6 to 8 glucoses are bound, such as γ-cyclodextrin (glucose unit = 8).
Examples of highly branched cyclic dextrin include cluster dextrin (registered trademark, manufactured by Glico Nutrition Foods Co., Ltd.).

 Although content of (C) component in a liquid cleaning agent is not specifically limited, The viscosity of a liquid cleaning agent will increase, so that the discharge property from a container deteriorates and usability tends to worsen as content increases. For this reason, 0.01-10 mass% is preferable, as for content of (C) component in a liquid cleaning agent, 0.05-5 mass% is more preferable, and 0.1-5 mass% is further more preferable. If it is more than the said lower limit, a deodorizing effect can be improved more, and if it is below the said upper limit, usability can be made favorable.

 In the liquid detergent, the mass ratio represented by the component (A) / component (C) (hereinafter sometimes referred to as A / C ratio) is preferably 2/1 to 50/1, and 10/3 to 20 /. 1 is more preferable. When the A / C ratio is less than the above lower limit, the dispersibility of the component (C) in the cleaning liquid described later may be decreased, and the cleaning power may be decreased. If it exceeds the upper limit, the effect of blending the component (C) may not be sufficiently exhibited.

 In the liquid detergent, the mass ratio represented by component (B) / component (C) (hereinafter sometimes referred to as B / C ratio) is preferably from 1/10 to 13/1, and from 1/5 to 1 / 1 is more preferable. When the B / C ratio is within the above range, the component (B) and the component (C) form a complex well, and the complex is more easily adsorbed to the object to be washed.

<Optional component>
The liquid detergent can contain optional components other than the components (A) to (C) as long as the effects of the present invention are not impaired.

≪Optional surfactant≫
The liquid detergent can contain a surfactant (optional surfactant) excluding the components (A) to (B).
Examples of the optional surfactant include an anionic surfactant and an amphoteric surfactant. Among these, an anionic surfactant is preferable. The liquid detergent can further enhance the effect of preventing recontamination and the liquid stability by having an anionic surfactant. In addition, the liquid detergent can improve the cleaning power against protein stains and the rinsing performance by having an anionic surfactant.
As the anionic surfactant, conventionally known anionic surfactants are used, for example, linear alkylbenzene sulfonic acid or a salt thereof, α-olefin sulfonate, linear or branched alkyl sulfate ester salt, alkyl ether sulfate ester. Salts or alkenyl ether sulfate esters, alkane sulfonates having alkyl groups, α-sulfo fatty acid ester salts and the like, anionic surfactants having SO ₃ groups or SO ₄ groups; higher fatty acid salts, alkyl ether carboxylates Carboxylic acid type anionic surfactants such as polyoxyalkylene ether carboxylate, alkyl (or alkenyl) amide ether carboxylate, acylaminocarboxylate; alkyl phosphate ester salt, polyoxyalkylene alkyl phosphate ester Salt, polyoxyalkylene alkyl group Nirurin acid ester salts, phosphoric acid ester type anionic surfactants such as glycerol fatty acid ester monophosphate ester salts. Among them, anionic surfactants having an SO ₃ group or SO ₄ groups are preferred.
Examples of the salt of the anionic surfactant include alkali metal salts such as sodium and potassium, alkaline earth metal salts such as magnesium, and alkanolamine salts such as monoethanolamine and diethanolamine.
These anionic surfactants may be used alone or in a combination of two or more.

As the linear alkylbenzene sulfonic acid or a salt thereof, one having 8 to 16 carbon atoms in the linear alkyl group is preferable, and one having 10 to 14 carbon atoms in the linear alkyl group 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, and an average of 1 What added 10 mol of ethylene oxide (namely, polyoxyethylene alkyl ether sulfate ester salt or polyoxyethylene alkenyl ether sulfate ester salt) is preferable.
The alkane sulfonate preferably has 10 to 20 carbon atoms, more preferably has 14 to 17 carbon atoms, and even more preferably a secondary alkane sulfonate.
As the α-sulfo fatty acid ester salt, fatty acid residues having 10 to 20 carbon atoms are preferable.
Among the anionic surfactants having an SO ₃ group or an SO ₄ group, linear alkylbenzene sulfonic acid or a salt thereof, alkane sulfonate, polyoxyethylene alkyl ether sulfate, and α-olefin sulfonate are preferable.

 The content of the anionic surfactant in the liquid detergent is preferably more than 0% by mass and 20% by mass or less, and more preferably 1 to 15% by mass. This is because the effect of containing an anionic surfactant is easily exerted if it is at least the above lower limit value, and the liquid stability at a low temperature (for example, 5 ° C. or less) is good if it is at most the above upper limit value.

As a combination of the component (A) and the anionic surfactant, R ¹ in the formula (a1) is a linear hydrocarbon group having 8 to 22 carbon atoms (preferably 10 to 18 carbon atoms), and X is A combination of an alcohol ethoxylate in which O, n is 5 to 15, m is 0, and R ² is H, and a linear alkylbenzene sulfonate are preferable.
When the liquid detergent contains an anionic surfactant, the mass ratio represented by (A) component / anionic surfactant is preferably 10/2 to 45/2, and 6/1 to 45 / 2 is more preferable. If it is in the said range, the cleaning power with respect to sebum dirt can be improved more.
When the liquid detergent contains an anionic surfactant, the total amount of the component (A) and the anionic surfactant is preferably 10 to 80% by mass, and 10 to 60% by mass in the liquid detergent. Is more preferable.

≪Water≫
The liquid detergent preferably contains water.
The water content in the liquid detergent is preferably 25 to 85% by mass, and more preferably 35 to 75% by mass. If it is at least the above lower limit, the usability is good and the dispersibility in the cleaning liquid is improved, and if it is not more than the above upper limit, the contents of the components (A) to (C) in the liquid detergent are sufficient. It becomes easy to exhibit suitable detergency with a small amount.

≪Silicone compound≫
The liquid detergent may contain a silicone compound.
Examples of the silicone compound include amino-modified silicone and polyether-modified silicone. The silicone compound is blended mainly for the purpose of removing flexibility and wrinkles of the object to be washed.

The amino-modified silicone is not particularly limited as long as it has an amino group as a functional group. Moreover, as long as the amino group is introduce | transduced, the other functional group may be introduce | transduced.
As commercially available amino-modified silicone compounds, BY16-871, BY16-853U, FZ-3705, SF8417, BY16-849, FZ-3785, BY16-890, BY16-208 manufactured by Toray Dow Corning Co., Ltd. are available. , BY16-893, FZ-3789, BY16-878, BY16-891, SM-8904, and the like.

The polyether-modified silicone is not particularly limited as long as it has a polyether group such as polyethylene oxide or polypropylene oxide as a functional group. In addition, other functional groups may be introduced as long as polyether groups such as polyethylene oxide and polypropylene oxide are introduced.
The polyether-modified silicone is preferably a compound represented by the following general formula (I).

In formula (I), R ³⁰ is a linear or branched alkylene group having 1 to 4 carbon atoms. If the number of carbon atoms of the alkylene group is within the above range, it is easy to synthesize industrially. R ³¹ is a linear or branched alkyl group having 1 to 4 carbon atoms, a linear or branched alkenyl group having 2 to 4 carbon atoms, or a hydrogen atom. When the carbon number of the alkyl group or alkenyl group is within the above range, the silicone compound has good fluidity and is easy to handle.
Y represents a (poly) oxyalkylene group.
p is an integer of 10 to 10000, and q is an integer of 1 to 1000. If p and q are in the said range, it will be easy to provide a to-be-washed object flexibility. The order of each structural unit to which p and q are attached may be different from the formula (I).

Commercially available polyether modified silicones include SH3772M, SH3775M, SH3749, SF8410, SH8700, BY22-008, SF8421, SILWET L-7001, SILWET L-7002, SILWET L- manufactured by Toray Dow Corning Co., Ltd. 7602, SILWET L-7604, SILWET FZ-2104, SILWET FZ-2164, SILWET FZ-2171, ABN SILWET FZ-F1-009, ABN SILWET FZ-F1-009-05, ABN SILWET FZ-F1-00 ABN SILWET FZ-F1-009-54, ABN SILWET FZ-2222, KF352A, KF6008, KF615A, KF manufactured by Shin-Etsu Chemical Co., Ltd. 016, KF6017, GE Toshiba made Silicone Co., Ltd. TSF4450, TSF4452, and the like.
A silicone compound may be used individually by 1 type, and may be used in combination of 2 or more type.

 In the liquid detergent, the content of the silicone compound is preferably 0.1 to 5% by mass, and more preferably 0.2 to 3% by mass. If content of a silicone compound is more than the said lower limit, a softness | flexibility favorable to a to-be-washed object can be given, or a wrinkle of a to-be-washed object can be removed favorably. Even if the content of the silicone compound exceeds the above upper limit value, the effect corresponding to the content is not improved, which is disadvantageous economically.

≪Solvent≫
The liquid detergent may contain a solvent.
Examples of the solvent include monohydric alcohols having 2 to 4 carbon atoms, polyhydric alcohols having 2 to 4 carbon atoms, and R ^40- (OR ⁴¹ ) _s OH (wherein R ⁴⁰ is an alkyl group having 1 to 6 carbon atoms or phenyl. R ⁴¹ is an alkylene group having 2 to 4 carbon atoms, and s is a number of 1 to 5 representing the average number of repetitions.) Selected from the group consisting of glycol ether solvents It is.
Examples of the monohydric alcohol having 2 to 4 carbon atoms include ethanol, 1-propanol, 2-propanol, 1-butanol and the like.
Examples of the polyhydric alcohol having 2 to 4 carbon atoms include ethylene glycol, propylene glycol, butylene glycol, glycerin and the like.
Examples of the glycol ether solvent represented by R ^40- (OR ⁴¹ ) _s OH include ethylene glycol monobutyl ether, ethylene glycol monohexyl ether, ethylene glycol monophenyl ether, propylene glycol monophenyl ether, diethylene glycol monomethyl ether, diethylene glycol monobutyl ether. Etc.
Among these, ethanol, propylene glycol, and diethylene glycol monobutyl ether are preferred because of the fluidity of the liquid detergent, the mild odor, and the availability of raw materials.
Said solvent may be used individually by 1 type, and may be used in combination of 2 or more type.
5-25 mass% is preferable, as for content of the solvent in a liquid detergent, 6-23 mass% is more preferable, and 7-21 mass% is further more preferable. If it is more than the said lower limit, the fluidity | liquidity of a liquid detergent will become favorable, will not gelatinize, and will improve usability more. Even if it exceeds the above upper limit value, the liquid fluidity improvement effect corresponding to it is not seen, and it becomes economically disadvantageous.

≪Stabilizer≫
The liquid detergent may contain a stabilizer. The stabilizer is used to further improve the liquid stability of the liquid detergent. Examples of stabilizers include triethylene glycol, tetraethylene glycol, glycols such as polyethylene glycol having an average molecular weight of about 200 to 5000, p-toluenesulfonic acid, cumene sulfonate, benzoate (also has an effect as a preservative). And so-called thickeners or solubilizers such as urea.
The content of the stabilizer in the liquid detergent is preferably, for example, 0.01 to 15% by mass.

≪Metal ion scavenger≫
The liquid detergent can contain, for example, 0.1 to 20% by mass of a metal ion scavenger such as malonic acid, succinic acid, malic acid, diglycolic acid, tartaric acid and citric acid.

≪Antioxidant≫
The liquid detergent can contain, for example, 0.01 to 2% by mass of an antioxidant such as butylhydroxytoluene, distyrenated cresol, sodium sulfite, and sodium hydrogen sulfite.

≪Preservatives≫
The liquid detergent can contain, for example, 0.001 to 1% by mass of an antiseptic such as an isothiazolone liquid (for example, Caisson CG (trade name) manufactured by Rohm & Haas).

≪Quality improver≫
Liquid detergents are alkali builders such as alkanolamines such as monoethanolamine, diethanolamine, triethanolamine, N-methyl-diethanolamine, N, N-dimethylmonoethanolamine for the purpose of improving detergency and stability. pH adjuster, hydrotrope agent, fluorescent agent, enzyme, dye transfer inhibitor, recontamination inhibitor (eg, copolymer of maleic acid and olefin monomer, polyvinyl pyrrolidone, carboxymethyl cellulose, etc.), pearl agent, soil release agent Etc. can be included.
As the enzyme, an enzyme contained in a liquid detergent is conventionally used, and examples thereof include protease, amylase, lipase, cellulase, and mannanase.
As proteases, trade names such as Savinase 16L, Savinase Ultra 16L, Savinase Ultra 16XL, Everase 16L Type 2.5, Eraase Ultra 16L, Esperase 2.5L, Esperase 2.5L, Esperase L , Liquanase Ultra 2.5L, Liquanase Ultra 2.5XL, Coronase 48L, trade names available from Genencor, Inc., Purefect L, Purefect OX, Properase L, and the like.
As amylases, trade names such as Termamyl 300L, Termamyl Ultra 300L, Duramyl 300L, Stainzyme 12L, Stainzyme Plus 12L, trade names available from Genencore Co., Ltd. Product name DB-250 etc. which can be obtained from Amano and Seikagaku Corporation are mentioned.
Examples of the lipase include trade names Lipex 100L and Lipolase 100L, which are available from Novozymes as lipase preparations.
Examples of the cellulase include trade names Endolase 5000L, Celluzyme 0.4L, Carzyme 4500L and the like which are available from Novozymes as cellulase preparations.
Examples of mannanases include Mannaway 4L, which is a mannanase preparation available from Novozymes.
An enzyme may be used individually by 1 type and may be used in combination of 2 or more type. The enzyme content in the liquid detergent is preferably, for example, 0.1 to 3% by mass.

≪Flavorant≫
The liquid detergent may contain a flavoring agent. Examples of the flavoring agent include fragrance compositions A to D described in Tables 11 to 18 of JP-A-2002-146399, and fragrances a to d described in JP-A-2009-108248.
The content of the flavoring agent in the liquid detergent is preferably 0.1 to 1% by mass, for example.

≪Colorant≫
The liquid detergent may contain a colorant. Colorants include general-purpose dyes and pigments such as Acid Red 138, Polar Red RLS, Acid Yellow 203, Acid Blue 9, Blue No. 1, Blue No. 205, Green No. 3, and Turquoise P-GR (all trade names) Is mentioned.
The content of the colorant in the liquid detergent is preferably, for example, 0.00005 to 0.005% by mass.

≪Emulsifier≫
The liquid detergent may contain an emulsion. Examples of the emulsion include polystyrene emulsion and polyvinyl acetate emulsion, and usually an emulsion having a solid content of 30 to 50% by mass is suitably used. Examples of emulsion emulsions include polystyrene emulsion (trade name: Cybinol RPX-196 PE-3, solid content 40% by mass, manufactured by Syden Chemical Co., Ltd.).
The content of the emulsion in the liquid detergent is preferably 0.01 to 0.5% by mass.

≪Extracts≫
The liquid detergent may contain extracts. Extracts include Inuenju, waurusushi, echinacea, koganebana, yellowfin, yellow spider, allspice, oregano, enju, chamomile, honeysuckle, clara, keigai, kei, bay geese, honoki, burdock, comfrey, ginger, walnut, ginger, ginger , Sequoia spp. , Pokeweed, cedar, yamajiso, eucalyptus, lavender, rose, rosemary, balun, cedar, gilead balsam, hakse , Kochia, Polygonum aviculare, Jingyou, sealed and Adenophortriphylla, Yamabishi, cayratia japonica, licorice, include plant extracts such as St. John's Wort.
The content of extracts in the liquid detergent is preferably 0 to 0.5% by mass.

≪pH adjuster≫
In order to adjust the pH of the liquid cleaning agent to a desired value, a pH adjusting agent may be blended. However, when the liquid cleaning agent has a desired pH only with the above-described components, the pH adjusting agent may not be used.
Examples of the pH adjuster include acidic compounds such as sulfuric acid and hydrochloric acid; alkanolamines such as monoethanolamine, diethanolamine and triethanolamine; and alkaline compounds such as sodium hydroxide and potassium hydroxide. From the viewpoint of increasing the temporal stability of the liquid detergent, the pH adjuster is preferably sulfuric acid, sodium hydroxide, potassium hydroxide, or alkanolamine, more preferably sulfuric acid or sodium hydroxide.
These pH adjusters may be used alone or in combination of two or more.

(Method for producing liquid detergent)
As a manufacturing method of a liquid cleaning agent, the method of disperse | distributing a component (A)-(C) and arbitrary components to dispersion media, such as water as needed, is mentioned. For example, the component (C) and an optional component as necessary are dispersed in a part of water, and then the component (A) and the component (B) are dispersed. Then, it adjusts to arbitrary pH and adds the remainder of water, and obtains a liquid cleaning agent.

(How to use liquid detergent)
The method of using the liquid cleaning agent (cleaning method) is the same as the method of using a general liquid cleaning agent. For example, a method in which a liquid cleaning agent is placed in water together with the object to be cleaned and washed in a washing machine, a method in which the liquid cleaning agent is applied directly to the object to be cleaned, a liquid cleaning agent dissolved in water to form a cleaning liquid, For example, a method of immersing the washing product. Moreover, after apply | coating a liquid cleaning agent to to-be-washed object and leaving it to stand suitably, you may wash | clean using a washing machine etc.
Although it does not specifically limit as a to-be-washed object, For example, textiles, such as clothing, a cloth, a sheet, a curtain, a carpet, are preferable.

As described above, the liquid cleaning agent of the present invention can exhibit excellent cleaning power by containing the component (A).
In addition, since the liquid cleaning agent has the components (B) to (C), the deodorizing effect on the object to be cleaned can be further enhanced without impairing the cleaning power exhibited by the component (A).
Although it is not clear why the components (B) to (C) are included, the reason why the deodorizing effect can be further enhanced with good detergency is estimated as follows.
(C) A part of component is disperse | distributed in a washing | cleaning liquid in the state which captured the odor component and dirt, and is discharged | emitted with the waste_water | drain of a washing | cleaning liquid. For this reason, an odor component and dirt can be satisfactorily removed from an object to be cleaned by cleaning the object to be cleaned using the liquid cleaning agent of the present invention.
In addition, part of the component (C) forms a complex with the component (B), and the complex is easily adsorbed to the object to be washed. The component (C) adsorbed as a complex on the article to be washed captures odor-causing substances such as the following (1) to (3).
(1) Odor components remaining in the washed object after washing.
(2) Odor components generated when the washed object is dried in the room.
(3) Odor components such as sweat odor that occur when using the item to be washed (for example, when wearing clothing).
And since (C) component does not remove | desorb the captured odor component easily, it is thought that the deodorizing effect which was excellent with respect to the to-be-washed | cleaned to-be-washed object can be exhibited.

  EXAMPLES Hereinafter, although an Example is shown and this invention is demonstrated in detail, this invention is not limited by the following description.

(Raw materials used)
<(A) component>
A-1: A product obtained by adding an average of 12 moles of ethylene oxide to natural alcohol CO-1270 (trade name, manufactured by Procter & Gamble Co.) (denoted as LMAL in the table). Prepared in Preparation Example 1 below.

<< Preparation Example 1 >> Synthesis of A-1 224.4 g of natural alcohol CO-1270 and 2.0 g of 30% NaOH aqueous solution were charged into 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 in the container was raised to 160 ° C. to obtain a reaction solution. Next, 610.2 g of ethylene oxide (gaseous) was gradually added to the reaction solution while stirring the reaction solution. At this time, ethylene oxide was added through the blowing tube while adjusting the addition rate so that the reaction temperature did not exceed 180 ° C.
After completion of the addition of ethylene oxide, aging was performed at a temperature of 180 ° C. and a pressure of 0.3 MPa or less for 30 minutes, and then unreacted ethylene oxide was distilled off at a temperature of 180 ° C. and a pressure of 6.0 kPa or less for 10 minutes.
Next, after cooling the temperature to 100 ° C. or lower, 70% p-toluenesulfonic acid was added to neutralize so that the pH of the 1% aqueous solution of the reaction was about 7, to obtain A-1.

 A-2: A product obtained by adding an average of 15 moles of ethylene oxide to natural alcohol CO-1214 (trade name, manufactured by Procter & Gamble Co.) (described as LMAO in the table). Prepared in Preparation Example 2 below.

<< Preparation Example 2 >> Synthesis of A-2 Except that 224.4 g of natural alcohol CO-1270 was changed to 861.2 g of natural alcohol CO-1214 and ethylene oxide was changed to 760.6 g, A- 2 was obtained.

A-3: Fatty acid methyl ester alkoxylate (described as MEE in the table). A mixture of C ₁₁ H ₂₃ CO (OCH ₂ CH ₂ ) _t OCH ₃ and C ₁₃ H ₂₇ CO (OCH ₂ CH ₂ ) _t OCH ₃ in a mass ratio of 8/2, t = average 15, narrow ratio 33% by mass . Synthesized in Preparation Example 3 below.
The narrow rate indicates the proportion of the distribution of the alkylene oxide adduct, and is a value obtained by the method described in JP 2011-137112 A.

<< Preparation Example 3 >> Synthesis of A-3 Manufactured according to Preparation Example 1 in the Examples described in JP-A No. 2000-144179.
Alumina-magnesium hydroxide (Kyoward 300 (trade name, manufactured by Kyowa Chemical Industry Co., Ltd.)) having a composition of 2.5 MgO.Al ₂ O ₃ .wH ₂ O was calcined at 600 ° C. for 1 hour in a nitrogen atmosphere. A calcined alumina hydroxide / magnesium (unmodified) catalyst was obtained, 2.2 g of calcined alumina hydroxide / magnesium (unmodified) catalyst, 2.9 mL of 0.5N potassium hydroxide ethanol solution, and methyl laurate. 280 g of ester and 70 g of myristic acid methyl ester were charged into a 4 L autoclave, and the catalyst was reformed in the autoclave, and then the inside of the autoclave was replaced with nitrogen, followed by a temperature of 180 ° C. and a pressure of 3 atm (0.3 MPa). ), While introducing 1052 g of ethylene oxide, the mixture was allowed to react with stirring.
The obtained reaction liquid was cooled to 80 ° C., and after adding 159 g of water and 5 g of activated clay and diatomaceous earth as filter aids, the catalyst was filtered off to obtain A-3. The narrow rate of A-3 was 33% by mass.

A-4: Lutensol TO-7 ( trade name, manufactured by _{BASF), C 13 H 27 O (} CH 2 CH 2 O) average of ethylene oxide 7-mole adduct of the branched alcohol represented by H (in the table, the TAG Description).
A-5: Softanol 50 (trade name, manufactured by Nippon Shokubai Co., Ltd.), ethylene oxide adduct of C12-14 secondary alcohol (polyoxyethylene alkyl ether. In the table, described as POE).

<(B) component>
B-1: Kachinal MPAS-R (trade name, manufactured by Toho Chemical Industry Co., Ltd.). Fatty acid (C16 / C18) dimethylaminopropylamide (mass ratio of stearic acid / palmitic acid = 7/3) (denoted as C1618 amidoamine in the table).
_{B-2: C 10 H 21} CONH (CH 2) 3 N (CH 3) 2, ( in the table, described as C10 amidoamine). Synthesized in Preparation Example 4 below.

<< Preparation Example 4 >> Synthesis of B-2 A 1-liter four-necked flask equipped with a reflux condenser was charged with 260.9 g of methyl caprate (manufactured by Lion Chemical Co., Ltd., Pastel M-10, molecular weight 186) at 60 ° C. The nitrogen substitution was performed twice. Thereafter, the temperature in the flask was raised to 150 ° C., and 186 g of dimethylaminopropylamine (molecular weight 102) (molar ratio to methyl caprate: 1.30) was added dropwise to methyl caprate over 1.5 hours. After completion of dropping, the mixture was kept at 185 to 190 ° C. and aged for 7 hours to obtain B-2.

 B-3: Arcade T-800 (trade name, manufactured by Lion Akzo Co., Ltd.), alkyl chloride (C16 to C18) trimethylammonium (denoted as C18 cation in the table).

 B-4: Arcade 12-37W (trade name, manufactured by Lion Akzo Corporation), alkyl chloride (C12) trimethylammonium chloride (denoted as C12 cation in the table).

<(C) component>
C-1: Celdex A-100 (trade name, manufactured by Nippon Shokuhin Kako Co., Ltd.), α-cyclodextrin (described as α-CD in the table).
C-2: Celdex B-100 (trade name, manufactured by Nippon Shokuhin Kako Co., Ltd.), β-cyclodextrin (described as β-CD in the table).
C-3: CAVAMAX (R) W8 Food (trade name, manufactured by Cyclochem Co., Ltd.), γ-cyclodextrin (described as γ-CD in the table).
C-4: described as cluster dextrin (trade name, manufactured by Glico Nutrition Foods Co., Ltd.), highly branched cyclic dextrin (in the table, CCD).
<(C ′) component: Comparative product of component (C)>
C′-1: Akadama dextrin No. 4-C (trade name, manufactured by Nissho Kagaku Co., Ltd.), white dextrin (described as WD in the table).
C′-2: Akadama dextrin No. 103 (trade name, manufactured by Nissho Kagaku Co., Ltd.), yellow dextrin (denoted as YD in the table).

≪Optional surfactant≫
Linear alkyl benzene sulfonic acid (described as LAS in the table): Raipon LH-200 (trade name, carbon number 10-14, average molecular weight 322, manufactured by Lion Corporation).
Coconut fatty acid: palm fatty acid (trade name, NOF Corporation).

<Common ingredients>
“Mass%” described at the end of each component in each composition is the content in the liquid detergent of each example.
≪Composition I≫
Polyether-modified silicone: CF1188N (trade name, manufactured by Toray Dow Corning Co., Ltd.) 0.25% by mass.
Sodium benzoate: Sodium benzoate (manufactured by Toagosei Co., Ltd.) 0.5% by mass.
Trisodium citrate: sodium citrate (trade name, manufactured by Miles) ... 0.13 mass%.
Ethanol: Specific alcohol 95 degree synthesis (trade name, manufactured by Nippon Alcohol Sales Co., Ltd.) ... 5.0% by mass.
Paratoluenesulfonic acid: PTS acid (trade name, manufactured by Kyowa Hakko Kogyo Co., Ltd.) ... 1.0% by mass.
Isothiazolone liquid: Caisson CG (trade name, 5-chloro-2-methyl-4-isothiazolin-3-one / 2-methyl-4-isothiazolin-3-one / magnesium salt / water mixture, Rohm and Haas Made) ... 0.01 mass%.
Sodium salt of copolymer of maleic acid and olefinic monomer (MA agent): Socaran CP9 (trade name, molecular weight 12000, manufactured by BASF) 0.2 mass%.
Fragrance: Fragrance a described in JP 2009-108248 A 0.3 mass%.
Sodium hydroxide: 0.5% by mass (the amount necessary to bring the liquid detergent to pH 7).
Water: Balance (amount for making the total amount of the liquid detergent 100% by mass).

≪Composition II≫
Polyether-modified silicone: CF1188N (trade name, manufactured by Toray Dow Corning Co., Ltd.) ... 1.0% by mass.
Sodium benzoate: Sodium benzoate (manufactured by Toagosei Co., Ltd.) 0.5% by mass.
Trisodium citrate: sodium citrate (trade name, manufactured by Miles) ... 0.1% by mass.
Ethanol: Specific alcohol 95 degree synthesis (trade name, manufactured by Nippon Alcohol Sales Co., Ltd.) 7.5% by mass.
P-Toluenesulfonic acid PTS acid (trade name, manufactured by Kyowa Hakko Kogyo Co., Ltd.): 1.0% by mass.
Polyethylene glycol: PEG # 1000-L60 (trade name, manufactured by Lion Corporation) 1.0 mass%.
Isothiazolone solution: Caisson CG (trade name, manufactured by Rohm and Haas) ... 0.01% by mass.
Fragrance: Fragrance a described in JP-A-2009-108248: 1.0% by mass.
Sodium hydroxide: 0.5% by mass (the amount necessary to bring the liquid detergent to pH 7).
Water: Balance (amount for making the total amount of the liquid detergent 100% by mass).

(Evaluation method)
<Detergency>
A fully automatic electric washing machine (Haier Co., JW-Z23A) and 5 wet artificially contaminated cloths (5cm x 5cm) and a commercial cotton skin shirt (BVD Co., 100% cotton) are put into the wash. (The input amount of the cotton skin shirt was adjusted so that the total mass of the objects to be washed was about 800 g). The liquid washing agent 16mL of each example was supplied into the fully automatic electric washing machine, and the washing process which wash | cleans, rinses, and spin-dry | dehydrates sequentially was performed. The standard settings of the fully automatic electric washing machine were used for the washing, rinsing and dewatering times of the washing process, and the amount of water for washing and rinsing (set to a low water level, water volume 12 L). The contaminated cloth (washing cloth) subjected to the washing treatment was sandwiched between filter papers and heated with an iron to dry.

 The reflectance of uncontaminated cloth (cloth before attaching dirt), wet artificially contaminated cloth, and washed cloth was measured with a spectroscopic color difference meter (manufactured by Nippon Denshoku Industries Co., Ltd., SE2000). The washing rate (%) was calculated using the formula (i). The calculated cleaning rate was classified into the following evaluation criteria, and the cleaning power was evaluated. The reflectance is an average value of 5 sheets each of uncontaminated cloth, wet artificially contaminated cloth and cleaning cloth.

Washing rate (%) = (K / S of contaminated cloth−K / S of washed cloth) / (K / S of contaminated cloth−K / S of uncontaminated cloth) × 100 (i)
In (i), K / S is (1−R / 100) ² / (2R / 100) (where R represents the reflectance (%) of uncontaminated cloth, wet artificially contaminated cloth, and washed cloth). .)

≪Evaluation criteria≫
A: The cleaning rate is 70% or more.
○: The cleaning rate is 65% or more and less than 70%.
Δ: The cleaning rate is 60% or more and less than 65%.
X: The cleaning rate is less than 60%.

<Deodorizing effect I>
The odor of the wash cloth (before heating with an iron) treated with “<Detergency>” and the odor of the wet artificially contaminated cloth are compared by sensory evaluation, and scored by 10 expert panelists based on the following evaluation criteria did. Average points scored by 10 expert panelists, average 4 or higher, ◎, average 3.5 or more, less than 4 ○, average 3 or more, less than 3.5, △, average 3 Less than a point was set as x.

≪Evaluation criteria≫
1 point: It has almost the same odor as the wet artificially contaminated cloth (the odor is hardly dropped).
2 points: The odor is slightly weaker than the wet artificially contaminated cloth (the odor is slightly reduced).
3 points: Slightly weak smell (smell slightly dropped) compared to wet artificially contaminated cloth.
4 points: The odor is considerably weaker than the wet artificially contaminated cloth (the odor is considerably reduced).
5 points: Almost no odor remains compared to wet artificially contaminated cloth.

<Deodorizing effect II>
A commercially available cotton shirt (BVD, 100% cotton) was put into the fully automatic electric washing machine (Haier, JW-Z23A) as the item to be washed. Was adjusted to be about 800 g). The liquid washing agent 16mL of each example was supplied into the fully automatic electric washing machine, and the washing process which wash | cleans, rinses, and spin-dry | dehydrates sequentially was performed. The standard settings of the fully automatic electric washing machine were used for the washing, rinsing and dewatering times of the washing process, and the amount of water for washing and rinsing (set to a low water level, water volume 12 L). The cotton skin shirt that had been subjected to the washing treatment was dried on a hanger overnight and used as test clothing.

 Specialized in test garments worn by five men in their 20s and 30s for one day and control garments (skin shirts not subjected to the above washing process) worn by five men in their 20s and 30s for one day Ten panelists scored by sensory evaluation according to the following evaluation criteria. Average points scored by 10 expert panelists, average 4 or higher, ◎, average 3.5 or more, less than 4 ○, average 3 or more, less than 3.5, △, average 3 Less than a point was set as x.

≪Evaluation criteria≫
1 point: The test garment and the control garment have almost the same odor.
2 points: The test garment has a slightly weaker odor than the control garment.
3 points: The test garment has a slightly weaker odor than the control garment.
4 points: The test garment has a considerably weaker odor than the control garment.
5 points: The test clothing hardly smells compared to the control clothing.

<Cryogenic liquid stability>
10 mL of the liquid cleaning agent of each example was placed in a plastic container (5 cm long × 5 cm wide × 3 cm high) and allowed to stand at 5 ° C. for 24 hours. Thereafter, the plastic container containing the liquid detergent was shaken for 10 seconds at 1 stroke / second in 1 L of cold water (5 ° C.) placed in a 1 L beaker. Subsequently, the plastic container was turned upside down to discharge the liquid cleaning agent, and the state was evaluated according to the following evaluation criteria.

≪Evaluation criteria≫
A: All liquid cleaning agents were discharged from the plastic container.
○: A little liquid detergent remained in the plastic container.
X: A large amount of liquid detergent remained in the plastic container.

(Examples 1-24, Comparative Examples 1-6)
According to the composition shown in Tables 1-2, the liquid cleaning agent of each example was prepared in the following procedures (1) to (4). About the obtained liquid cleaning agent, detergency, the deodorizing effect I, the deodorizing effect II, and low temperature liquid stability were evaluated, and the result is shown in a table | surface.
(1) Ethanol and polyether-modified silicone in common components were placed in a 300 mL beaker and sufficiently stirred with a magnetic stirrer (MITAMURA KOGYO INC.) To prepare a first liquid.
(2) In a separately prepared 300 mL beaker, put a part of water (40 ° C.) in the common component and the component (C) or (C ′), and stir well with a magnetic stirrer to prepare the second liquid Was prepared.
(3) (A) component, (B) component, and arbitrary surfactant were added to the 1st liquid, and after fully stirring, the 2nd liquid was added and it was fully dissolved.
(4) Next, components other than sodium hydroxide and the remainder of water are added, and stirred sufficiently, the pH is adjusted to 7 with an aqueous sodium hydroxide solution, and the remainder of water is added to obtain the liquid detergent of each example. It was.

As shown in Tables 1 and 2, in Examples 1 to 24 to which the present invention was applied, all of the cleaning power, deodorizing effects I and II, and low-temperature liquid stability were “◯” to “◎”. Examples 21 and 23 are reference examples.
On the other hand, in Comparative Examples 1 and 2 using the component (C ′) instead of the component (C), the deodorizing effects I and II were “Δ” and the low-temperature liquid stability was “x”. In Comparative Example 3 containing no component (C), the deodorizing effects I and II were “Δ”, and the low-temperature liquid stability was “◯”. Comparative Example 4 containing no component (B) and Comparative Example 5 containing no component (B) to (C) have a deodorizing effect I of “◯”, a deodorizing effect II of “Δ”, and low temperature liquid stability. Was “◎”. In Comparative Example 6 containing no component (A), the cleaning power, deodorizing effects I and II, and low-temperature liquid stability were all “x”.
From these results, it was found that by containing the components (A) to (C), it is possible to obtain a liquid cleaning agent having a good detergency and further improved deodorizing effect.

Claims (2)

(A) component: a nonionic surfactant,
(B) component: 1 or more types selected from a tertiary amine compound and a quaternary ammonium compound,
(C) component: cyclic dextrin,
A liquid cleaning agent for textile products containing,
Content of the said (C) component is 0.05-5 mass% with respect to the total mass of a liquid detergent,
(B) The liquid cleaning agent whose mass ratio represented by a component / (C) component is 1 / 10-13 / 1 . The component (C) is a highly branched cyclic dextrin having a degree of polymerization of 50 to 10,000 having an inner branched cyclic structure portion and an outer branched structure portion, and the inner branched cyclic structure portion is α-1,4. A cyclic glucan chain formed by a glucoside bond and an α-1,6-glucoside bond, and the outer branched structure portion is an acyclic glucan chain bonded to the inner branched cyclic structure portion. The liquid detergent for textiles as described in 1.