JP2016199748A - Liquid detergent composition - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a liquid detergent composition high in detergency, excellent in storage stability even in a blend of super condensed composition and a dispersibility of function adding components such as capsule flavor, and excellent in usability.SOLUTION: There is provided a liquid detergent composition containing (A) component: a nonionic surfactant selected from specific compounds, (B) component: a copolymer of specific methacrylate ester or acrylate ester, and (C) component: a specific tertiary amine type surfactant with the total amount of surfactants of 25 mass% or more.SELECTED DRAWING: None

Description

  The present invention relates to a liquid detergent composition.

  Liquid detergent compositions are widely used as household detergents. Detergents for clothing need cleaning power against various stains attached to clothing or the like (objects to be washed). For example, a liquid detergent composition containing a surfactant and an acrylic polymer has been proposed as a liquid detergent composition having good foaming and high detergency (Patent Document 1).

  In addition to the detergency, it is also important that the detergent for clothing can impart flexibility, fragrance sustainability, and the like. For example, as a method for increasing the sustainability of a fragrance imparted to an object to be washed, a method in which capsule particles containing a fragrance (capsule fragrance) are blended in a liquid detergent composition and dispersed is known. However, in a liquid detergent composition in which an insoluble function-imparting component such as capsule particles is dispersed, the function-imparting component tends to settle or float when stored for a long period of time.

  In recent years, liquid detergent compositions having a surfactant concentration of 25% by mass or more are often used. In particular, in an ultra-concentrated composition having a surfactant concentration of 40% by mass or more, it is difficult to obtain sufficient storage stability due to the small amount of water, and the dispersibility of the function-imparting component tends to be lowered, so that it can be stored for a long time. Later, the function-imparting component is more likely to settle or float. Also in the liquid detergent composition of Patent Document 1, particularly in the case of an ultra-concentrated composition, the acrylic polymer is difficult to swell and it is difficult to obtain sufficient storage stability and dispersibility of the function-imparting component.

  As a liquid detergent composition excellent in storage stability, a liquid detergent composition in which another polymer such as a polysaccharide is combined with a thickener such as an acrylic acid polymer has been proposed (Patent Document 2). ). However, since the liquid detergent composition has a high viscosity, the usability is poor.

Japanese Patent Laid-Open No. 10-183179 Special table 2008-510862 gazette

  An object of the present invention is to provide a liquid detergent composition having high detergency, excellent storage stability and dispersibility of function-imparting components such as capsule fragrances even in a superconcentrated composition, and excellent usability. To do.

  The liquid detergent composition of the present invention comprises (A) component: one or more nonionic interfaces selected from the group consisting of a compound represented by the following general formula (A1) and a compound represented by the following general formula (A2) Activator, component (B): a copolymer having a repeating unit derived from a monomer represented by the following general formula (b1) and a repeating unit derived from a monomer represented by the following general formula (b2), and Component (C): containing at least one surfactant selected from the group consisting of a compound represented by the following general formula (C1) and a compound represented by the following general formula (C2), The total amount is 25% by mass or more.

(In the general formula, ^{R 1} is a hydrocarbon group having 9 to 13 carbon atoms, ^{R 2} is an alkylene group having 2 to 4 carbon atoms, ^{R 3} is an alkyl group having 1 to 4 carbon atoms M is the average number of repetitions of OR ² and is 5 to 25. R ⁴ is a hydrocarbon group having 10 to 22 carbon atoms, EO is an oxyethylene group, and PO is an oxypropylene group. s is the average number of repetitions of EO and is 5 to 20. t is the average number of repetitions of PO and is 0 to 4. R ⁵ is a hydrogen atom or a methyl group, and R ⁶ is a hydrogen atom. R ⁷ is a hydrogen atom or a methyl group, R ⁸ is an alkyl group having 1 to 40 carbon atoms, R ⁹ is a hydrocarbon group having 7 to 27 carbon atoms, and at least one hydrogen atom is Placed on one or more substituents selected from the group consisting of a hydroxy group and an amino group R ¹⁰ is a group that may have one or more linking groups selected from the group consisting of an amide group, an ester group, and an ether group in the carbon chain. R ¹¹ is a group having 1 to 4 carbon atoms, wherein at least one hydrogen atom may be substituted with a hydroxy group and may have the linking group in a carbon chain. An alkyl group, a hydroxyalkyl group having 1 to 4 carbon atoms, or a polyoxyethylene group having 1 to 25 moles of ethylene oxide added, and R ¹² is an alkyl group having 8 to 18 carbon atoms or an alkyl group having 8 to 18 carbon atoms. An alkenyl group, Q is an amide group, an ester group or a carbonate group, R ¹³ is an alkylene group having 1 to 5 carbon atoms, and R ¹⁴ and R ¹⁵ are each independently an alkyl group having 1 to 3 carbon atoms. Or 1 to 1 carbon atoms Is a hydroxyalkyl group .p is 0 or 1.)

The liquid detergent composition of the present invention preferably further contains (D) component: an anionic surfactant and (E) component: a polyether-modified silicone compound.
The component (A) is preferably a compound represented by the general formula (A1).
The component (C) is preferably a compound represented by the general formula (C1).

  The liquid detergent composition of the present invention has a high detergency, is excellent in storage stability and dispersibility of function-imparting components such as capsule fragrances even in a superconcentrated composition, and is excellent in usability.

  The liquid cleaning composition of this invention contains the (A) component, (B) component, and (C) component which are mentioned later.

[(A) component]
The component (A) is one or more nonionic surfactants selected from the group consisting of a compound represented by the following general formula (A1) and a compound represented by the following general formula (A2). When the liquid detergent composition of the present invention contains the component (A), a good detergency against sebum dirt is imparted. (A) A component may be used individually by 1 type and may be used in combination of 2 or more type.
Hereinafter, the compound represented by the general formula (A1) is referred to as a compound (A1), and the same applies to compounds represented by other general formulas.

However, in formula (A1), R ¹ is a hydrocarbon group having 9 to 13 carbon atoms, R ² is an alkylene group having 2 to 4 carbon atoms, and R ³ is an alkyl group having 1 to 4 carbon atoms. . m is the average number of repetitions of OR ² and is 5-25.
In formula (A2), R ⁴ is a hydrocarbon group having 10 to 22 carbon atoms, EO is an oxyethylene group, and PO is an oxypropylene group. s is the average number of repetitions of EO, and is 5-20. t is the average number of repetitions of PO and is 0-4.

(Compound (A1))
The hydrocarbon group for R ¹ in the compound (A1) may be linear, branched, or may contain a cyclic structure. R ¹ is preferably an aliphatic hydrocarbon group, more preferably a linear or branched alkyl group, or a linear or branched alkenyl group.
The number of carbon atoms in the hydrocarbon group R ¹ is 9-13, preferably 10-13, 11-13 are more preferred. If carbon number is 9 or more, detergency will increase. When the number of carbon atoms is 13 or less, the storage stability is improved, and particularly gelation is suppressed.
R ¹ is derived from the starting fatty acid (R ¹ —COOH).

R ² is preferably an ethylene group or a propylene group.
The m OR ² may be the same as or different from each other. That is, the alkylene group in one molecule of the compound (A1) may be one type or a combination of two or more types. In particular, since the foaming at the time of washing is good and the cost is low, it is preferable that all m pieces of OR ² are oxyethylene groups or a group in which oxyethylene groups and oxypropylene groups are mixed.

When the alkylene group of OR ² is a combination of two or more kinds, these alkylene groups may be added in a block shape or may be added in a random shape.
The method for adding OR ² is not particularly limited. For example, the addition method in the case where an oxyethylene group and an oxypropylene group are mixed may be random addition or block addition. Examples of the block addition method include a method of adding propylene oxide after adding ethylene oxide, a method of adding ethylene oxide after adding propylene oxide, a method of adding propylene oxide after adding ethylene oxide, and further adding ethylene oxide. Can be mentioned.

The carbon number of the alkyl group of R ³ is 1 to 4, 1 to 3 are preferred. If the carbon number is 1 or more, precipitation during low-temperature storage is likely to be suppressed. If carbon number is 4 or less, the solubility with respect to the water of the liquid cleaning composition under low-temperature conditions will improve.
The alkyl group for R ³ may be linear or branched. Examples of R ³ include a methyl group, an ethyl group, an n-propyl group, an isopropyl group, and an n-butyl group. Of these, a methyl group and an ethyl group are preferable, and a methyl group is more preferable.

m is 5-25. If m is 5 or more, the detergency, particularly the detergency against sebum stains is improved. If m is 25 or less, the solubility with respect to the water of a liquid detergent composition will improve.
When all m pieces of OR ² are oxyethylene groups, m is preferably 5 to 20, and more preferably 12 to 18.
In m OR < ² >, when oxyethylene group and oxypropylene group are mixed, 12-21 are preferable for m. In this case, the average number of repeating oxypropylene groups is preferably 5 or less, more preferably 4 or less, and even more preferably 3 or less. When the average number of repeating oxypropylene groups is 5 or less, the detergency and storage stability (transparency uniformity, stability over time, etc.) of the liquid detergent composition are unlikely to decrease.

  The compound (A1) may be composed of only a single chain length compound or a mixture of compounds having different chain lengths.

In the compound (A1), the narrow rate _{N A} represented by the following formula (I), the preferably at least 20 mass%. Narrow ratio N _A of the compound (A1) indicates the percentage distribution of the number of repetitions is different compound of OR ² (alkylene oxide adducts). More narrow ratio N _A high good detergency can be easily obtained. Upper limit of the narrow ratio N _A is substantially 80% by weight.
Narrow ratio _{N A} is more preferably 20 to 50 mass%, since the solubility storage stability and water is improved, and further preferably 30 to 45 wt%. Narrow ratio N _A is 20 mass% or more, in particular is 30 mass% or more, the compound (A1) less liquid detergent composition of the raw material odor derived can be easily obtained. This is the amount of the fatty acid ester that is the raw material of the compound (A1) that coexists with the compound (A1) after the production of the compound (A1), and the alkylene oxide adduct in which m is 1 or 2 in the general formula (A1). This is because there is less.

In formula (I), m _max represents the number of OR ² repeats of the compound (alkylene oxide adduct) that is most abundant in the entire compound (A1). i represents the number of repetitions of OR ² . Y _i represents the ratio (mass%) of the compound (alkylene oxide adduct) in which the number of repeating OR ² present in the entire compound (A1) is i.

Narrow ratio _{N A} can be controlled by the manufacturing method of the example compound (A1).
The production method of the compound (A1) is not particularly limited. For example, a method of addition polymerization of an alkylene oxide to a fatty acid alkyl ester using a surface-modified composite metal oxide catalyst (see JP 2000-144179 A). Can be manufactured more easily.

Suitable examples of such surface-modified composite metal oxide catalysts include metal ions (Al ³⁺ , Ga ³⁺ , In ³⁺ , Tl ³⁺ , Co ³⁺ , Sc ³⁺ , La ³⁺ , Mn ^{2+) and the like.} Etc.) is added to the composite metal oxide catalyst whose surface is modified with a metal hydroxide or the like, or the hydrotalcite whose surface is modified with a metal hydroxide and / or a metal alkoxide or the like And physical catalysts.
In the surface modification of the composite metal oxide catalyst, the mixing ratio of the metal hydroxide and / or metal alkoxide to 100 parts by weight of the composite metal oxide is preferably 0.5 to 10 parts by weight, and 1 to 5 parts by weight. Part is more preferred.
A compound (A1) may be used individually by 1 type, and may be used in combination of 2 or more type.

(Compound (A2))
The hydrocarbon group for R ⁴ in the compound (A2) may be linear, branched, or may contain a cyclic structure. The hydrocarbon group for R ⁴ may have an unsaturated bond. R ⁴ is preferably an aliphatic hydrocarbon group, more preferably a linear or branched alkyl group, or a linear or branched alkenyl group.

The number of carbon atoms in the hydrocarbon group R ⁴ is 10 to 22, preferably 10 to 20, 10 to 18 is more preferable. If the carbon number is 10 or more, the detergency is improved. If carbon number is 22 or less, storage stability will improve and gelatinization will be suppressed more.

R ⁴ is a group derived from a raw material alcohol (R ⁴ —OH). Examples of the alcohol include alcohols derived from natural fats and oils such as palm oil, palm oil, and beef tallow, and synthetic alcohols derived from petroleum.

s is 5-20, 12-18 are preferable and 12-16 are more preferable. If s is 12 or more, it becomes easy to obtain a liquid detergent composition with less raw material odor derived from the compound (A2). If s is 20 or less, it can suppress that an HLB value becomes high too much, and can maintain the detergency with respect to sebum dirt favorably. In particular, when s is 12 to 16, it exhibits a high detergency against sebum dirt.
t is preferably from 0 to 3, particularly preferably 0. If t is in the above range, gelation of the liquid detergent composition is easily suppressed, and good foaming properties are easily obtained at the time of rinsing.

In the compound (A2), EO and PO may be added in a block form or may be added in a random form.
When EO and PO are added in the form of a block, the addition method includes adding ethylene oxide followed by propylene oxide, adding propylene oxide followed by ethylene oxide, and adding ethylene oxide followed by propylene oxide. And a method of adding ethylene oxide further. In particular, since the rinsing property in washing in a fully automatic washing machine is better, a method of adding ethylene oxide after adding ethylene oxide and further adding ethylene oxide (the terminal is -O-CH ₂ CH ₂ O-H and Is preferred).

The addition mole number distribution of EO in the compound (A2) is not particularly limited. The added mole number distribution can be controlled by the production method of the compound (A2).
For example, when EO is added to a hydrophobic raw material using a general alkali catalyst such as sodium hydroxide or potassium hydroxide, the distribution tends to be relatively wide. Using a specific alkoxylation catalyst in which metal ions (Al ³⁺ , Ga ³⁺ , In ³⁺ , Tl ³⁺ , Co ³⁺ , Sc ³⁺ , La ³⁺ , Mn ^2+, etc.) are added to magnesium oxide or the like, EO is used as a hydrophobic raw material. When added (Japanese Patent Publication No. 6-15038), it tends to be a relatively narrow distribution of added moles.

Specific examples of the compound (A2) include the following compounds.
・ Sell: Alcohol with a trade name of Neodol (mixture of 12 carbons and 13 carbons), Sasol: Safol23 (mixture of 12 carbons and 13 carbons), etc. A compound to which EO corresponding to mol or 15 mol is added.
-P & G: A compound obtained by adding 9 mol, 12 mol, or 15 mol of EO to natural alcohols such as trade names CO-1214 and CO-1270.
A compound obtained by adding 9 mol, 12 mol, or 15 mol of EO to a secondary alcohol having 12 to 14 carbon atoms (Nippon Shokubai Co., Ltd., Softanol 90, Softanol 120, Softanol 150).

The compound (A2) may be composed of only a single chain length compound or a mixture of compounds having different chain lengths.
A compound (A2) may be used individually by 1 type, and may be used in combination of 2 or more type.

As the component (A), the compound (A1) may be used alone, the compound (A2) may be used alone, or the compound (A1) and the compound (A2) may be used in combination.
As the component (A), it is preferable to use the compound (A1), and it is more preferable to use only the compound (A1).

[Component (B)]
The component (B) is a copolymer having a repeating unit derived from a monomer represented by the following general formula (b1) and a repeating unit derived from a monomer represented by the following general formula (b2). (B) A component may be used individually by 1 type and may be used in combination of 2 or more type.
Hereinafter, the monomer represented by the general formula (b1) is referred to as a monomer (b1), and the monomers represented by other general formulas are also described in the same manner.

However, in formula (b1), R ⁵ is a hydrogen atom or a methyl group, and R ⁶ is a hydrogen atom. In formula (b2), R ⁷ is a hydrogen atom or a methyl group, and R ⁸ is an alkyl group having 1 to 40 carbon atoms.

(Monomer (b1))
Examples of the monomer (b1) include acrylic acid and methacrylic acid.
In the component (B), as the monomer (b1), one type may be used alone, or two types may be used in combination.

(Monomer (b2))
The alkyl group for R ⁸ may be linear, branched, or may contain a cyclic structure.
The carbon number of the alkyl group of R ⁸ is 1 to 40, preferably from 1 to 20, 1 to 10 is more preferable.

Examples of the monomer (b2) include acrylic acid esters such as methyl acrylate, ethyl acrylate, n-propyl acrylate, n-butyl acrylate, octyl acrylate, decyl acrylate, dodecyl acrylate, and icosyl acrylate; Examples include methacrylic acid esters such as methyl methacrylate, ethyl methacrylate, n-propyl methacrylate, n-butyl methacrylate, decyl methacrylate, dodecyl methacrylate and icosyl methacrylate.
As the monomer (b2), an acrylic ester is preferable.
In the component (B), the monomer (b2) may be used alone or in combination of two or more.

The component (B) is preferably cross-linked. The component (B) may not be crosslinked.
Examples of the crosslinked copolymer (B) include those crosslinked with a crosslinking agent (polymer crosslinked product).
Examples of the crosslinking agent include allyl ether compounds.

Examples of the allyl ether compound include allyl ether, sugar allyl ether, sugar alcohol allyl ether, and the like.
Examples of the sugar in the allyl ether of sugar include sucrose.
Examples of the sugar alcohol in the allyl ether of the sugar alcohol include pentaerythritol.

As a commercial item of (B) component, the following are mentioned, for example.
As a commercial item of (B) component of a bridge | crosslinking type, it is a brand name which is a bridge | crosslinking type copolymer which consists of two or more types of monomers chosen, for example from Lubrizol alkyl acrylate, alkyl methacrylate, acrylic acid, and methacrylic acid, for example. “Carbopol Aqua 30”, a cross-linked copolymer consisting of two or more monomers selected from alkyl acrylates (C1 to C4 and C8), alkyl methacrylates (C1 to C4 and C8), acrylic acid and methacrylic acid manufactured by Lubrizol. "Carbopol Aqua SF-1" which is a coalescence, a cross-linked copolymer comprising two or more monomers selected from alkyl acrylate (C10-30), alkyl methacrylate (C10-30) and acrylic acid manufactured by Lubrizol Product name "Carbopol EZ -4 ", trade name" ACUSOL 830 "which is a cross-linked copolymer composed of a monomer of alkyl acrylate and acrylic acid or methacrylic acid manufactured by DOW.
As the non-crosslinking type (B) component, for example, trade name “Novethix HC200” which is a copolymer composed of two or more monomers selected from alkyl acrylate, alkyl methacrylate, acrylic acid and methacrylic acid manufactured by Lubrizol. Etc.

[Component (C)]
The component (C) is one or more surfactants selected from the group consisting of the following compound (C1) and the following compound (C2), so-called tertiary amine type surfactants. When the liquid detergent composition of the present invention contains the component (C), the thixotropy index (TI value) is sufficiently high even in a superconcentrated composition in which the proportion of the surfactant is 40% by mass or more. As the component (C), one type may be used alone, or two or more types may be used in combination.
As the component (C), it is preferable to use the compound (C1), and it is more preferable to use only the compound (C1).

However, in the formula (C1), R ⁹ is a hydrocarbon group having 7 to 27 carbon atoms, and at least one hydrogen atom is substituted with one or more substituents selected from the group consisting of a hydroxy group and an amino group. The carbon chain may have one or more linking groups selected from the group consisting of an amide group, an ester group and an ether group. R ¹⁰ is a hydrocarbon group having 1 to 25 carbon atoms, and at least one hydrogen atom may be substituted with a hydroxy group, and is a group that may have the linking group in a carbon chain. R ¹¹ is an alkyl group having 1 to 4 carbon atoms, a hydroxyalkyl group having 1 to 4 carbon atoms, or a polyoxyethylene group having 1 to 25 moles of ethylene oxide added.
In Formula (C2), R ¹² is an alkyl group having 8 to 18 carbon atoms or an alkenyl group having 8 to 18 carbon atoms. Q is an amide group, an ester group or a carbonate group. R ¹³ is an alkylene group having 1 to 5 carbon atoms, and R ¹⁴ and R ¹⁵ are each independently an alkyl group having 1 to 3 carbon atoms or a hydroxyalkyl group having 1 to 3 carbon atoms. p is 0 or 1.

(Compound (C1))
The hydrocarbon group for R ⁹ of the compound (C1) may be linear or branched. The hydrocarbon group for R ⁹ may have an unsaturated bond.
The number of carbon atoms in the hydrocarbon group R ⁹ is 7-27, preferably 7-25. However, the carbon number of the substituent or the linking group is not included in the carbon number of the hydrocarbon group.
When the hydrocarbon group for R ⁹ has a linking group, the linking group is preferably an amide group or an ester group.

R ⁹ is —R ⁹¹ —W (wherein R ⁹¹ is an alkylene group having 1 to 4 carbon atoms, W is —NHCO—R ⁹² or —OOC—R ⁹³ , and R ⁹² is 7 carbon atoms) Is a hydrocarbon group having ˜23, and ^R93 is a hydrocarbon group having 11 to 23 carbon atoms).
The hydrocarbon group of R ⁹² and R ⁹³ may be linear or branched. The hydrocarbon group of R ⁹² and R ⁹³ may have an unsaturated bond. As for carbon number of the hydrocarbon group of ^R92 , 7-21 are preferable. As for carbon number of the hydrocarbon group of ^R93 , 12-20 are preferable.

The hydrocarbon group for R ¹⁰ may be linear or branched. The hydrocarbon group for R ¹⁰ may have an unsaturated bond.
The number of carbon atoms in the hydrocarbon group R ¹⁰ is 1 to 4 is preferred. However, the carbon number of the substituent or the linking group is not included in the carbon number of the hydrocarbon group.
R ¹⁰ is preferably a linear or branched alkyl group having 1 to 4 carbon atoms or a linear or branched hydroxyalkyl group having 1 to 4 carbon atoms.

The alkyl group, hydroxyalkyl group and polyoxyethylene group of R ¹¹ may be linear or branched.
R ¹¹ is preferably a linear or branched alkyl group having 1 to 4 carbon atoms or a linear or branched hydroxyalkyl group having 1 to 4 carbon atoms.

  As the compound (C1), the following compound (C11) and compound (C12) are preferable.

However, R ^{91 to} R ⁹³ in Formula (C11) and Formula (C12) are the same as those described in Formula (C1). R ¹⁰¹ and R ¹¹¹ are each independently a linear or branched alkyl group having 1 to 4 carbon atoms or a linear or branched hydroxyalkyl group having 1 to 4 carbon atoms.
R ⁹¹ , R ¹⁰¹ and R ¹¹¹ in the compound (C11) and the compound (C12) may be the same or different.

<Compound (C11)>
Examples of the compound (C11) include caprylic acid dimethylaminopropylamide, capric acid dimethylaminopropylamide, lauric acid dimethylaminopropylamide, myristic acid dimethylaminopropylamide, palmitic acid dimethylaminopropylamide, 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 An amine etc. are mentioned.
As the compound (C11), one type may be used alone, or two or more types may be used in combination.

As the compound (C11), a synthesized product or a commercially available product may be used. The long-chain aliphatic amide dialkyl tertiary amine and the long-chain aliphatic amide dialkanol tertiary amine can be synthesized, for example, by the following method.
A fatty acid or a fatty acid derivative (fatty acid lower alkyl ester or animal / vegetable oil or fat) is subjected to a condensation reaction with a dialkyl (or alkanol) aminoalkylamine. Subsequently, unreacted dialkyl (or alkanol) aminoalkylamine is distilled off under reduced pressure or nitrogen blowing.

  Examples of fatty acids or fatty acid derivatives include caprylic acid, capric acid, lauric acid, myristic acid, palmitic acid, stearic acid, oleic acid, behenic acid, erucic acid, 12-hydroxystearic acid, coconut oil fatty acid, cottonseed oil fatty acid, corn oil fatty acid And beef tallow fatty acid, palm kernel oil fatty acid, soybean oil fatty acid, linseed oil fatty acid, castor oil fatty acid, olive oil fatty acid and other vegetable oils and animal oil fatty acids, and methyl esters, ethyl esters and glycerides thereof. Among these, caprylic acid, capric acid, lauric acid, myristic acid, palmitic acid, stearic acid, oleic acid, and behenic acid are preferable. These fatty acids and fatty acid derivatives may be used individually by 1 type, and may be used in combination of 2 or more type.

  Examples of the dialkyl (or alkanol) aminoalkylamine include dimethylaminopropylamine, dimethylaminoethylamine, diethylaminopropylamine, diethylaminoethylamine and the like. Of these, 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, based on the fatty acid or fatty acid derivative.

  The reaction temperature is preferably 100 to 220 ° C, more preferably 150 to 200 ° C. If reaction temperature is 100 degreeC or more, it will be easy to keep reaction rate moderate. If reaction temperature is 220 degrees C or less, coloring of the tertiary amine compound obtained can be prevented or reduced.

<Compound (C12)>
Examples of the compound (C12) include aliphatic ester dialkyl tertiary amines such as palmitate ester propyldimethylamine and stearate ester propyldimethylamine.
As the compound (C12), one type may be used alone, or two or more types may be used in combination.

As the compound (C12), a synthesized product or a commercially available product may be used. The aliphatic ester dialkyl tertiary amine can be synthesized, for example, by the following method.
A fatty acid or a fatty acid derivative (fatty acid lower alkyl ester or animal / vegetable oil) is condensed with a dialkylamino alcohol. Subsequently, unreacted dialkylamino alcohol is distilled off under reduced pressure or nitrogen blowing.

Examples of the fatty acid or fatty acid derivative used for the synthesis of the aliphatic ester dialkyl tertiary amine are the same as those exemplified in the synthesis of the long-chain aliphatic amide dialkyl tertiary amine and the long-chain aliphatic amide dialkanol tertiary amine. Can be mentioned.
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 fatty acid derivative. 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. If reaction temperature is in the said range, coloring of the tertiary amine which is a product can be suppressed, maintaining a suitable reaction rate.

<Compound (C13)>
As the compound (C1), a compound (C13) other than the compound (C11) and the compound (C12) may be used.
Examples of the compound (C13) include lauryl dimethylamine, myristyl dimethylamine, palm alkyl dimethyl amine, palmityl dimethyl amine, beef tallow alkyl dimethyl amine, cured beef tallow alkyl dimethyl amine, stearyl dimethyl amine, stearyl diethanol amine, polyoxyethylene cured beef tallow Examples include alkylamines (manufactured by Lion Akzo, trade name: ETHOMEEN HT / 14, etc.).
A compound (C13) may be used individually by 1 type, and may be used in combination of 2 or more type.

As the compound (C1), one type may be used alone, or two or more types may be used in combination.
As the compound (C1), the compound (C11) may be used alone, the compound (C12) may be used alone, the compound (C13) may be used alone, the compound (C11), the compound ( Two or more of C12) and compound (C13) may be used in combination.

  As compound (C1), compound (C11) is more preferred, and it is particularly preferred 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, more preferably 20:80 to 40:60. If the mass ratio is within the above range, it is easy to obtain a liquid detergent composition that is excellent in stability and has a high effect of improving the residual fragrance.

(Compound (C2))
The compound (C2) is an amine oxide type surfactant.
The alkyl group and alkenyl group for R ¹² in the compound (C2) may be linear or branched.
R ¹² is preferably a linear or branched alkyl group having 8 to 18 carbon atoms, and more preferably a linear or branched alkyl group having 10 to 14 carbon atoms.

Q is preferably -CONH- or -NHCO-, more preferably -CONH-.
As R < ¹³ >, a C1-C3 alkylene group is preferable and a propylene group is more preferable.
R ¹⁴ and R ¹⁵ are each independently preferably an alkylene group having 1 to 3 carbon atoms, and preferably a methyl group. In the compound (C2), it is preferable that both R ¹⁴ and R ¹⁵ are methyl groups.
p is preferably 1.

  As the compound (C2), the following compound (C21) and compound (C22) are preferable.

However, R ¹² , R ^14, and R ¹⁵ in Formula (C21) and Formula (C22) are the same as those described in Formula (C2). q is the average number of repetitions of CH ₂ and is 1-5.

<Compound (C21)>
Examples of the compound (C21) include capryl dimethylamine oxide, lauryl dimethylamine oxide, myristyl dimethylamine oxide, palmityl dimethylamine oxide, stearyl dimethylamine oxide, oleyl dimethylamine oxide, coconut alkyl dimethylamine oxide, lauryl diethylamine oxide, and the like. Is mentioned.
As the compound (C21), one type may be used alone, or two or more types may be used in combination.

<Compound (C22)>
1-3 in the compound (C22) is preferable, and 3 is more preferable.
Examples of the compound (C22) include caprylic amidopropyl dimethylamine oxide, lauric amidopropyl dimethylamine oxide, myristic amidopropyl dimethylamine oxide, palmitic amidopropyl dimethylamine oxide, stearic acid amidopropyl dimethylamine oxide, and behenine. Examples include acid amidopropyl dimethylamine oxide, oleic acid amidopropyl dimethylamine oxide, and coconut fatty acid amidopropyl dimethylamine oxide.
As the compound (C22), one type may be used alone, or two or more types may be used in combination.

A compound (C2) may be used individually by 1 type, and may be used in combination of 2 or more type.
As the compound (C2), the compound (C21) may be used alone, the compound (C22) may be used alone, or the compound (C21) and the compound (C22) may be used in combination.

[(D) component]
The liquid detergent composition of the present invention preferably contains (D) component: an anionic surfactant in addition to the components (A) to (C). When the liquid cleaning composition of the present invention contains the component (D), the cleaning performance is improved, and it becomes easy to give a dry feel to the object to be cleaned.
(D) A component may be used individually by 1 type and may be used in combination of 2 or more type.

It does not specifically limit as an anionic surfactant, A well-known thing can be used. Specifically, for example, linear alkylbenzene sulfonic acid or a salt thereof; α-olefin sulfonate; linear or branched alkyl sulfate ester salt; alkyl ether sulfate ester salt or alkenyl ether sulfate ester salt; Examples include alkane sulfonates; α-sulfo fatty acid ester salts and the like.
Examples of these salts include alkali metal salts such as sodium salt and potassium salt, alkaline earth metal salts such as magnesium salt, and alkanolamine salts such as monoethanolamine salt and diethanolamine salt.

As the linear alkylbenzene sulfonic acid or a salt thereof, one having 8 to 16 carbon atoms in the linear alkyl group is preferable, and one having 10 to 14 carbon atoms is particularly preferable.
The α-olefin sulfonate is preferably one having 10 to 20 carbon atoms.
As the alkyl sulfate ester salt, those having 10 to 20 carbon atoms are preferable.
The alkyl ether sulfate ester salt or alkenyl ether sulfate ester salt has a linear or branched alkyl group having 10 to 20 carbon atoms or an alkenyl group, and an average of 1 to 10 moles of ethylene oxide added. (That is, polyoxyethylene alkyl ether sulfate salt or polyoxyethylene alkenyl ether sulfate salt) is preferable.
As the alkane sulfonate, a secondary alkane sulfonate having 10 to 20 carbon atoms is preferable, and a secondary alkane sulfonate having 14 to 17 carbon atoms is more preferable.
The α-sulfo fatty acid ester salt is preferably one having 10 to 20 carbon atoms.

(D) Component anionic surfactants include carboxylic acids such as higher fatty acid salts, alkyl ether carboxylates, polyoxyalkylene ether carboxylates, alkyl (or alkenyl) amide ether carboxylates, and acylaminocarboxylates. Type anionic surfactants; phosphoric acid ester type anionic surfactants such as alkyl phosphoric acid ester salts, polyoxyalkylene alkyl phosphoric acid ester salts, polyoxyalkylene alkyl phenyl phosphoric acid ester salts, glycerin fatty acid ester monophosphoric acid ester salts, etc. It may be used.
Examples of these salts include alkali metal salts such as sodium salts and potassium salts; alkaline earth metal salts such as magnesium salts; alkanolamine salts such as monoethanolamine salts and diethanolamine salts.

(D) As a component, what was synthesize | combined may be used and a commercial item may be used.
As the component (D), one or more anions selected from the group consisting of linear alkylbenzene sulfonic acid or a salt thereof, alkane sulfonate, polyoxyethylene alkyl ether sulfate, α-olefin sulfonate, and higher fatty acid salt A surfactant is preferred.

[(E) component]
In addition to the components (A) to (C), the liquid detergent composition of the present invention preferably contains (E) component: a polyether-modified silicone compound (hereinafter referred to as “PE-modified silicone”). . When the liquid cleaning composition of the present invention contains the component (E), excellent rinsing properties are easily obtained.
(E) A component may be used individually by 1 type and may be used in combination of 2 or more type.

  The PE-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 the PE-modified silicone, a functional group other than the polyether group may be introduced.

Examples of commercially available PE-modified silicones include the following.
・ SH3772M, SH3775M, SH3749, SF8410, SH8700, BY22-008, SF8421, SILWET L-7001, SILWET L-7602, SILWET L-7602, SILWET L-7604, SILWET FZ-2, manufactured by Toray Dow Corning FZ-2164, SILWET FZ-2171, ABN SILWET FZ-F1-009, ABN SILWET FZ-F1-009-05, ABN SILWET FZ-F1-009-09, ABN SILWET FZ-F1-009-54, ABN -2222.
-KF352A, KF6008, KF615A, KF6016, KF6017 manufactured by Shin-Etsu Chemical Co., Ltd.
-TSF4450 and TSF4452 made by GE Toshiba Silicone.

[solvent]
The liquid detergent composition of the present invention preferably contains water as a solvent from the viewpoint of ease of handling during production, solubility in water when used, and the like.

The liquid detergent composition of the present invention may contain a solvent.
As a solvent, the solvent conventionally mix | blended with a liquid detergent etc. can be used. Specific examples include monohydric alcohols having 2 to 4 carbon atoms, polyhydric alcohols having 2 to 4 carbon atoms, and glycol ether solvents.

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.

The glycol ether-based solvents represented by the general _{^{formula: R 16 - (OR 17)}} u OH ( In the ^{formula, R 16} is ^{.R 17} is an alkyl group or a phenyl group having 1 to 6 carbon atoms, 2 carbon atoms An alkylene group of ˜4, u represents an average number of repetitions of OR ¹⁷ and is 1 to 5.). Specific examples 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 and the like.

As the solvent, ethanol, propylene glycol, and diethylene glycol monobutyl ether are preferable from the viewpoint of fluidity of the liquid detergent composition, reduction of odor, and availability of raw materials.
A solvent may be used individually by 1 type and may be used in combination of 2 or more type.

[Other ingredients]
In the liquid cleaning composition of the present invention, as long as it is within the range not impairing the effects of the present invention, as necessary, the liquid cleaning composition as a component other than the components (A) to (E) and the solvent. You may mix | blend the component used normally.
Other components include, for example, enzymes, hydrotropes (polyethylene glycol, aromatic sulfonic acid or salts thereof), detergency builders, stabilizers, alkali agents (alkanols such as monoethanolamine, diethanolamine, triethanolamine) Amines), metal ion scavengers, texture improvers such as silicone, preservatives, fluorescent agents, dye transfer inhibitors, pearl agents, antioxidants, general-purpose dyes or pigments as colorants, emulsifying agents, perfumes, A pH adjuster etc. are mentioned.

The liquid detergent composition of the present invention may contain particles (water-soluble particles, water-insoluble particles) that are hardly soluble in the components constituting the liquid detergent composition. The particles may be used alone or in combination of two or more.
Specific examples of the particles include a capsule containing a capsule fragrance and an active ingredient instead thereof, beads and a pearlescent agent for imparting specific aesthetics, bentonite, carboxymethylcellulose (CMC) and the like.

The capsule fragrance is one in which a fragrance component is encapsulated by a capsule wall formed of a polymer compound.
Examples of the polymer compound that forms the capsule wall include polyacrylic acid-based, polyvinyl-based, polymethacrylic acid-based, melamine-based, and urethane-based synthetic polymers. These may be used individually by 1 type and may be used in combination of 2 or more type.

Specific examples of the capsule flavor include the following capsule flavors A to C.
(Capsule flavor A)
Capsule flavor A contains the following flavor components.
Tripral (2.36% by mass), cyclaset (10.83% by mass), tricyclodecenyl propionate (10.04% by mass), isopropylmethyl-2-butyrate (1.72% by mass), manzanate (2.07% by mass), bellodox (13.58% by mass), allyl amyl glycolate (2.23% by mass), allyl cyclohexylpropionate (5.45% by mass), γ-decalactone (0.58) Mass%), γ-undecalactone (7.68 mass%), α-damascon (0.25 mass%), nerol (0.15 mass%), hedion (5.14 mass%), lyial (12. 22% by mass), linalool (23.18% by mass), pt-butylcyclohexyl acetate (0.16% by mass), vanillin (0.03% by mass), lime oxa De (2.33 mass%).

(Capsule flavor B)
Capsule flavor B contains the following flavor components.
Tripral (6.25% by mass), olivine (1.70% by mass), galvascon (0.62% by mass), follion (0.39% by mass), isobornyl acetate (23.50% by mass), isoborneol (0.14 mass%), manzanate (3.02 mass%), bellodox (28.80 mass%), ethyl 2-methylbutyrate (5.46 mass%), nectaryl (3.20 mass%), α-Damascon (2.04% by mass), dimethylbenzylcarbinyl acetate (9.99% by mass), duplex (0.57% by mass), aldehyde C-12MNA (5.30% by mass), pinoacetaldehyde (0.3% by mass). 52% by mass), ethyl laurate (8.26% by mass), dibutylhydroxytoluene (0.24% by mass).

(Capsule flavor C)
Capsule flavor C includes the following flavor components.
Hexyl salicylate (3.71% by mass), ethyl 2-methylbutyrate (3.30% by mass), dihydroeugenol (8.49% by mass), camphor (1.46% by mass), 1,4-cineole (1.28% by mass), Beldox (9.04% by mass), γ-nonalactone (0.84% by mass), γ-decalactone (2.58% by mass), γ-undecalactone (3.70% by mass) %), Allyl caproate (7.47 mass%), hexyl acetate (1.27 mass%), geranyl propionate (6.38 mass%), prenyl acetate (1.52 mass%), allyl phenoxy acetate (0.60% by mass), dimethylbenzylcarbinyl butyrate (0.95% by mass), nectaryl (8.54% by mass), geranyl acetate (11.13% by mass), lily (11.51% by mass), cyclamenaldehyde (3.05% by mass), amyl salicylate (1.39% by mass), ISOE super (1.06% by mass), γ-methylionone (1.34) Mass%), ambroxane (0.13 mass%), havanolide (0.37 mass%), anisaldehyde (8.46 mass%), lime oxide (0.41 mass%).

[Ratio of each component]
The liquid detergent composition of the present invention is a composition in which the ratio of the total amount of the surfactant is 25% by mass or more with respect to 100% by mass of the total mass of the liquid detergent composition. The total amount of the surfactant is the total amount of all the surfactants including the component (A), the component (C) and the component (D).
The ratio of the total amount of the surfactant in the liquid detergent composition (100% by mass) of the present invention is preferably 25 to 60% by mass, and more preferably 40 to 55% by mass.

  15-60 mass% is preferable and, as for content of (A) component in the liquid cleaning composition (100 mass%) of this invention, 25-55 mass% is more preferable. If content of (A) component is more than a lower limit, the good detergency with respect to sebum dirt will be acquired. If content of (A) component is below an upper limit, gelatinization with time will become difficult to occur.

  0.5-5 mass% is preferable and, as for content of (B) component in the liquid cleaning composition (100 mass%) of this invention, 1-4 mass% is more preferable. If content of (B) component is more than the said lower limit, a liquid will express structural viscosity (thixotropic property) easily, and the dispersibility of a function provision component will improve. If content of (B) component is below the said upper limit, the viscosity of a liquid detergent composition will not become high too much and it is excellent in usability.

  10-200 are preferable, as for mass ratio A / B of (A) component with respect to (B) component in a liquid detergent composition, 10-150 are more preferable, and 12-120 are more preferable.

  The mass ratio B / M of the component (B) to the total amount (mass M) of the surfactant is preferably 1/500 to 1/20, more preferably 1/100 to 1/10, and 1/50 to 1 /. 10 is more preferable. If B / M is within the above range, the TI value tends to be sufficiently high.

  The content of the component (C) in the liquid detergent composition (100% by mass) of the present invention is preferably 0.1 to 10% by mass, more preferably 0.3 to 7.0% by mass, and 5-5.0 mass% is further more preferable. If content of (C) component is more than a lower limit, a liquid will express structural viscosity (thixotropic property) easily, and the dispersibility of a function provision component will improve. If content of (C) component is below the said upper limit, the viscosity of a liquid cleaning composition will not become high too much and it is excellent in usability.

  0.1-50 are preferable and, as for mass ratio B / C of (B) component with respect to (C) component, 1-10 are more preferable. If mass ratio B / C is more than the said lower limit, a liquid will express structural viscosity (thixotropic property) easily, and the dispersibility of a function provision component will improve. If mass ratio B / C is below the said upper limit, the viscosity of a liquid detergent composition will not become high too much and it is excellent in usability.

  The mass ratio C / M of the component (C) to the total amount (mass M) of the surfactant is preferably 1/1000 to 1/10, and more preferably 1/500 to 1/200. If C / M is in the above range, the TI value tends to be sufficiently high.

  When the liquid detergent composition of the present invention contains the component (D), the content of the component (D) in the liquid detergent composition of the present invention (100% by mass) is preferably 5 to 20% by mass, 6-10 mass% is more preferable. If content of (D) component is more than the said lower limit, cleaning performance will improve and it will be easy to give the tactile dryness to the to-be-washed object. If content of (D) component is below an upper limit, storage stability will improve and it will be easy to give the to-be-washed object the dry touch.

  When the liquid detergent composition of the present invention contains the component (E), the content of the component (E) in the liquid detergent composition of the present invention (100% by mass) is 0.1 to 5% by mass. Preferably, 0.2-3 mass% is more preferable. If content of (E) component is more than the said lower limit, the outstanding rinse property will be easy to be obtained. (E) Even if content of a component exceeds the said upper limit, the effect of a rinse property is saturated and it is hard to be obtained beyond it.

  The content of water in the liquid detergent liquid detergent composition (100% by mass) is preferably more than 0% by mass and 20% by mass or less, more preferably 1 to 18% by mass, further preferably 2 to 15% by mass, 3-10 mass% is especially preferable, and 3-5 mass% is the most preferable. If the water content is less than or equal to the above upper limit, the effects of the present invention are remarkably obtained. Moreover, if content of water is in the said range, gelatinization will be suppressed and the fluidity | liquidity of a liquid detergent composition will be easy to be maintained.

  When the liquid detergent composition of the present invention contains a solvent, the content of the solvent in the liquid detergent composition (100% by mass) is preferably 5 to 30% by mass, more preferably 6 to 25% by mass, and 7 -20 mass% is further more preferable. If content of a solvent is more than the said lower limit, gelling will be suppressed and the fluidity | liquidity of a liquid detergent composition will become easy to be maintained. Even if the content of the solvent exceeds the above upper limit value, the liquid fluidity improvement effect corresponding to the solvent content is hardly seen, which is economically disadvantageous.

[Physical properties]
4-10 are preferable, as for pH of the liquid cleaning composition of this invention, 5-9 are more preferable, and 6-8 are more preferable. When the pH is within the above range, the storage stability of the liquid detergent composition is better maintained.
The pH of the liquid detergent composition means a value measured by adjusting the liquid detergent composition to 25 ° C. and using a pH meter or the like.

The viscosity η _A of the liquid detergent composition of the present invention is preferably 1000 mPa · s or less, more preferably 200 to 500 mPa · s, and even more preferably 300 to 500 mPa · s. When the viscosity η _A is equal to or less than the upper limit, the fluidity of the liquid detergent composition is easily maintained, and the measurement with a measurement cap or the like is facilitated. In addition, when the liquid cleaning composition is directly applied to the object to be cleaned, the liquid cleaning composition can be easily applied. If viscosity (eta) _A is more than the said lower limit, it is excellent in the dispersion stability of function provision components, such as a capsule particle.
The viscosity η _A of the liquid detergent composition is a value measured at 60 ° C. using a Brookfield viscometer, setting the number of rotations of the rotor to 60 rpm, and measuring 60 seconds later. means.

  The thixotropy index (TI value) represented by the following formula (II) of the liquid detergent composition of the present invention is preferably 2.0 or more, more preferably 2.0 to 4.0, and more preferably 2.0 to 3. 0 is more preferable. When the TI value is 2.0 or more, it has excellent thixotropic properties and is excellent in dispersion stability of function-imparting components such as capsule particles. If the TI value is 4.0 or less, the fluidity of the liquid detergent composition is unlikely to be impaired.

TI value = η _B / η _A (II)
However, in formula (II), η _B is the viscosity of the liquid detergent composition at 25 ° C., and using a Brookfield viscometer, the rotation speed of the rotor is set to 6 rpm, and measurement is started. It means a value measured after 600 seconds.

The TI value is a numerical value indicating the dependence of the viscosity on the shear rate (rotor rotation speed of the viscometer) (ie, thixotropy). For Newtonian fluids such as water whose viscosity does not depend on the shear rate, the TI value is 1. When the TI value is larger than 1, the viscosity increases as the shearing force decreases, and the thixotropic property is exhibited.
The TI value of the liquid detergent composition of the present invention can be adjusted by the concentration of the component (B), the concentration of the component (C), the mass ratio B / C, the mass ratio B / M, the mass ratio C / M, and the like.

[Production method]
The production method of the liquid detergent composition of the present invention is not particularly limited. For example, the components (A) to (C), and the components (D), (E) and other components used as necessary are used. The method of melt | dissolving in a solvent and adjusting to predetermined | prescribed pH is mentioned.

[Function and effect]
In the liquid detergent composition of the present invention described above, the combination of the (B) component and the (C) component with the (A) component makes it possible to sufficiently increase the TI value even when blended with a super concentrated composition. Excellent stability. Moreover, since the dispersibility of the function-imparting component is also excellent, the degree of freedom of blending various function-imparting components including capsule fragrance is high.
In addition, the liquid detergent composition of the present invention is excellent in usability because it can maintain the low viscosity and sufficiently increase the TI value to realize excellent storage stability and dispersibility of the function-imparting component. . In addition, the liquid detergent composition of the present invention has a high detergency.

EXAMPLES Hereinafter, although an Example demonstrates this invention in detail, this invention is not limited by the following description.
[material]
The raw materials used in this example are as follows.
((A) component)
A1-1: MEE, fatty acid methyl ester ethoxylate (16 to 18 carbon atoms of fatty acid, average addition mole number of EO 15), manufactured by Lion Chemical Co., Ltd., trade name “CEAO-90”.
A2-1: AE (15), polyoxyethylene alkyl ether (carbon number 12-14, average addition mole number of EO 15), manufactured by Lion Chemical Co., Ltd., trade name “LMAO-90”.

A2-2: A nonionic surfactant obtained by blocking addition of 16 mol of ethylene oxide and 2 mol of propylene oxide to a primary alcohol having 12 to 14 carbon atoms. The nonionic surfactant was synthesized by the following method.
A primary alcohol having 12 to 14 carbon atoms and a 30% by mass NaOH aqueous solution were charged into a pressure-resistant reaction vessel, and the inside of the vessel was replaced with nitrogen. Next, after dehydrating for 30 minutes at a temperature of 100 ° C. and a pressure of 2.0 kPa or less, the temperature was raised to 160 ° C., and ethylene oxide (gaseous) was added little by little until a predetermined amount was reached and reacted. After completion of the addition of ethylene oxide, aging was performed for 30 minutes. Thereafter, the temperature was set to 150 ° C., and propylene oxide was added little by little until a predetermined amount was reached, and reacted. After completion of the addition of propylene oxide, aging was performed for 60 minutes.
After cooling the temperature to 100 ° C. or lower, 70% by weight p-toluenesulfonic acid is added to neutralize so that the pH of the 1% by weight aqueous solution of the reaction product is about 7, and the first carbon number 12-14. A nonionic surfactant obtained by blocking addition of 16 moles of ethylene oxide and 2 moles of propylene oxide with respect to the secondary alcohol was obtained.

((A ′) component: comparison target)
A′-1: AE (4), polyoxyethylene alkyl ether (carbon number 12-14, average addition mole number 4 of EO), manufactured by Nippon Emulsifier Co., Ltd., trade name “Newco 3504-C”.

((B) component)
B-1: A cross-linked copolymer (trade name “Carbopol Aqua 30” manufactured by Lubrizol) composed of two or more monomers selected from alkyl acrylate, alkyl methacrylate, acrylic acid and methacrylic acid.
B-2: Cross-linked copolymer composed of alkyl acrylate and acrylic acid or methacrylic acid monomers (trade name “ACUSOL 830” manufactured by DOW).
B-3: a copolymer composed of two or more monomers selected from alkyl acrylate, alkyl methacrylate, acrylic acid and methacrylic acid (trade name “Novethix HC200” manufactured by Lubrizol).
B-4: Cross-linked acrylic acid copolymer (Lublizol) comprising two or more monomers selected from alkyl acrylates (C1 to C4 and C8), alkyl methacrylates (C1 to C4 and C8), acrylic acid and methacrylic acid Product name “Carbopol Aqua SF-1”).

((B ′) component: comparison target)
B′-1: Polyacrylic acid (manufactured by Nippon Shokubai Co., Ltd., trade name “AQUALIC L-DL”).

((C) component)
C1-1: Dimethylaminopropylamide stearate (long-chain aliphatic amide dialkyl tertiary amine, manufactured by Lion Specialty Chemicals, trade name “Lipomin APA168-65E”).
C2-1: AX (dodecyldimethylamine oxide, manufactured by Lion Specialty Chemicals, trade name “AX-CS”).
C2-2: APAX (lauramide amidopropyl dimethylamine oxide, manufactured by Yushi Kogyo Co., Ltd., trade name “KADENAX APA-12W”).

((C ′) component: comparison target)
C′-1: C16 cation (alkyl chloride (carbon number 16) trimethylammonium, manufactured by Lion Corporation, trade name “Lipocard 16-50E”).

((D) component)
D-1: Linear alkylbenzene sulfonic acid (LAS, manufactured by Lion Corporation, trade name: Raipon LS-200).
D-2: Isogo fatty acid (manufactured by NOF Corporation).
D-3: Polyoxyethylene alkyl ether sulfate (AES (1), manufactured by Shin Nippon Chemical Co., Ltd., trade name: Sinoline 1150).

((E) component)
E-1: PE-modified silicone (trade name “Polyether-modified silicone CF1188N RPS-122” manufactured by Toray Dow Corning).

(Other ingredients)
p-TSH: p-toluenesulfonic acid (manufactured by Kyowa Hakko Kogyo Co., Ltd.),
PEG: Polyethylene glycol (manufactured by Lion Chemical Co., Ltd., trade name “PEG # 1000-L60”,
Citric acid: manufactured by Otsuka Oil Co., Ltd.
Benzoic acid Na: sodium benzoate (manufactured by Toa Gosei Co., Ltd.),
Ethanol (made by Nippon Alcohol Sales Co., Ltd., trade name “specific alcohol 95 degree synthesis”),
MEA: monoethanolamine (manufactured by Nippon Shokubai Co., Ltd.),
Capsule flavor A,
Capsule flavor B,
Capsule flavor C,
Fragrance: Fragrance composition A described in Tables 11 to 18 of JP-A-2002-146399,
water.

[Examples 1 to 19, Comparative Examples 1 to 6]
A predetermined amount of blending components were blended so as to have the compositions shown in Tables 1 to 3, and liquid detergent compositions were prepared.
Specifically, water and components (B) to (E) were placed in a beaker having a capacity of 500 mL, and sufficiently stirred with a magnetic stirrer (MITAMURA KOGYOINC.). Next, after adding a part of other components (sodium benzoate), monoethanolamine was added so that the pH at 25 ° C. was the value shown in Table 1. Furthermore, component (A) and other components (other than the above-mentioned other components) were added, and water was added so that the whole would have the composition shown in Table 1 to prepare a liquid detergent composition.

[Measurement of viscosity η _A and TI value]
The PS11 bottle was filled with 80 g of the liquid detergent composition (sample solution) and adjusted to 25 ° C. in a thermostatic bath. A constant temperature sample solution was set using a Brookfield viscometer. First, the rotational speed of the rotor was set to 6 rpm, and the viscosity η _B after 600 seconds was measured. Then, set the rotation speed to 60 rpm, the viscosity was measured eta _A after 60 seconds. _A TI value (= η _B / η _A ) was calculated from the viscosity η _A and the viscosity η _B and evaluated according to the following evaluation criteria.
(Evaluation criteria)
_A : Viscosity η _A is 500 mPa · s or less, and TI value is 2.0 or more.
○: Viscosity η _A is more than 500 mPa · s and not more than 1000 mPa · s, and TI value is 2.0 or more.
X: Viscosity η _A exceeds 1000 mPa · s and / or TI value is less than 2.0.

[Storage stability]
A wide-mouth bottle (PS-No. 6 bottle) was filled with 30 g of the liquid detergent composition, stored in a thermostatic bath at -5 ° C for 1 month, visually confirmed, and storage stability was evaluated according to the following evaluation criteria.
(Evaluation criteria)
(Double-circle): It is transparent and has fluidity even in an environment of −5 ° C.
○: Transparent, and not fluid under an environment of −5 ° C. However, when returned to room temperature, there is fluidity and no practical problem.
X: There is a precipitate or suspended matter.

[Sebum detergency]
As the dirt cloth, “face dirt cloth” produced by rubbing the dirt on the face and neck around the cotton cloth was used. The cleaning liquid was prepared by dispersing and dissolving 6 mL of the liquid cleaning composition in 15 L of water.
Using a Terg-O-meter (manufactured by UNITED STATES TESTING) as a cleaning tester, put 10 facial cloths, a cleaning knitted fabric, and the washing liquid into the cleaning tester and adjust the bath ratio to 30 times. And washed at 120 rpm and 15 ° C. for 10 minutes. Next, it was transferred to a two-tank washing machine (manufactured by Mitsubishi Electric Corporation, product number: CW-C30A1-H1), dehydrated for 1 minute, rinsed in 30 L of tap water (15 ° C., 4 ° DH) for 3 minutes, and air-dried. The reflectance was measured with a color difference meter (product name: SE200 type) manufactured by Nippon Denshoku Co., Ltd. for the unstained cloth, the unclean cloth, the unclean cloth, and the unclean cloth. The washing rate (%) was calculated by the following formula. The cleaning rate (%) was calculated for 10 soiled cloths, and the sebum cleaning power was evaluated based on the following criteria using the average value.
Cleaning rate (%) = (K / S of soiled cloth before cleaning−K / S of soiled cloth after cleaning) / (K / S of soiled cloth before cleaning−K / S of unsoiled cloth) × 100
However, K / S is a value calculated | required by a formula: K / S = (1-R / 100) ² / (2R / 100), and R is a reflectance (%).
(Evaluation criteria)
A: The cleaning rate is 70% or more.
○: The cleaning rate is 60% or more and less than 70%.
X: The cleaning rate is less than 60%.

[Dispersibility]
Filled with 30 g of the liquid detergent composition in a wide-mouth standard bottle (PS-No. 6 bottle), and added 0.5 g of beads (TOSHIKI PIGMENT. CO. LTD, “PFL-RED 7155T Lot. 0308”) to disperse. It was. It preserve | saved for 60 days in a 25 degreeC thermostat. During the storage period, the bottle was taken out from the thermostatic bath every day, and the dispersion state of the beads in the liquid detergent composition was visually confirmed, and the dispersibility was evaluated according to the following evaluation criteria.
(Evaluation criteria)
A: The beads were uniformly dispersed in the liquid detergent composition for 60 days.
○: The beads are uniformly dispersed in the liquid detergent composition for 30 to 59 days.
X: The beads are floating or settling in less than 30 days.

Tables 1 to 3 show the compositions and evaluation results of the respective components in Examples and Comparative Examples.
In addition, the “appropriate amount” of the MEA content in Tables 1 to 3 is an amount required to adjust the pH of the liquid detergent composition to 7.5. The “balance” of the water content is an amount required to make 100% by mass of the entire liquid detergent composition.

As shown in Tables 1 to 3, the liquid detergent compositions of Examples 1 to 19 containing the components (A) to (C) have low viscosity and excellent usability, and also have storage stability and dispersibility. Excellent and detergency was high.
The liquid detergent compositions of Comparative Examples 1 to 6 that did not contain any of the components (A) to (C) did not have high detergency, usability due to low viscosity, storage stability, and dispersibility.

Claims (4)

(A) component: one or more nonionic surfactants selected from the group consisting of a compound represented by the following general formula (A1) and a compound represented by the following general formula (A2),
(B) component: a copolymer having a repeating unit derived from a monomer represented by the following general formula (b1) and a repeating unit derived from a monomer represented by the following general formula (b2);
And
Component (C): containing one or more surfactants selected from the group consisting of a compound represented by the following general formula (C1) and a compound represented by the following general formula (C2),
A liquid detergent composition, wherein the total amount of the surfactant is 25% by mass or more.

(In the general formula, ^{R 1} is a hydrocarbon group having 9 to 13 carbon atoms, ^{R 2} is an alkylene group having 2 to 4 carbon atoms, ^{R 3} is an alkyl group having 1 to 4 carbon atoms .
m is the average number of repetitions of OR ² and is 5-25.
R ⁴ is a hydrocarbon group having 10 to 22 carbon atoms, EO is an oxyethylene group, and PO is an oxypropylene group.
s is the average number of repetitions of EO, and is 5-20.
t is the average number of repetitions of PO and is 0-4.
R ⁵ is a hydrogen atom or a methyl group, and R ⁶ is a hydrogen atom.
R ⁷ is a hydrogen atom or a methyl group, and R ⁸ is an alkyl group having 1 to 40 carbon atoms.
R ⁹ is a hydrocarbon group having 7 to 27 carbon atoms, and at least one hydrogen atom may be substituted with one or more substituents selected from the group consisting of a hydroxy group and an amino group, Are groups that may have one or more linking groups selected from the group consisting of an amide group, an ester group and an ether group.
R ¹⁰ is a hydrocarbon group having 1 to 25 carbon atoms, and at least one hydrogen atom may be substituted with a hydroxy group, and is a group that may have the linking group in a carbon chain.
R ¹¹ is an alkyl group having 1 to 4 carbon atoms, a hydroxyalkyl group having 1 to 4 carbon atoms, or a polyoxyethylene group having 1 to 25 moles of ethylene oxide added.
R ¹² is an alkyl group having 8 to 18 carbon atoms or an alkenyl group having 8 to 18 carbon atoms.
Q is an amide group, an ester group or a carbonate group.
R ¹³ is an alkylene group having 1 to 5 carbon atoms, and R ¹⁴ and R ¹⁵ are each independently an alkyl group having 1 to 3 carbon atoms or a hydroxyalkyl group having 1 to 3 carbon atoms.
p is 0 or 1. )   Furthermore, the liquid cleaning composition of Claim 1 containing (D) component: anionic surfactant and (E) component: a polyether modified silicone compound.   The liquid cleaning composition according to claim 1 or 2, wherein the component (A) is a compound represented by the general formula (A1).   The liquid cleaning composition according to any one of claims 1 to 3, wherein the component (C) is a compound represented by the general formula (C1).