JP2017075295A - Liquid detergent - Google Patents

Abstract

An object of the present invention is to provide a liquid detergent that maintains detergency, has low viscosity, can be structured, and has excellent storage stability. The liquid detergent of the present invention comprises (A) component: a surfactant, and (B) component: a repeating unit represented by the following general formula (b1) and a repeating unit represented by the following general formula (b2): A polymer having one or more repeating units selected from the group consisting of units and one or more repeating units selected from the group consisting of repeating units derived from acrylic acid and repeating units derived from acrylamide; C) component: containing a polymer having repeating units derived from a monomer represented by the following general formula (c1) and repeating units derived from a monomer represented by the following general formula (c2), The content of component (A) is 15% by mass or more, and the mass ratio represented by component (B)/component (C) is 0.05 to 1.25. [Chemical 1] [Selection drawing] None

Description

  The present invention relates to a liquid detergent.

In recent years, liquid detergents are often used as clothing detergents. For the purpose of changing the rheological properties of a liquid detergent, the liquid detergent may be structured by adding a structurant to the liquid detergent. As such a structuring agent, for example, an acrylic acid polymer is used.
As a composition containing an acrylic acid polymer, for example, Patent Document 1 includes a surfactant, an acrylic acid copolymer, water, an alkaline material, and an acidic material. The aqueous surfactant composition used is disclosed.

JP 2014-28957 A

However, when an acrylic acid polymer is added to a liquid detergent, the viscosity tends to increase, and the usability such as difficulty in discharging the liquid detergent from the container may be inferior.
Thus, it was difficult to structure a liquid detergent while suppressing an increase in viscosity.
In recent years, concentrated liquid detergents with a high surfactant concentration are often used. However, since the amount of water decreases, the storage stability decreases and the components contained in the liquid detergent precipitate. It was easy to separate.

  The present invention has been made in view of the above circumstances, and an object of the present invention is to provide a liquid detergent that can be structured while maintaining a detergency and that has a low viscosity and is excellent in storage stability.

The present invention has the following aspects.
[1] Component (A): surfactant and component (B): 1 selected from the group consisting of the repeating unit represented by the following general formula (b1) and the repeating unit represented by the following general formula (b2) A polymer having one or more kinds of repeating units, one or more kinds of repeating units selected from the group consisting of repeating units derived from acrylic acid and repeating units derived from acrylamide, and component (C): a polymer having a repeating unit derived from the monomer represented by c1) and a repeating unit derived from the monomer represented by the following general formula (c2), and the content of the component (A) is The liquid detergent which is 15 mass% or more and whose mass ratio represented by (B) component / (C) component is 0.05-1.25.

In formula (b1), R ¹ and R ² are each independently an alkyl group having 1 to 3 carbon atoms or a hydroxyalkyl group having 1 to 3 carbon atoms, and X ⁻ is a counter ion.
In formula (b2), R ³ and R ⁴ are each independently an alkyl group having 1 to 3 carbon atoms or a hydroxyalkyl group having 1 to 3 carbon atoms, and X ⁻ is a counter ion.

In formula (c1), R ⁵ is a hydrogen atom or a methyl group, and R ⁶ is a hydrogen atom.
In formula (c2), R ⁷ is a hydrogen atom or a methyl group, and R ⁸ is an alkyl group having 1 to 40 carbon atoms.

[2] The component (A) includes a nonionic surfactant and an anionic surfactant, and the nonionic surfactant is represented by the compound represented by the following general formula (a1) and the following general formula (a2). One or more selected from the group consisting of the following compounds: the anionic surfactant is a linear alkylbenzene sulfonic acid, a linear alkylbenzene sulfonate, a polyoxyethylene alkyl ether sulfate, a fatty acid having 8 to 18 carbon atoms And at least one selected from the group consisting of fatty acid salts having 8 to 18 carbon atoms, and the component (B) has a repeating unit derived from a diallyldialkylammonium salt and a repeating unit derived from acrylamide. The liquid detergent according to [1], which is a polymer.

In formula (a1), R ⁹ is a hydrocarbon group having 9 to 13 carbon atoms, R ¹⁰ is an alkylene group having 2 to 4 carbon atoms, and R ¹¹ is an alkyl group having 1 to 4 carbon atoms. m represents an average repeating number of ^{OR 10,} a number of 5-25.
In the formula (a2), R ¹² is a hydrocarbon group having 10 to 22 carbon atoms, EO is an oxyethylene group, and PO is an oxypropylene group. s represents the average number of repetitions of EO and is a number of 5 to 20, and t represents the average number of repetitions of PO and is a number of 0 to 4.

[3] The liquid detergent according to [2], wherein the content of the nonionic surfactant is 10 to 50% by mass with respect to the total mass of the liquid detergent.
[4] The liquid detergent according to [2] or [3], wherein the content of the anionic surfactant is 2 to 20% by mass with respect to the total mass of the liquid detergent.
[5] The liquid detergent according to any one of [1] to [4], wherein the content of the component (A) is 60% by mass or less.
[6] The liquid detergent according to any one of [1] to [5], wherein the content of the component (B) is 0.01 to 5% by mass.
[7] The liquid detergent according to any one of [1] to [6], wherein the content of the component (C) is 0.01 to 8% by mass.
[8] The liquid detergent according to any one of [1] to [7], further containing water.
[9] The liquid detergent according to any one of [1] to [8], further containing insoluble particles.
[10] The liquid detergent according to any one of [1] to [9], which is for clothing.
[11] The component (A) is a cationic surfactant that is at least one selected from the group consisting of a compound represented by the following general formula (a3) and a compound represented by the following general formula (a4). The liquid detergent according to any one of [1] to [10].

In formula (a3), R ¹³ and R ¹⁴ are each independently a hydrogen atom, a hydrocarbon group having 1 to 25 carbon atoms, or a group represented by — (CH ₂ CH ₂ O) _q —H (q is 1 And R ¹⁵ is a hydrocarbon group having 8 to 25 carbon atoms, and R ¹⁶ is a hydrogen atom, an alkyl group having 1 to 3 carbon atoms, or a hydroxyalkyl group having 1 to 3 carbon atoms. or _{- (CH} 2 CH 2 _O) groups represented by r -H (r is an integer of 1 to 25.) is, Z ^- is a counterion.
In the formula (a4), R ¹⁷ is a hydrocarbon group having 7 to 27 carbon atoms, R ¹⁸ is a hydrocarbon group having 1 to 25 carbon atoms, R ¹⁹ is an alkyl group having 1 to 4 carbon atoms, carbon number 1 to 4 hydroxyalkyl groups or a group represented by — (CH ₂ CH ₂ O) _p —H (p represents an integer of 1 to 25).

  The liquid detergent of the present invention can be structured while maintaining a detergency, while having a low viscosity, and is excellent in storage stability.

Hereinafter, the present invention will be described in detail.
The liquid detergent of the present invention contains the following components (A), (B) and (C).
In the present invention, “structured” means having 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 is lowered and fluidity is expressed.
Further, “low viscosity” means that the viscosity after stirring for 60 seconds at 60 rpm is 1000 mPa · s or less.

<(A) component>
The component (A) is a surfactant. When the liquid detergent contains the component (A), the detergency (particularly the detergency against sebum dirt) is increased.
Examples of the component (A) include nonionic surfactants, anionic surfactants, cationic surfactants, and amphoteric surfactants. These may be used alone or in combination of two or more.
As the component (A), it is preferable to use a nonionic surfactant and an anionic surfactant in combination from the viewpoint of excellent sebum detergency.

(Nonionic surfactant)
A nonionic surfactant is a surfactant mainly used for imparting detergency to a liquid detergent.
Although it does not specifically limit as a nonionic surfactant, For example, alkylene oxide adducts, such as a polyoxyalkylene type nonionic surfactant, alkylphenol, a C8-C22 fatty acid, or a C8-C22 amine, polyoxyethylene polyoxy Propylene block copolymer, fatty acid alkanolamine, fatty acid alkanolamide, polyhydric alcohol fatty acid ester or its alkylene oxide adduct, polyhydric 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 amides, alkyl glycosides and the like. These may be used alone or in combination of two or more.
Among the above, the nonionic surfactant is preferably a polyoxyalkylene type nonionic surfactant from the viewpoint of improving the appearance stability while appropriately maintaining the viscosity of the liquid detergent.

  Examples of the polyoxyalkylene-type nonionic surfactant include a compound represented by the following general formula (a1) (hereinafter referred to as “compound (a1)”), a compound represented by the following general formula (a2) (hereinafter, "Compound (a2)"). These may be used alone or in combination of two or more.

In formula (a1), R ⁹ is a hydrocarbon group having 9 to 13 carbon atoms, R ¹⁰ is an alkylene group having 2 to 4 carbon atoms, and R ¹¹ is an alkyl group having 1 to 4 carbon atoms. m represents an average repeating number of ^{OR 10,} a number of 5-25.
In the formula (a2), R ¹² is a hydrocarbon group having 10 to 22 carbon atoms, EO is an oxyethylene group, and PO is an oxypropylene group. s represents the average number of repetitions of EO and is a number of 5 to 20, and t represents the average number of repetitions of PO and is a number of 0 to 4.

Compound (a1):
In the formula (a1), the hydrocarbon group for R ⁹ may be linear or branched, or may contain a cyclic structure.
The hydrocarbon group for R ⁹ is preferably an aliphatic hydrocarbon group, more preferably a linear or branched alkyl group, or a linear or branched alkenyl group.
R ⁹ has 9 to 13 carbon atoms, preferably 10 to 13 carbon atoms, and more preferably 11 to 13 carbon atoms. When the carbon number of R ⁹ is 9 or more, the detergency is further increased. On the other hand, when the carbon number of R ⁹ is 13 or less, the storage stability is improved, and in particular, gelation is easily suppressed.
The compound (a1) may be a mixture having a single chain length or a mixture having a plurality of chain lengths. R ⁹ is derived from the starting fatty acid (R ⁹ -COOH).

In the formula ^{(a1), R 11} is an alkyl group having 1 to 4 carbon atoms, preferably an alkyl group having 1 to 3 carbon atoms. Specific examples of R ¹¹ include a methyl group, an ethyl group, an n-propyl group, an isopropyl group, and an n-butyl group. A methyl group and an ethyl group are preferable, and a methyl group is more preferable. When the carbon number of R ¹¹ is 1 or more, precipitation during low-temperature storage is easily suppressed. On the other hand, when the carbon number of R ¹¹ is 4 or less, the solubility of the liquid detergent in water under low temperature conditions is further increased.

In the formula ^{(a1), R 10} is an alkylene group having 2 to 4 carbon atoms, an ethylene group or a propylene group is preferred.
A plurality of R ¹⁰ in the formula may be the same as or different from each other. That is, the alkylene group for R ¹⁰ may be a single type or a combination of two or more types. Among them, it is preferable that m OR ¹⁰ in the formula is an oxyethylene group or an oxyethylene group and an oxypropylene group are mixed because foaming during washing is good and inexpensive. .
When two or more alkylene groups of R ¹⁰ are combined, the addition method of OR ¹⁰ is not particularly limited. For example, when oxyethylene group and oxypropylene group are mixed, random addition It may be a block addition. Examples of the block addition method include a method of adding propylene oxide after adding ethylene oxide, a method of adding ethylene oxide after adding propylene oxide, a method of adding propylene oxide after adding ethylene oxide, and further adding ethylene oxide. Can be mentioned.

In the formula (a1), m represents an average repeating number of ^{OR 10,} a number of 5-25. When m is at least the lower limit value, the cleaning power, particularly the cleaning power against sebum stains is further improved. On the other hand, the solubility with respect to the water of a liquid detergent improves more as m is below an upper limit.
When OR ¹⁰ is all oxyethylene groups, m is preferably from 5 to 20, and more preferably from 12 to 18.
When OR ¹⁰ is a mixture of an oxyethylene group and an oxypropylene group, m is particularly preferably 12-21. Among these, the average number of repeating oxypropylene groups is preferably 5 or less, more preferably 4 or less, and even more preferably 3 or less. If the average number of repeating oxypropylene groups exceeds 5, the cleaning power and storage stability as a liquid detergent (transparency uniformity, stability over time, etc.) may be reduced.

In the compound (a1), it is preferable that the narrow ratio indicating the distribution ratio of the compounds having different OR ¹⁰ repeat numbers is 20% by mass or more. The upper limit of the narrow ratio is preferably substantially 80% by mass or less.
The narrow ratio is more preferably 20 to 50% by mass, and more preferably 30 to 45% by mass because storage stability and solubility in water are further improved.
The higher the narrow rate, the easier it is to obtain good detergency. Further, when the narrow ratio is preferably 20% by mass or more, and particularly preferably 30% by mass or more, a liquid detergent with less raw material odor derived from the compound (a1) is easily obtained. This is because, after the production of the compound (a1), a fatty acid ester which is a raw material of the compound (a1) coexisting with the compound (a1), an alkylene oxide adduct wherein m in the formula (a1) is 1 or 2, This is because there is less.

  Of the compounds contained as impurities in the compound (a1), the total ratio of the fatty acid ester that is the raw material of the compound (a1) and the alkylene oxide adduct having m of 1 or 2 in the formula (a1) is: It is preferable that it is 0.5 mass% or less with respect to the total mass of a compound (a1), and it is more preferable that it is 0.2 mass% or less. When this proportion is 0.5% by mass or less, a liquid detergent with less raw material odor of the surfactant is easily obtained.

  In this specification, the “narrow ratio” refers to a value represented by the following mathematical formula (S), which indicates a distribution ratio of alkylene oxide adducts having different numbers of added moles of alkylene oxide.

In the formula (S), m _max represents the number of repetitions of OR ¹⁰ (number of added moles) of the alkylene oxide adduct most present in the entire compound (a1).
i represents the number of repetitions of OR ¹⁰ ;
Yi represents the proportion (% by mass) of an alkylene oxide adduct having an added mole number of alkylene oxide present in the whole compound (a1).

The narrow rate can be controlled by, for example, the production method of the compound (a1).
The method for producing the compound (a1) is not particularly limited. For example, a method of addition polymerization of an alkylene oxide to a fatty acid alkyl ester using a surface-modified composite metal oxide catalyst (see JP 2000-144179 A). ) Can be easily manufactured.
As a preferable example of such a surface-modified composite metal oxide catalyst, specifically, metal ions (Al ³⁺ , Ga ³⁺ , In ³⁺ , Tl ³⁺ , Co 1) surface-modified with a metal hydroxide or the like are used. ³⁺ , Sc ³⁺ , La ³⁺ , Mn ^2+, etc.) or a composite metal oxide catalyst such as magnesium oxide, or a calcined hydrotalcite surface-modified with a metal hydroxide and / or metal alkoxide A catalyst is mentioned.
Further, in the surface modification of the composite metal oxide catalyst, the mixing ratio of the composite metal oxide and the metal hydroxide and / or metal alkoxide is changed to metal water with respect to 100 parts by mass of the composite metal oxide. The ratio of the oxide and / or metal alkoxide is preferably 0.5 to 10 parts by mass, and more preferably 1 to 5 parts by mass.

  As a production method of the compound (a1), there is also a method of adding an alkylene oxide to a fatty acid alkyl ester with an alkoxylation catalyst prepared from a mixture of an alkaline earth metal compound and oxyacid. The above alkoxylation catalyst is disclosed in Japanese Patent No. 04977609, International Publication No. 1993/004030, International Publication No. 2002/038269, International Publication No. 2012/028435, and the like. For example, alkaline earth of carboxylic acid Examples include an alkoxylation catalyst prepared from a mixture of a metal salt and / or an alkaline earth metal salt of hydroxycarboxylic acid and sulfuric acid.

Compound (a2):
In the formula (a2), the hydrocarbon group for R ¹² may be linear or branched, or may contain a cyclic structure.
The hydrocarbon group for R ¹² is preferably an aliphatic hydrocarbon group, more preferably a linear or branched alkyl group, or a linear or branched alkenyl group.
R ¹² has 10 to 20 carbon atoms, preferably 12 to 18 carbon atoms, and more preferably 12 to 14 carbon atoms. When the carbon number of R ¹² is 10 or more, the detergency is further increased. On the other hand, when the carbon number of R ¹² is 20 or less, storage stability is improved, and in particular, gelation is easily suppressed.
The compound (a2) may be a mixture having a single chain length or a mixture having a plurality of chain lengths. R ¹² is derived from the raw material alcohol (R ¹² —OH). Examples of the alcohol include alcohols derived from natural fats and oils such as palm oil, palm oil and beef tallow, and synthetic alcohols derived from petroleum.

In said formula (a2), s shows the average repetition number of EO, is a number of 5-20, the number of 12-18 is preferable, and the number of 12-16 is more preferable. When s is within the above range, the cleaning power of the liquid detergent, particularly the cleaning power against sebum dirt, is further improved.
t represents the average number of repetitions of PO, is a number of 0 to 4, is preferably a number of 0 to 3, and is particularly preferably 0. When t is within the above range, gelation of the liquid detergent is likely to be suppressed, and good foamability is easily obtained at the time of rinsing.

In the formula (a2), EO and PO may be added in a block shape or may be added in a random shape. When EO and PO are added in the form of a block, the addition method includes adding ethylene oxide followed by propylene oxide, adding propylene oxide followed by ethylene oxide, and adding ethylene oxide followed by propylene oxide. And a method of adding ethylene oxide further. In particular, since the rinsing property in washing in a fully automatic washing machine is better, a method of adding ethylene oxide after adding ethylene oxide and further adding ethylene oxide (the terminal is -O-CH ₂ CH ₂ O-H and Is preferred).

In compound (a2), the addition mole number distribution of alkylene oxide (ethylene oxide, propylene oxide) is not particularly limited and can be controlled by the production method of compound (a2) and the like. For example, when an alkylene oxide is added to a hydrophobic raw material using a general alkali catalyst such as sodium hydroxide or potassium hydroxide, a relatively wide addition mole number distribution tends to be obtained. Further, specific alkoxyl 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 JP-B-615038 are added. When alkylene oxide is added to a hydrophobic raw material using a catalyst, it tends to have a relatively narrow addition mole number distribution.

Specific examples of the compound (A2) include the following compounds.
・ Product name Leox CL-70 (mixture of 12 carbon alcohols and 14 carbon alcohols) manufactured by Lion Co., Ltd. or trade name Safol 23 (12 carbons alcohols and 13 carbons alcohols) manufactured by Sasol A compound obtained by adding 12 mol or 15 mol of EO to an alcohol such as a mixture).
A compound obtained by adding 9 mol, 12 mol or 15 mol of EO to a natural alcohol such as “CO-1214” or “CO-1270” manufactured by P & G.
Compounds having 9 mol, 12 mol, or 15 mol of EO added to a secondary alcohol having 12 to 14 carbon atoms (trade names “Softanol 90”, “Softanol 120”, “Softanol 150” manufactured by Nippon Shokubai Co., Ltd.) ").

The nonionic surfactant is preferably at least one selected from the group consisting of the compound (a1) and the compound (a2), particularly from the viewpoints of detergency against sebum stains and difficulty in gelation in a high concentration region. Among these, it is more preferable to use a combination of the compound (a1) and the compound (a2) or the compound (a1).
The compound (a1) is preferably a polyoxyethylene fatty acid alkyl ester in which R ¹⁰ is an ethylene group, among which the polyoxyethylene fatty acid methyl ester in which R ¹¹ is a methyl group (hereinafter referred to as “MEE”). Are particularly preferred.
As the compound (a2), a secondary alcohol ethoxylate obtained by adding EO to a secondary alcohol (for example, Softanol series manufactured by Nippon Shokubai Co., Ltd.) is particularly preferable.
Since these gel regions are small even at high concentrations, gelation is unlikely to occur at high blending.
These may be used in combination with a primary alcohol ethoxylate obtained by adding ethylene oxide to a primary alcohol.

Moreover, when a liquid detergent contains a polyoxyethylene fatty acid alkyl ester, the solubility in water becomes favorable and high detergency can be easily obtained. Moreover, even if it contains a high concentration surfactant, it is difficult to cause a significant increase in viscosity (gelation), and a concentrated liquid detergent having good fluidity can be obtained. In addition, a tactile sensation providing effect is also obtained. The reason for this is considered as follows.
Polyoxyethylene fatty acid alkyl esters, especially MEE, are nonionic surfactants with weak molecular orientation in aqueous systems and unstable micelles. It is estimated that a large amount can be blended in a liquid detergent. Moreover, it is estimated that the solubility to water improves. Furthermore, it is thought that it contributes to good fluidity at a high concentration. Therefore, when the polyoxyethylene fatty acid alkyl ester is poured into the water in the washing machine tub, the concentration of the polyoxyethylene fatty acid alkyl ester in the washing liquid quickly becomes uniform and comes into contact with the object to be washed at a predetermined concentration from the initial stage of washing. Therefore, it is considered that high detergency can be obtained.

  The content of the nonionic surfactant is preferably 10 to 50% by mass, more preferably 10 to 40% by mass, and still more preferably 15 to 30% by mass with respect to the total mass of the liquid detergent. If the content of the nonionic surfactant is 10% by mass or more with respect to the total mass of the liquid detergent, sufficient detergency can be obtained, and if it is 50% by mass or less, thickening is suppressed and the liquid detergent is stored. Stability can be maintained better.

  As for content of nonionic surfactant, 5-95 mass% is preferable with respect to the total mass of (A) component, 10-90 mass% is more preferable, and 20-80 mass% is more preferable. In particular, when the content of the nonionic surfactant is 80% by mass or less with respect to the total mass of the component (A), the storage stability becomes better.

(Anionic surfactant)
An anionic surfactant is mix | blended in order to improve the softness | flexibility of clothing by using together with the cationic surfactant mentioned later.
Examples of the anionic surfactant having such a function include linear alkylbenzene sulfonic acid or a salt thereof, α-olefin sulfonate, linear or branched alkyl sulfate, alkyl ether sulfate or alkenyl ether sulfate. Examples thereof include ester salts, alkane sulfonates having an alkyl group, and α-sulfo fatty acid ester salts. 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.

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 oxyethylene group (EO) was added. Those having an average of 0 to 6 moles of oxypropylene group (PO) added (that is, polyoxyethylene (propylene) alkyl ether sulfate or polyoxyethylene (propylene) alkenyl ether sulfate) are preferred.
In the case of an adduct in which both EO and PO are added, the addition method of EO and PO is not particularly limited, and may be random addition or block addition, for example. 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.
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 them, 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.

  Among these, linear alkylbenzene sulfonic acid or a salt thereof, alkane sulfonate, polyoxyethylene alkyl ether sulfate, and α-olefin sulfonate are preferable in terms of excellent detergency and stability. Acid or a salt thereof, polyoxyethylene alkyl ether sulfate is more preferable, sodium alkylbenzene sulfonate (LAS) is particularly preferable in terms of high handling properties and excellent recontamination prevention performance.

Moreover, in addition to the anionic surfactant mentioned above, it is preferable to use together a C8-18 fatty acid (higher fatty acid) or a salt thereof (higher fatty acid salt).
The above-mentioned anionic surfactant may form an anion-cation complex in the presence of a cationic surfactant. The anion-cation complex stabilizes the foam film being washed, so that the defoaming property is deteriorated, and as a result, the rinsing property is sometimes deteriorated. If a higher fatty acid or a salt thereof is used in combination, the higher fatty acid or a salt thereof binds to calcium ions in laundry tap water and destabilizes the foam film, thereby improving the rinsing property.
Examples of higher fatty acids include salts of single fatty acids such as caprylic acid, capric acid, lauric acid, myristic acid, palmitic acid, stearic acid, isostearic acid, hydroxystearic acid, oleic acid, behenic acid, coconut oil fatty acid, beef tallow fatty acid And mixed fatty acids.
Examples of salts in these higher fatty acids include alkali metal salts such as sodium salts and potassium salts, ammonium salts, monoethanolamine salts, diethanolamine salts, triethanolamine salts, 2-amino-2-methylpropanol salts, 2-amino- Examples include alkanolamine salts such as 2-methylpropanediol, and basic amino acid salts such as lysine and arginine.

As an anionic surfactant, you may use other anionic surfactants other than the anionic surfactant mentioned above, a higher fatty acid, or its salt.
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; Examples thereof include 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.
Any one of these anionic surfactants may be used alone, or two or more thereof may be used in combination.

  The content of the anionic surfactant is preferably 2 to 20% by mass, more preferably 5 to 20% by mass, and still more preferably 8 to 15% by mass with respect to the total mass of the liquid detergent. If the content of the anionic surfactant is 2% by mass or more with respect to the total mass of the liquid detergent, the effect of preventing recontamination and the dispersion stability of the component (A) are sufficiently exhibited. On the other hand, when the content of the anionic surfactant exceeds 20% by mass, the ratio of counter ions may be excessively increased. If the counter ion is excessive, the amount of gas absorption increases, and as a result, the container for storing the liquid detergent may be recessed.

  5-95 mass% is preferable with respect to the total mass of (A) component, as for content of an anionic surfactant, 10-90 mass% is more preferable, and 20-80 mass% is further more preferable. In particular, when the content of the anionic surfactant is 20% by mass or more with respect to the total mass of the component (A), the stability becomes better. On the other hand, if the content of the anionic surfactant is 80% by mass or less, the detergency becomes better.

(Cationic surfactant)
The cationic surfactant is blended for the purpose of increasing the flexibility of the garment by using in combination with the above-described anionic surfactant.
As the cationic surfactant, a compound represented by the following general formula (a3) (hereinafter referred to as “compound (a3)”) A compound represented by the following general formula (a4) (hereinafter referred to as “compound (a4)”) Etc.). These may be used alone or in combination of two or more.

In formula (a3), R ¹³ and R ¹⁴ are each independently a hydrogen atom, a hydrocarbon group having 1 to 25 carbon atoms, or a group represented by — (CH ₂ CH ₂ O) _q —H (q is 1 And R ¹⁵ is a hydrocarbon group having 8 to 25 carbon atoms, and R ¹⁶ is a hydrogen atom, an alkyl group having 1 to 3 carbon atoms, or a hydroxyalkyl group having 1 to 3 carbon atoms. or _{- (CH} 2 CH 2 _O) groups represented by r -H (r is an integer of 1 to 25.) is, Z ^- is a counterion.
In the formula (a4), R ¹⁷ is a hydrocarbon group having 7 to 27 carbon atoms, R ¹⁸ is a hydrocarbon group having 1 to 25 carbon atoms, R ¹⁹ is an alkyl group having 1 to 4 carbon atoms, carbon number 1 to 4 hydroxyalkyl groups or a group represented by — (CH ₂ CH ₂ O) _p —H (p represents an integer of 1 to 25).

Compound (a3):
In the formula (a3), R ¹³ and R ¹⁴ are each independently a hydrogen atom, a hydrocarbon group having 1 to 25 carbon atoms, or a group represented by — (CH ₂ CH ₂ O) _q —H (q is Represents an integer of 1 to 25).
The hydrocarbon group in R ¹³ and R ¹⁴ may be linear or branched, or may contain a cyclic structure. The hydrocarbon group in R ¹³ and R ¹⁴ may be a saturated hydrocarbon group or an unsaturated hydrocarbon group.
The hydrocarbon groups for R ¹³ and R ¹⁴ may each independently have a substituent, and may have a linking group in the carbon chain. The carbon number of the substituent or the linking group that R ¹³ and R ¹⁴ may have is not included in the carbon number 1 to 25 of the hydrocarbon group in R ¹³ and R ¹⁴ . Examples of the substituent that the hydrocarbon group may have include a hydroxy group. Examples of the linking group that may be present in the carbon chain include an amide group (—C (═O) —NH—), an ester group (—C (═O) —O—), or an ether group (—O—). ) And the like.
Among these, R ¹³ and R ¹⁴ are each preferably a hydrogen atom or a linear or branched hydrocarbon group which may have a substituent. Among these, a hydrogen atom, a linear or branched alkyl group having 1 to 4 carbon atoms, or a linear or branched hydroxyalkyl group having 1 to 4 carbon atoms is preferable, and a hydrogen atom or a carbon number having 1 to 4 carbon atoms is preferable. 4 linear or branched alkyl groups are more preferable, and a hydrogen atom and a methyl group are more preferable.
R ¹³ and R ¹⁴ are each preferably a linear or branched hydrocarbon group having an ester group in the carbon chain.

In the formula (a3), R ¹⁵ is a hydrocarbon group having 8 to 25 carbon atoms.
The hydrocarbon group for R ¹⁵ may be linear or branched, or may contain a cyclic structure.
The number of carbon atoms of the hydrocarbon group for R ¹⁵ is 8-25, preferably 16-22.
The hydrocarbon group for R ¹⁵ may have a substituent and may have a linking group in the carbon chain. In addition, the carbon number of the substituent or the linking group that R ¹⁵ may have is not included in the carbon number 8 to ²⁵ of the hydrocarbon group in R ¹⁵ . Examples of the substituent that the hydrocarbon group may have include a hydroxy group. Examples of the linking group that may be present in the carbon chain include an amide group (—C (═O) —NH—), an ester group (—C (═O) —O—), or an ether group (—O—). ) And the like. Among them, an ester group is preferable.

In the formula (a3), R ¹⁶ is a hydrogen atom, an alkyl group having 1 to 3 carbon atoms, a hydroxyalkyl group having 1 to 3 carbon atoms, or a group represented by — (CH ₂ CH ₂ O) _r —H (r Represents an integer of 1 to 25).
The alkyl group and hydroxyalkyl group in R ¹⁶ may be linear or branched.
Among these, R ¹⁶ is preferably a hydrogen atom, a linear or branched alkyl group having 1 to 3 carbon atoms, or a linear or branched hydroxyalkyl group having 1 to 3 carbon atoms, and hydrogen. A linear or branched alkyl group having 1 to 3 carbon atoms is more preferred, and a hydrogen atom and a methyl group are more preferred.

In the formula (a3), Z ⁻ is a counter ion.
Specific examples of Z ⁻ include halogen atom ions such as chlorine ion, bromine ion and iodine ion; general formula R ²⁰ SO ⁴⁻ , wherein R ²⁰ is an alkyl group having 1 to 3 carbon atoms (for example, methyl group, Ethyl group, propyl group, etc.), particularly preferably a methyl group. And the like. Among these, halogen atom ions are preferable, and chlorine ions are more preferable.

As the compound (a3), any one type may be used alone, or two or more types may be used in combination.
Specific examples of the compound (a3) include mono long-chain alkyl quaternary ammonium salts such as cetyltrimethylammonium chloride, cetostearyltrimethylammonium chloride, stearyltrimethylammonium chloride, and behenyltrimethylammonium chloride; monoester ammonium salt, diester ammonium salt , Ester ammonium salts such as triester ammonium salts, or mixtures thereof. Of these, mono long-chain alkyl quaternary ammonium salts are preferred.

Compound (a4):
In the formula (a4), R ¹⁷ is a hydrocarbon group having 7 to 27 carbon atoms.
The hydrocarbon group for R ¹⁷ may be linear or branched, or may contain a cyclic structure. The hydrocarbon group for R ¹⁷ may be a saturated hydrocarbon group or an unsaturated hydrocarbon group.
The number of carbon atoms of the hydrocarbon group for R ¹⁷ is 7-27, preferably 7-25.
The hydrocarbon group for R ¹⁷ may have at least one substituent selected from the group consisting of a hydroxy group and an amino group (—NH ₂ ), and may have a linking group in the carbon chain. Good. Note that the carbon number of the substituent or the linking group that R ¹⁷ may have is not included in the carbon number of 7 to 27 of the hydrocarbon group in R ¹⁷ .
Examples of the linking group that may be present in the carbon chain in R ¹⁷ include an amide group (—C (═O) —NH—), an ester group (—C (═O) —O—), and an ether group. (-O-) is mentioned, and an amide group and an ester group are preferable.

Among the above, R ¹⁷ is preferably a linear or branched hydrocarbon group having 7 to 27 carbon atoms and having a linking group in the carbon chain.
Preferable R ¹⁷ includes, for example, a group represented by —R ²¹ —R ²² .
R ²¹ represents a linear or branched alkylene group having 1 to 4 carbon atoms. Among these, a linear alkylene group having 1 to 4 carbon atoms is preferable, and a linear alkylene group having 1 to 3 carbon atoms is more preferable.
R ²² represents a group represented by —NH—C (═O) —R ²³ or —O—C (═O) —R ²⁴ .
R ²³ represents a hydrocarbon group having 7 to ²³ carbon atoms, preferably a hydrocarbon group having 7 to 21 carbon atoms. The hydrocarbon group for R ²³ may be linear or branched, and may be a saturated hydrocarbon group or an unsaturated hydrocarbon group.
R ²⁴ represents a hydrocarbon group having 11 to 23 carbon atoms, and preferably represents a hydrocarbon group having 12 to 20 carbon atoms. The hydrocarbon group for R ²⁴ may be linear or branched, and may be a saturated hydrocarbon group or an unsaturated hydrocarbon group.

In the formula ^{(a4), R 18} is a hydrocarbon group having 1 to 25 carbon atoms.
The hydrocarbon group for R ¹⁸ may be linear or branched, or may contain a cyclic structure. The hydrocarbon group for R ¹⁸ may be a saturated hydrocarbon group or an unsaturated hydrocarbon group.
The number of carbon atoms of the hydrocarbon group for R ¹⁸ is 1 to 25, preferably from 1 to 20, 1 to 4 is more preferred.
The hydrocarbon group for R ¹⁸ may have a hydroxy group as a substituent and may have a linking group in the carbon chain. The number of carbon atoms in the or linking group which may R ¹⁸ is had shall not be included in the 1 to 25 carbon atoms hydrocarbon group for R ^18.
Examples of the linking group that may be present in the carbon chain in R ¹⁸ include an amide group (—C (═O) —NH—), an ester group (—C (═O) —O—), and an ether group. (-O-) is mentioned.
Among these, R ¹⁸ is preferably a linear or branched hydrocarbon group having 1 to 25 carbon atoms, which may have a hydroxy group as a substituent. Among these, a linear or branched alkyl group having 1 to 4 carbon atoms and a linear or branched hydroxyalkyl group having 1 to 4 carbon atoms are more preferable, and a linear chain having 1 to 4 carbon atoms. Or a branched alkyl group is more preferable.

In the formula (a4), R ¹⁹ is an alkyl group having 1 to 4 carbon atoms, a hydroxyalkyl group having 1 to 4 carbon atoms, or a group represented by — (CH ₂ CH ₂ O) _p —H (p is 1). Represents an integer of ˜25).
The alkyl group and hydroxyalkyl group in R ¹⁹ may be linear or branched.
R ¹⁹ is preferably a linear or branched alkyl group having 1 to 4 carbon atoms, a linear or branched hydroxyalkyl group having 1 to 4 carbon atoms, and a linear chain having 1 to 4 carbon atoms. Or a branched alkyl group is more preferred.

As the compound (a4), any one type may be used alone, or two or more types may be used in combination.
Among the compounds (a4), a compound represented by the following general formula (a4-1) or a salt thereof is preferable.

In formula (a4-1), R ²⁵ and R ²⁶ each independently represent an alkyl group having 1 to 4 carbon atoms or a hydroxyalkyl group having 1 to 4 carbon atoms. R ²¹ represents an alkylene group having 1 to 4 carbon atoms. R ²² represents a group represented by —NH—C (═O) —R ²³ or —O—C (═O) —R ²⁴ . R ²³ represents a hydrocarbon group having 7 to ²³ carbon atoms. R ²⁴ represents a hydrocarbon group having 11 to ²³ carbon atoms.

In the formula (a4-1), R ²⁵ and R ²⁶ are each preferably a linear or branched alkyl group having 1 to 4 carbon atoms, and a linear alkyl group having 1 to 4 carbon atoms. More preferably, a linear alkyl group having 1 to 3 carbon atoms is more preferable, and a methyl group is particularly preferable.
In formula (a4-1), R ²¹ , R ²² , R ²³ and R ²⁴ are the same as described above.

As the compound (a4), any one type may be used alone, or two or more types may be used in combination.
Specific examples of the compound (a4) include caprylic acid dimethylaminopropylamide, capric acid dimethylaminopropylamide, lauric acid dimethylaminopropylamide, myristic acid dimethylaminopropylamide, palmitic acid dimethylaminopropylamide, stearic acid dimethylaminopropyl. Long chain aliphatic amide dialkyl tertiary amines such as amides, behenic acid dimethylaminopropylamide, oleic acid dimethylaminopropylamide; long chain aliphatic amide dialkanols such as palmitic acid diethanolaminopropylamide, stearic acid diethanolaminopropylamide 3 Tertiary amines; aliphatic ester dialkyl tertiary amines such as palmitate ester propyldimethylamine and stearate ester propyldimethylamine; Dimethylamine, myristyl dimethylamine, coconut alkyl dimethylamine, palmityl dimethyl amine, tallow alkyl dimethylamine, hydrogenated tallow alkyl dimethyl amine, stearyl dimethylamine, stearyl diethanolamine, polyoxyethylene hardened beef tallow alkyl amine.

  Any one of these cationic surfactants may be used alone, or two or more thereof may be used in combination.

(Amphoteric surfactant)
Examples of amphoteric surfactants include alkylbetaine type, alkylamide betaine type, imidazoline type, alkylaminosulfone type, alkylaminocarboxylic acid type, alkylamidecarboxylic acid type, amide amino acid type, and phosphoric acid type amphoteric surfactant. Can be mentioned.
Any one of these amphoteric surfactants may be used alone, or two or more thereof may be used in combination.

<(B) component>
The component (B) is one or more repeating units selected from the group consisting of the repeating unit represented by the following general formula (b1) and the repeating unit represented by the following general formula (b2) (hereinafter referred to as “repeating unit”). b3) "), and one or more repeating units selected from the group consisting of repeating units derived from acrylic acid and repeating units derived from acrylamide (hereinafter referred to as" repeating units (b4) "). It is a polymer having The component (B) serves as a structuring agent. The liquid detergent is structured by containing the component (B). Therefore, for example, when the liquid detergent contains insoluble particles described later, the insoluble particles can be uniformly dispersed in the liquid detergent, and the state can be maintained. In addition, the storage stability of the liquid detergent is increased.

In formula (b1), R ¹ and R ² are each independently an alkyl group having 1 to 3 carbon atoms or a hydroxyalkyl group having 1 to 3 carbon atoms, and X ⁻ is a counter ion.
In formula (b2), R ³ and R ⁴ are each independently an alkyl group having 1 to 3 carbon atoms or a hydroxyalkyl group having 1 to 3 carbon atoms, and X ⁻ is a counter ion.

  The repeating unit (b3) is a repeating unit derived from the dialkyl diallylammonium salt when a monomer component containing a dialkyl diallylammonium salt represented by the following general formula (b3) is polymerized.

In the formula, R ²⁷ and R ²⁸ are each independently an alkyl group having 1 to 3 carbon atoms or a hydroxyalkyl group having 1 to 3 carbon atoms, and X ⁻ is a counter ion.

X ⁻ in the above general formulas (b1), (b2) and (b3) includes halogen ions such as chlorine ions and bromine ions, inorganic acid ions such as sulfate ions, nitrate ions and sulfite ions, methyl sulfate ions and acetate ions. And organic acid ions such as lactic acid ions.

The repeating unit derived from acrylic acid is a repeating unit derived from acrylic acid or a derivative thereof when a monomer component containing acrylic acid or a derivative thereof is polymerized.
Examples of the derivatives of acrylic acid include alkyl acrylate and alkyl methacrylate.

  A repeating unit derived from acrylamide is a repeating unit derived from acrylamide or a derivative thereof when a monomer component containing acrylamide or a derivative thereof is polymerized.

  The mass average molecular weight of the component (B) is usually 1,000 to 5,000,000, preferably 3,000 to 2,000,000, and more preferably 10,000 to 2,000,000. In addition, the mass mean molecular weight in this specification means the value calculated | required by gel permeation chromatography (GPC) by using polyethyleneglycol as a standard substance.

The form of polymerization of component (B) is not particularly limited, and may be any of block polymerization, random polymerization, or graft polymerization.
The content ratio of the repeating unit (b3) and the repeating unit (b4) in the component (B) is not particularly limited, but the molar ratio of the repeating unit (b3) to the repeating unit (b4) (repeating unit (b3): repeating) The unit (b4)) is preferably in a ratio of 1: 9 to 7: 3, more preferably 2: 8 to 6: 4.

The component (B) is preferably a polymer having a repeating unit derived from a diallyldialkylammonium salt and a repeating unit derived from acrylamide in terms of structuring and storage stability, specifically, diallyldimethyl. Ammonium chloride / acrylamide copolymer and diallyldimethylammonium chloride / acrylamide / acrylic acid copolymer are more preferable.
As these polymers, synthetic products or commercially available products may be used.

  (B) A component can be manufactured by normal radical polymerization. For example, it can be produced by polymerizing a monomer constituting the component (B) such as diallyldimethylammonium chloride or acrylamide by a polymerization method such as bulk polymerization, solution polymerization, emulsion polymerization, suspension polymerization or the like. Further, in the polymerization, it is preferable to use a polymerization initiator used in ordinary radical polymerization, for example, peroxides such as benzoyl peroxide and potassium persulfate, azobisisobutyronitrile, azobiscyanovaleric acid An azo compound such as can be used.

Examples of commercial products of the above-mentioned copolymer include trade names “MARCOAT 550”, “MARCOAT 740”, “MARCOAT 2200” manufactured by Lubrizol.
Moreover, as a commercial item of the said terpolymer, brand name "Mercoat 3330", "Mercoat 3940", etc. by Lubrizol are mentioned, for example.
These (B) components may be used alone or in combination of two or more.

<(C) component>
The component (C) is a polymer having a repeating unit derived from a monomer represented by the following general formula (c1) and a repeating unit derived from a monomer represented by the following general formula (c2). The component (C) serves as a structuring agent. The liquid detergent is structured by containing the component (C). Therefore, for example, when the liquid detergent contains insoluble particles described later, the insoluble particles can be uniformly dispersed in the liquid detergent, and the state can be maintained. In addition, the storage stability and re-contamination prevention property of the liquid detergent are enhanced.

In formula (c1), R ⁵ is a hydrogen atom or a methyl group, and R ⁶ is a hydrogen atom.
In formula (c2), R ⁷ is a hydrogen atom or a methyl group, and R ⁸ is an alkyl group having 1 to 40 carbon atoms.

The repeating unit derived from the monomer represented by the general formula (c1) is derived from the monomer represented by the general formula (c1) when the monomer component including the monomer represented by the general formula (c1) is polymerized. It is a repeating unit.
Examples of the monomer represented by the general formula (c1) include acrylic acid and methacrylic acid.
Any one of these monomers represented by the general formula (c1) may be used alone, or two or more thereof may be used in combination.

In the formula (c2), R ⁷ is a hydrogen atom or a methyl group.
In the formula (c2), the alkyl group in R ⁸ may be linear or branched, or may contain a cyclic structure.
The number of carbon atoms in the alkyl group in R ⁸ is 1 to 40, preferably 1 to 20 carbon atoms, 1 to 10 carbon atoms is more preferred.

The repeating unit derived from the monomer represented by the general formula (c2) is derived from the monomer represented by the general formula (c2) when the monomer component including the monomer represented by the general formula (c2) is polymerized. It is a repeating unit.
Examples of the monomer represented by the general formula (c2) include methyl acrylate, ethyl acrylate, n-propyl acrylate, n-butyl acrylate, octyl acrylate, decyl acrylate, dodecyl acrylate, and icosyl acrylate. Acrylic acid esters such as methyl methacrylate, ethyl methacrylate, n-propyl methacrylate, n-butyl methacrylate, octyl methacrylate, decyl methacrylate, dodecyl methacrylate, icosyl methacrylate, and the like. .
Any one of these monomers represented by the general formula (c2) may be used alone, or two or more thereof may be used in combination.

Component (C) may be cross-linked or non-cross-linked, but is preferably cross-linked.
Examples of the crosslinked component (C) include those crosslinked with a crosslinking agent (polymer crosslinked product).
As said crosslinking agent, an allyl ether compound is mentioned suitably, for example.
Examples of the allyl ether compound include allyl ether, sugar allyl ether, sugar alcohol allyl ether, and the like.
Examples of the sugar in the allyl ether of sugar include sucrose.
Examples of the sugar alcohol in the allyl ether of the sugar alcohol include pentaerythritol.

As the component (C), any one type may be used alone, or two or more types may be used in combination.
The component (C) is a repeating unit other than the repeating unit derived from the monomer represented by the general formula (c1) and the repeating unit derived from the monomer represented by the general formula (c2) (other repeating units) ).
Other repeating units include repeating units derived from other monomers.
The other monomer is not particularly limited as long as it is copolymerizable with the monomer represented by the general formula (c1) and the monomer represented by the general formula (c2), and one or more kinds can be used.

Specific examples of the component (C) include the following trade names.
As a commercial item of a crosslinking type (C) component, it is a brand name which is a crosslinking type copolymer which consists of two or more types of monomers chosen from alkyl acrylate, an alkyl methacrylate, acrylic acid, and methacrylic acid made from Lubrizol, for example. “Carbopol Aqua 30”; a cross-linked copolymer consisting of two or more monomers selected from alkyl acrylates (C1 to C4 and C8), alkyl methacrylates (C1 to C4 and C8), acrylic acid and methacrylic acid manufactured by Lubrizol “Carbopol Aqua SF-1” which is a coalescence; a cross-linked copolymer comprising two or more monomers selected from alkyl acrylate (C10 to C30), alkyl methacrylate (C10 to C30) and acrylic acid manufactured by Lubrizol Product name "Carbopol E" -4 "; and DOW Corp. alkyl acrylate, trade name is crosslinked copolymer consisting of acrylic acid or methacrylic acid" ACUSOL 830, "and the like.
As a commercial item of the non-crosslinking type (C) component, for example, a trade name “Lbrizol Co., Ltd., which is a copolymer composed of two or more monomers selected from alkyl acrylate, alkyl methacrylate, acrylic acid and methacrylic acid” Novexix HC200 "and the like.

<Content>
(A) Content of a component is 15 mass% or more with respect to the total mass of a liquid detergent, 15-60 mass% is preferable, and 30-50 mass% is more preferable. When the content of the component (A) is 15% by mass or more, sufficient detergency is obtained, and when the content is 60% by mass or less, the storage stability of the liquid detergent is further increased.

  The content of the component (B) is preferably 0.01% by mass or more, more preferably 0.2% by mass or more, still more preferably 0.3% by mass or more, based on the total mass of the liquid detergent. A mass% or more is particularly preferred. Further, the content of the component (B) is preferably 5% by mass or less, more preferably 3% by mass or less, and further preferably 2% by mass or less with respect to the total mass of the liquid detergent. If the content of the component (B) is 0.01% by mass or more, the liquid detergent is more easily structured, and a sufficient tactile sensation imparting effect is obtained. If the content is 5% by mass or less, the storage stability of the liquid detergent is obtained. And usability increases.

  The content of the component (C) is preferably 0.01% by mass or more, more preferably 0.1% by mass or more, still more preferably 0.5% by mass or more, and 1% by mass with respect to the total mass of the liquid detergent. The above is particularly preferable. Further, the content of the component (C) is preferably 8% by mass or less, more preferably 5% by mass or less, and further preferably 2.5% by mass or less with respect to the total mass of the liquid detergent. When the content of the component (C) is 0.01% by mass or more, the storage stability is further increased, and when it is 8% by mass or less, the liquid detergent is more easily structured.

10-4500 are preferable, as for mass ratio (A / B ratio) represented by (A) component / (B) component, 10-200 are more preferable, and 20-130 are more preferable. If the A / B ratio is 10 or more, thickening of the liquid detergent can be suppressed, and if it is 4500 or less, the liquid detergent is more easily structured.
(B) The mass ratio (B / C ratio) represented by the component / (C) component is 0.05 to 1.25, preferably 0.1 to 1.25, and 0.2 to 1.0. More preferred. If the B / C ratio is 0.05 or more, the liquid detergent is sufficiently structured, and if it is 1.25 or less, the storage stability of the liquid detergent is increased.
5-4500 are preferable, as for the mass ratio (A / C ratio) represented by (A) component / (C) component, 5-100 are more preferable, and 10-50 are more preferable. If the A / C ratio is 5 or more, thickening of the liquid detergent can be suppressed, and if it is 4500 or less, the liquid detergent is more easily structured.
The mass ratio (A / (B + C) ratio) represented by (A) component / {(B) component + (C) component} is preferably 5-2000, more preferably 5-450, and even more preferably 10-30. . If the A / (B + C) ratio is 5 or more, thickening of the liquid detergent can be suppressed, and if it is 2000 or less, the liquid detergent is more easily structured.

In addition, "mass ratio represented by (A) component / (B) component" means the ratio (mass ratio) of the content of (A) component to the content of (B) component in the liquid detergent. It is.
“Mass ratio represented by component (B) / component (C)” is the ratio (mass ratio) of the content of component (B) to the content of component (C) in the liquid detergent. .
“Mass ratio represented by component (A) / component (C)” is the ratio (mass ratio) of the content of component (A) to the content of component (C) in the liquid detergent. .
“Mass ratio represented by (A) component / {(B) component + (C) component} component” ”means (A) with respect to the total content of (B) component and (C) component in the liquid detergent. ) Component content ratio (mass ratio).

<Solvent>
The liquid detergent of the present invention preferably contains water as a solvent from the viewpoints of ease of handling during production, solubility in water during use, and the like.

The liquid detergent of the present invention may contain a solvent for the purpose of improving storage stability and reducing the viscosity.
Examples of the solvent include water-miscible organic solvents, and specifically include ethanol, propylene glycol, polyethylene glycol, butyl carbitol and the like. Any one of these water-miscible organic solvents may be used alone, or two or more thereof may be used in combination.
The content of the water-miscible organic solvent is preferably 3 to 20% by mass with respect to the total mass of the liquid detergent.

<Other ingredients>
The liquid detergent may contain components (other components) other than the components (A), (B) and (C) as long as the effects of the present invention are not impaired.
Examples of other components include metal ion scavengers, antioxidants, cleaning performance improvers / stability improvers, colorants, emulsifiers, fragrances, insoluble particles, and the like.

(Metal ion supplement)
Examples of the metal ion scavenger include malonic acid, succinic acid, malic acid, diglycolic acid, tartaric acid, citric acid and the like. Any one of these metal ion scavengers may be used alone, or two or more thereof may be used in combination.
The content of the metal ion scavenger is preferably 0.1 to 20% by mass with respect to the total mass of the liquid detergent.

(Antioxidant)
Examples of the antioxidant include mabutyl hydroxytoluene, distyrenated cresol, sodium sulfite, sodium hydrogen sulfite and the like. Any one of these antioxidants may be used alone, or two or more thereof may be used in combination.
As for content of antioxidant, 0.01-2 mass% is preferable with respect to the total mass of liquid detergent.

(Cleaning performance improver / stability improver)
Examples of cleaning performance improvers / stability improvers include enzymes (proteases, lipases, cellulases, etc.), texture improvers, alkali builders such as alkanolamines, hydrotropes, fluorescent agents, dye transfer inhibitors, recontamination inhibitors. Pearl agent, soil release agent and the like. Any one of these cleaning performance improvers and stability improvers may be used alone, or two or more thereof may be used in combination.

(Coloring agent)
Examples of the colorant include general-purpose dyes such as Acid Red 138, Polar Red RLS, Acid Yellow 203, Acid Blue 9, Blue No. 1, Blue No. 205, Green No. 3, Turquoise P-GR (all trade names), and the like. And pigments. Any one of these colorants may be used alone, or two or more thereof may be used in combination.
The content of the colorant is preferably 0.00005 to 0.005% by mass with respect to the total mass of the liquid detergent.

(Emulsifier)
Examples of the emulsifying agent include a polystyrene emulsion and a polyvinyl acetate emulsion. Usually, an emulsion having a solid content of 30 to 50% by mass is used. Specifically, a polystyrene emulsion (trade name, manufactured by Seiden Chemical Co., Ltd.) ) Cybinol RPX-196 PE-3, solid content 40% by mass). Any one of these emulsifying agents may be used alone, or two or more thereof may be used in combination.
The content of the emulsifying agent is preferably 0.01 to 0.5% by mass with respect to the total mass of the liquid detergent.

(Fragrance)
As a fragrance | flavor, the fragrance | flavor component etc. which are described in Unexamined-Japanese-Patent No. 2002-146399 are mentioned, for example. These fragrance | flavors may be used individually by 1 type, and may use 2 or more types together.
The content of the fragrance is preferably 0.01 to 2% by mass with respect to the total mass of the liquid detergent.

(Insoluble particles)
The liquid detergent may contain particles (insoluble particles) that are difficult to dissolve in the components constituting the liquid detergent.
Specific examples of the insoluble particles include capsule particles, beads and pearlescent agents for imparting unique product aesthetics, bentonite, carboxymethylcellulose (CMC), and the like. Any one type of insoluble particles may be used alone, or two or more types may be used in combination.

Capsule particles are those in which an active ingredient is encapsulated by a capsule wall formed of a polymer compound.
The capsule particles can be produced by a known method, and examples thereof include an interfacial polymerization method and an in-situ polymerization method.

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. Any of these may be used alone or in combination of two or more.
Examples of the active ingredient include a fragrance ingredient and a sunscreen ingredient (such as an ultraviolet absorber and an ultraviolet scattering agent).
Hereinafter, capsule particles in which a fragrance component is encapsulated by a capsule wall formed of a polymer compound are also referred to as “capsule fragrance”.

  Specific examples of the capsule flavor include capsule flavor A, capsule flavor B, and capsule flavor C shown below.

Capsule flavor A:
Capsule flavor A contains the following flavor components.
Limonene (0.10% by mass), ethyl 2-methylbutyrate (3.50% by mass), tripral (5.00% by mass), galvascon (0.20% by mass), spirogalvanone (0.60% by mass) ), Cyclaset (9.00% by mass), cyclobate (0.10% by mass), tricyclodecenyl acetate (19.00% by mass), bellox (18.00% by mass), nectaryl (15.00) Mass%), tetrahydrolinalol (14.00 mass%), α-ionone (0.50 mass%), β-ionone (14.00 mass%), dipropylene glycol (1.00 mass%).

Capsule flavor B:
Capsule flavor B contains the following flavor components.
Tripral (2.40% by mass), cyclaset (10.00% by mass), tricyclodecenyl propionate (10.00% by mass), isopropylmethyl-2-butyrate (1.70% by mass), manzanate (2.00% by mass), Beldox (14.00% by mass), allyl amyl glycolate (2.00% by mass), allyl cyclohexylpropionate (5.00% by mass), γ-decalactone (0.50) Mass%), γ-undecalactone (7.50 mass%), α-damascon (0.25 mass%), nerol (0.20 mass%), Hedion (5.00 mass%), lyial (12. 00 mass%), linalool (23.00 mass%), pt-butylcyclohexyl acetate (0.20 mass%), vanillin (0.10 mass%), lime oxa De (2.40 wt%), dipropylene glycol (1.75 wt%).

Capsule flavor C:
Capsule flavor C includes the following flavor components.
Hexyl salicylate (3.71% by mass), ethyl 2-methylbutyrate (3.30% by mass), dihydroeugenol (8.49% by mass), camphor (1.46% by mass), 1,4-cineole (1.28% by mass), Beldox (9.04% by mass), γ-nonalactone (0.84% by mass), γ-decalactone (2.58% by mass), γ-undecalactone (3.70% by mass) %), Allyl caproate (7.47 mass%), hexyl acetate (1.27 mass%), geranyl propionate (6.38 mass%), prenyl acetate (1.52 mass%), allyl phenoxy acetate (0.60% by mass), dimethylbenzylcarbinyl butyrate (0.95% by mass), nectaryl (8.54% by mass), geranyl acetate (11.13% by mass), lily (11.51% by mass), cyclamenaldehyde (3.05% by mass), amyl salicylate (1.39% by mass), ISOE super (1.08% by mass), γ-methylionone (1.34) Mass%), ambroxane (0.13 mass%), havanolide (0.37 mass%), anisaldehyde (8.46 mass%), lime oxide (0.41 mass%).

  The content of insoluble particles is preferably 0.01 to 20% by mass with respect to the total mass of the liquid detergent.

<Physical properties>
4-9 are preferable and, as for pH of the liquid detergent of this invention, 4-8 are more preferable. When the pH of the liquid detergent is within the above range, the storage stability is maintained well even when the liquid detergent is stored for a long time.
The pH of the liquid detergent means a value measured by a pH meter or the like after adjusting the liquid detergent to 25 ° C.
What is necessary is just to adjust pH of liquid detergent using pH adjusters, such as a sulfuric acid, sodium hydroxide, potassium hydroxide, and alkanolamine.

  The liquid detergent of the present invention preferably has a viscosity of 1000 mPa · s or less, more preferably 5 to 800 mPa · s, even more preferably 5 to 500 mPa · s after stirring for 60 seconds at 25 ° C. and 60 rpm. . If the viscosity after stirring for 60 seconds at a rotational speed of 60 rpm is within the above range, the viscosity is sufficiently low, and thus, for example, it is excellent in usability when discharging a liquid detergent from a container.

<Manufacturing method>
The method for producing the liquid detergent of the present invention is not particularly limited. For example, the (A) component, the (B) component, the (C) component, and other components as necessary are dissolved in a solvent and adjusted to a predetermined pH. The method of doing is mentioned.

<Effect>
In the liquid detergent of the present invention described above, the (A) component is combined with the (B) component and the (C) component having a specific mass ratio, thereby maintaining the detergency and maintaining the low viscosity. In addition, it has excellent storage stability.
By the way, particles (insoluble particles) that are difficult to dissolve in the components constituting the liquid detergent, such as capsule particles, are difficult to disperse uniformly in the liquid detergent, and even if the particles can be evenly dispersed, the insoluble particles settle over time. It is difficult to maintain a uniform dispersion state.
However, since the liquid detergent of the present invention is structured, when the liquid detergent contains insoluble particles, the insoluble particles can be uniformly dispersed in the liquid detergent and the state can be maintained.
Moreover, since the liquid detergent of the present invention has a low viscosity, it is excellent in usability. In addition, since the liquid detergent of the present invention is excellent in storage stability, it is difficult for the components contained in the liquid detergent to precipitate or separate even in a blended composition.
The liquid detergent of the present invention is suitable as a liquid detergent for clothing.

  EXAMPLES Hereinafter, although an Example is shown and this invention is demonstrated in detail, this invention is not limited by the following description. In addition, the compounding quantity of the component used in each example is a pure conversion value unless there is particular notice.

"Raw material"
As the component (A), the following compounds were used.
A-1: Polyoxyethylene fatty acid methyl ester (MEE, manufactured by Lion Corporation, carbon number 17 to 19 of fatty acid, average number of repeated EO (average number of added moles of EO) 15, R ⁹ in the above formula (a1) Is an alkyl group having 16 to 18 carbon atoms, R ¹⁰ is an ethyl group, R ¹¹ is a methyl group, and m is 15.)
A-2: polyoxyethylene alkyl ether (AE (15), manufactured by Lion Corporation, alkyl group having 12 to 14 carbon atoms, average number of repeating EO (average number of added moles of EO) 15, in the above formula (a2) Wherein R ¹² is an alkyl group having 12 to 14 carbon atoms, s is 15, and t is 0.)
A-3: polyoxyethylene polyoxypropylene alkyl ether (EOPO-type nonion, alkyl group having 10 to 14 carbon atoms, EO average number of repetitions (average added mole number of EO) 5, PO average number of repetitions (of PO (Average addition mole number) 2, EO and PO are block addition, R ¹² in the above formula (a2) is an alkyl group having 10 to 14 carbon atoms, s is 5 and t is 2.
A-4: Sodium linear alkylbenzene sulfonate (LAS, manufactured by Lion Corporation, alkyl group having 10 to 14 carbon atoms).
A-5: Polyoxyethylene alkyl ether sulfate (AES, a compound obtained by adding 1 mol of EO to natural alcohol (trade name “CO-1270” manufactured by P & G)).
A-6: Sodium coconut fatty acid (trade name “coconut fatty acid” manufactured by NOF Corporation neutralized with sodium hydroxide).
A-7: alkyltrimethylammonium chloride (trade name “ARCARD 12-37w” manufactured by Lion Akzo Co., C12-14 of alkyl group, R ¹³ , R ¹⁴ and R ¹⁶ in the above formula (a3) are A methyl group, R ¹⁵ is an alkyl group having 12 to 14 carbon atoms, and Z ⁻ is Cl ⁻ ).
A-8: dimethylaminopropylamide stearate (long-chain aliphatic amide dialkyl tertiary amine, trade name “Lipomin APA168-65E” manufactured by Lion Specialty Chemicals, Inc.).

As the component (B), the following compounds were used.
B-1: diallyldimethylammonium acrylamide copolymer (trade name “Mercoat 550PR” manufactured by Lubrizol).
B-2: diallyldimethylammonium acrylamide copolymer (trade name “Mercoat 740” manufactured by Lubrizol).
B-3: diallyldimethylammonium acrylamide acrylic acid copolymer (trade name “Murcoat 3940” manufactured by Lubrizol).
B-4: diallyldimethylammonium acrylamide copolymer (trade name “Mercoat 2200” (powder) manufactured by Lubrizol).
B-5: diallyldimethylammonium polymer (trade name “MARCOAT 100” manufactured by Lubrizol).

As the component (C), the following compounds were used.
C-1: a cross-linked copolymer (trade name “Carbopol Aqua 30” manufactured by Lubrizol) composed of two or more monomers selected from alkyl acrylate, alkyl methacrylate, acrylic acid and methacrylic acid.
C-2: a cross-linked copolymer composed of alkyl acrylate and acrylic acid or methacrylic acid (trade name “ACUSOL 830” manufactured by DOW).
C-3: a copolymer composed of two or more monomers selected from alkyl acrylate, alkyl methacrylate, acrylic acid and methacrylic acid (trade name “Novethix HC200” manufactured by Lubrizol).
C-4: polyacrylic acid (trade name “AQUALIC L-DL” manufactured by Nippon Shokubai Co., Ltd.)
C-5: a cross-linked copolymer composed of two or more monomers selected from alkyl acrylate (C10 to C30), alkyl methacrylate (C10 to C30) and acrylic acid (trade name “Carbopol EZ manufactured by Lubrizol”) -4 "
C-6: a cross-linked copolymer composed of two or more monomers selected from alkyl acrylates (C1 to C4 and C8), alkyl methacrylates (C1 to C4 and C8), acrylic acid and methacrylic acid (Lublizol) Product name “Carbopol Aqua SF-1”).

As the optional component (X), the following compounds and the like were used. In addition, the numerical value described at the end of each component is the content in the liquid detergent.
-PEG1000: Polyethylene glycol (trade name "PEG # 1000-L60" manufactured by Lion Chemical Co., Ltd.) ... 2% by mass.
-Ethanol: Trade name "Specific alcohol 95 degree synthesis" manufactured by Nippon Alcohol Sales Co., Ltd. 7% by mass.
Sodium benzoate: trade name “Sodium benzoate” manufactured by Toagosei Co., Ltd. 0.5 mass%.
Citric acid: trade name “Liquid Citric Acid” manufactured by Otsuka Kogyo Co., Ltd. 0.1 mass%.
P-TSH: p-toluenesulfonic acid (manufactured by Kanto Chemical Co., Inc.) 0.5% by mass.
MEA: Monoethanolamine (manufactured by Nippon Shokubai Co., Ltd.) ... A proper amount.
-NaOH: Sodium hydroxide (manufactured by Tsurumi Soda Co., Ltd.) ... A proper amount.
-Capsule perfume A: The above-mentioned capsule perfume A ... 0.1 mass%.
Fragrance: Fragrance composition A described in Tables 11 to 18 of JP 2002-146399 A: 0.5% by mass.
-Isotidiazolone solution: manufactured by Rohm and House Co., Ltd. 0.001% by mass.
-BHT: Dibutylhydroxytoluene ... 0.01 mass%.
・ Water: Purified water ... balance.
The “appropriate amount” of the MEA and NaOH contents is the amount required to adjust the liquid detergent to pH 7.0.
The “balance” of the water content is an amount necessary to make 100% by mass of the entire liquid detergent.

"Examples 1 to 24, Comparative Examples 1 to 8"
<Preparation of liquid detergent>
According to the composition shown in Tables 1-3, (A) component, (B) component, (C) component and optional component (X) (however, excluding water, MEA and NaOH) were added to water and mixed. Then, using a pH adjuster (MEA, NaOH), the pH of the mixed solution at 25 ° C. was adjusted to 7.0 to prepare a liquid detergent. In addition, the pH meter (The product name "HM-30G" by the Toa DK company) was used for the measurement of pH.
About the obtained liquid detergent of each example, a viscosity was measured as follows and dispersibility, storage stability, and sebum detergency were evaluated. The results are shown in Tables 1-3.

<Measurement / Evaluation>
(Measurement of viscosity)
The PS11 bottle was filled with 80 g of liquid detergent and adjusted to 25 ° C. in a thermostatic bath. A constant temperature sample solution was set using a Brookfield viscometer. The rotation speed was set to 60 rpm, and the viscosity after 60 seconds was measured.
Evaluation criteria:
A: The viscosity is 500 mPa · s or less.
○: The viscosity is higher than 500 mPa · s and 1000 mPa · s or less.
X: The viscosity is higher than 1000 mPa · s.

(Evaluation of dispersibility)
Fill 30g of wide detergent bottle (PS-No6 bottle) with liquid detergent and add 0.5g of beads (TOSHIKI PIGMENT. CO. LTD, "PFL-RED 7155T Lot. 0308") as insoluble particles to disperse. It was. It preserve | saved for 60 days in a 25 degreeC thermostat. During the storage period, the bottle was taken out from the thermostat every day, and the dispersion state of the beads in the liquid detergent was visually confirmed, and the dispersibility was evaluated according to the following evaluation criteria. The better the dispersibility, the better the liquid detergent is structured.
Evaluation criteria:
A: The beads are uniformly dispersed in the liquid detergent for 60 days.
○: The beads are uniformly dispersed in the liquid detergent for 30 to 59 days.
X: The beads are floating or settling in less than 30 days.

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

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

  As is clear from Tables 1 and 2, the liquid detergents of each Example had a low viscosity and excellent storage stability and sebum detergency. Moreover, since the liquid detergent of each Example was excellent in the dispersibility of a bead (insoluble particle | grains), it was shown that it has fully structured.

On the other hand, as is clear from Table 3, the liquid detergent of Comparative Example 1 using acrylamide polymer as the component (B) and polyacrylic acid as the component (C) has high viscosity and inferior bead dispersibility. It was.
The liquid detergent of Comparative Example 2 using polyacrylic acid as the component (C) had a high viscosity and was inferior in bead dispersibility.
The liquid detergent of Comparative Example 3 containing no component (A) had a high viscosity and was poor in sebum detergency.
(A) The liquid detergent of the comparative example 4 whose content of a component is 14 mass% had high viscosity, and was also inferior to sebum detergency.
The liquid detergent of Comparative Example 5 containing no component (B) was inferior in bead dispersibility and storage stability.
The liquid detergent of Comparative Example 6 containing no component (C) was inferior in bead dispersibility and storage stability.
The liquid detergent of Comparative Example 7 having a mass ratio represented by (B) component / (C) component of 1.33 was inferior in storage stability.
The liquid detergent of Comparative Example 8 in which the mass ratio represented by (B) component / (C) component was 0.04 was inferior in bead dispersibility.

Claims (2)

(A) component: surfactant,
Component (B): derived from acrylic acid and at least one repeating unit selected from the group consisting of repeating units represented by the following general formula (b1) and repeating units represented by the following general formula (b2) A polymer having one or more repeating units selected from the group consisting of repeating units and repeating units derived from acrylamide;
Component (C): a polymer having a repeating unit derived from a monomer represented by the following general formula (c1) and a repeating unit derived from a monomer represented by the following general formula (c2) ,
(A) component content is 15% by mass or more,
(B) Liquid detergent whose mass ratio represented by a component / (C) component is 0.05-1.25.

(In formula (b1), R ¹ and R ² are each independently an alkyl group having 1 to 3 carbon atoms or a hydroxyalkyl group having 1 to 3 carbon atoms, and X ⁻ is a counter ion.
In formula (b2), R ³ and R ⁴ are each independently an alkyl group having 1 to 3 carbon atoms or a hydroxyalkyl group having 1 to 3 carbon atoms, and X ⁻ is a counter ion. )

(In formula (c1), R ⁵ is a hydrogen atom or a methyl group, and R ⁶ is a hydrogen atom.
In formula (c2), R ⁷ is a hydrogen atom or a methyl group, and R ⁸ is an alkyl group having 1 to 40 carbon atoms. ) The component (A) includes a nonionic surfactant and an anionic surfactant,
The nonionic surfactant is at least one selected from the group consisting of a compound represented by the following general formula (a1) and a compound represented by the following general formula (a2).
The anionic surfactant is selected from the group consisting of linear alkylbenzene sulfonic acid, linear alkylbenzene sulfonate, polyoxyethylene alkyl ether sulfate, fatty acid having 8 to 18 carbon atoms and fatty acid salt having 8 to 18 carbon atoms. One or more,
The liquid detergent according to claim 1, wherein the component (B) is a polymer having a repeating unit derived from a diallyldialkylammonium salt and a repeating unit derived from acrylamide.

(In formula (a1), R ⁹ is a hydrocarbon group having 9 to 13 carbon atoms, R ¹⁰ is an alkylene group having 2 to 4 carbon atoms, and R ¹¹ is an alkyl group having 1 to 4 carbon atoms. m represents an average repeating number of ^{OR 10,} a number of 5-25.
In the formula (a2), R ¹² is a hydrocarbon group having 10 to 22 carbon atoms, EO is an oxyethylene group, and PO is an oxypropylene group. s represents the average number of repetitions of EO and is a number of 5 to 20, and t represents the average number of repetitions of PO and is a number of 0 to 4. )