JP7004537B2 - Particle dispersion detergent composition - Google Patents

Description

The present invention relates to a liquid detergent composition.

The liquid detergent composition for textile products such as clothing (hereinafter, also referred to as a liquid detergent) has a purpose of improving the fragrance or imparting the aesthetics peculiar to the liquid detergent. May contain water-insoluble particles such as capsule fragrances and beads. A method of blending a structuring agent in a liquid detergent is known in order to stably disperse such water-insoluble particles in the liquid detergent. The structuring agent can increase the viscosity of the liquid detergent or structure the liquid detergent to prevent precipitation, suspension, and precipitation of water-insoluble particles. The term "structuring" refers to a state in which the viscosity changes before and after a force is applied. As an example of a structured liquid detergent composition, a liquid detergent composition that has a certain viscosity in a state where no force is applied such as a stationary state, but the viscosity decreases when a force is applied and exhibits fluidity. Can be mentioned.

On the other hand, in the concentrated liquid detergent composition containing 30% by mass or more of the surfactant with respect to the total mass of the liquid detergent (hereinafter, also referred to as a concentrated liquid detergent), free water is scarce. There is a problem that stable dispersion of the water-insoluble particles is more difficult.
To solve such a problem, Patent Document 1 describes a liquid detergent composition containing a surfactant, a cleaning aid, a specific amount of cured 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 a specific hardened castor oil as a structuring agent.

Special Table 2007-500268 Gazette

Since the liquid detergent composition of Patent Document 1 is heated to nearly 90 ° C. to emulsify the cured castor oil, a heating / cooling facility is required at the time of production. Therefore, there is a demand for a detergent composition that does not require special equipment during production and has excellent dispersion stability of water-insoluble particles even when a concentrated liquid detergent is used.
Therefore, an object of the present invention is 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 nonionic surfactants (A1) and anionic surfactants (A2), and compounds having a molecular weight of 100 or more and having a urea group in the molecule (B). ), And the viscosity _v1 when measured after 60 seconds under the conditions of a measurement temperature of 25 ° C. and a rotation speed of 6 rpm using a B-type viscometer, and rotation at a measurement temperature of 25 ° C. using a B-type viscometer. A particle dispersion cleaning agent composition comprising a liquid cleaning agent composition having a viscosity _v2 measured after 60 seconds under the condition of several 60 rpm and satisfying the following conditions , and particles dispersed in the liquid cleaning agent composition .
180mPa ・ s ≤ viscosity _v2 ≤ 500mPa ・ s
Viscosity _v1 / Viscosity _v2 ≧ 1.1
[2] The particle dispersion detergent composition according to [1], wherein the component (A) contains both a nonionic surfactant (A1) and an anionic surfactant (A2).
[3] The particle dispersion detergent composition according to [1] or [2], wherein the component (B) is a compound having a urea group in the molecule (excluding triclocarban) having a molecular weight of 200 or more. thing.
[4] The particles according to any one of [1] to [3], wherein the content of the component (B) is 0.01 to 5% by mass with respect to 100% by mass of the liquid detergent composition. Dispersion detergent composition.
[5] The particle dispersion detergent composition according to any one of [1] to [4], wherein the liquid detergent composition further contains water.
[6] The item according to any one of [1] to [5], wherein the particles are one or more selected from the group consisting of a packaging agent, beads, a pearl brightener, bentonite, zeolite, and carboxymethyl cellulose. Particle dispersion detergent composition.
[7] The particle dispersion cleaning agent according to any one of [1] to [6], wherein the content of the particles is 0.0001 to 10% by mass with respect to 100% by mass of the liquid cleaning agent composition. Composition.
[8] The liquid detergent according to any one of [1] to [7], wherein the mass ratio (A) / (B) of the component (A) to the component (B) is 1 to 1000. Composition .

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).

The component (A) is one or more surfactants selected from the nonionic surfactant (A1) and the anionic surfactant (A2). By containing the component (A), the liquid detergent of the present invention exhibits cleaning performance against various stains.
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 them, the component (A) preferably contains a nonionic surfactant (A1) and an anionic surfactant (A2). When the component (A) contains a nonionic surfactant (A1) and an anionic surfactant (A2), the cleaning performance can be further enhanced. In addition, it becomes easy to adjust the viscosity of the liquid detergent within an appropriate range, and it becomes easy to improve the dispersion stability of water-insoluble particles such as capsule fragrance.

The content of the component (A) in the liquid detergent is preferably 10 to 60% by mass, more preferably 25 to 55% by mass, still more preferably 35 to 55% by mass, based on the total mass of the liquid detergent. ..
When 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.

[Nonion Surfactant (A1)]
The nonionic surfactant (A1) (hereinafter, may be simply referred to as the component (A1)) is not particularly limited as long as it has the effect of the present invention, but for example, a polyoxyalkylene type nonionic surfactant, an alkylphenol, and 8 to 8 carbon atoms. 22 fatty acids or alkylene oxide adducts such as alkylamines with 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 thereof include alcohol fatty acid ethers, alkyl (or alkenyl) amine oxides, alkylene oxide adducts of hardened castor oil, sugar fatty acid esters, N-alkyl polyhydroxy fatty acid amides, and alkyl glycosides. These may be used alone or in combination of two or more.
Among the above, the component (A1) contains a polyoxyalkylene type nonionic surfactant because the viscosity of the liquid detergent tends to be in an appropriate range and the dispersion stability of water-insoluble particles is more likely to be improved. Is preferable.

Examples of the polyoxyalkylene type nonionic surfactant include a compound represented by the following general formula (a1) (hereinafter referred to as a component (a1)).
R ¹ -X- (EO) _s (PO) _t -R ² ... (a1)
[In the formula (a1), R ¹ represents a hydrocarbon group having 8 to 22 carbon atoms, -X- represents a divalent linking group, and R ² represents a hydrogen atom, an alkyl group having 1 to 6 carbon atoms, or an alkyl group having 1 to 6 carbon atoms. It represents an alkenyl group having 2 to 6 carbon atoms, EO represents an oxyethylene group, and PO represents an oxypropylene group. s represents the average number of repetitions of EO, and is a number of 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 ^R1 has 8 to 22 carbon atoms, preferably 10 to 18 and more preferably 12 to 18. The hydrocarbon group may be linear or branched. It may also have an unsaturated bond.
In the 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 (R1 ^- OH, or ( ^R1 ) ₂ -CH-OH). , Fatty acid having 8 to 22 carbon atoms (R ¹ -COOH), or fatty acid amide having 8 to 22 carbon atoms (R ¹ -CONH) can be obtained as a raw material.
In the formula (a1), the number of carbon atoms of the alkyl group in ^R2 is 1 to 6, preferably 1 to 3. The alkenyl group has 2 to 6 carbon atoms, preferably 2 to 3 carbon atoms.

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 a number of 3 to 20, preferably a number of 5 to 18, and more preferably a number of 7 to 16. When the average number of repetitions s of EO is within the above range, it is easy to prevent the HLB value from becoming too high and the cleaning performance for sebum cleaning from deteriorating.
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 of 0 to 6, preferably a number of 0 to 3. When the average number of repetitions t of PO is 6 or less, the storage stability of the liquid detergent under high temperature (that is, 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 method of adding EO and PO is not particularly limited, and may be, for example, random addition. , May be block addition. Examples of the block addition method include a method of adding EO and then PO; a method of adding PO and then adding EO; a method of adding EO and then PO and further adding EO. Can be mentioned.

In the component (a1), the distribution of the number of added moles of ethylene oxide and the distribution of the number of added moles of propylene oxide are not particularly limited as long as they have the effect of the present invention.
The distribution of the number of added moles varies depending on the reaction method when producing the component (a1). For example, ethylene oxide or propylene oxide is added to a raw material for a hydrocarbon group (primary or secondary higher alcohol, higher fatty acid, higher fatty acid amide, etc.) using a general alkaline catalyst such as sodium hydroxide or potassium hydroxide. When this is done, the distribution of the number of added moles of EO or PO tends to be relatively wide. In addition, 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⁺ , and Mn ²⁺ described in JP-A-6-15038 are added. When ethylene oxide or propylene oxide is added to the hydrocarbon-based raw material using a catalyst, the distribution of the number of added moles of EO or PO tends to be relatively narrow.

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 preferable.
When —X— is —O—, the carbon number of R ¹ is preferably 10 to 22, more preferably 10 to 20, and particularly preferably 10 to 18. Further, R ² is preferably a hydrogen atom.
When -X- is -COO-, the carbon number of R ¹ is preferably 9 to 21, and more preferably 11 to 21. ^R2 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.

As the component (a1) in which -X- is -O- or -COO-, a commercially available product may be used. Specific examples of commercially available products include Diego (registered trademark) manufactured by Mitsubishi Chemical Corporation (trade name, C13 and C indicate the number of carbon atoms; the same applies hereinafter) and Neodol (registered trademark) manufactured by Shell (trade name, C12). Ethylene oxide equivalent to 12 mol or 15 mol is added to alcohol such as Safol® 23 (trade name, a mixture of C12 and C13) manufactured by Sasol. Ethylene oxide equivalent to 12 mol or 15 mol is added to natural alcohol such as CO-1214 (trade name) or CO-1270 (trade name) manufactured by P &G; obtained by quantifying butene. Ethylene oxide equivalent to 7 mol was added to C13 alcohol obtained by subjecting C12 alken to the oxo method (Lutensol® TO7 (trade name) manufactured by BASF); pentanol was subjected to a garbet reaction. 7 mol of ethylene oxide added to the obtained C10 alcohol (Butensol XL70 (trade name) manufactured by BASF); 6 mol equivalent to the C10 alcohol obtained by subjecting pentanol to a garbet reaction. Ethylene oxide added (Butensol XA60 (trade name) manufactured by BASF); 9 mol or 15 mol of ethylene oxide added to the secondary alcohol of C12-14 (Nippon Catalyst Co., Ltd.) Softanol (registered trademark) 90 (trade name) and Softanol 150 (trade name)); equivalent to 15 mol of coconut fatty acid methyl (lauric acid / myristic acid = 8/2) using an alkoxylation catalyst. Examples thereof include those to which ethylene oxide is added (polyoxyethylene coconut fatty acid methyl ester (EO 15 mol)).

Among the components (a1), among the above, a compound in which -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 is used. Preferably, a polyoxyethylene fatty acid methyl ester in which R ² is a methyl group (hereinafter, may be referred to as “MEE”) is particularly preferable. That is, in the liquid detergent 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 detergent of the present invention in water becomes better, and better cleaning performance can be 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 with 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 is performed. The dispersion stability of the water-insoluble particles in the agent can be improved. In addition, the storage stability of the liquid detergent tends to be good.

Polyoxyethylene fatty acid alkyl ester is a nonionic surfactant in which the orientation of molecules in an aqueous solution system is weak and micelles are unstable. Therefore, gelation and the like are unlikely to occur even when the polyoxyethylene fatty acid alkyl ester is blended at a high concentration. Therefore, the polyoxyethylene fatty acid alkyl ester can be blended alone and in a high concentration in a liquid detergent. In one embodiment of the present invention, the content of the MEE in the liquid detergent is preferably 5 to 50% by mass, more preferably 10 to 40% by mass, and 15 to 30% by mass with respect to the total mass of the liquid detergent. Mass% is particularly preferred.
Further, since the polyoxyethylene fatty acid alkyl ester has good solubility in water, the concentration in the washing solution tends to be uniform in a short time. Further, by blending the polyoxyethylene fatty acid alkyl ester in the liquid detergent at a high concentration, the fluidity of the liquid detergent tends to be improved. Therefore, by including the polyoxyethylene fatty acid alkyl ester, it becomes easy to obtain a liquid detergent having better cleaning performance.
Such a polyoxyethylene fatty acid alkyl ester can be 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 an oxyacid. It can be produced by a method of adding an alkylene oxide or the like.

In the component (a1), the narrow ratio determined by the following formula (S) is preferably 20 to 60% by mass, more preferably 30 to 45% by mass. When the narrow ratio of the component (a1) is 20 to 60% by mass, the effects of high detergency and liquid stability at low temperature can be easily obtained. Further, the narrow ratio can be controlled by, for example, a method for producing the component (a1).

(In the formula (S), S _max represents the number of moles of alkylene oxide added (value of s + t) in the alkylene oxide adduct most abundant in the component (a1). I represents the number of moles of alkylene oxide added. . Yi represents the ratio (% by mass) of the alkylene oxide adduct in which the number of moles of the alkylene oxide present in the component (a1) is i to the whole component (a1).

Further, in one embodiment of the present invention, further, in MEE and the polyoxyethylene alkyl ether (in the formula (a1), ^R1 is an alkyl group having 12 to 14 carbon atoms, and —X— is —O—. It is preferable to use in combination with an alcohol alkoxylate in which ^R2 is hydrogen, s is 15, and t is 0. Hereinafter, it may be referred to as “AE (15)”). By using MEE and AE (15) in combination, the dispersion stability of water-insoluble particles is likely to be further improved.
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, more preferably 2 to 10% by mass. The mass ratio of MEE to AE (15) (MEE / AE (15)) in the liquid detergent is preferably 1 to 20, more preferably 3 to 10.
The content of the component (A1) in the liquid detergent is preferably 5 to 50% by mass, more preferably 15 to 40% by mass, based on the total mass of the liquid detergent. When the content of the component (A1) in the liquid detergent is 5 to 50% by mass, the effect of high cleaning power can be easily obtained.
The content of the component (a1) in the liquid detergent is preferably 5 to 50% by mass, more preferably 10 to 40% by mass, and particularly preferably 15 to 30% by mass with respect to 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 cleaning power can be easily obtained.

[Anionic surfactant (A2)]
The anionic surfactant (A2) (hereinafter, may be referred to as a component (A2)) is not particularly limited as long as it has the effect of the present invention, and is, for example, a linear alkylbenzene sulfonic acid or a salt thereof (LAS); α-. Olefin Sulfonate (AOS); Linear or Branched Alkyl Sulfonate (AS); Alkyl Ether Sulfate or Alkenyl Ether Sulfate (AES); Alcan Sulfonate with Alkyl Group; α-Sulfate Fattenant Ester salts (MES); higher fatty acid salts and the like. Examples of the salt 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, those having 8 to 16 carbon atoms are preferable, and those having 10 to 14 carbon atoms are particularly preferable.
The α-olefin sulfonate is preferably one having 10 to 20 carbon atoms.
The alkyl sulfate ester salt preferably has 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 has an average of 1 to 10 mol of ethylene oxide added, and an average of 0. It is preferably added with up to 6 mol of propylene oxide (that is, polyoxyethylene (propylene) alkyl ether sulfate ester salt or polyoxyethylene (propylene) alkenyl ether sulfate ester salt; AEPS). When the alkyl ether sulfate ester salt or the 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.
The alkane sulfonate is preferably an alkyl group having 10 to 20 carbon atoms, and more preferably 14 to 17 carbon atoms. Among them, those in which the alkyl group is a secondary alkyl group (that is, a secondary alkane sulfonate) are particularly preferable.
The α-sulfofatty acid ester salt preferably has a fatty acid residue having 10 to 20 carbon atoms.
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 thereof include soap having the same number of carbon atoms and sodium coconut fatty acid.
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 ester salt, α-olefin sulfonate, and higher fatty acid salt. At least one anionic surfactant preferably selected from the group consisting of linear alkylbenzene sulfonic acid or a salt thereof, an alkyl ether sulfate ester salt or an alkenyl ether sulfate ester salt, and a higher fatty acid salt. It is more preferable to contain an agent, and it is particularly preferable to contain a linear alkylbenzene sulfonic acid or a salt thereof. If the component (A2) is these preferable anionic surfactants, the handling performance of the liquid detergent is better and the recontamination prevention performance is excellent. In addition, the rinsing property tends to be better.
Here, the "recontamination prevention property" is a property of preventing the stains removed from the object to be washed by the washing treatment from adhering to the object to be washed again.

As the component (A2), an anionic surfactant other than the above may be used. Examples of other anionic surfactants include carboxylic acid type anionic surfactants such as alkyl ether carboxylate, polyoxyalkylene ether carboxylate, alkyl (or alkenyl) amide ether carboxylate, and acylaminocarboxylate. Examples thereof include phosphate ester type anionic surfactants such as alkyl phosphate ester salt, polyoxyalkylene alkyl phosphate ester salt, polyoxyalkylene alkylphenyl phosphate ester salt, and glycerin fatty acid ester monophosphate ester salt.
These anionic surfactants are readily available on the market.
The other anionic surfactant may be used alone or in combination of two or more.

The content of the component (A2) in the liquid detergent is preferably 3 to 25% by mass, more preferably 5 to 20% by mass, and particularly preferably 15 to 20% by mass with respect to 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 having excellent anti-recontamination properties, and it becomes easy to stably disperse the component (A2) in the liquid detergent. Further, when the content of the component (A2) is 20% by mass or less, it is easy to suppress an increase in the amount of gas absorption due to an excessive amount of counterions, so that the storage container for the liquid detergent is less likely to be deformed.

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

<Ingredient (B)>
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) acts as a structuring agent, and by containing the component (B), a liquid detergent having excellent dispersion stability of water-insoluble particles such as capsule fragrance can be obtained. Further, even when the liquid detergent of the present invention is a concentrated liquid detergent, water-insoluble particles can be stably dispersed.

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

[In formula (I), A is 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 represents one or more groups independently selected from COO, OCO, NHCO, CONH, NHCOO, OOCNH, and NHCONH.
Z represents O, NH, or NR ¹⁹ groups.
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 independently have 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, and 5 to 40 carbon atoms. It represents an arylene group of 40, 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.
^R15 has 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, and a cycloalkyl group having 5 to 12 carbon atoms. Hydroxyalkyl, N with 5 to 12 carbon atoms, N'-dialkylamino group, hydroxyl group, alkoxy group with 1 to 22 carbon atoms, cycloalkoxy group with 5 to 12 carbon atoms, aralkylpoly with 7 to 12 carbon atoms An oxyalkylene group or an alkanol having 1 to 22 carbon atoms, a cycloalkanol having 5 to 12 carbon atoms, or a polyester group starting from an aralkanol having 7 to 12 carbon atoms, or an alkoxy group having 1 to 22 carbon atoms, carbon. Represents a polyester group starting from a compound having a cycloalkoxy group having 5 to 12 or an aralkylpolyoxyalkylene group having 7 to 12 carbon atoms.
R ¹⁶ has 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, and an aryl group having 4 to 13 carbon atoms. , Or an aralkyl group having 7 to 12 carbon atoms.
R ¹⁸ has 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, and an alkoxy group having 1 to 22 carbon atoms. , A cycloalkoxy group having 5 to 12 carbon atoms, an aralkylpolyoxyalkylene group having 7 to 12 carbon atoms, or an alkanol having 1 to 22 carbon atoms, a cycloalkanol having 5 to 12 carbon atoms, or 7 to 12 carbon atoms. Starting material is a polyester group using aralkanol as a starting material, or a compound having 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 cyclo having 5 to 12 carbon atoms. Represents an alkyl group.
a and b each independently represent a number from 1 to 19. ]

In the above formula (I), R ¹² and R ¹⁴ are each independently preferably an alkylene group having 2 to 18 carbon atoms and an aralkylene group having 7 to 15 carbon atoms, and an alkylene group having 2 to 12 carbon atoms and a carbon number of carbon atoms. An aralkylene group having 7 to 12 carbon atoms is more preferable, and an alkylene group having 2 to 8 carbon atoms and an aralkyllene group having 7 to 9 carbon atoms are particularly preferable. Specifically, a hexamethylene group, an octamethylene group or an m-xylene group is particularly preferable.
Further, in the formula (I), it is preferable that R ¹² and R ¹⁴ have 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. Further, as R13, an ^aralkylene group having 30 to 40 carbon atoms is more preferable, and the aralkylene group is preferably derived from dimer acid. Further, 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 having 12 carbon atoms. An alkyl group having to 20 alkyl groups or an alkenyl group having 12 to 20 carbon atoms is more preferable, and an alkyl group having 17 carbon atoms or an alkenyl group having 17 carbon atoms 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 independently numbers 1 to 19, and 2 to 7 are more preferable. Further, it is preferable that a and b have the same number.

Further, the compound represented by the formula (I) is preferably a compound having a urethane group (-NHCOO-) in the molecule. That is, in the compound represented by the formula (I), it is preferable that at least one selected from R', B, and Y is a group containing a urethane group, and R'or Y contains a urethane group. It is more preferable that 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, it is easy to obtain a liquid detergent having better dispersion stability of water-insoluble particles.
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 one or more urea groups in the molecule and having at least one structural unit selected from the structural unit of the fatty acid and the structural unit obtained by the reaction between the fatty acid and urea. Be done.
The fatty acid used for 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. Further, the structural unit may be present at either the terminal 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-OR ²⁰ -... (V)
(In 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, and R ²¹ is a number from the following equations (j-1) to (j-4). Each is a group represented by each, and R ²² is a group represented by the following formulas (k-1) to (k-8), respectively.)

As the modified urea, a substituent was introduced into a compound having at least one urea group in the molecule and a copolymer obtained by copolymerizing another compound, or a compound having at least one urea group in the molecule. Examples include 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. Moreover, as a substituent, a urethane group, a polyoxyalkylene group and the like can be mentioned. Of these, a urea urethane compound having two or more urea groups and at least one urethane group is preferable because the dispersion stability of the water-insoluble particles is more likely to be improved. Further, a compound in which a urethane group is introduced into the connecting portion between the urea group and the urea group and the terminal portion of the compound also has a urethane group is more preferable. Further, 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.

Examples of the high molecular weight urea include 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 the GPC method. Among them, polymer urea having at least two urea groups in the molecule and having a polystyrene-equivalent number average molecular weight of 3,000 to 70,000 according to the GPC method, because the dispersion stability of water-insoluble particles is more likely to be improved. Is preferable. The polymer urea is not particularly limited as long as it has the effect of the present invention, and examples thereof include compounds represented by the following formula (VI).

In formula (VI), 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- , etc. 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, Alternatively, it represents an oligomer having a urethane group.
R ³¹ and R ³⁵ have an 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 cyclo having 3 to 20 carbon atoms, which may have a branched chain. Alkyl group, aryl group having 5 to 12 carbon atoms or alkyl substituted aryl group, polyoxyalkylene monoalkyl group represented by C _{m'H 2m'+ 1-} ( _{OC 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- (OC n'H _{2n '} ) _p' -(O-CH (C) ₆ H ₅ ) -CH ₂ ) _u- (OOC-C _v H _2v ) _x , hydroxyalkyl group with 4 to 32 carbon atoms, carboxyalkyl group with 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) NR ⁴¹ R ⁴² Represents a radical. .. The radical may have a substituent, and at least one group selected from an amino group and a carboxyl group may contain a salt thereof or a quaternary structure.
R ⁴¹ and R ⁴² are hydrogen, an alkyl group having 1 to 32 carbon atoms which may have a branched chain, an alkenyl group having 3 to 18 carbon atoms, an alkynyl group having 2 to 20 carbon atoms, and 3 to 20 carbon atoms. Cycloalkyl group, cycloalkenyl group having 3 to 20 carbon atoms, aryl group having 5 to 12 carbon atoms or alkyl substituted aryl group, alkoxyalkyl group having 1-32 carbon atoms, or acyloxyalkyl group having 1 to 32 carbon atoms. show.
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 above ( _{OC n'H 2n' )} may be a combination of two or more kinds of oxyalkylene groups such as an oxyethylene group and an oxypropylene group, and 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 have an alkylene group having 4 to 22 carbon atoms, an alkenylene group having 3 to 18 carbon atoms, an alkynylene group having 2 to 20 carbon atoms, and a cyclo having 3 to 20 carbon atoms, which may have a branched chain. It represents an alkylene group, a cycloalkenylene group having 3 to 20 carbon atoms, an arylene group having 5 to 12 carbon atoms, or an arylalkylene radical.
R ³³ includes a polyester group, a polyether group, a polyamide group, an alkylene group having 4 to 22 carbon atoms, an alkenylene group having 3 to 18 carbon atoms, and an alkynylene group having 2 to 20 carbon atoms, which may have a branched chain. A cycloalkylene group having 3 to 20 carbon atoms, a cycloalkenylene group having 3 to 20 carbon atoms, and an arylene group having 5 to 12 carbon atoms represent an arylalkylene radical.
A', X', Y', Z'represent -O- or -NR ⁵⁰ .
R ⁵⁰ is hydrogen, an alkyl group having 1 to 32 carbon atoms which may have a branched chain, an alkenyl group having 3 to 18 carbon atoms, an alkynyl group having 2 to 20 carbon atoms, and a cycloalkyl group having 3 to 20 carbon atoms. Represents a 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 high molecular weight urea may be in a solid or liquid state by itself, but it should be easily added in the manufacturing process. It is preferable that it is liquid from the viewpoint that it can be formed. When the urea derivative is a liquid substance, the urea derivative may be dissolved or dispersed in a solvent to form a liquid substance.

As the component (B), a commercially available product may be used. Specific examples thereof include BYK-410, BYK-411, BYK-420, BYK-425, BYK-428, BYK-7411ES, BYK-7420ET, BYK-D410 and the like manufactured by Big Chemie.

The content of the component (B) in the liquid detergent is preferably 0.01 to 5% by mass, more preferably 0.01 to 2% by mass, based on the total mass of the liquid detergent.
When the content of the 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 easily dispersed more uniformly. Further, when the content of the component (B) is 5% by mass or less, the viscosity of the liquid detergent does not become too high and the fluidity does not easily decrease. In addition, the storage stability becomes better.

The mass ratio of the component (A) to the component (B) in the liquid detergent, (A) / (B), is preferably 1 to 1000, more preferably 6 to 550, still more preferably 20 to 500. When (A) / (B) is within the above range, the effect of structuring can be easily obtained.
When the liquid detergent of the present invention contains MEE in the component (A), the mass ratio (MEE / (B)) between the MEE and the component (B) is preferably 10 to 5000, more preferably 15 to 500. preferable. When the mass ratio of MEE and the component (B) is within the above range, the effect of structuring can be easily obtained.

<Water-insoluble particles>
The liquid detergent of the present invention preferably contains particles (water-insoluble particles) that are difficult to dissolve 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 packaging materials containing capsule fragrances and active ingredients in place of them, beads and pearl brighteners for imparting unique product aesthetics, bentonite, zeolites, carboxymethyl cellulose (CMC) and the like. Can be mentioned.
These water-insoluble particles may be used alone or in combination of two or more.
Capsule fragrances are those in which a fragrance component is encapsulated by a capsule wall formed of a polymer compound. Examples of the polymer compound forming the capsule wall include synthetic polymers such as polyacrylic acid-based, polyvinyl-based, polymethacrylic acid-based, melamine-based, and urethane-based. These may be used individually by 1 type, or may be used in combination of 2 or more type.
The fragrance contained in the capsule fragrance is not particularly limited, and examples thereof include the fragrance compositions shown in Table 1 below.

The content of the water-insoluble particles in the liquid detergent is preferably 0.0001 to 10% by mass, more preferably 0.1 to 3% by mass, based on the total mass of the liquid detergent. When the content of the water-insoluble particles is within the above range, the dispersion stability of the water-insoluble particles in the liquid cleaning agent tends to be good.

The liquid detergent of the present invention has a viscosity (value measured after 60 seconds under the conditions of a measurement temperature of 25 ° C. and a rotation speed of 60 rpm using a B-type viscometer, hereinafter referred to as viscosity _v2 ) of 50 to. It is preferably 500 mPa · s. If the viscosity is within the above range, the structuring tends to be better.
Further, the liquid cleaning agent of the present invention has a viscosity v ₂ of 50 to 500 mPa · s, and has a viscosity v ₁ (25 ° C.) when measured after 60 seconds under the condition of a rotation speed of 6 rpm using a B-type viscometer. And the ratio of viscosity v ₂ (viscosity v ₁ / viscosity v ₂ ) is preferably 1.1 or more. Further, the viscosity v ₁ / viscosity v ₂ is more preferably 1.2 or more. When the viscosity v ₁ / viscosity v ₂ is 1.1 or more, the dispersion stability of the water-insoluble particles tends to be good.

<Arbitrary ingredient>
The liquid detergent of the present invention may contain any component other than the above components (A) to (B), if necessary, as long as the effect of the present invention is not impaired.
Examples of the optional component include water, a surfactant other than the component (A1) and the component (A2) (arbitrary surfactant), a water-miscible organic solvent, a metal ion scavenger, an antioxidant, and a cleaning performance improver. Examples thereof include stability improvers, colorants / emulsions, thickeners / solubilizers, enzyme stabilizers, pH adjusters, and fragrances other than capsule fragrances.

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, 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% by mass, more preferably 10 to 60% by mass, and 10 to 40% by mass. % Is particularly preferable.

<Arbitrary surfactant>
The optional surfactant is a cleaning component, and a known surfactant can be used in the liquid detergent. For example, a cationic surfactant, an amphoteric surfactant, or the like can be blended in one type or in 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 to 60% by mass is more preferable. When the total amount of the surfactant is within the above range, the detergency tends to be better.

Further, the ratio of the component (A) to the total amount of the surfactant is preferably 30 to 100% by mass, more preferably 60 to 100% by mass, based on the total mass of the surfactant from the viewpoint of detergency.

[Cationic surfactant]
As the cationic surfactant, conventionally known ones can be appropriately selected and used. Specific examples thereof include stearic acid dimethylaminopropylamide and alkyltrimethylammonium salts. When the liquid detergent of the present invention contains a cationic surfactant, the blending amount thereof is preferably 0 to 30% by mass with respect to the total mass of the liquid detergent from the viewpoint of detergency.

[Amphoteric surfactant]
Examples of amphoteric surfactants include alkylbetaine type, alkylamide betaine type, imidazoline type, alkylaminosulfone type, alkylaminocarboxylic acid type, alkylamide carboxylic acid type, amide amino acid type, phosphoric acid type amphoteric surfactant and the like. Can be mentioned. When the liquid detergent of the present invention contains an amphoteric surfactant, the blending amount thereof 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 the water-miscible organic solvent 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 and tetraethylene glycol. Examples thereof include polyethylene glycol having a mass average molecular weight of about 200 to 1000, polyglycols such as dipropylene glycol, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, diethylene glycol monobutyl ether (butyl carbitol), and alkyl ethers such as diethylene glycol dimethyl ether. ..
Among these, ethanol, propylene glycol, polyethylene glycol, diethylene glycol monobutyl ether (butyl carbitol), 3- Preference is given to methoxy-3-methyl-1-butanol.
The water-miscible organic solvent may be used alone or in combination of two or more. In particular, it is preferable to use ethanol and butyl carbitol in combination, 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 to 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, more preferably 4 to 10% by mass, based on the total mass of the liquid detergent.
In the present invention, the water-miscible organic solvent means an organic solvent that dissolves in 1 L of ion-exchanged water at 25 ° C. in an amount of 50 g or more.

As the metal ion scavenger, a metal ion scavenger such as malonic acid, succinic acid, malic acid, diglycolic acid, tartaric acid, and citric acid is used, for example, 0.1 to 20% by mass based on the total mass of the liquid cleaning agent. Can include. The metal ion scavenger may be used alone or in combination of two or more.

As the antioxidant, butylhydroxytoluene (BHT), cresol distyrene, sodium sulfite, sodium hydrogen sulfite and the like can be contained, for example, in an amount of 0.01 to 2% by mass based on the total mass of the liquid detergent. The antioxidant may be used alone or in combination of two or more.

Enzymes (proteases, lipases, cellulase, etc.), texture improvers, alkaline builders such as alkanolamines, hydrotropes, fluorescent agents, stain transfer inhibitors, recontamination inhibitors, pearls for the purpose of improving cleaning performance and stability. Agents, soil release agents and the like can be included.

Colorants include Acid Red 138, Polar Red RLS, Liquid Yellow 203, Liquid Yellow 203, Acid Blue 9, Blue 1, Blue 205, Green 3, and Turquoise P-GR (all trade names). ) And the like, for example, about 0.00005 to 0.005% by mass with respect to the total mass of the liquid cleaning agent.

Examples of the emulsion include polystyrene emulsions and polyvinyl acetate emulsions, and emulsions having a solid content of 30 to 50% by mass are usually preferably used. As a specific example, polystyrene emulsion (trade name: Cybinol (registered trademark) RPX-196 PE-3, solid content 40% by mass, manufactured by Saiden Chemical Co., Ltd.) or the like is used with respect to the total mass of the liquid detergent. It can contain 0.001 to 0.5% by mass.

Examples of the thickener and solubilizer include aromatic sulfonic acid or a salt thereof, for example, toluene sulfonic acid, xylene sulfonic acid, cumene sulfonic acid, substituted or unsubstituted naphthalene sulfonic acid, toluene sulfonic acid salt, xylene sulfonic acid salt, and the like. Examples thereof include cumene sulfonate, substituted or unsubstituted naphthalene sulfonate and the like.
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 slimming agent is preferably 0.01 to 10% by mass with respect to the total mass of the liquid detergent.
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 the fragrance other than the capsule fragrance for fragrance, conventionally known fragrances can be appropriately selected and used, and for example, the fragrance component described in JP-A-2002-146399 can be used. The blending amount of the fragrance is preferably 0.01 to 2% by mass with respect to the total mass of the liquid detergent.

The liquid detergent of the present invention preferably has a pH of 4 to 9 at 30 ° C., 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 adding a pH adjuster, if necessary. The pH adjuster is optional as long as the effect of the present invention is not impaired, but sulfuric acid, sodium hydroxide, potassium hydroxide, alkanolamine and other sulfuric acid, hydrochloric acid, sodium hydroxide, potassium hydroxide, alkanolamine and the like are stable. It is preferable 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, if necessary, other components in water as a dispersion medium. Specifically, it can be produced by adding each component to water as a dispersion medium, stirring and mixing. Therefore, the method for producing a 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 method of putting the liquid detergent alone or by putting it in water with a known bleaching agent or a softening agent to make a washing liquid, and putting an object to be washed in this washing liquid and washing with a washing machine, a washing liquid. , Or a method of applying a liquid detergent to an object to be washed and washing it with a washing machine.
Examples of the object to be washed include textile products such as clothing, cloth, sheets, curtains, and rugs. That is, the liquid detergent of the present invention is suitable as a detergent for clothing.
The content of the liquid detergent in the cleaning liquid is not particularly limited. The amount of the 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 contains (a1) component, (A2) component, (B) component, water-insoluble particles, and water, and the (A2) component contains LAS, AES, AEPS, and coconut fatty acid. At least one anionic surfactant selected from the group consisting of salts, the compound (B) having a component represented by the formula (I), and at least selected from fatty acid-modified urea, modified urea, and high molecular weight urea. It is preferably at least one selected from one urea derivative. The content of the component (a1) is preferably 5 to 50% by mass, more preferably 10 to 40% by mass, and particularly preferably 15 to 30% by mass with respect to the total mass of the liquid detergent. Further, the content of the component (A2) is preferably 3 to 25% by mass, more preferably 5 to 20% by mass, and 15 to 20 with respect to the total mass of the liquid detergent. Is particularly preferred. Further, (A) / (B) is preferably 1 to 1000, more preferably 6 to 550, and even more preferably 20 to 500.

Hereinafter, the present invention will be described in detail with reference to examples, but the present invention is not limited to the following description.

(Raw materials used)
The abbreviations in Tables 2 and 3 represent the following.
<Ingredient (A)>
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, t is 0. Narrow rate: 33%) (manufactured by Lion Chemical Co., Ltd., trade name: CEAO-90).
A1-2: AE15: 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, and s. Alkyl alkoxylate having a value of 15 and t of 0. Narrow ratio: 33% (manufactured by 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, and s. Is 7 and t is 0. Alchol ethoxylate. Narrow rate: 33%.)
A1-4: EOPO nonionic: polyoxyethylene polyoxypropylene alkyl ether (in the formula (a1), R ¹ is an alkyl group having 10 to 14 carbon atoms, -X- is -O-, and R ² is hydrogen. A compound in which s is 5 and t is 2. EO and PO are block adducts. Narrow ratio: 33%.)
A2-1: LAS: A linear or branched alkylbenzene sulfonic acid having an alkyl group having 10 to 14 carbon atoms (manufactured by Lion Corporation, trade name: Lipon (registered trademark) LH-200).
A2-2: AES: Polyoxyethylene alkyl ether sulfate (natural alcohol (trade name "CO-1270" manufactured by P & G) to which 1 mol of EO is added is sulfated and neutralized with sodium hydroxide. (Manufactured by this) (manufactured by Lion Co., Ltd., product name: BRES (1)).
A2-3: AEPS: Monoethanolamine salt of polyoxyalkylene alkyl ether sulfuric acid ester (propylene oxide with an average addition mole number of 1.0 mol and ethylene oxide with an average addition mole number of 2.0 mol are added in this order to 1-dodecanol. After that, it was produced by sulfating it and neutralizing it with monoethanolamine).
A2-4: Palm fatty acid (manufactured by NOF CORPORATION, trade name: palm fatty acid).
<Ingredient (B)>
B-1: A compound having a urea group in the molecule (solution containing modified urea (active ingredient: 25%). Main solvent: N-methylpyrrolidone) (manufactured by 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) (manufactured by BYK, trade name: BYK-7411ES).
B-3: A compound having a urea group in the molecule (solution containing modified urea (active ingredient: 52%). Main solvent: N-methylpyrrolidone) (manufactured by 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: dimethylsulfoxide) (manufactured by BYK, trade name: BYK-D410).
B-5: A compound having a urea group in the molecule (solution containing modified urea (active ingredient: 40%). Main solvent: amid ether) (manufactured by 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) (manufactured by BYK, trade name: BYK-420).
<Arbitrary ingredient>
Citric acid: (On the other hand, manufactured by Yushi Kogyo Co., Ltd., trade name: liquid citric acid).
Sodium benzoate: (manufactured by Toagosei Co., Ltd., trade name: sodium benzoate).
Ethanol: (Made by Japan Alcohol Trading Co., Ltd., Product name: Specified alcohol 95 degree synthesis.
Butyl carbitol: (manufactured by Nippon Embroidery 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: paratoluenesulfonic 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 fragrance: Capsule A shown in Table 1.
Fragrance: 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: Product name "Red No. 106", manufactured by Ami Kasei Co., Ltd .... 0.0001% by mass.
-Isothiazolinone solution: 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 the company: 0.01% by mass.
-SR agent: Product name "TexCare SRN-170C", manufactured by Clariant Japan Co., Ltd .... 0.5% by mass.
In the table, the water content "balance" is an amount required to make the total amount of the liquid detergent 100% by mass. The "appropriate amount" of the pH adjuster is the amount required to bring the liquid detergent to the pH in the table.
Further, "A / B" in the table represents the mass ratio of the component (A) and the component (B) in the liquid detergent.

(Examples 1 to 22, Comparative Examples 1 to 2)
According to the compositions shown in Tables 2 to 3, the components (A) to (B) and the optional components and water were all stirred and mixed to obtain a liquid detergent.
The blending amount in the table is a net conversion value. In addition, the components whose blending amount is not described in the table are not blended.

<Evaluation method>
(Evaluation of thickening and structuring)
80 g of the liquid cleaning composition shown in Tables 2 to 3 was filled in a glass bottle (PS11 bottle), and the temperature was adjusted to 25 ° C. in a constant temperature bath. A sample solution adjusted to 25 ° C. was set in a Brookfield type viscometer (B type viscometer). First, the rotation speed of the rotor was set to 6 rpm, and the viscosity v ₁ (mPa · s) after 600 seconds was measured. After that, the rotation speed of the rotor was set to 60 rpm, and the viscosity _v2 (mPa · s) after 60 seconds was measured. Regarding the relationship between viscosity _v1 and viscosity _v2 , thickening and structuring were evaluated according to the following evaluation criteria. When the determination results of the viscosity v2 _were A and B and the determination results of structuring were A and B, it was determined that the thickening and structuring of the liquid composition had sufficiently progressed. The results are shown in Tables 2 and 3. In the table, the upper part shows the evaluation result, and the lower part shows the viscosity.
[Evaluation criteria (viscosity v ₂ )]
A: Viscosity _v2 is 300 mPa · s or less.
B: Viscosity _v2 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 the liquid cleaning composition shown in Tables 2 to 3 is filled in a wide-mouth standard bottle (PS-No6 bottle), and beads (TPSHIKI PIGMENT. Co., manufactured by LTD., Trade name: PFL-RED 7155T Lot. 0308) are added thereto. 0.5 g was added and dispersed. After storing in a constant temperature bath at 25 ° C. for 60 days, the bottle was taken out from the constant temperature 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 and 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: Beads were floating or settling in less than 30 days.

(Storage stability)
A wide-mouth standard bottle (PS-No6 bottle) was filled with 30 g of the liquid detergents shown in Tables 2 and 3, stored in a constant temperature bath at −5 ° C. for 1 month, visually confirmed, and evaluated according to the following evaluation criteria. The results are shown in Tables 2 and 3.
A: It is transparent and the solution is fluid.
B: It is transparent, but the solution is not fluid.
C: There is a precipitate or suspended matter.

(Cleaning performance)
The cleaning performance of the liquid detergents in Tables 2 and 3 was evaluated by the following methods.
As a dirt cloth, we used a "face dirt cloth" made by rubbing dirt on the face and neck with a cotton cloth. The washing liquid was prepared by dispersing and dissolving 6 mL of the liquid detergent in 15 L of water.
Using a Terg-O-tometer (manufactured by UNITED STATES TESTING) as a cleaning tester, 10 sheets of dirty cloth, a cleaning knitted cloth, and the washing liquid were placed in the washing tester, and the bath ratio was 30 times (washing water). / Washing treatment was performed at 120 rpm and 15 ° C. for 10 minutes according to the total mass of the object to be washed. Next, it was transferred to a two-tank washing machine (manufactured by Mitsubishi Electric Corporation, product number "CW-C30A1-H1"), dehydrated for 1 minute, and then placed in 30 L of tap water (15 ° C, 4 ° DH) for 3 minutes. It was rinsed and air-dried.
The reflectance of unstained cloth, which is a cotton cloth that has not been stained, before cleaning, and after cleaning, is measured by a color difference meter (manufactured by Nippon Denshoku Kogyo Co., Ltd., product name "SE200 type". ”), And the cleaning rate (%) was calculated by the following formula. The cleaning rate (%) was calculated for 10 dirty cloths, and the average value was used to evaluate the sebum detergency based on the following criteria.
Cleaning rate (%) = (K / S of dirty cloth before cleaning-K / S of dirty cloth after cleaning) / (K / S of dirty cloth before cleaning-K / S of uncleaned cloth) × 100
However, K / S is a value obtained by the formula: K / S = (1-R / 100) ² / (2R / 100), and R is the reflectance (%).
The results are shown in Tables 2 and 3. In the table, the upper part shows the evaluation result, and the lower part 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 fragrance could be stably dispersed. Further, from the results of Example 2 or 5, it was confirmed that the capsule fragrance can be stably dispersed even when the liquid detergent of the present invention is a concentrated liquid detergent. 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 structuring was sufficiently advanced.
On the other hand, the liquid detergent of Comparative Example 2 containing no component (B) was inferior in dispersion stability. The liquid detergent of Comparative Example 1 containing no component (A) was judged to be unsuitable for use as a liquid detergent because it had excellent dispersion stability but poor cleaning performance.
From the above results, it was confirmed that the liquid detergent of the present invention can stably disperse water-insoluble particles.

Claims (7)

One or more surfactants (A) selected from a nonionic surfactant (A1) and an anionic surfactant (A2), and a compound (B) having a molecular weight of 100 or more and having a urea group in the molecule. It contains viscosity _v1 when measured after 60 seconds under the conditions of measurement temperature 25 ° C and rotation speed 6 rpm using a B-type viscometer, and measurement temperature 25 ° C and rotation speed 60 rpm using a B-type viscometer. A particle dispersion cleaning agent composition comprising a liquid cleaning agent composition having a viscosity _v2 measured after 60 seconds under the conditions and satisfying the following conditions , and particles dispersed in the liquid cleaning agent composition .
180mPa ・ s ≤ viscosity _v2 ≤ 500mPa ・ s
Viscosity _v1 / Viscosity _v2 ≧ 1.1 The particle dispersion detergent composition according to claim 1, wherein the component (A) contains both a nonionic surfactant (A1) and an anionic surfactant (A2). The particle dispersion cleaning agent composition according to claim 1 or 2, wherein the component (B) is a compound having a urea group in the molecule (excluding triclocarban) having a molecular weight of 200 or more. The particle dispersion detergent composition according to any one of claims 1 to 3, wherein the content of the component (B) is 0.01 to 5% by mass with respect to 100% by mass of the liquid detergent composition. .. The particle dispersion detergent composition according to any one of claims 1 to 4, wherein the liquid detergent composition further contains water. The particle dispersion cleaning agent according to any one of claims 1 to 5, wherein the particles are one or more selected from the group consisting of a packaging agent, beads, a pearl brightener, bentonite, zeolite, and carboxymethyl cellulose. Composition. The particle dispersion detergent composition according to any one of claims 1 to 6, wherein the content of the particles is 0.0001 to 10% by mass with respect to 100% by mass of the liquid detergent composition.