JP2018059096A - Liquid detergent composition - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a liquid detergent composition excellent in dispersion stability of water-insoluble particles.SOLUTION: This invention relates to a liquid detergent composition, comprising: one or more surfactants (A) chosen from an anionic surfactant (A1) and a nonionic surfactant (A2); and a compound (B) whose molecular weight is 100 or more and which has an urea group in a molecule. Preferably the (A) component contains both the nonionic surfactant (A1) and the anionic surfactant (A2).SELECTED DRAWING: None

Description

  The present invention relates to a liquid detergent composition.

  In the liquid detergent composition for textile products such as clothing (hereinafter sometimes referred to as liquid detergent), for the purpose of improving the fragrance, or imparting aesthetic properties peculiar to the liquid detergent, Water-insoluble particles such as capsule flavors and beads may be added. In order to stably disperse such water-insoluble particles in a liquid detergent, a method of blending a structurant in the liquid detergent is known. The structurant can increase the viscosity of the liquid detergent or structure the liquid detergent so that the water-insoluble particles are less likely to precipitate, float and precipitate. “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.

On the other hand, in a concentrated liquid detergent composition (hereinafter sometimes referred to as a concentrated liquid detergent) containing 30% by mass or more of a surfactant with respect to the total mass of the liquid detergent, there is little free water. There is a problem that it is more difficult to stably disperse the water-insoluble particles.
For such a problem, Patent Document 1 describes a liquid detergent composition containing a surfactant, a cleaning aid, a specific amount of hardened castor oil, and microcapsules. According to the invention of Patent Document 1, microcapsules can be stably dispersed for a long period of time by blending specific hardened castor oil as a structuring agent.

Special table 2007-500288

Since the liquid detergent composition of patent document 1 is heated to near 90 degreeC and the hardened castor oil is emulsified, a heating / cooling installation is required at the time of manufacture. For this reason, there is a need for a detergent composition that does not require special equipment during production and that is excellent in dispersion stability of water-insoluble particles even when a concentrated liquid detergent is used.
Accordingly, an object of the present invention is to provide a liquid detergent composition having excellent dispersion stability of water-insoluble particles.

The present invention has the following aspects.
[1] One or more surfactants (A) selected from an anionic surfactant (A1) and a nonionic surfactant (A2), a compound having a molecular weight of 100 or more and having a urea group in the molecule (B And a liquid detergent composition.
[2] The liquid detergent composition according to [1], wherein the component (A) contains both a nonionic surfactant (A1) and an anionic surfactant (A2).
[3] The liquid detergent composition according to [1] or [2], wherein the mass ratio (A) / (B) of the component (A) and the component (B) is 1-1000.
[4] The liquid detergent composition according to any one of [1] to [3], comprising water-insoluble particles and water.

  According to the liquid detergent composition of the present invention, the dispersion stability of water-insoluble particles is excellent.

(Liquid detergent composition)
The liquid detergent composition of the present invention is a composition containing the component (A) and the component (B).

<(A) component>
The component (A) is one or more surfactants selected from an anionic surfactant (A1) and a nonionic surfactant (A2). (A) By containing a component, the liquid cleaning agent of this invention exhibits the washing | cleaning performance with respect to various stain | pollution | contamination.
As the component (A), only one of the component (A1) and the component (A2) may be used, or both the component (A1) and the component (A2) may be used.
Among these, the component (A) preferably includes a nonionic surfactant (A1) and an anionic surfactant (A2). (A) A cleaning performance can be improved more because a component contains a nonionic surfactant (A1) and an anionic surfactant (A2). Moreover, it becomes easy to adjust the viscosity of the liquid detergent to an appropriate range, and the dispersion stability of water-insoluble particles such as capsule fragrances is likely to be improved.

As content of (A) component in a liquid detergent, 10-60 mass% is preferable with respect to the total mass of a liquid detergent, 25-55 mass% is more preferable, 35-55 mass% is still more preferable. .
If the content of the component (A) in the liquid detergent is within the above range, the viscosity of the liquid detergent tends to be appropriate, and the dispersion stability of the water-insoluble particles tends to be better.

[Nonionic surfactant (A1)]
The nonionic surfactant (A1) (hereinafter sometimes simply referred to as the component (A1)) is not particularly limited as long as it has the effect of the present invention. For example, the polyoxyalkylene type nonionic surfactant, alkylphenol, carbon number of 8 to Alkylene oxide adducts such as 22 fatty acids or alkylamines having 8 to 22 carbon atoms, polyoxyethylene polyoxypropylene block copolymers, fatty acid alkanolamines, fatty acid alkanolamides, polyhydric alcohol fatty acid esters or alkylene oxide adducts thereof, polyvalent Examples include alcohol fatty acid ether, alkyl (or alkenyl) amine oxide, alkylene oxide adduct of hydrogenated castor oil, sugar fatty acid ester, N-alkyl polyhydroxy fatty acid amide, alkyl glycoside and the like. These may be used alone or in combination of two or more.
Among the above, the component (A1) includes a polyoxyalkylene type nonionic surfactant from the viewpoint that the viscosity of the liquid detergent is likely to be in an appropriate range and the dispersion stability of the water-insoluble particles is more easily improved. It is preferable.

As a polyoxyalkylene type nonionic surfactant, the compound (henceforth (a1) component) represented by the following general formula (a1) is mentioned, for example.
^{_{R 1 -X- (EO) s (}} PO) t -R 2 ··· (a1)
[In formula (a1), R ¹ represents a hydrocarbon group having 8 to 22 carbon atoms, —X— represents a divalent linking group, R ² represents a hydrogen atom, an alkyl group having 1 to 6 carbon atoms, or An alkenyl group having 2 to 6 carbon atoms is represented, EO represents an oxyethylene group, and PO represents an oxypropylene group. s represents the average number of repetitions of EO, and is a number from 3 to 20. t represents the average number of repetitions of PO and is a number from 0 to 6. ]

In the formula (a1), the hydrocarbon group of R ¹ has 8 to 22 carbon atoms, preferably 10 to 18 and more preferably 12 to 18. The hydrocarbon group may be linear or branched. Moreover, you may have an unsaturated bond.
In formula (a1), examples of the divalent linking group of —X— include —O—, —COO—, and —CONH—. The compound in which —X— is —O—, —COO— or —CONH— is a primary or secondary alcohol having 8 to 22 carbon atoms (R ¹ —OH or (R ¹ ) ₂ —CH—OH). A fatty acid amide having 8 to 22 carbon atoms (R ¹ —COOH) or a fatty acid amide having 8 to 22 carbon atoms (R ¹ —CONH) can be obtained as a raw material.
Wherein (a1), the number of carbon atoms in the alkyl group in ^{R 2} is 1-6, 1-3 are preferred. Moreover, carbon number of an alkenyl group is 2-6, and 2-3 are preferable.

s is a number representing the average number of repetitions of EO. That is, s is a number representing the average number of moles of ethylene oxide added.
s is the number of 3-20, the number of 5-18 is preferable, and the number of 7-16 is more preferable. If the average number of repetitions s of EO is in the above range, it is easy to suppress the HLB value from becoming too high and deteriorating the cleaning performance for sebum cleaning.
t is a number representing the average number of repetitions of PO. That is, t is a number representing the average number of moles of propylene oxide added.
t is a number from 0 to 6, and a number from 0 to 3 is preferred. When the average number of repetitions t of PO is 6 or less, the storage stability of the liquid detergent at high temperatures (ie, 40 to 60 ° C.) is unlikely to decrease.
When t is 1 or more, that is, when the component (a1) is an adduct to which both EO and PO are added, the addition method of EO and PO is not particularly limited, and may be, for example, random addition Block addition may also be possible. As a block addition method, for example, a method of adding PO after adding EO; a method of adding EO after adding PO; a method of adding PO after adding EO, and further adding EO Is mentioned.

In the component (a1), the distribution of the added mole number of ethylene oxide and the distribution of the added mole number of propylene oxide are not particularly limited as long as the effects of the present invention are obtained.
The added mole number distribution varies depending on the reaction method in producing the component (a1). For example, ethylene oxide or propylene oxide is added to hydrocarbon group raw materials (primary or secondary higher alcohols, higher fatty acids, higher fatty acid amides, etc.) using a general alkali catalyst such as sodium hydroxide or potassium hydroxide. When this is done, the distribution of added moles of EO or PO tends to be relatively wide. Also, specific alkoxylation such as magnesium oxide to which metal ions such as Al ³⁺ , Ga ³⁺ , In ³⁺ , Tl ³⁺ , Co ³⁺ , Sc ³⁺ , La ³⁺ , Mn ^{2+ and the} like described in Japanese Patent Publication No. 6-15038 are added. When ethylene oxide or propylene oxide is added to the hydrocarbon group raw material using a catalyst, the added mole number distribution of EO or PO tends to be a relatively narrow distribution.

As the component (a1), in particular, a compound in which —X— is —O— (alkyl (alkenyl) ether type surfactant); —X— is —COO—, and R ² has 1 to 6 carbon atoms. A compound (fatty acid alkyl (alkenyl) ester type surfactant) which is an alkyl group or an alkenyl group having 2 to 6 carbon atoms is preferred.
When -X- is -O-, the carbon number of R ¹ is preferably 10-22, more preferably 10-20, and particularly preferably 10-18. R ² is preferably a hydrogen atom.
When -X- is -COO-, the carbon number of R ¹ is preferably 9-21, more preferably 11-21. R ² is preferably an alkyl group having 1 to 6 carbon atoms or an alkenyl group having 2 to 6 carbon atoms, and more preferably an alkyl group having 1 to 3 carbon atoms.

  The (a1) component in which —X— is —O— or —COO— may be a commercially available product. Specific examples of commercially available products include Diadol (registered trademark) manufactured by Mitsubishi Chemical Corporation (trade name, C13, C represents the number of carbons; the same shall apply hereinafter), Neodol (registered trademark) manufactured by Shell (trade name, C12). A mixture of C13 and C13), and Safo (registered trademark) 23 (trade name, a mixture of C12 and C13) manufactured by Sasol, etc., with 12 mol equivalent or 15 mol equivalent ethylene oxide added; A product obtained by adding 12 moles or 15 moles of ethylene oxide to a natural alcohol such as CO-1214 (trade name) or CO-1270 (trade name) manufactured by P &G; 7 mol equivalent of ethylene oxide added to C13 alcohol obtained by subjecting C12 alkene to oxo process (Lu manufactured by BASF) ensol (registered trademark) TO7 (trade name)); 7 mole equivalent of ethylene oxide added to C10 alcohol obtained by subjecting pentanol to garvet reaction (Lutensol XL70 (trade name) manufactured by BASF); 6 mole equivalent ethylene oxide added to C10 alcohol obtained by subjecting pentanol to gerbet reaction (BASF's Lutensol XA60 (trade name)); to C12-14 secondary alcohol, 9 mol equivalent or 15 mol equivalent of ethylene oxide added (Nippon Shokubai Co., Ltd. Softanol (registered trademark) 90 (trade name) or Softanol 150 (trade name)); Palm fatty acid methyl (lauric acid / myristic acid) = 8/2), using an alkoxylation catalyst, Obtained by adding the Le corresponding ethylene oxide (polyoxyethylene coconut fatty acid methyl ester (EO15 mol)) and the like.

As the component (a1), among the above, -X- is -COO-, R ² is an alkyl group having 1 to 6 carbon atoms, and t is 0, that is, a polyoxyethylene fatty acid alkyl ester. Polyoxyethylene fatty acid methyl ester (hereinafter sometimes referred to as “MEE”) in which R ² is a methyl group is preferable. That is, in the liquid cleaning agent of the present invention, it is particularly preferable that the component (A) contains MEE.
By containing the polyoxyethylene fatty acid alkyl ester, the solubility of the liquid cleaning agent of the present invention in water becomes better, and better cleaning performance is easily obtained. Further, even when the content of the surfactant in the liquid detergent is increased, a significant increase in viscosity (gelation) is unlikely to occur. Therefore, it is easy to obtain a concentrated liquid detergent having better fluidity.
Further, by combining a polyoxyethylene fatty acid alkyl ester such as MEE and the component (B), hydrogen bonds are likely to occur between the polyoxyethylene fatty acid alkyl ester and the component (B), and as a result, liquid washing The dispersion stability of the water-insoluble particles in the agent can be made better. In addition, the storage stability of the liquid detergent tends to be good.

The polyoxyethylene fatty acid alkyl ester is a nonionic surfactant having a weak molecular orientation in an aqueous solution system and unstable micelles. Therefore, gelation or the like hardly occurs even when polyoxyethylene fatty acid alkyl ester is blended at a high concentration. Therefore, the polyoxyethylene fatty acid alkyl ester can be blended in the liquid detergent alone and at a high concentration. In one aspect of the present invention, the content of the MEE in the liquid cleaning agent is preferably 5 to 50% by mass, more preferably 10 to 40% by mass, with respect to the total mass of the liquid cleaning agent, and 15 to 30. Mass% is particularly preferred.
Furthermore, since the polyoxyethylene fatty acid alkyl ester has good solubility in water, the concentration in the cleaning liquid tends to be uniform in a short time. Furthermore, the fluidity | liquidity of a liquid detergent tends to become better by mix | blending the said polyoxyethylene fatty-acid alkylester with a high concentration in a liquid detergent. Therefore, by including the polyoxyethylene fatty acid alkyl ester, it becomes easy to obtain a liquid cleaning agent having better cleaning performance.
Such a polyoxyethylene fatty acid alkyl ester is converted into a fatty acid alkyl ester by, for example, the method described in JP-A-2000-144179 or an alkoxylation catalyst prepared from a mixture of an alkaline earth metal compound and oxyacid. It can be produced by a method of adding an alkylene oxide or the like.

  In the component (a1), the narrow ratio obtained by the following mathematical formula (S) is preferably 20 to 60% by mass, and more preferably 30 to 45% by mass. If the narrow ratio of the component (a1) is 20 to 60% by mass, the effect of high detergency and liquid stability at low temperatures is easily obtained. Moreover, the said narrow rate can be controlled by the manufacturing method etc. of (a1) component, for example.

(In the formula (S), S _max represents the number of added moles of alkylene oxide (value of s + t) in the alkylene oxide adduct most frequently present in the component (a1). I represents the number of added moles of alkylene oxide. Yi represents the ratio (mass%) of the alkylene oxide adduct having the added number of moles of alkylene oxide present in component (a1) to i based on the total amount of component (a1).

Further, in one embodiment of the present invention, MEE and polyoxyethylene alkyl ether (in formula (a1), R ¹ is an alkyl group having 12 to 14 carbon atoms, -X- is -O-, An alcohol alkoxylate in which R ² is hydrogen, s is 15, and t is 0. Hereinafter, it may be preferably used in combination with “AE (15)”. By using MEE and AE (15) in combination, the dispersion stability of the water-insoluble particles can be improved more easily.
When MEE and AE (15) are used in combination, the content of AE (15) in the liquid detergent is preferably 1 to 15% by mass, and more preferably 2 to 10% by mass. Moreover, 1-20 are preferable and, as for the mass ratio (MEE / AE (15)) of MEE and AE (15) in a liquid detergent, 3-10 are more preferable.
As content of (A1) component in a liquid cleaning agent, 5-50 mass% is preferable with respect to the total mass of a liquid cleaning agent, and 15-40 mass% is more preferable. When the content of the component (A1) in the liquid detergent is 5 to 50% by mass, it is easy to obtain a high detergency effect.
Further, the content of the component (a1) in the liquid detergent is preferably 5 to 50 mass%, more preferably 10 to 40 mass%, particularly preferably 15 to 30 mass%, based on the total mass of the liquid detergent. preferable. When the content of the component (a1) in the liquid detergent is 5 to 50% by mass, high detergency is easily obtained.

[Anionic surfactant (A2)]
The anionic surfactant (A2) (hereinafter sometimes referred to as the component (A2)) is not particularly limited as long as it has the effect of the present invention. For example, linear alkylbenzenesulfonic acid or a salt thereof (LAS); α- Olefin sulfonate (AOS); linear or branched alkyl sulfate (AS); alkyl ether sulfate or alkenyl ether sulfate (AES); alkane sulfonate having an alkyl group; α-sulfo fatty acid Ester salt (MES); higher fatty acid salt and the like. Examples of salts in these anionic surfactants include alkali metal salts such as sodium and potassium, alkaline earth metal salts such as magnesium, and alkanolamine salts such as monoethanolamine and diethanolamine.
These may be used alone or in combination of two or more.

As the linear alkylbenzene sulfonic acid or a salt thereof, one having 8 to 16 carbon atoms in the linear alkyl group is preferable, and one having 10 to 14 carbon atoms is particularly preferable.
The α-olefin sulfonate is preferably one having 10 to 20 carbon atoms.
The alkyl sulfate ester salt is preferably an alkyl group having 10 to 20 carbon atoms.
The alkyl ether sulfate ester salt or alkenyl ether sulfate ester salt has a linear or branched alkyl group or alkenyl group having 10 to 20 carbon atoms, and an average of 1 to 10 moles of ethylene oxide added. What added -6 mol propylene oxide (namely, polyoxyethylene (propylene) alkyl ether sulfate ester salt or polyoxyethylene (propylene) alkenyl ether sulfate ester salt; AEPS) is preferable. When the alkyl ether sulfate ester salt or alkenyl ether sulfate ester salt is an adduct to which both ethylene oxide and propylene oxide are added, these may be random adducts or block adducts.
As the alkane sulfonate, those having 10 to 20 carbon atoms in the alkyl group are preferable, and those having 14 to 17 are more preferable. Among these, those in which the alkyl group is a secondary alkyl group (that is, secondary alkane sulfonate) are particularly preferable.
As the α-sulfo fatty acid ester salt, fatty acid residues having 10 to 20 carbon atoms are preferable.
The higher fatty acid salt preferably has 10 to 20 carbon atoms (preferably 12 to 18 carbon atoms), and preferably has 12 to 18 carbon atoms. Specific examples include soaps having the above carbon number, sodium coconut fatty acid and the like.
Among these, the component (A2) is 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. And at least one anionic surfactant selected from the group consisting of linear alkylbenzene sulfonic acid or a salt thereof, alkyl ether sulfate ester salt or alkenyl ether sulfate ester salt, and higher fatty acid salt It is more preferable to include an agent, and it is particularly preferable to include a linear alkylbenzene sulfonic acid or a salt thereof. If the component (A2) is any of these preferable anionic surfactants, the handling performance of the liquid detergent becomes better, and the anti-recontamination performance is excellent. Moreover, the rinsing property tends to be better.
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.

As the component (A2), other anionic surfactants other than those described above may be used. Examples of other anionic surfactants include carboxylic acid type anionic surfactants such as alkyl ether carboxylates, polyoxyalkylene ether carboxylates, alkyl (or alkenyl) amide ether carboxylates, and acylaminocarboxylates. And 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, and glycerin fatty acid ester monophosphoric acid ester salts.
These anionic surfactants can be easily obtained on the market.
The other anionic surfactants may be used alone or in combination of two or more.

The content of the component (A2) in the liquid detergent is preferably from 3 to 25 mass%, more preferably from 5 to 20 mass%, particularly preferably from 15 to 20 mass%, based on the total mass of the liquid detergent.
When the content of the component (A2) is 2% by mass or more, it becomes easy to obtain a liquid detergent excellent in recontamination prevention property, and the component (A2) is easily dispersed stably in the liquid detergent. Moreover, if content of (A2) component is 20 mass% or less, since it will be easy to suppress that a counter ion increases too much and gas absorption amount will increase, the storage container of a liquid cleaning agent becomes difficult to deform | transform.

  The mass ratio (A1) / (A2) of the component (A1) and the component (A2) in the component (A) is preferably 0.8 to 25 and more preferably 1 to 10 from the viewpoint of detergency. If (A1) / (A2) is within the above range, the cleaning power tends to be better.

<(B) component>
The component (B) is a compound having a molecular weight of 100 or more and having a urea group (—NHCONH—) in the molecule. The component (B) serves as a structurant, and by containing the component (B), a liquid detergent having excellent dispersion stability of water-insoluble particles such as capsule fragrance can be obtained. Even when the liquid detergent of the present invention is a concentrated liquid detergent, water-insoluble particles can be stably dispersed.

(B) The molecular weight of a component is 100 or more, 200 or more are preferable and 300 or more are more preferable. (B) The upper limit of the molecular weight of a component is not specifically limited, 100,000 or less are preferable and 70,000 or less are more preferable.
In addition, when (B) component is a polymer, the molecular weight of (B) component is a mass average molecular weight measured by gel permeation chromatography (GPC) method.
Component (B) is at least one selected from compounds represented by the following general formula (I) and at least one urea derivative selected from fatty acid-modified urea, modified urea, and polymer urea. Is preferred.

[In formula (I), ^{A, R 15,} or _{^{R 16 -Y- [R 14 -Y-}} R 13 -Y] b -R 12 -NR 11 - (CH 2) 2 -CO-Z-R 17 Represents.
B represents Y—R ¹⁶ or NR ¹¹ — (CH ₂ ) ₂ —CO—X—R ¹⁵ .
Y each independently represents one or more groups selected from COO, OCO, NHCO, CONH, NHCOO, OOCNH, and NHCONH.
Z represents an O, NH or NR ¹⁹ group.
R ¹¹ represents one or more groups selected from a hydrogen atom, (CH ₂ ) ₂ —CO—Z—R ¹⁵ , and CONH—R ′.
R ′ represents R ¹⁸ or C ₆ H ₃ (CH ₃ ) —NHCOOR ¹⁸ .
R ¹² , R ¹³ , R ¹⁴ and R ¹⁷ are each independently an alkylene group having 1 to 40 carbon atoms, an alkenylene group having 3 to 40 carbon atoms, a cycloalkylene group having 5 to 40 carbon atoms, or 5 to 5 carbon atoms. Represents an arylene group having 40 carbon atoms, an aralkylene group having 7 to 40 carbon atoms, a polyoxyalkylene group having 7 to 40 carbon atoms, or a polyester group having 7 to 40 carbon atoms in a fatty acid residue.
R ¹⁵ is a hydrogen atom, an alkyl group having 1 to 22 carbon atoms, an aryl group having 1 to 22 carbon atoms, an aralkyl group having 7 to 12 carbon atoms, a cycloalkyl group having 5 to 12 carbon atoms, or a 5 to 12 carbon atom. Hydroxyalkyl, N, N′-dialkylamino group having 5 to 12 carbon atoms, hydroxyl group, alkoxy group having 1 to 22 carbon atoms, cycloalkoxy group having 5 to 12 carbon atoms, aralkoxypoly having 7 to 12 carbon atoms An oxyalkylene group, a C1-C22 alkanol, a C5-C12 cycloalkanol, or a polyester group starting from a C7-C12 aralkanol, or a C1-C22 alkoxy group, carbon Polyester starting from a compound having a cycloalkoxy group having 5 to 12 carbon atoms or an aralkoxypolyoxyalkylene group having 7 to 12 carbon atoms A representative.
R ¹⁶ is an alkyl group having 1 to 30 carbon atoms, an alkenyl group having 3 to 22 carbon atoms, a hydroxyalkyl group having 3 to 22 carbon atoms, a cycloalkyl group having 4 to 13 carbon atoms, or an aryl group having 4 to 13 carbon atoms. Or an aralkyl group having 7 to 12 carbon atoms.
R ¹⁸ is an alkyl group having 1 to 22 carbon atoms, an aryl group having 1 to 22 carbon atoms, an aralkyl group having 7 to 12 carbon atoms, a cycloalkyl group having 5 to 12 carbon atoms, or an alkoxy group having 1 to 22 carbon atoms. , C5-C12 cycloalkoxy group, C7-C12 aralkoxypolyoxyalkylene group, C1-C22 alkanol, C5-C12 cycloalkanol, or C7-C12 Starting material using a compound having a polyester group starting from aralkanol, or an alkoxy group having 1 to 22 carbon atoms, a cycloalkoxy group having 6 to 12 carbon atoms, or an aralkoxypolyoxyalkylene group having 7 to 12 carbon atoms Represents a polyester group.
X represents the same or different O, NH, or NR ¹⁹ .
R ¹⁹ is an alkyl group having 1 to 22 carbon atoms, an aryl group having 1 to 22 carbon atoms, an aralkyl group having 7 to 12 carbon atoms, a hydroxyalkyl group having 7 to 12 carbon atoms, or a cyclohexane having 5 to 12 carbon atoms. Represents an alkyl group.
a and b each independently represent a number from 1 to 19; ]

In the formula (I), R ¹² and R ¹⁴ are each independently preferably an alkylene group having 2 to 18 carbon atoms or an aralkylene group having 7 to 15 carbon atoms, an alkylene group having 2 to 12 carbon atoms, or a carbon number. A 7-12 aralkylene group is more preferable, and a C2-C8 alkylene group and a C7-9 aralkylene group are particularly preferable. Specifically, a hexamethylene group, an octamethylene group, or an m-xylene group is particularly preferable.
In the formula (I), R ¹² and R ¹⁴ are preferably the same group.

R ¹³ is preferably an alkylene group having 30 to 40 carbon atoms, an alkenylene group having 3 to 40 carbon atoms, a cycloalkylene group having 30 to 40 carbon atoms, or an arylene group having 30 to 40 carbon atoms. R ¹³ is more preferably an aralkylene group having 30 to 40 carbon atoms, and the aralkylene group is preferably derived from dimer acid. R ¹³ is particularly preferably an aralkylene group having 34 carbon atoms.

R ¹⁵ is preferably an alkyl group having 1 to 22 carbon atoms, a hydroxyl group, or an alkoxypolyoxyalkylene group having 1 to 22 carbon atoms.

R ¹⁶ is preferably an alkyl group having 1 to 30 carbon atoms or an alkenyl group having 3 to 22 carbon atoms, more preferably an alkyl group having 12 to 30 carbon atoms or an alkenyl group having 12 to 22 carbon atoms, and 12 carbon atoms. A -20 alkyl group or a C12-20 alkenyl group is more preferable, and a C17 alkyl group or a C17 alkenyl group is particularly preferable.

R ¹⁷ is preferably an alkylene group having 1 to 18 carbon atoms or a polyoxyalkylene group having 1 to 18 carbon atoms. When R ¹⁷ is an alkylene group having 1 to 18 carbon atoms or a polyoxyalkylene group having 1 to ¹⁸ carbon atoms, R ¹⁸ is preferably an alkyl group having 1 to 22 carbon atoms.

X is preferably O or NH, and Y is preferably at least one group selected from NHCO and CONH.
a and b are each independently a number of 1 to 19, and 2 to 7 are more preferable. Moreover, it is preferable that a and b are the same numbers.

In addition, the compound represented by the formula (I) is preferably a compound further having a urethane group (—NHCOO—) in the molecule. That is, in the compound represented by the formula (I), at least one selected from R ′, B and Y is preferably a group containing a urethane group, and R ′ or Y contains a urethane group. More preferably, it is a group. If the compound represented by the formula (I) is a compound having a urea group and a urethane group in the molecule, a liquid detergent excellent in dispersion stability of water-insoluble particles can be easily obtained.
The compound represented by the formula (I) can be produced by reacting a monoisocyanate or diisocyanate compound with a primary or secondary polyamine. Specifically, it can be produced by the production method described in JP-A 2007-107002.

Examples of the fatty acid-modified urea include compounds having at least one urea group in the molecule and having at least one structural unit selected from a structural unit of a fatty acid and a structural unit obtained by a reaction between a fatty acid and urea. It is done.
The fatty acid used for the fatty acid modification is not particularly limited as long as it has the effects of the present invention, such as the number of hydroxyl groups, the number of double bonds, and the number of carbon atoms, and any commercially available fatty acid can be used. The structural unit may be present at either the end of the fatty acid-modified urea or in the molecule.
Examples of such fatty acid-modified urea derivatives include compounds having at least one structural unit selected from the following formulas (II) to (V).
R ²⁰ —O—CO—NH—R ²¹ − (II)
^{-NH-CO-NH-R 22} - ··· (III)
^{-NH-CO-NH-R 21} - ··· (IV)
^{-NH-CO-O-R 20} - ··· (V)
(In the formulas (II) to (V), R ²⁰ represents a group represented by C _n H _{2n + 1} or C _m H _2m (C _p H _2p O) _r , and n is a number of 4 to 22, m is a number from 1 to 18, p is a number from 2 to 4, r is a number from 1 to 10. R ²¹ is represented by the following formulas (j-1) to (j-4). And R ²² is a group represented by each of the following formulas (k-1) to (k-8).)

  As a modified urea, a substituent is introduced into a compound obtained by copolymerizing a compound having at least one urea group in the molecule and another compound, or a compound having at least one urea group in the molecule. Compounds. The other compound to be copolymerized with the compound having at least one urea group in the molecule is not particularly limited as long as it has the effect of the present invention, and examples thereof include acrylic acid and vinyl chloride. Examples of the substituent include a urethane group and a polyoxyalkylene group. Among these, a urea urethane compound having two or more urea groups and at least one urethane group is preferable from the viewpoint that the dispersion stability of water-insoluble particles can be more easily improved. Further, a compound in which a urethane group is introduced into a connecting portion between a urea group and a urea group and a urethane group is also present at a terminal portion of the compound is more preferable. Furthermore, it is preferable that the polarity of the urethane group at the terminal portion of the compound is higher than the polarity of the urethane group in the molecule.

  The high molecular weight urea includes a high molecular weight urea derivative having one or more urea groups in the molecule and having a polystyrene-equivalent number average molecular weight of 1,000 to 70,000 by GPC method. Among them, a polymer urea having at least two urea groups in the molecule and having a number average molecular weight of 3,000 to 70,000 in terms of polystyrene by GPC method from the viewpoint that the dispersion stability of water-insoluble particles can be more easily improved. Is preferred. Such a polymer urea is not particularly limited as long as it has the effects of the present invention, and examples thereof include a compound represented by the following formula (VI).

Formula (VI) in, T _{is, -C 6 H 4 -CH 2 -C} 6 H 4 -, - C 6 H 3 (-CH 3) -, - CH 2 -C 6 H 4 -CH 2 -, - (CH ₂ ) ₆ —, —C ₆ H ₇ (—CH ₃ ) ₃ —CH ₂ — and the like, at least one group selected from an alkylene group having 1 to 20 carbon atoms or an arylene group, an amide group, and a urethane group, Or the oligomer which has a urethane group is represented.
R ³¹ and R ³⁵ are each an optionally substituted alkyl group having 4 to 32 carbon atoms, an alkenyl group having 3 to 18 carbon atoms, an alkynyl group having 2 to 20 carbon atoms, and a cyclohexane having 3 to 20 carbon atoms. An alkyl group, an aryl group having 5 to 12 carbon atoms or an alkyl-substituted aryl group, a polyoxyalkylene monoalkyl group represented by C _{m ′} H _{2m ′ + 1} — (O—C _{n ′} H _{2n ′} ) _{p ′} , C _{m 'H 2m' + 1 - (} OC n 'H 2n') p '- (O-CH (C 6 H 5) -CH 2) u, Q-C 6 H 4 - (CH 2) s - (OC _{n 'H 2n') x -} (O-CH (C 6 H 5) -CH 2) u -C m 'H 2m' - (OC n 'H 2n') p '- (O-CH (C 6 H _{5) -CH 2) u - (} OOC-C v H 2v) x, Q-C 6 H 4 - (CH 2) s - (O-C n 'H 2 _{') P' - (O-} CH (C 6 H 5) -CH 2) u - (OOC-C v H 2v) x, hydroxyalkyl group 4 to 32 carbon atoms, a carboxyalkyl group 4 to 32 carbon atoms , C _{m ′} H _{2m ′} C (═O) R ⁴¹ , —C _{m ′} H _{2m ′} COOR ⁴¹ , —C _{m ′} H _{2m ′} C (═O) NR ⁴¹ R ⁴² , or C _{m ′} H _{2m ′} OC (═O) represents an NR ⁴¹ R ⁴² radical. The radical may have a substituent, and at least one group selected from an amino group and a carboxyl group may include a salt thereof or a quaternary structure.
R ⁴¹ and R ⁴² are hydrogen, an optionally substituted alkyl group having 1 to 32 carbon atoms, an alkenyl group having 3 to 18 carbon atoms, an alkynyl group having 2 to 20 carbon atoms, or 3 to 20 carbon atoms. A cycloalkyl group having 3 to 20 carbon atoms, an aryl group having 5 to 12 carbon atoms or an alkyl-substituted aryl group, an alkoxyalkyl group having 1 to 32 carbon atoms, or an acyloxyalkyl having 1 to 32 carbon atoms. Represent.
m ′ is a number from 0 to 32, n ′ is a number from 2 to 4, x is a number from 0 to 100, u is a number from 0 to 100, and v is a number from 1 to 22. Yes, p ′ is a number from 0 to 100, and s is a number from 0 to 1.
The (O—C _{n ′} H _{2n ′} ) may be a combination of two or more oxyalkylene groups such as an oxyethylene group and an oxypropylene group, an oxyethylene group and an oxybutylene group.
Q represents hydrogen, an alkyl group having 1 to 12 carbon atoms, or a phenyl group.
R ³² and R ³⁴ are optionally substituted alkylene groups having 4 to 22 carbon atoms, alkenylene groups having 3 to 18 carbon atoms, alkynylene groups having 2 to 20 carbon atoms, and cyclohexane having 3 to 20 carbon atoms. An alkylene group, a C3-C20 cycloalkenylene group, a C5-C12 arylene group, or an arylalkylene radical is represented.
R ³³ is an optionally branched polyester group, polyether group, polyamide group, alkylene group having 4 to 22 carbon atoms, alkenylene group having 3 to 18 carbon atoms, alkynylene group having 2 to 20 carbon atoms, A C3-C20 cycloalkylene group, a C3-C20 cycloalkenylene group, and a C5-C12 arylene group represent an aryl alkylene radical.
A ′, X ′, Y ′, and Z ′ represent —O— or —NR ⁵⁰ .
R ⁵⁰ is hydrogen, an optionally substituted alkyl group having 1 to 32 carbon atoms, an alkenyl group having 3 to 18 carbon atoms, an alkynyl group having 2 to 20 carbon atoms, or a cycloalkyl having 3 to 20 carbon atoms. Group, an alkenyl group having 2 to 20 carbon atoms, an aryl group having 5 to 12 carbon atoms, or an arylalkyl radical.

  At least one urea derivative selected from fatty acid-modified urea, modified urea, and polymer urea may be in a solid or liquid state alone, but is easily added in the manufacturing process. It is preferable that it is liquid from the point which can do. Further, when the urea derivative is a liquid, a liquid obtained by dissolving or dispersing the urea derivative in a solvent may be used.

  (B) As a component, you may use a commercial item. Specific examples include BYK-410, BYK-411, BYK-420, BYK-425, BYK-428, BYK-7411ES, BYK-7420ET, BYK-D410 and the like manufactured by Big Chemie.

As content of (B) component in a liquid cleaning agent, 0.01-5 mass% is preferable with respect to the total mass of a liquid cleaning agent, and 0.01-2 mass% is more preferable.
If the content of component (B) is 0.01% by mass or more, the liquid detergent can be sufficiently structured, and water-insoluble particles such as beads can be more uniformly dispersed. Moreover, if content of (B) component is 5 mass% or less, the viscosity of a liquid detergent will not become high too much and fluidity | liquidity will not fall easily. Further, the storage stability becomes better.

1-1000 are preferable, as for mass ratio (A) / (B) of (A) component and (B) component in a liquid detergent, 6-550 are more preferable, and 20-500 are more preferable. If (A) / (B) is within the above range, a structuring effect can be easily obtained.
Moreover, when the liquid detergent of this invention contains MEE in (A) component, 10-5000 are preferable and, as for mass ratio (MEE / (B)) of MEE and (B) component, 15-500 are more. preferable. If the mass ratio of MEE and (B) component is in the said range, the effect of structuring will be easy to be obtained.

<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 fragrance | flavor included in the capsule fragrance | flavor is not specifically limited, For example, the fragrance | flavor composition described in following Table 1 is mentioned.

  0.0001-10 mass% is preferable with respect to the total mass of a liquid cleaning agent, and, as for content of the water-insoluble particle | grains in a liquid cleaning agent, 0.1-3 mass% is more preferable. 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 detergent of the present invention has a viscosity (value when measured after 60 seconds using a B-type viscometer at a measurement temperature of 25 ° C. and a rotation speed of 60 rpm, hereinafter referred to as viscosity v ₂ ) of 50 to 50. It is preferably 500 mPa · s. If the viscosity is within the above range, the structuring tends to be better.
The liquid detergent of the present invention has a viscosity v ₂ of 50 to 500 mPa · s and a viscosity v ₁ (25 ° C.) measured after 60 seconds using a B-type viscometer at a rotation speed of 6 rpm. And the ratio of the viscosity v ₂ (viscosity v ₁ / viscosity v ₂ ) is preferably 1.1 or more. The viscosity v ₁ / viscosity v ₂ is more preferably 1.2 or more. If the viscosity v ₁ / viscosity v ₂ is 1.1 or more, the dispersion stability of the water-insoluble particles tends to be good.

<Optional component>
The liquid detergent of this invention can contain arbitrary components other than the said (A)-(B) component in the range which does not impair the effect of this invention as needed.
Examples of optional components include water, surfactants other than the components (A1) and (A2) (optional surfactants), water-miscible organic solvents, metal ion scavengers, antioxidants, and cleaning performance improvers. Stability improvers, colorants / emulsifiers, thickeners / solubilizers, enzyme stabilizers, pH adjusters, flavors other than capsule flavors, and the like.

The content of water with respect to the total amount of the liquid detergent is, for example, preferably 0 to 90% by mass, more preferably 10 to 80% by mass, and still more preferably 30 to 70% by mass.
When the liquid detergent of the present invention is a concentrated liquid detergent, the content of water with respect to the total amount of the liquid detergent is preferably 0 to 70 mass%, more preferably 10 to 60 mass%, and more preferably 10 to 40 mass%. % Is particularly preferred.

<Optional surfactant>
The optional surfactant is a cleaning component, and a known surfactant can be used in the liquid cleaning agent. For example, a cationic surfactant, an amphoteric surfactant, or the like can be blended in one or a combination of two or more.
The total amount (total amount) of the surfactant (including the component (A)) in the liquid detergent is preferably 5 to 80% by mass, more preferably 10 to 60% by mass, based on the total mass of the liquid detergent. 30-60 mass% is further more preferable. If the total amount of the surfactant is within the above range, the detergency tends to be better.

  In addition, the ratio of the component (A) to the total amount of the surfactant is preferably 30 to 100% by mass and more preferably 60 to 100% by mass with respect to the total mass of the surfactant from the viewpoint of detergency.

[Cationic surfactant]
Conventionally known cationic surfactants can be appropriately selected and used. Specific examples include dimethylaminopropylamide stearate and alkyltrimethylammonium salts. When the liquid detergent of this invention contains a cationic surfactant, the compounding quantity has the preferable 0-30 mass% with respect to the total mass of a liquid detergent from a viewpoint of detergency.

[Amphoteric surfactant]
Examples of amphoteric surfactants include alkyl betaine type, alkyl amide betaine type, imidazoline type, alkyl amino sulfone type, alkyl amino carboxylic acid type, alkyl amide carboxylic acid type, amide amino acid type, phosphoric acid type amphoteric surfactant. Is mentioned. When the liquid detergent of this invention contains an amphoteric surfactant, the compounding quantity is preferably 0 to 30% by mass with respect to the total mass of the liquid detergent from the viewpoint of detergency.

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, diethylene glycol monobutyl ether (butyl carbitol), 3-, in terms of low odor, availability, liquid stability when used as a liquid detergent, and fluidity. Methoxy-3-methyl-1-butanol is preferred.
A water-miscible organic solvent may be used individually by 1 type, and may be used in combination of 2 or more type. In particular, it is preferable to use ethanol and butyl carbitol or ethanol and 3-methoxy-3-methyl-1-butanol in combination. When ethanol and butyl carbitol are used in combination, the mass ratio of ethanol and butyl carbitol is preferably 1:10 to 10: 1. When ethanol and 3-methoxy-3-methyl-1-butanol are used in combination, the mass ratio of ethanol and 3-methoxy-3-methyl-1-butanol is preferably 1:10 to 10: 1.
The content of the water-miscible organic solvent is preferably 3 to 20% by mass and more preferably 4 to 10% 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 the metal ion scavenger include metal ion scavengers such as malonic acid, succinic acid, malic acid, diglycolic acid, tartaric acid, citric acid, etc., for example, 0.1 to 20% by mass relative to the total mass of the liquid detergent. Can be included. A metal ion capture agent may be used individually by 1 type, and 2 or more types may be used in combination.

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

  Enzymes (proteases, lipases, cellulases, etc.), texture improvers, alkali builders such as alkanolamines, hydrotropes, fluorescent agents, dye transfer inhibitors, recontamination inhibitors, pearls for the purpose of improving cleaning performance and stability Agents, soil release agents and the like.

  Coloring agents include Acid Red 138, Polar Red RLS, Liquid PINK AL, Acid Yellow 203, Liquid Bright Yellow, Acid Blue 9, Blue 1, Blue 205, Green 3, Turquoise P-GR (all trade names) ) And other general-purpose dyes and pigments, for example, can be included in an amount of about 0.00005 to 0.005 mass% with respect to the total mass of the liquid detergent.

  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. As a specific example, polystyrene emulsion (trade name: Cybinol (registered trademark) RPX-196 PE-3, solid content 40% by mass, manufactured by Seiden Chemical Co., Ltd.) and the like are used with respect to the total mass of the liquid detergent. 0.001-0.5 mass% can be included.

Thickeners and solubilizers include aromatic sulfonic acids or salts thereof such as toluene sulfonic acid, xylene sulfonic acid, cumene sulfonic acid, substituted or unsubstituted naphthalene sulfonic acid, toluene sulfonate, xylene sulfonate, Examples include cumene sulfonate and substituted or unsubstituted naphthalene sulfonate.
Examples of the salt include sodium salt, potassium salt, calcium salt, magnesium salt, ammonium salt, alkanolamine salt and the like.
These acids or salts thereof may be used alone or in combination of two or more.
The content of the thinning agent is preferably 0.01 to 10% by mass with respect to the total mass of the liquid detergent.
Further, the content of the solubilizer is preferably 0.01 to 10% by mass with respect to the total mass of the liquid detergent.

Examples of the enzyme stabilizer include boric acid, borax, formic acid or a salt thereof, benzoic acid, lactic acid or a salt thereof, and calcium salts such as calcium chloride and calcium sulfate. These may be used alone or in combination of two or more.
The content of the enzyme stabilizer is preferably 0.01 to 20% by mass with respect to the total mass of the liquid detergent.

  As fragrance | flavors other than the capsule fragrance | flavor for fragrance | flavors, a conventionally well-known thing can be selected suitably and can be used, for example, the fragrance | flavor component etc. which are described in Unexamined-Japanese-Patent No. 2002-146399 etc. can be 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 at 30 ° C. of 4 to 9, more preferably 4 to 8. When the pH is in such a range, the long-term storage stability of the liquid detergent composition tends to be better.
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, sodium hydroxide, potassium hydroxide, alkanolamine and other sulfuric acids, hydrochloric acid, sodium hydroxide, potassium hydroxide, alkanolamine and the like are stable. From the viewpoint of sex.

(Production method)
The liquid detergent of the present invention can be obtained, for example, by dispersing the components (A) to (B) and other components as necessary in water as a dispersion medium. Specifically, it can be produced by adding each component to water as a dispersion medium and stirring and mixing. Therefore, the manufacturing method of the liquid detergent of the present invention does not require special equipment such as heating and cooling equipment.

(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. That is, the liquid cleaning agent of the present invention is suitable as a cleaning agent for clothing.
The content of the liquid cleaning agent in the cleaning liquid is not particularly limited. The amount of liquid detergent added to water is preferably 2 to 10 mL per 10 L of water, for example.

  The liquid detergent of the present invention comprises (a1) component, (A2) component, (B) component, water-insoluble particles, and water, and (A2) component is LAS, AES, AEPS, and coconut fatty acid. And at least one anionic surfactant selected from the group consisting of salts, wherein (B) component is a compound represented by formula (I), and at least selected from fatty acid-modified urea, modified urea, and polymer urea It is preferably at least one selected from one urea derivative. Moreover, 5-50 mass% is preferable with respect to the total mass of a liquid detergent, as for content of the said (a1) component, 10-40 mass% is more preferable, and 15-30 mass% is especially preferable. Moreover, it is preferable that content of the said (A2) component is 3-25 mass% with respect to the total mass of a liquid detergent, It is more preferable that it is 5-20 mass%, It is 15-20. It is particularly preferred. Moreover, 1-1000 are preferable, (A) / (B) is more preferable, 6-550 are more preferable, and 20-500 are more preferable.

  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 2-3 represent the following.
<(A) component>
A1-1: MEE: polyoxyethylene fatty acid methyl ester (in formula (a1), R ¹ is an alkyl group having 11 to 13 carbon atoms, -X- is -COO-, and R ² is a methyl group , S is 15, and t is 0. Narrow rate: 33%) (Lion Chemical Co., Ltd., trade name: CEAO-90).
A1-2: AE15: polyoxyethylene alkyl ether (in formula (a1), R ¹ is an alkyl group having 12 to 14 carbon atoms, -X- is -O-, R ² is hydrogen, s Alcohol alkoxylate in which t is 15 and t is 0. Narrow ratio: 33%) (Lion Chemical Co., Ltd., trade name: LMAO-90).
A1-3: AE7: polyoxyethylene alkyl ether (in the formula (a1), R ¹ is an alkyl group having 12 to 14 carbon atoms, -X- is -O-, R ² is hydrogen, s Is an alcohol alkoxylate having a t of 0 and a narrow ratio of 33%.)
A1-4: EOPO nonion: polyoxyethylene polyoxypropylene alkyl ether (in formula (a1), R ¹ is an alkyl group having 10 to 14 carbon atoms, -X- is -O-, and R ² is hydrogen. And s is 5 and t is 2. EO and PO are block adducts. Narrow ratio: 33%.)
A2-1: LAS: linear or branched alkylbenzenesulfonic acid having an alkyl group having 10 to 14 carbon atoms (manufactured by Lion Corporation, trade name: Raipon (registered trademark) LH-200).
A2-2: AES: polyoxyethylene alkyl ether sulfate (natural alcohol (trade name “CO-1270” manufactured by P & G) with 1 mol equivalent of EO added to sulfate and neutralized with sodium hydroxide (Manufactured by Lion Corporation), trade name: BRES (1)).
A2-3: AEPS: monoethanolamine salt of polyoxyalkylene alkyl ether sulfate ester (addition of 1.0 mol of average added mole number of propylene oxide and 2.0 mol of average added mole number of ethylene oxide to 1-dodecanol in this order) After that, it was produced by sulfating and neutralizing with monoethanolamine).
A2-4: Palm fatty acid (manufactured by NOF Corporation, trade name: coconut fatty acid).
<(B) component>
B-1: A compound having a urea group in the molecule (solution containing modified urea (active ingredient: 25%). Main solvent: N-methylpyrrolidone) (BYK, trade name: BYK-411).
B-2: a compound having a urea group in the molecule (solution containing modified urea (active ingredient: 25%). Main solvent: amide ester) (product name: BYK-7411ES, manufactured by BYK).
B-3: Compound having a urea group in the molecule (solution containing modified urea (active ingredient: 52%). Main solvent: N-methylpyrrolidone) (BYK, trade name: BYK-410).
B-4: A compound having a urea group in the molecule (solution containing modified urea (active ingredient: 52%). Main solvent: dimethyl sulfoxide) (product name: BYK-D410, manufactured by BYK).
B-5: Compound having a urea group in the molecule (solution containing modified urea (active ingredient: 40%). Main solvent: amide ether) (BYK, trade name: BYK-7410ET).
B-6: A compound having a urea group in the molecule (solution containing modified urea (active ingredient: 52%); main solvent: N-methylpyrrolidone) (product name: BYK-420, manufactured by BYK).
<Optional component>
Citric acid: (manufactured by Yushi Co., Ltd., trade name: liquid citric acid).
Sodium benzoate: (Toa Gosei Co., Ltd., trade name: sodium benzoate).
Ethanol: (manufactured by Nippon Alcohol Sales Co., Ltd., trade name: specific alcohol 95 degree synthesis
Butyl carbitol: (Nippon Emulsifier Co., Ltd., trade name: butyl diglycol).
3-methoxy-3-methyl-1-butanol: (manufactured by Kuraray Co., Ltd., trade name: Solfit (fine grade).
p-Toluenesulfonic acid: (manufactured by Kanto Chemical Co., Inc., trade name: p-toluenesulfonic acid).
pH adjuster: sodium hydroxide (manufactured by Tsurumi Soda Co., Ltd.), monoethanolamine (manufactured by Nippon Shokubai Co., Ltd.).
PEG1000: (manufactured by Lion Corporation, trade name: PEG # 1000-L60).
Capsule flavor: Capsule A described in Table 1.
Perfume: Perfume component a described in JP-A-2009-108248.
Water: Purified water.
<Common ingredient A>
BHT: dibutylhydroxytoluene, trade name “SUMILZER BHT-R”, manufactured by Sumitomo Chemical Co., Ltd .: 0.05% by mass.
-Dye: Trade name "Red No. 106", manufactured by Sakai Kasei Co., Ltd .... 0.0001% by mass.
-Isothiazolone liquid: 5-chloro-2-methyl-4-isothiazolin-3-one / 2-methyl-4-isothiazolin-3-one / magnesium salt / water mixture, trade name "Caisson CG", Dow Chemical Made by company: 0.01% by mass.
SR agent: Trade name “TexCare SRN-170C”, manufactured by Clariant Japan, Inc. 0.5 mass%.
In the table, the water content “balance” is an amount necessary to make the liquid detergent 100% by mass as a whole. The content “appropriate amount” of the pH adjusting agent is an amount required to bring the liquid cleaning agent to the pH shown in the table.
“A / B” in the table represents the mass ratio of the component (A) and the component (B) in the liquid detergent.

(Examples 1-22, Comparative Examples 1-2)
According to the composition shown in Tables 2-3, the components (A) to (B) and optional components and water were all stirred and mixed 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)
80 g of the liquid cleaning composition of Tables 2-3 was filled in a glass bottle (PS11 bottle) and adjusted to 25 ° C. in a thermostatic bath. A sample solution adjusted to 25 ° 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 v ₁ (mPa · s) after 600 seconds was measured. Then, the rotation speed of the rotor was set to 60 rpm, and the viscosity v ₂ (mPa · s) after 60 seconds was measured. 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. Incidentally, a determination is A, B of the viscosity v _2, the determination result is A structured, those of B, thickening of the liquid composition was determined structured has progressed sufficiently. The results are shown in Tables 2-3. In the table, the upper part shows the evaluation results, and the lower part shows the viscosity.
[Evaluation criteria (viscosity v ₂ )]
A: Viscosity v ₂ is 300 mPa · s or less.
B: Viscosity v ₂ is more than 300 mPa · s and less than 500 mPa · s.
C: Viscosity v ₂ is 500 mPa · s or more.
[Evaluation criteria (structured)]
A: The value of (viscosity v ₁ ) / (viscosity v ₂ ) is 1.5 or more.
B: The value of (viscosity v ₁ ) / (viscosity v ₂ ) is 1.1 or more and less than 1.5.
C: The value of (viscosity v ₁ ) / (viscosity v ₂ ) is less than 1.1.

(Evaluation of dispersion stability)
30 g of a wide mouth standard bottle (PS-No. 6 bottle) is filled with the liquid cleaning composition of Tables 2-3, and beads (TPSHKI PIGMENT. Co., Ltd., trade name: PFL-RED 7155T Lot. 0308) are filled therein. 0.5 g was added and dispersed. After storing in a thermostatic bath at 25 ° C. for 60 days, the bottle was taken out from the thermostatic bath, the dispersion state of the beads in the liquid detergent was visually confirmed, and the dispersion stability was evaluated according to the following evaluation criteria. The results are shown in Tables 2-3.
[Evaluation criteria]
A: The beads were uniformly dispersed in the liquid detergent for 60 days.
B: The beads were uniformly dispersed in the liquid detergent for 30 to 59 days.
C: The beads were suspended or settled in less than 30 days.

(Storage stability)
A wide-mouthed standard bottle (PS-No. 6 bottle) was filled with 30 g of the liquid detergents shown in Tables 2-3, stored in a thermostatic bath at -5 ° C for 1 month, visually confirmed, and evaluated according to the following evaluation criteria. The results are shown in Tables 2-3.
A: Transparent and fluidity of the solution.
B: Transparent but not fluid.
C: There is a precipitate or suspended matter.

(Cleaning performance)
The cleaning performance of the liquid cleaning agents in Tables 2 to 3 was evaluated by the following method.
As the dirt cloth, “face dirt cloth” produced by rubbing the dirt on the face and neck around the cotton cloth was used. The washing liquid was prepared by dispersing and dissolving 6 mL of liquid detergent in 15 L of water.
Using a Terg-O-meter (manufactured by UNITED STATES TESTING) as a cleaning tester, 10 pieces of dirt cloth, a cleaning knitted fabric, and the washing liquid are put into the washing tester, and the bath ratio is 30 times (washing water) / Washing treatment was performed at 120 rpm and 15 ° C. for 10 minutes. Next, it is transferred to a two-tank washing machine (product number “CW-C30A1-H1” manufactured by Mitsubishi Electric Corp.), dehydrated for 1 minute, and then in 30 L of tap water (15 ° C., 4 ° DH) for 3 minutes. It was rinsed and air-dried.
The color difference meter (made by Nippon Denshoku Industries Co., Ltd., product name “SE200 type” is used for the unstained cloth, the uncleaned cloth, the uncleaned cloth, and the cleaned dirty cloth. ]), And 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 (%).
The results are shown in Tables 2-3. In the table, the upper row shows the evaluation results, and the lower row shows the cleaning rate.
[Evaluation criteria]
A: The cleaning rate is 70% or more.
B: The cleaning rate is 60% or more and less than 70%.
C: The cleaning rate is less than 60%.

As shown in Tables 2 to 3, the liquid detergents of Examples 1 to 22 had good dispersion stability, and the capsule flavor could be stably dispersed. From the results of Example 2 or 5, it was confirmed that the capsule flavor could be stably dispersed even when the liquid detergent of the present invention was a concentrated liquid detergent. From the results of the viscosity measurement, it is considered that the liquid detergents of these examples were sufficiently structured so that the capsule flavor could be stably dispersed.
On the other hand, the liquid detergent of Comparative Example 2 containing no component (B) was inferior in dispersion stability. Although the liquid detergent of Comparative Example 1 containing no component (A) was excellent in dispersion stability, it was judged that it was not suitable for use as a liquid detergent because of poor washing performance.
From the above results, it was confirmed that the liquid detergent of the present invention can stably disperse water-insoluble particles.

Claims (2)

  One or more surfactants (A) selected from an anionic surfactant (A1) and a nonionic surfactant (A2), and a compound (B) having a molecular weight of 100 or more and having a urea group in the molecule A liquid detergent composition containing.   The liquid detergent composition according to claim 1, wherein the component (A) contains both a nonionic surfactant (A1) and an anionic surfactant (A2).