JP2017214563A - Liquid detergent composition for fiber product - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a liquid detergent composition for fiber product which is excellent in dispersion stability of water-insoluble particles such as capsule perfume and has good coating washability.SOLUTION: A liquid detergent composition for fiber product contains an anionic surface active agent (A), and a crosslinked polymer (B) having a repeating unit derived from a specific monomer (b1) and a repeating unit derived from a specific monomer (b2), where a content of the (B) component is 0.1 mass% or more and less than 3 mass% with respect to the total mass of the liquid detergent composition for fiber product. The (A) component may contain an α-sulfo fatty acid ester salt.SELECTED DRAWING: None

Description

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

For the purpose of improving the fragrance of a textile product such as clothing, a capsule flavor may be blended in the liquid detergent composition for the textile product. For example, when a capsule fragrance is blended in a liquid detergent composition containing a nonionic surfactant as a main component, an acrylic polymer is blended. By blending an acrylic polymer, the viscosity of the liquid detergent composition is increased, or the liquid detergent composition is structured, and the capsule perfume is less likely to precipitate, float and precipitate (that is, stable dispersion). To enhance sex). “Structured” means a state in which the viscosity changes before and after a force is applied. As an example of a structured liquid detergent composition, there is a liquid detergent composition that has a certain degree of viscosity in a state where no force is applied, such as a stationary state, but when the force is applied, the viscosity decreases and fluidity is exhibited. Can be mentioned.
As a liquid detergent composition for the purpose of improving detergency against protein stains, particle stains, etc., there is a liquid detergent composition mainly composed of an anionic surfactant (hereinafter referred to as an anionic liquid detergent). . In order to increase the dispersion stability of the capsule fragrance in the liquid detergent with an anionic composition, if the acrylic acid polymer is added, the acrylic acid polymer is degenerated, and it is difficult to increase the viscosity and structure. There is a problem that it is difficult to increase the dispersion stability of the fragrance. There is a method of adding water-soluble salts such as mirabilite and salt in order to increase the viscosity of a liquid detergent with an anionic composition, but it is difficult to stably disperse capsule fragrance for a long period of time. .
Furthermore, when an acrylic polymer is blended with a liquid detergent having an anionic composition, there is a problem in that the washability (that is, the washability of application) is reduced when the liquid detergent is directly applied to an object to be washed. There is also.
For such problems, Patent Document 1 contains a specific amount of a surfactant, a specific alkali-swelling acrylate copolymer rheology modifier, an alkaline material, an acidic material, water, and a water-insoluble material. A composition is described. Patent Document 2 describes a liquid detergent containing a solvent component containing polyacrylate and dipropylene glycol.

JP 2014-28957 A Special table 2008-534718 gazette

However, Patent Documents 1 and 2 do not consider at all about achieving both the dispersion stability of water-insoluble particles such as capsule fragrances and the coating cleaning properties.
Accordingly, an object of the present invention is to provide a liquid detergent composition for textiles that is excellent in dispersion stability of water-insoluble particles such as capsule fragrances and that has good coating and detergency.

The present invention has the following aspects.
[1] Crosslinking having an anionic surfactant (A), a repeating unit derived from a monomer represented by the following formula (1), and a repeating unit derived from a monomer represented by the following formula (2) A liquid detergent composition for textiles comprising a polymer (B) of a mold,
The liquid for textiles characterized by content of the said (B) component being 0.1 to 3 mass% with respect to the total mass of the liquid detergent composition for said textiles Cleaning composition.

（式（１）中、Ｒ^５は水素原子、又はメチル基を表し、Ｒ^６は水素原子を表す。また式（２）中、Ｒ^７は水素原子、又はメチル基を表し、Ｒ^８は炭素数１〜４０のアルキル基、又は炭素数１〜４０のヒドロキシアルキル基を表す。）

(In Formula (1), R ⁵ represents a hydrogen atom or a methyl group, R ⁶ represents a hydrogen atom. In Formula (2), R ⁷ represents a hydrogen atom or a methyl group, and R ⁸ represents carbon. Represents an alkyl group having 1 to 40 carbon atoms or a hydroxyalkyl group having 1 to 40 carbon atoms.)

[2] The liquid detergent composition for textiles according to [1], wherein the component (A) includes an α-sulfo fatty acid ester salt.
[3] The liquid detergent composition for textiles according to [1] or [2], further comprising an alkylene oxide adduct (C) of polyalkyleneamine.
[4] The liquid detergent composition for textiles according to any one of [1] to [3], further comprising water-insoluble particles.
[5] The liquid detergent composition for textiles according to any one of [1] to [4], wherein the ratio of the component (A) to the total mass of the surfactant is 40 to 100% by mass. object.
[6] Viscosity v ₁ (30 ° C.) measured after 60 seconds using a B-type viscometer at 60 rpm, and after 60 seconds using a B-type viscometer at 60 rpm. The liquid for textiles according to any one of [1] to [5], wherein the ratio (viscosity v ₁ / viscosity v ₂ ) to the viscosity v ₂ (30 ° C.) is 1.9 or more. Cleaning composition.

  According to the liquid detergent composition for textiles of the present invention, the dispersion stability of water-insoluble particles such as capsule fragrances is excellent, and the coating detergency is good.

(Liquid detergent composition for textile products)
The liquid detergent composition for textiles of the present invention (hereinafter sometimes simply referred to as a liquid detergent) is a composition containing the component (A) and the component (B).

<(A) component>
The component (A) is an anionic surfactant. Examples of the anionic surfactant include the following (1) to (12).
(1) A linear or branched alkylbenzene sulfonate (LAS or ABS) having an alkyl group having 8 to 18 carbon atoms.
(2) Alkanesulfonate having 10 to 20 carbon atoms.
(3) C10-20 α-olefin sulfonate (AOS).
(4) Alkyl sulfate or alkenyl sulfate (AS) having 10 to 20 carbon atoms.
(5) Any of alkylene oxides having 2 to 4 carbon atoms, or ethylene oxide (EO) and propylene oxide (PO) (EO / PO molar ratio is 0.1 / 9.9 to 9.9 / 0.1) Alkyl (or alkenyl) ether sulfate (AES) having a linear or branched alkyl (or alkenyl) group having 10 to 20 carbon atoms to which an average of 0.5 to 10 mol is added. AES having a straight-chain alkyl group having 12 to 18 carbon atoms with an average of 1 to 2 moles of EO added thereto is preferred because good appearance stability is easily obtained with AES.
(6) Any one of alkylene oxides having 2 to 4 carbon atoms, or ethylene oxide and propylene oxide (EO / PO molar ratio is 0.1 / 9.9 to 9.9 / 0.1), average 3 to 30 An alkyl (or alkenyl) phenyl ether sulfate having a linear or branched alkyl (or alkenyl) group having 10 to 20 carbon atoms added in a mole form.
(7) Any one of alkylene oxides having 2 to 4 carbon atoms, or ethylene oxide and propylene oxide (EO / PO molar ratio is 0.1 / 9.9 to 9.9 / 0.1), an average of 0.5 An alkyl (or alkenyl) ether carboxylate having a linear or branched alkyl (or alkenyl) group having 10 to 20 carbon atoms added by 10 mol.
(8) Alkyl polyhydric alcohol ether sulfates such as alkyl glyceryl ether sulfonic acids having 10 to 20 carbon atoms.
(9) Long chain monoalkyl, dialkyl or sesquialkyl phosphates.
(10) Polyoxyethylene monoalkyl, dialkyl or sesquialkyl phosphate.
(11) Soap. A higher fatty acid salt having an average carbon number of 10 to 20 (preferably having 12 to 18 carbon atoms).
(12) α-sulfo fatty acid ester salt (MES).

Anionic surfactants other than those exemplified above may be used. For example, carboxylic acid type anionic surfactants such as alkyl ether carboxylates, polyoxyalkylene ether carboxylates, alkylamide ether carboxylates or alkenylamide ether carboxylates, acylaminocarboxylates; alkyl phosphate ester salts And phosphoric acid ester type anionic surfactants such as polyoxyalkylene alkyl phosphoric acid ester salt, polyoxyalkylene alkyl phenyl phosphoric acid ester salt and glycerin fatty acid ester monophosphoric acid ester salt.
Examples of the salt form of the anionic surfactant 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; ammonium salts and the like. It is done. Of these, alkali metal salts are preferred.

(A) A component may be used individually by 1 type and may be used in combination of 2 or more type.
As the component (A), at least one selected from the group consisting of the above (1), (4), (5), and (12) can be obtained because it is easy to obtain better application cleaning properties. Preferably, it contains one anionic surfactant, a combination of (5) and (12), a combination of (1) and (5), a combination of (1) and (12), and (1) and (5 And at least one anionic surfactant selected from the group consisting of a combination of (12) and (12).

The content of the component (A) is preferably 3 to 30% by mass, more preferably 4 to 20% by mass, and still more preferably 6 to 16% by mass with respect to the total mass of the liquid detergent. When the content of the component (A) is equal to or more than the lower limit, it is easy to obtain a liquid detergent excellent in coating detergency and dispersion stability of water-insoluble particles such as capsule flavor. Moreover, it becomes easy to obtain the liquid cleaning agent excellent in recontamination prevention property. Further, when the content of the component (A) is not more than the above upper limit value, it is easy to obtain the effect of thickening and structuring the liquid detergent.
Here, the “anti-contamination prevention property” is a property that prevents the dirt detached from the object to be washed by performing the washing process from adhering to the object to be washed again.

In one embodiment of the present invention, the component (A) may contain the above-mentioned (12). Further, (12) is preferably an α-sulfo fatty acid salt ester represented by the following formula (a1) (hereinafter referred to as component (a)).
R ³ CH (SO ₃ M) COOR ⁴ (a1)
(In formula (a1), R ³ is a hydrocarbon group having 10 to 16 carbon atoms, R ⁴ is a hydrocarbon group having 1 to 6 carbon atoms, and M is a counter ion.)

<(A) component>
In the formula (a1), the carbon number of the hydrocarbon group ^{R 3} is 10-16. That is, carbon number of the fatty acid residue which (a) component has is 12-18. A fatty acid residue refers to an acyl group moiety. If the carbon number of R ³ is 10 or more, the surface activity is strong, and the coating cleaning property becomes better. When the carbon number of R ³ is 16 or less, the low temperature stability of the liquid detergent is excellent.

The hydrocarbon group for R ³ may be linear, branched, or may contain a cyclic structure. The hydrocarbon group for R ³ is preferably an aliphatic hydrocarbon group, more preferably a linear or branched alkyl group, or a linear or branched alkenyl group, and a linear alkyl group. Or a straight-chain alkenyl group is more preferable.

In formula (a1), R ⁴ has 1 to 6 carbon atoms, preferably 1 to 3 carbon atoms.
The hydrocarbon group for R ⁴ may be linear, branched, or may contain a cyclic structure. The hydrocarbon group for R ⁴ is preferably an aliphatic hydrocarbon group, more preferably a linear or branched alkyl group, or a linear or branched alkenyl group, and a linear alkyl group. A group or a branched alkyl group is more preferable.
R ⁴ is preferably a methyl group, an ethyl group, an n-propyl group, an isopropyl group, etc., preferably a methyl group, an ethyl group, or an n-propyl group, and particularly preferably a methyl group, since the coating detergency is further improved. .

In the formula (a1), as the counter ion of M, those capable of forming a water-soluble salt with R ³ CH (COOR ⁴ ) SO ₃ ^— are preferable, and examples thereof include alkali metal ions, protonated amines, ammonium ions, and the like. Can be mentioned. Examples of the alkali metal that can be the counter ion include sodium. Examples of the amine that can be the counter ion include primary to tertiary amines. The total number of carbon atoms of the amine is preferably 1-6. The amine may have a hydroxy group. Since the solubility of the component (a) in water is increased, the amine preferably has a hydroxy group. Examples of the amine having a hydroxy group include alkanolamine, and the alkanol group preferably has 1 to 3 carbon atoms. Examples of the alkanolamine include monoethanolamine, diethanolamine, and triethanolamine.
M is preferably an alkali metal ion and particularly preferably a sodium ion because it is easily available and the low-temperature stability of the liquid detergent can be further enhanced.
As the component (a), R ³ in the formula (a1) is a linear or branched alkyl group having 14 to 16 carbon atoms, or a linear or branched alkenyl group, and R ⁴ A compound in which is a methyl group is particularly preferred.

As the component (a), any one type may be used alone, or two or more types may be used in combination.
The component (a) is preferably a mixture in which compounds having different numbers of carbon atoms of fatty acid residues are mixed, since the coating detergency increases and the solubility in water increases. In particular, the compound ^{wherein R 3} is a hydrocarbon group having 14 carbon atoms in the (a1) and (a1), the formula ^{R 3} is a hydrocarbon group having 16 carbon atoms in the (a1) (a- A mixture with 2) is preferred. In such a mixture, the mass ratio of the compound (a-1) to the compound (a-2) is preferably (a-1) :( a-2) = 45: 55 to 95: 5, and 60:40 to 90. : 10 is more preferable, and 80:20 to 85:15 is more preferable. When the mass ratio is within the above-described preferable range, the coating cleaning property, the solubility in water, and the low-temperature stability of the liquid cleaning agent tend to be better.

The component (a) is obtained by a known production method, for example, by using a tank reactor equipped with a stirrer, etc. by a regular method, and bringing the fatty acid ester of the raw material into contact with sulfuric anhydride or the like for sulfonation. A product obtained by preparing an α-sulfo fatty acid ester (α-SF acid) and then neutralizing the α-SF acid with sodium hydroxide or the like may be used, or a commercially available product may be used. Also good. In addition, you may bleached with hydrogen peroxide etc. before and after neutralization.
(A) 0-7 mass% is preferable with respect to the total mass of a liquid detergent, as for content of a component, 1-6 mass% is more preferable, and 1.5-5 mass% is further more preferable. When the content of the component (a) is within the above range, it becomes easy to obtain a liquid detergent that is excellent in coating detergency, recontamination prevention property, dispersion stability, and enzyme stability. Moreover, it becomes easy to maintain the freedom degree of mixing | blending of another component.
The proportion of the component (a) in the component (A) is preferably (a) / (A) = 0/100 to 70/100, more preferably 10/100 to 65/100, 20/100 to 60 / 100 is more preferable.

<(B) component>
The component (B) is a crosslinked polymer having a repeating unit derived from a monomer represented by the following formula (1) and a repeating unit derived from a monomer represented by the following formula (2). In the structure, it is derived from a repeating unit derived from a monomer represented by formula (1) (hereinafter referred to as monomer (b1)) and a monomer represented by formula (2) (hereinafter referred to as monomer (b2)). In addition, the effect of thickening and structuring the liquid detergent can be obtained. (B) A component may be used individually by 1 type and may be used in combination of 2 or more type.

（式（１）中、Ｒ^５は水素原子、又はメチル基を表し、Ｒ^６は水素原子を表す。また式（２）中、Ｒ^７は水素原子、又はメチル基を表し、Ｒ^８は炭素数１〜４０のアルキル基、又は炭素数１〜４０のヒドロキシアルキル基を表す。）

(In Formula (1), R ⁵ represents a hydrogen atom or a methyl group, R ⁶ represents a hydrogen atom. In Formula (2), R ⁷ represents a hydrogen atom or a methyl group, and R ⁸ represents carbon. Represents an alkyl group having 1 to 40 carbon atoms or a hydroxyalkyl group having 1 to 40 carbon atoms.)

<Monomer (b1), (b2)>
The monomer (b1) is a monomer represented by the above formula (1), that is, (meth) acrylic acid. A monomer (b1) may be used individually by 1 type, and may use 2 types together.
The monomer (b2) is a (meth) acrylate represented by the above formula (2).
In the above formula (2), the alkyl group having 1 to 40 carbon atoms of 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 1 to 30, 10 to 30 is more preferable. When the carbon number is 1 or more, the component (B) tends to swell with water, and the dispersion stability of water-insoluble particles such as capsule fragrances tends to be good. When the carbon number is 40 or less, the solubility of the component (B) in water tends to be good.
The alkyl group of the hydroxyalkyl group having 1 to 40 carbon atoms of R ⁸ also may be linear, may be branched, it may contain a cyclic structure. Carbon number of the alkyl group of a hydroxyalkyl group is 1-40, 1-30 are preferable and 10-30 are more preferable. If the said carbon number is 1-40, the effect of thickening and structuring a liquid detergent will be acquired.
A monomer (b2) may be used individually by 1 type, and may be used in combination of 2 or more type.

Component (B) is a crosslinked polymer. Here, the “crosslinked polymer” refers to a partially or substantially crosslinked polymer. The component (B) of the present invention is preferably obtained by polymerizing a monomer mixture containing the monomer (b1), the monomer (b2), and a crosslinking agent.
As a crosslinking agent, an allyl ether compound is mentioned, for example.
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 the component (B), any one type may be used alone, or two or more types may be used in combination.
As the component (B), a repeating unit derived from a monomer represented by the general formula (1) (R ⁵ is hydrogen), a general formula (2) (R ⁷ is a methyl group, and R ⁸ is a carbon number) A cross-linked polymer having a repeating unit derived from a monomer represented by formula (1) (R ⁵ is hydrogen). And a repeating polymer derived from a monomer represented by the general formula (2) (R ⁷ is a methyl group and R ⁸ is an alkyl group having 1 to 6 carbon atoms) is preferable. .

In addition, the component (B) is a repeating unit other than the repeating unit derived from the monomer represented by the general formula (1) and the repeating unit derived from the monomer represented by the general formula (2) (other repeating units). Unit).
Other repeating units include repeating units derived from other monomers.
The other monomer is not particularly limited as long as it is copolymerizable with the monomer (b1) and the monomer (b2), and one or more types can be used.

  The content of the component (B) is 0.1% by weight or more and less than 3% by weight, preferably 0.5% by weight or more and less than 3% by weight, based on the total weight of the liquid detergent, and is 0.6-2. 0.5% by mass is more preferable, and 0.65 to 2.0% by mass is even more preferable. If content of (B) component is more than the said lower limit, (B) component can fully be structured in a liquid detergent, and the dispersion stability of a capsule fragrance | flavor will become favorable. If it is less than the said upper limit, the viscosity at the time of liquid detergent use will not become high too much, but the usability of a liquid detergent will not fall easily.

  As a commercial item of (B) component, the Carbopol (trademark) series etc. by Lubrizol are mentioned, for example. Examples of the Carbopol series include Carbopol ETD 2623, Carbopol EZ3, Carbopol EZ4, Carbopol Ultraz 20, Carbopol Ultraz 21, Carbopol Aqua 30 and the like. Among these, Carbopol ETD 2623, Carbopol EZ4, and Carbopol Aqua 30 are preferable, and Carbopol EZ4 is more preferable. These may be used individually by 1 type and may be used in combination of 2 or more type.

Moreover, 4-60 are preferable, as for mass ratio (A / B ratio) represented by (A) component / (B) component, 5-35 are more preferable, and 7-25 are more preferable. If A / B ratio is more than the said lower limit, it will be easy to obtain the liquid cleaning agent which is generally excellent in cleaning property. In addition, when the A / B ratio is not less than the above lower limit, the viscosity when using the liquid detergent does not become too high, and a liquid detergent excellent in usability is easily obtained. On the other hand, if the A / B ratio is not more than the above upper limit value, the liquid detergent can be sufficiently structured, and the dispersion stability of the capsule flavor becomes better.
In addition, normal washing | cleaning means wash | cleaning a to-be-washed object with a washing machine etc. using the washing | cleaning liquid which disperse | distributed the liquid detergent in water.

  Moreover, 0-15 are preferable, as for mass ratio (a / B ratio) represented by (a) component / (B) component, 0.5-10 are more preferable, and 1.5-8 are more preferable. If the a / B ratio is equal to or higher than the lower limit, a liquid cleaning agent having excellent coating cleaning properties, normal cleaning properties, and recontamination prevention properties can be easily obtained. The viscosity at the time of using the liquid detergent does not become too high, and a liquid detergent excellent in usability is easily obtained. On the other hand, if the a / B ratio is not more than the above upper limit value, the liquid detergent can be sufficiently structured, and the dispersion stability of the capsule fragrance becomes good. In addition, when the a / B ratio is not more than the above upper limit, a liquid detergent having excellent low-temperature stability can be obtained.

<(C) component>
It is preferable that the liquid cleaning composition of this invention contains (C) component. Component (C) is an alkylene oxide adduct of polyalkyleneamine.
(C) As a component, the following (c1) component and the following (c2) component are mentioned, for example.

<(C1) component>
The component (c1) is an alkylene oxide adduct of polyalkyleneimine.
The (c1) component polyalkyleneimine is represented, for example, by the following general formula (3).
NH ₂ —R ²¹ — (NA—R ²¹ ) _n —NH ₂ (3)
In formula (3), each R ²¹ is independently an alkylene group having 2 to 6 carbon atoms, A represents a hydrogen atom or another polyamine chain due to branching, and n is a number of 1 or more. However, not all of the A are hydrogen atoms.
That is, the polyalkyleneimine represented by the formula (3) has a branched polyamine chain in the structure.

R ²¹ is a linear alkylene group having 2 to 6 carbon atoms or a branched alkylene group having 3 to 6 carbon atoms. R ²¹ is preferably an alkylene group having 2 to 4 carbon atoms, and more preferably an alkylene group having 2 carbon atoms.
The polyalkyleneimine can be obtained by polymerizing one or more of alkyleneimines having 2 to 6 carbon atoms by a conventional method. Examples of the alkyleneimine having 2 to 6 carbon atoms include ethyleneimine, propyleneimine, 1,2-butyleneimine, 2,3-butyleneimine, 1,1-dimethylethyleneimine and the like.
As polyalkyleneimine, polyethyleneimine (PEI) and polypropyleneimine are preferable, and PEI is more preferable. PEI is obtained by polymerizing ethyleneimine and has a branched chain structure containing primary, secondary and tertiary amine nitrogen atoms in the structure.

  The mass average molecular weight of the polyalkyleneimine is preferably 200 to 2000, more preferably 300 to 1500, still more preferably 400 to 1000, and particularly preferably 500 to 800.

  As polyalkyleneimine, those having 5 to 30 active hydrogens in one molecule are preferable, those having 7 to 25 are more preferable, and those having 10 to 20 are more preferable.

The component (c1) is obtained by adding alkylene oxide to polyalkyleneimine. As this method, for example, an alkylene oxide such as ethylene oxide is added to a polyalkyleneimine which is a starting material in the presence of a basic catalyst such as sodium hydroxide, potassium hydroxide or sodium methylate at 100 to 180 ° C. And the like.
Examples of the alkylene oxide include alkylene oxides having 2 to 4 carbon atoms. Examples of the alkylene oxide include ethylene oxide, propylene oxide, and butylene oxide. Ethylene oxide and propylene oxide are preferable, and ethylene oxide is more preferable.

Examples of the component (c1) include polyalkyleneimine ethylene oxide adducts, polyalkyleneimine propylene oxide adducts, and polyalkyleneimine ethylene oxide-propylene oxide adducts. In addition, the ethylene oxide-propylene oxide adduct of polyalkyleneimine is obtained by adding ethylene oxide and propylene oxide to polyalkyleneimine, and the addition order and addition form of ethylene oxide and propylene oxide to polyalkyleneimine (block shape, random shape). ) Is optional.
As the component (c1), an ethylene oxide adduct of polyalkyleneimine and an ethylene oxide-propylene oxide adduct of polyalkyleneimine are preferable, and an ethylene oxide adduct of polyalkyleneimine is more preferable.

  As the component (c1), an average of 5 to 40 alkylene oxides are preferably added to one active hydrogen atom of the polyalkyleneimine as a raw material, and an average of 10 to 30 alkylene oxides are added. Those are more preferred. That is, an average of 5 to 40 moles of alkylene oxide added is preferable per mole of active hydrogen of the polyalkyleneimine as a raw material, and an average of 10 to 30 moles of alkylene oxide is more preferable.

(C1) As for the mass mean molecular weight of a component, 1000-80000 are preferable, 2000-50000 are more preferable, 5000-30000 are further more preferable, and 10000-20000 are especially preferable.
Examples of the component (c1) include compounds represented by the formula (3-a).

In formula (3-a), R ²² is each independently an alkylene group having 2 to 6 carbon atoms, and m is independently a number of 1 or more.
R ²² is preferably an alkylene group having 2 or 3 carbon atoms, and more preferably an alkylene group having 2 carbon atoms. m is the average number of repetitions of (R ²² O), preferably 5 to 40, more preferably 10 to 30, each independently.
As the component (c1), a synthetic product may be used, or a commercially available product may be used.
As a commercial item, the brand name "Sokalan (trademark) HP20" by BASF Corporation etc. are mentioned, for example.

<(C2) component>
The component (c2) is, for example, an alkylene oxide adduct of a polyalkyleneamine represented by the following general formula (4).
NH ₂ (R ³¹ NH) ₁ H (4)
In formula (4), R ³¹ is an alkylene group having 2 to 6 carbon atoms, and l is a number of 1 or more.

R ³¹ is a linear alkylene group having 2 to 6 carbon atoms or a branched alkylene group having 3 to 6 carbon atoms. R ³¹ is preferably an alkylene group having 2 to 4 carbon atoms, and more preferably an alkylene group having 2 carbon atoms.
As the polyalkyleneamine, polyethyleneamine is preferable. Examples of polyethyleneamine include ethylenediamine, diethylenetriamine, triethylenetetramine, tetraethylenepentamine, and pentaethylenehexamine. These polyethyleneamines can be obtained by a known production method, for example, by reacting ammonia and ethylene dichloride.

  The mass average molecular weight of the polyalkyleneamine is preferably 60 to 1800, more preferably 60 to 1000, and still more preferably 60 to 800.

  As the polyalkyleneamine, those having 6 to 30 active hydrogens in one molecule are preferable, and those having 7 to 20 active hydrogens are more preferable.

  The component (c2) is obtained by adding an alkylene oxide to a polyalkyleneamine. This reaction can be performed in the same manner as the component (c1). Examples of the alkylene oxide include alkylene oxides having 2 to 4 carbon atoms. Examples of the alkylene oxide include ethylene oxide, propylene oxide, and butylene oxide. Ethylene oxide and propylene oxide are preferable, and ethylene oxide is more preferable.

Examples of the component (c2) include an ethylene oxide adduct of polyalkyleneamine, a propylene oxide adduct of polyalkyleneamine, and an ethylene oxide-propylene oxide adduct of polyalkyleneamine.
The alkylene oxide adduct of polyalkyleneamine is preferably an ethylene oxide adduct of polyalkyleneamine or an ethylene oxide-propylene oxide adduct of polyalkyleneamine, more preferably an ethylene oxide adduct of polyalkyleneamine.

  As the component (c2), an average of 5 to 40 alkylene oxides is preferably added to one active hydrogen atom of the polyalkyleneamine as a raw material, and an average of 10 to 30 alkylene oxides are added. Those are more preferred. That is, an average of 5 to 40 moles of alkylene oxide added per mole of active hydrogen contained in the polyalkyleneamine as a raw material, and an average of 10 to 30 moles of alkylene oxide added is more preferable.

  (C2) 1000-80000 are preferable, as for the mass average molecular weight of a component, 2000-50000 are more preferable, 5000-30000 are further more preferable, and 10000-20000 are especially preferable.

As the component (C), the component (c1) is preferable. Among the components (c1), an ethylene oxide adduct of polyethyleneimine represented by the above formula (3-a) is particularly preferable.
As the component (C), any one type may be used alone, or two or more types may be used in combination.

  The content of the component (C) is preferably 0.1 to 2% by mass, more preferably 0.2 to 1.5% by mass, and 0.3 to 1.0% by mass with respect to the total mass of the liquid detergent. % Is more preferable. When the content of the component (C) is equal to or higher than the lower limit, a liquid detergent excellent in coating cleaning property, recontamination preventing property, dispersion stability, and enzyme stability is easily obtained. Moreover, it becomes easy to maintain the freedom degree of the mixing | blending of another component as content of (C) component is below the said upper limit.

  Moreover, 0.15-5 are preferable, as for mass ratio (C / B ratio) represented by (C) component / (B) component, 0.2-3 are more preferable, and 0.3-2 are more preferable. . If C / B ratio is more than the said lower limit, it will become easy to obtain the liquid cleaning agent which is excellent in normal washing | cleaning property, recontamination prevention property, and liquid stability. In addition, when the C / B ratio is equal to or higher than the above lower limit, the viscosity at the time of using the liquid detergent does not become too high, and a liquid detergent excellent in usability is easily obtained. On the other hand, if the C / B ratio is not more than the above upper limit value, the liquid detergent can be sufficiently structured, and the dispersion stability of the capsule fragrance becomes good.

<Water-insoluble particles>
The liquid detergent of the present invention preferably contains particles (water-insoluble particles) that are hardly soluble in the components constituting the liquid detergent. Since the liquid detergent of the present invention contains the above-mentioned components (A) and (B), water-insoluble particles can be stably dispersed.
Examples of such water-insoluble particles include capsules containing capsule fragrances and active ingredients instead thereof, beads and pearlescent agents for imparting unique product aesthetics, bentonite, zeolite, carboxymethylcellulose (CMC), and the like. Is mentioned.
These water-insoluble particles may be used alone or in combination of two or more.
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.
The content of the water-insoluble particles in the liquid detergent is preferably 0.01 to 1% by mass and more preferably 0.03 to 0.7% by mass with respect to the total mass of the liquid detergent. If the content of the water-insoluble particles is within the above range, the dispersion stability of the water-insoluble particles in the liquid detergent tends to be good.

The liquid cleaning agent of the present invention has a viscosity (value when measured after 60 seconds using a B-type viscometer at a measurement temperature of 30 ° C. and a rotation speed of 60 rpm, hereinafter referred to as viscosity v ₂ ) of 100 to 100. It is preferably 4000 mPa · s. If the viscosity is within the above range, the applicability to the object to be washed, ease of pouring, rich feeling and the like tend to be good.
The liquid detergent of the present invention has a viscosity v ₂ of 100 to 4000 mPa · s and a viscosity v ₁ (30 ° C.) measured after 60 seconds using a B-type viscometer at a rotation speed of 6 rpm. And the ratio of viscosity v ₂ (viscosity v ₁ / viscosity v ₂ ) is preferably 1.9 or more. The viscosity v ₁ / viscosity v ₂ is more preferably 2.5 or more. When the viscosity v ₁ / viscosity v ₂ is 1.9 or more, the dispersion stability of water-insoluble particles such as capsule flavors tends to be good. The upper limit of the viscosity v ₁ / viscosity v ₂ is preferably 5 or less.

<Optional component>
The liquid cleaning agent of the present invention can contain optional components other than the above components (A) to (C) and water-insoluble particles, as long as the effects of the present invention are not impaired.
Examples of optional components include water, surfactants other than component (A) (optional surfactant), water-miscible organic solvents, organic acids, antioxidants, cleaning performance improvers / stability improvers, preservatives Fragrance precursors, colorants / emulsifiers, extracts of natural products, pH adjusters, fragrances other than capsule fragrances, and the like.

  The content of water with respect to the total amount of the liquid detergent is, for example, preferably 10 to 95% by mass, more preferably 20 to 90% by mass, and still more preferably 40 to 90% by mass.

<Optional surfactant>
The optional surfactant is a cleaning component, and a known surfactant can be used in the liquid cleaning agent. For example, a nonionic surfactant, a cationic surfactant, an amphoteric surfactant, and a semipolar surfactant can be blended in one kind or a combination of two or more kinds.
The total amount (total amount) of the surfactant (including the component (A)) in the liquid detergent is preferably 8 to 30% by mass, more preferably 9 to 20% by mass, based on the total mass of the liquid detergent. 10-17 mass% is further more preferable. When the total amount of the surfactant is not less than the lower limit of the above range, good coating detergency can be easily obtained. When it is at most the upper limit value, it is easy to obtain sufficient coating cleaning properties while suppressing an increase in cost.

  Further, the ratio of the component (A) to the total amount of the surfactant is preferably 40% by mass or more, more preferably 50% by mass or more with respect to the total mass of the surfactant, from the viewpoint of detergency and re-contamination prevention. Preferably, 60 mass% or more is more preferable. 100 mass% may be sufficient as the upper limit of (A) component with respect to the total amount of surfactant, 95 mass% or less is preferable from the point of balance with other surfactant, and 93 mass% or less is more preferable. That is, the ratio of the component (A) to the total mass of the surfactant is preferably 40 to 100% by mass, more preferably 50 to 95% by mass, and further preferably 60 to 93% by mass.

[Nonionic surfactant]
As the surfactant other than the component (A), it is preferable to include a nonionic surfactant in terms of the stability of the liquid detergent.
1-10 mass% is preferable with respect to the total mass of a liquid detergent, and, as for content of nonionic surfactant, 1-5 mass% is more preferable.
In this case, the total amount of the component (A) and the nonionic surfactant with respect to the total mass of the surfactant is preferably 80% by mass or more, more preferably 85% by mass or more, further preferably 90% by mass or more, and 100% by mass. %. That is, the total amount of the component (A) and the nonionic surfactant with respect to the total mass of the surfactant is preferably 80 to 100% by mass, and more preferably 85 to 100% by mass.
Moreover, 50-100 mass% is preferable, as for the ratio of (A) component among the total amount (100 mass%) of (A) component and nonionic surfactant, 55-97 mass% is more preferable, and 60-95 mass. % Is more preferable. When the proportion of the component (A) is not less than the lower limit of the above range, the recontamination prevention property is hardly lowered, and if it is not more than the upper limit, the dispersion stability of water-insoluble particles such as capsule fragrance is lowered at low temperature. Hateful.

The liquid detergent may contain a known nonionic surfactant. A nonionic surfactant may be used individually by 1 type, and may be used in combination of 2 or more type.
As the nonionic surfactant, a linear or branched alcohol alkoxylate represented by the following formula (5) is preferable.
R ⁴¹ —O— (AO) _x —H (5)
In Formula (5), R ⁴¹ is a linear or branched hydrocarbon group having 8 to 18 carbon atoms, AO is an oxyalkylene group having 2 to 4 carbon atoms, and x is an average of oxyalkylene groups. It represents the number of repetitions and is a number from 0 to 30.

In the formula (5), examples of R ⁴¹ include a linear or branched alkyl group, or a linear or branched alkenyl group. The number of carbon atoms of R ⁴¹ is from 8 to 18, preferably from 10 to 16 from the viewpoint of the coating detergency improving, 10 to 14 is more preferable.
AO may be any one of an oxyethylene group, an oxypropylene group, and an oxybutylene group, or a mixture of two or more of these.
Among AO, at least one alkenyl group composed of an oxyethylene group and an oxypropylene group is preferable, and an oxyethylene group is more preferable. When two or more of an oxyethylene group, an oxypropylene group or an oxybutylene group are mixed, these may be mixed in a random form or in a block form.
In said Formula (5), x is a number of 0-30, and the number of 3-15 is preferable from the point of application | coating washing | cleaning property and storage stability, and the number of 3-10 is more preferable.
X represents the “average” number of repetitions of the oxyethylene group. That is, the linear or branched alcohol alkoxylate represented by the formula (5) is an aggregate of molecules having different oxyethylene group repeating numbers. Alternatively, it may be an assembly of different molecules of R ⁴¹ .
As a combination of an anionic surfactant and a nonionic surfactant, a combination of LAS, AES, MES and alcohol ethoxylate, a combination of AES, MES and alcohol ethoxylate, or a combination of LAS, AES and alcohol ethoxylate is preferable.

[Cationic surfactant]
Conventionally known cationic surfactants can be appropriately selected and used. Specific examples include dodecyl trimethyl ammonium salt, cetyl trimethyl ammonium salt, cetostearyl trimethyl ammonium salt, stearyl trimethyl ammonium salt, behenyl trimethyl ammonium salt, didecyl dimethyl ammonium salt, benzalkonium chloride and the like. When the liquid detergent of the present invention contains a cationic surfactant, the blending amount is 0.1 to 2% by mass with respect to the total mass of the liquid detergent from the viewpoints of detergency, antibacterial activity, and appearance stability. Is preferred.

[Amphoteric surfactant]
Examples of amphoteric surfactants include alkylbetaine type, alkylamide betaine type, imidazoline type, alkylaminosulfone type, alkylaminocarboxylic acid type, alkylamidecarboxylic acid type, amide amino acid type, and phosphoric acid type amphoteric surfactant. It is done. When the liquid detergent of the present invention contains an amphoteric surfactant, the blending amount thereof is preferably 0.1 to 1% by mass with respect to the total mass of the liquid detergent from the viewpoint of detergency and appearance stability.

[Semipolar surfactant]
As the semipolar surfactant, a conventionally known one can be appropriately selected and used. Specifically, dodecyl dimethylamine oxide, lauric acid amide propylamine oxide, etc. are mentioned. When the liquid detergent of the present invention contains a semipolar surfactant, the blending amount thereof is preferably 0.1 to 1% by mass with respect to the total mass of the liquid detergent from the viewpoint of detergency and appearance stability. .

The liquid detergent of the present invention preferably contains a water-miscible organic solvent.
Examples of water-miscible organic solvents include alcohols such as ethanol, 1-propanol, 2-propanol and 1-butanol, glycols such as propylene glycol, butylene glycol and hexylene glycol, diethylene glycol, triethylene glycol, tetraethylene glycol, Examples include polyglycols such as polyethylene glycol and dipropylene glycol having a mass average molecular weight of about 200 to 1000, alkyl ethers such as diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, diethylene glycol monobutyl ether (butyl carbitol), and diethylene glycol dimethyl ether. .
Among these, ethanol, propylene glycol, polyethylene glycol, and diethylene glycol monobutyl ether (butyl carbitol) are preferable from the viewpoints of low odor, availability, liquid stability when used as a liquid detergent, fluidity, and the like.
A water-miscible organic solvent may be used individually by 1 type, and may be used in combination of 2 or more type.
The content of the water-miscible organic solvent is preferably 0.3 to 20% by mass with respect to the total mass of the liquid detergent.
In the present invention, the water-miscible organic solvent means an organic solvent that dissolves 50 g or more in 1 L of ion-exchanged water at 25 ° C.

  Examples of organic acids include malonic acid, succinic acid, malic acid, diglycolic acid, tartaric acid, citric acid, aminocarboxylic acid, lactic acid, benzoic acid, paratoluenesulfonic acid, metaxylenesulfonic acid, etc., and their sodium and potassium salts For example, 0.05-5 mass% can be included with respect to the total mass of a liquid detergent. An organic acid may be used individually by 1 type, and 2 or more types may be used in combination. Of these, citric acid, aminocarboxylic acid, lactic acid, benzoic acid, paratoluenesulfonic acid, metaxylenesulfonic acid and sodium salts thereof are preferred.

  As antioxidant, butylhydroxytoluene, distyrenation cresol, sodium sulfite, sodium hydrogensulfite, etc. can be contained 0.01-2 mass% with respect to the total mass of a liquid cleaning agent, for example. An antioxidant may be used individually by 1 type and may be used in combination of 2 or more type.

  For the purpose of improving washing performance and stability, enzymes (proteases, lipases, cellulases, amylases, mannanases, etc.), enzyme stabilizers (boric acid, borax, formic acid or salts thereof, benzoic acid, lactic acid or salts thereof and Calcium salts such as calcium chloride and calcium sulfate), texture improver, alkali builder such as alkanolamine, hydrotrope agent, fluorescent agent, dye transfer inhibitor, recontamination inhibitor, pearl agent, soil release agent, etc. it can.

[Fragrance precursor]
In this specification, the fragrance precursor refers to a compound obtained by chemically combining a fragrance and a non-volatile substrate. Although the fragrance precursor itself does not give a fragrance, the fragrance is released when the bond between the fragrance and the substrate is cut by a trigger such as heat, light, water, etc. to give a fragrance. For this reason, it is known that when a garment is washed with a liquid detergent containing a fragrance precursor, the effect as a fragrance is exhibited even after the garment is worn or stored.
The fragrance precursor is not particularly limited as long as it has the effects of the present invention, and those generally used for detergents such as garment detergents can be used.
In this invention, a fragrance | flavor precursor should just be suitably selected according to the kind etc. of a fragrance | flavor precursor, for example, the fragrance | flavor precursor (sulfur containing fragrance | flavor precursor) containing sulfur etc. are mentioned.
As a sulfur containing fragrance | flavor precursor, the compound represented by the following general formula (d-1) is mentioned, for example.

JSGQ (d-1)
However, in formula (d-1), J represents at least one group selected from the group consisting of groups represented by the following chemical formulas (J-1) to (J-7) and isomers thereof. Represents. In the following chemical formulas (J-1) to (J-7), the wavy line represents a bond that bonds to S. In the following chemical formulas (J-1) to (J-2), a dotted line means that one or more bonds between carbon atoms provided with a dotted line are double bonds. In the following chemical formula (J-4), j represents an integer of 0 to 20.
S is a sulfur atom.
G represents a linear or branched hydrocarbon group having 2 to 15 carbon atoms which may have a substituent.
Q is a group represented by —S—J, a group represented by —NR ⁶¹ —J, or a hydrogen atom. However, S in the group represented by -S-J is a sulfur atom, J represents a group represented by the following chemical formulas (J-1) to (J-7), and a group consisting of these isomers. Represents at least one group selected from N in the group represented by —NR ⁶¹ —J is a nitrogen atom, J is the same as J in the group represented by —SJ, and R ⁶¹ is a hydrogen atom or a methyl group.

“These isomers” in J in the above formula (d-1) are isomers in which the groups represented by the chemical formulas (J-1) to (J-7) can be taken from the chemical structure, for example, stereo Isomers and the like.
In the chemical formula (J-4), j is an integer of 0 to 20 (when j is 0 (J-4) is a 5-membered ring), and an integer of 5 to 15 is preferable.
As J in the formula (d-1), a group represented by the chemical formula (J-1) and a group represented by the chemical formula (J-2) are preferable.
In the above formula (d-1), G may be a saturated hydrocarbon group or an unsaturated hydrocarbon group. As G, an alkyl group or an alkenyl group is preferable, and a linear alkyl group is more preferable. As for carbon number of the hydrocarbon group in G, 10-14 are preferable. Examples of the substituent of the hydrocarbon group in G include —OR ⁶² , —N (R ⁶² ) ₂ , —COOR ⁶² (wherein R ⁶² is an alkyl group having 1 to 6 carbon atoms or 1 to 1 carbon atoms, respectively). 6 represents an alkenyl group or a hydrogen atom).

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

  Moreover, as another fragrance | flavor precursor other than the above, the compound represented by the following general formula (I) is mentioned, for example.

In formula (I), Y represents a group represented by the following chemical formula (I-1) or (I-2).
R ¹ is a linear hydrocarbon group having 1 to 30 carbon atoms, a branched hydrocarbon group having 1 to 30 carbon atoms, an alicyclic hydrocarbon group having 1 to 30 carbon atoms, or an aromatic group having 6 to 30 carbon atoms. Is at least one selected from
R ¹ may have at least one selected from an oxygen atom, a carbonyl group (CO group), an alkoxy group, and a silyl group. R ¹ may be linear or branched. R ¹ may be a saturated hydrocarbon group or an unsaturated hydrocarbon group.
Examples of R ¹ include nonyl alcohol, 3,5,5-trimethyl-hexanol, cis-6-nonenol, 2,6-nonadien-1-ol, 2-phenylpropanol, 3-phenylpropanol, 2- (2 -From methylphenyl) -ethanol, cinnamyl alcohol, ethyl vanillin, 4-isopropyl-cyclohexanol, 3,3,5-trimethyl-cyclohexanol, 2-cyclohexyl-propanol and 2,6-dimethyl-heptan-2-ol Examples thereof include hydrocarbon groups derived from at least one selected.
R ² in the 2- or 3-position represents a hydrogen atom or a methyl group.

In formulas (I-1) and (I-2), R ³ and R ⁴ each independently represent a hydrogen atom, a linear alkyl group having 1 to 6 carbon atoms, or a C 1 to 6 carbon atom. A five-membered member containing at least one selected from a branched alkyl group, a linear alkoxy group having 1 to 6 carbon atoms, a branched alkoxy group having 1 to 6 carbon atoms, a nitrogen atom and an oxygen atom A heterocyclic group, a 5-membered heterocyclic group substituted with at least one selected from aliphatic and aromatic substituents having 1 to 6 carbon atoms (having oxygen and nitrogen atoms as heteroatoms), -OH, -NO _{^{2, -NH 2, -NR 71 2}} , -NHCO 2 CH 3, or an ^{-NR 72.} However, ^R71 represents a C1-C6 linear alkyl group, a C1-C6 branched alkyl group, or a C1-C6 hydroxyalkyl group. R ⁷² represents a C 3-6 heterocycle having a nitrogen atom (which may contain an oxygen atom as a hetero atom).
X represents —OH, —NHR ⁷³ or —SiR ⁷⁴ .
R ⁷³ is a hydrogen atom, a linear saturated hydrocarbon group having 1 to 20 carbon atoms, a linear unsaturated hydrocarbon group having 1 to 20 carbon atoms, or a branched saturated carbon atom having 1 to 20 carbon atoms. A hydrogen group, a branched unsaturated hydrocarbon group having 1 to 20 carbon atoms, an aromatic group or a heterocyclic group having a specific carbon number (having nitrogen and oxygen atoms as heteroatoms);
When R ⁷³ is an unsaturated hydrocarbon group, this unsaturated hydrocarbon group preferably has the E configuration.
R ⁷⁴ represents a linear alkyl group having 1 to 6 carbon atoms or a branched alkyl group having 1 to 6 carbon atoms.
R ² , R ³ and R ⁴ in formulas (I), (I-1) and (I-2) may be the same or different.

In formula (I), R ¹ may include both a chain of an alicyclic moiety and a chain of an aromatic moiety in one R ¹ group. For example, such R ¹ includes a hydrocarbon group derived from a predetermined alcohol (R ¹ OH), an enol-type group of a predetermined aldehyde (R ¹ HO), or a predetermined ketone (R ¹ O). Examples include enol-type groups.
R ¹ is preferably dec-9-enyl, ethyl, 2-ethyl-4- (2,2,3-trimethyl-cyclopent-3-enyl) -but-2-enyl, 3-methyl-5 -Phenyl-pentyl, 3- (3-isopropyl-phenyl) -but-1-enyl, 1-ethoxy-3- (3-isopropyl-phenyl) -butyl, 3- (4-tert-butyl-phenyl)- 1-ethoxy-propyl, methyl, 3,7-dimethyl-oct-6-enyl, or phenethyl. More preferred are dec-9-enyl, ethyl, 3,7-dimethyl-oct-6-enyl, and phenethyl.
In formulas (I-1) and (I-2), R ³ and R ⁴ are each independently hydrogen, a linear alkyl group having 1 to 6 carbon atoms, or a branched chain having 1 to 6 carbon atoms. Is preferably a linear alkoxy group having 1 to 6 carbon atoms or a branched alkoxy group having 1 to 6 carbon atoms, hydrogen, a linear alkyl group having 1 to 6 carbon atoms, or It is more preferably a branched alkyl group having 1 to 6 carbon atoms.
R ³ and R ⁴ are each independently preferably hydrogen, a linear alkyl group having 1 to 4 carbon atoms, or a branched alkyl group having 1 to 4 carbon atoms, and hydrogen, 1 to 3 carbon atoms. A linear alkyl group or a branched alkyl group having 1 to 3 carbon atoms is more preferable, hydrogen, a methyl group or an ethyl group is particularly preferable, and hydrogen is most preferable.

The perfume precursor is easily available on the market and can also be synthesized by a known method.
Any one of the perfume precursors may be used alone, or two or more of the perfume precursors may be used in combination.
When the liquid detergent of the present invention contains a fragrance precursor, the content of the fragrance precursor in the liquid detergent is preferably 0.0001 to 3% by mass relative to the total mass of the liquid detergent. 001-0.5 mass% is more preferable, 0.006-0.2 mass% is further more preferable, and 0.01-0.1 mass% is especially preferable.
When the content of the fragrance precursor is not less than the preferable lower limit, the fragrance strength is further increased, and the fragrance maintenance property is further increased. On the other hand, if it is less than said preferable upper limit, since a fragrance does not remain strongly, it is preferable.

Coloring agents include Acid Red 138, Polar Red RLS, Liquidint PIN AL, Acid Yellow 203, Liquid Bright
General-purpose dyes and pigments such as Yellow, Acid Blue 9, Blue No. 1, Blue No. 205, Green No. 3, Turquoise P-GR, Liquid Blue BLE SE, Levanyl Violet (all trade names), for example, liquid detergent About 0.00005-0.005 mass% can be included with respect to the total mass.

  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. Specific examples include polystyrene emulsion (trade name: Cybinol (registered trademark) RPX-196 PE-3, solid content 40% by mass, manufactured by Seiden Chemical Co., Ltd.), Opulyn 301, Acusol OP 301, etc. 0.001 to 0.5 mass% can be included with respect to the total mass.

  As the fragrance other than the capsule fragrance for fragrance, a conventionally known one can be appropriately selected and used. As for the compounding quantity of the said fragrance | flavor, 0.01-2 mass% is preferable with respect to the total mass of a liquid detergent.

The liquid detergent of the present invention preferably has a pH of 6 to 10 at 30 ° C., more preferably 7 to 9.5. When the pH is in such a range, the dispersion stability of water-insoluble particles such as capsule flavors in the liquid detergent composition can be favorably maintained.
The pH of the liquid detergent can be adjusted by blending a pH adjuster as necessary. The pH adjuster is optional as long as the effects of the present invention are not impaired, but sulfuric acid, hydrochloric acid, sodium hydroxide, potassium hydroxide, alkanolamine and the like are preferable from the viewpoint of enzyme stability.

(Production method)
The liquid detergent of the present invention is produced by a conventionally known production method.
The manufacturing method of a liquid detergent is obtained by disperse | distributing (A)-(C) component and another component as needed to the water which is a dispersion medium, for example.

(how to use)
As a method of using the liquid detergent, for example, a liquid detergent alone or in a water together with a known bleaching agent or softening agent is used as a washing liquid. Or a method of applying a liquid cleaning agent to an object to be washed and washing it with a washing machine.
Examples of the articles to be washed include textiles such as clothes, fabrics, sheets, curtains, and carpets.
Since the liquid cleaning agent of the present invention is also excellent in coating and cleaning properties, it can be suitably used for a method of washing directly with a washing machine and then washing with a washing machine.
The content of the liquid cleaning agent in the cleaning liquid is not particularly limited. The amount of the liquid detergent added to water is preferably 0.5 to 30 mL per 10 L of water, for example.

  The liquid detergent of the present invention comprises components (A) to (C), a nonionic surfactant, water-insoluble particles, and water, and (A) the component is selected from the group consisting of MES, AES, and LAS. It is preferable that the component (C) is EPEI (ethylene oxide adduct of polyethyleneimine).

  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)
The abbreviations in Tables 1 to 4 represent the following.
MES: sodium salt of α-sulfo fatty acid ester (in formula (a1), R ³ is an alkyl group having 14 carbon atoms, α-sulfo fatty acid ester salt (C16), and in formula (a1), R ³ is carbon number Mixture of α-sulfo fatty acid ester salt (C18) which is an alkyl group of 16 (mixing mass ratio C16 / C18 = 8/2) (manufactured by Lion Eco Chemicals Sdn. Bhd., Trade name: “MIZULAN (registered trademark) FL” -80 ").
AES: ether sulfate having an alkyl group having 12 or 14 carbon atoms obtained by adding an average of 2 moles of alkylene oxide having 2 carbon atoms (trade name: “EMAL (registered trademark) 270N” manufactured by Kao Corporation).
LAS: linear or branched alkylbenzene sulfonate having an alkyl group having 8 to 18 carbon atoms ("Lypon (registered trademark) LH-200" (trade name) manufactured by Lion Specialty Chemicals Co., Ltd.) Neutralized with sodium hydroxide).
EZ4: a crosslinked polymer (in formula (1), R ⁵ is hydrogen, in formula (2), R ⁷ is a methyl group, and R ⁸ is an alkyl group having 10 to 30 carbon atoms) Polymer) (manufactured by Lubrizol, trade name: Carbopol EZ4).
Aqua 30: cross-linked polymer (in formula (1), R ⁵ is hydrogen, in formula (2), R ⁷ is a methyl group, and R ⁸ is an alkyl group having 1 to 6 carbon atoms) Polymer (manufactured by Lubrizol, trade name: Carbopol Aqua 30).
EZ2: A homopolymer of acrylic acid (manufactured by Lubrizol, trade name: “Carbopol EZ2”).
EPEI: Polyethyleneimine ethylene oxide adduct (in the formula (3-a), R ²² is an ethylene group, m is 20, a compound having a mass average molecular weight of 15000, AI (pure content) = 80%) (product of BASF, product) Name: “Sokalan HP20”).
AE5: polyoxyethylene alkyl ether (alcohol alkoxylate in which R ¹ is an alkyl group having 12 to 14 carbon atoms, AO is an oxyethylene group, and x is 5 in the formula (5)) (manufactured by THAI ETHOXYLATE) , Trade name: “DEHYDOL (registered trademark) LS5 TH”).
AE7: polyoxyethylene alkyl ether (alcohol alkoxylate in which R ¹ is an alkyl group having 12 to 14 carbon atoms, AO is an oxyethylene group, and x is 7 in formula (5)) (manufactured by ECOGREEN OLEOCHEMICALS) , Trade name: “ECOLAT (registered trademark) 24-7”).
Protease: (manufactured by Novozymes, trade name: “Savinase Evity 16L”).
Calcium chloride: (Kanto Chemical Co., Ltd., trade name: “Calcium chloride”).
Benzoic acid: Sodium benzoate (manufactured by Toagosei Co., Ltd., trade name: “Sodium benzoate”).
Citric acid: (Kanto Chemical Co., Ltd., trade name: “citric acid”).
MEA: monoethanolamine (Nippon Shokubai Co., Ltd., trade name: “monoethanolamine”).
Capsule fragrance: (INTERITIONAL FLAGORS & FRAGRANCES, trade name: “Mysterious Fly M2”).
Perfume precursor 1: 3- (dodecylthio) -1- (2,6,6-trimethylcyclohex-3-en-1-yl) -1-butanone (described in Example 4 of JP 2005-511710 A) Compound: In the above general formula (d-1), J is a group represented by the chemical formula (J-1) (having a double bond between the 3rd and 4th positions), G is a dodecyl group, and Q is a hydrogen atom. Compound).
Perfume precursor 2: 4- (dodecylthio) -4- (2,6,6-trimethylcyclohex-2-en-1-yl) -2-butanone (dodecanethiol (manufactured by Tokyo Chemical Industry Co., Ltd.) as a raw material) A compound synthesized in the same manner as in the synthesis method described in Example 4 of JP-T-2005-511710 using β-Yonon (manufactured by Ve Manfis Fragrance Co., Ltd.), wherein J in the general formula (d-1) is A group represented by the chemical formula (J-2) (having a double bond between positions 1 and 2, a compound in which G is a dodecyl group and Q is a hydrogen atom).
Perfume precursor 3: (E) -3- (2-hydroxyphenyl) -acrylic acid dec-9-enyl ester (compound described in paragraph No. 0040 of JP-A No. 2000-63328).
Perfume precursor 4: (E) -3- (2-hydroxy-5-methyl-phenyl) -acrylic acid ethyl ester (compound described in paragraph No. 0038 of JP-A No. 2000-63328).
Perfume precursor 5: (E) -3- (2-hydroxy-phenyl) -2-methyl-acrylic acid 3,7-dimethyl-oct-6-enyl ester (see paragraph No. 0034 of JP-A-2000-63328) Described compounds).
Perfume precursor 6: (E) -3- (2-hydroxy-phenyl) -2-methyl-acrylic acid phenethyl ester (compound described in paragraph No. 0035 of JP-A No. 2000-63328).
Water: Purified water.
In addition, the content “balance” of water in the table is an amount necessary to make the liquid detergent 100% by mass as a whole.
Moreover, "MES / B" in a table | surface represents the mass ratio of MES in a liquid cleaning agent, and (B) component.
“Surfactant / B” represents the total mass of the surfactant in the liquid detergent and the mass ratio of the component (B). “C / B” represents the mass ratio of the component (C) and the component (B) in the liquid detergent. “Nonion / anion” represents a mass ratio of the nonionic surfactant and the component (A) (anionic surfactant) in the liquid detergent.

(Examples 1-24, Comparative Examples 1-3)
According to the composition shown in Tables 1 to 4, the components (A) to (C) and optional components and water are all stirred and mixed, and an aqueous NaOH solution or an aqueous HCl solution is used as necessary so that the pH is 9.2. The pH was adjusted to obtain a liquid detergent.
In addition, the compounding quantity in a table | surface is a pure part conversion value. Moreover, the component whose compounding quantity is not described in the table | surface is not mix | blended.

<Evaluation method>
(Evaluation of thickening and structuring)
60 g of the liquid cleaning composition of each example was filled in a glass bottle and adjusted to 30 ° C. in a thermostatic bath. A sample solution adjusted to 30 ° C. was set in a Brookfield viscometer (B type viscometer). _First , the rotational speed of the rotor was set to 6 rpm, and the viscosity v1 after 60 seconds was measured. Then, set the rotational speed of the rotor 60 rpm, the viscosity was measured _{v 2} after 60 seconds. Regarding the relationship between the viscosity v ₁ and the viscosity v _2, the thickening and structuring were evaluated according to the following evaluation criteria. In addition, when the determination results of the viscosity v ₂ were A and B and the determination results of the structuring were A and B, it was determined that the thickening and structuring of the liquid composition was sufficiently advanced. The results are shown in Tables 1-4.
[Evaluation criteria (viscosity v ₂ )]
A: viscosity of less than _{v 2} is 400mPa · s or more 4000mPa · s.
B: viscosity of less than _{v 2} is 100mPa · s or more 400mPa · s.
C: Viscosity v ₂ is less than 100 mPa · s, or 4000 mPa · s or more.
[Evaluation criteria (structured)]
A: The value of (viscosity v ₁ ) / (viscosity v ₂ ) is 2.5 or more.
B: The value of (viscosity v ₁ ) / (viscosity v ₂ ) is 1.9 or more and less than 2.5.
C: The value of (viscosity v ₁ ) / (viscosity v ₂ ) is less than 1.9.

(Evaluation of dispersion stability)
After 60 g of the liquid cleaning composition of each example was filled in a glass bottle and stored in a thermostatic bath at 20 ° C. and 50 ° C. for 1 month, it was visually confirmed and the dispersion stability was evaluated according to the following evaluation criteria. The results are shown in Tables 1 to 4 with a dispersion stability evaluation of 1 at 20 ° C. and a dispersion stability evaluation of 2 after 1 month at 50 ° C.
[Evaluation criteria]
A: There is no precipitation or suspended matter, and the appearance is uniform.
B: Precipitation, suspension, and precipitation are present.

(Normal cleaning performance evaluation)
The washability against protein stains was evaluated by a normal washing method.
First, using a color difference meter (manufactured by Nippon Denshoku Industries Co., Ltd., product name: SE-2000), the absolute reflectance R of five artificially contaminated cloths before washing was measured. The absolute reflectance R was calculated from Hunter chromaticity Z as R = Z / 100 (hereinafter, the reflectance R was measured by the same method). Using Terg-O-Tometer (manufactured by U.S. Testing) as a cleaning tester, 5 artificially contaminated cloths and charge cloth (finely cut knitted cloth, washed thoroughly, rinsed and dried) The same applies hereinafter) were weighed so that the bath ratio (washing water / total weight of washing object) was 30 times, and placed in a washing tub. Then, what put liquid detergent in 2000 mL of 25 degreeC 3 degree DH hard water so that a density | concentration might be 2000 ppm was added to the washing tub. After washing for 10 minutes under the conditions of a rotation speed of 120 rpm and a temperature of 25 ° C., rinsing treatment was performed twice with 900 mL of 3 ° DH hard water at 25 ° C. for 3 minutes. After the rinsing treatment, the article to be washed was dried, the reflectance of the artificially contaminated cloth after washing was measured using a 460 nm filter, and the washing rate was calculated by the following formula. In addition, the value after the decimal point was rounded off.

上記数式中、汚染布とは上記人工汚染布を意味し、洗浄布とは前記汚染布を洗浄した後の布を意味し、未汚垢布とは、汚れを付着させていない元の白布（原布）を意味する。また、Ｋは吸光係数、Ｓは散乱係数、Ｒは絶対反射率を表す。なお、原布のＲは８０とした。

In the above formula, the contaminated cloth means the artificially contaminated cloth, the cleaning cloth means a cloth after the contaminated cloth is washed, and the unstained cloth is an original white cloth (not attached with dirt) ( Raw fabric). K represents an extinction coefficient, S represents a scattering coefficient, and R represents an absolute reflectance. The R of the raw cloth was 80.

It means that the larger the value of the obtained washing rate, the better the normal washing property. The average value of the washing rate of the five artificially contaminated cloths was obtained and evaluated according to the following evaluation criteria. In addition, among the following evaluation criteria, A and B were determined to be acceptable (usually excellent in cleanability). The results are shown in Tables 1-4.
[Evaluation criteria]
A: The average value of the cleaning rate is 74% or more.
B: The average value of the cleaning rate is 70% or more and less than 74%.
C: The average value of the cleaning rate is less than 70%.

(Evaluation of coating cleaning properties)
Evaluation of detergency against sebum dirt was performed by applying a liquid detergent directly to the soiled area.
Using a color difference meter (manufactured by Nippon Denshoku Industries Co., Ltd., product name: SE-2000), the absolute reflectance R of five artificially contaminated cloths before washing was measured. Using a Terg-O-Tometer (manufactured by U.S. Testing) as a cleaning tester, weighed 0.36 g of each liquid detergent and applied 5 pieces of artificially contaminated cloth to the soil for 5 minutes, and a charge cloth Was weighed so that the bath ratio would be 30 times, put in a washing tub, and 900 mL of 3 ° DH hard water at 25 ° C. was added.
After washing for 10 minutes under the conditions of a rotation speed of 120 rpm and a temperature of 25 ° C., rinsing treatment was performed twice with 900 mL of 3 ° DH hard water at 25 ° C. for 3 minutes. After the rinsing treatment, the article to be washed was dried, the reflectance of the artificially contaminated cloth after washing was measured using a 460 nm filter, and the washing rate was calculated by the above formula. In addition, the value after the decimal point was rounded off.
It means that it is excellent in application | coating washing | cleaning property, so that the value of the obtained washing | cleaning rate is large. The average value of the washing rate of the artificially contaminated cloth was determined and evaluated according to the following evaluation criteria. In addition, among the following evaluation criteria, A was determined to be acceptable (excellent in application cleaning properties). The results are shown in Tables 1-4.
[Evaluation criteria]
A: The average value of the cleaning rate is 85% or more.
B: The average value of the cleaning rate is less than 85%.

(Evaluation of recontamination prevention)
Using the obtained liquid detergent, a washing process in which the following washing process, rinsing process, and drying process were repeated three times in this order was performed.
Cleaning process:
The following cotton cloth, wet artificial contamination cloth and skin shirt were used as the objects to be washed.
Cotton: Recontamination determination cloth. Five cotton knitted fabrics (made by Tanigami Shoten, cut into 5cm x 5cm squares).
Wet artificial contamination cloth: Contamination cloth manufactured by Japan Association for Laundry Science (28.3% oleic acid, 15.6% triolein, 12.2% cholesterol oleate, 2.5% liquid paraffin, 2.5% squalene, cholesterol 20 sheets of fabric with 1.6% gelatin, 7.0% gelatin, 29.8% mud, and 0.5% carbon black (mass ratio).
Skin shirt: A skin shirt (LL size, manufactured by BVD) cut to about 3 cm × 3 cm.
In a Terg-O-meter (manufactured by U.S. Testing), 900 mL of 3 ° DH hard water at 25 ° C. was added, 1.8 g of each liquid cleaning agent was added thereto, and then the article to be cleaned was added. Thereafter, 3 ° DH hard water was added to adjust the bath ratio to 30 times, and washing was performed at a rotation speed of 120 rpm and 25 ° C. for 10 minutes.
Rinsing process:
The object to be washed after the washing step was dehydrated for 1 minute, and then 900 mL of 3 ° DH hard water at 25 ° C. was added and rinsed at a rotation speed of 120 rpm and 25 ° C. for 3 minutes. This operation (dehydration, rinsing) was repeated twice. In the second time, a predetermined amount of softening agent (0.2 mL with respect to 900 mL of water) was added to 900 mL of 3 ° DH hard water at 25 ° C. for rinsing. As the softening agent, “sophane aroma rich of fragrance and deodorant” (trade name, manufactured by Lion Corporation) was used.
Drying process:
After the rinsing step, the object to be washed was dehydrated for 1 minute, and then only the recontamination determination cloth was taken out and sandwiched between filter papers and dried with an iron.
After the washing process is completed, the reflectance (Z value) of the recontamination determination cloth before and after the washing process is measured using a reflectometer (spectral color difference meter, product name: SE-2000, manufactured by Nippon Denshoku Industries Co., Ltd.). It measured and (DELTA) Z was calculated | required from the following Formula.
ΔZ = (Z value before washing process) − (Z value after washing process)
For ΔZ in the recontamination determination cloth, an average value of 5 sheets was obtained. And according to the following criteria, the recontamination prevention effect of the liquid detergent was evaluated. In addition, among the following evaluation criteria, A and B were judged to be acceptable (excellent in anti-recontamination property). The results are shown in Tables 1-4.
[Evaluation criteria]
A: ΔZ is less than 4.
B: ΔZ is 4 or more and less than 6.
C: ΔZ is 6 or more.

As shown in Tables 1 to 4, the liquid detergents of Examples 1 to 24 had good appearance evaluation, and the capsule flavor could be stably dispersed. From the results of the viscosity measurement, it is considered that the liquid detergents of these examples were able to stably disperse the capsule fragrance because the thickening and structuring proceeded sufficiently. Furthermore, the liquid cleaning agents of these examples also had good coating cleaning properties.
On the other hand, the liquid detergents of Comparative Examples 1 and 3 that do not contain the component (B) and the liquid detergent of Comparative Example 2 in which the content of the component (B) was more than 3% by mass have dispersion stability and coating washing. It was not possible to balance sex.
From the above results, it was confirmed that the liquid cleaning agent of the present invention was excellent in dispersion stability of water-insoluble particles such as capsule fragrances, and also had good coating cleaning properties.

Claims (3)

A crosslinked polymer having an anionic surfactant (A), a repeating unit derived from a monomer represented by the following formula (1), and a repeating unit derived from a monomer represented by the following formula (2) And (B) a liquid detergent composition for textiles,
The liquid for textiles characterized by content of the said (B) component being 0.1 to 3 mass% with respect to the total mass of the liquid detergent composition for said textiles Cleaning composition.

(In Formula (1), R ⁵ represents a hydrogen atom or a methyl group, R ⁶ represents a hydrogen atom. In Formula (2), R ⁷ represents a hydrogen atom or a methyl group, and R ⁸ represents carbon. Represents an alkyl group having 1 to 40 carbon atoms or a hydroxyalkyl group having 1 to 40 carbon atoms.)   The liquid detergent composition for textiles according to claim 1, wherein the component (A) contains an α-sulfo fatty acid ester salt.   Furthermore, the liquid detergent composition for textiles of Claim 1 or 2 containing the alkylene oxide adduct (C) of polyalkyleneamine.