JP5597371B2 - Liquid detergent composition for clothing - Google Patents

Description

  The present invention relates to a liquid cleaning composition for clothing.

  As liquid detergent compositions for clothing, those based on a nonionic surfactant as a main base are widely used. As the nonionic surfactant, for example, an alcohol alkoxylate such as a primary alcohol ethoxylate is used. Conventionally, in such a detergent composition for clothing, 10 to 40 mass of nonionic surfactant is used in order to express sufficient detergency in the amount used when performing ordinary washing in an electric washing machine. About%.

In recent years, the importance of development and sales of products that are friendly to the global environment has been increasing, and products that are friendly to the global environment are also demanded in the daily necessities field such as detergent compositions for clothing. Under such circumstances, since the reduction of energy and the amount of waste in logistics are expected, miniaturization of containers for storing the cleaning composition is progressing. Accordingly, there is a demand for a detergent composition that exhibits high detergency with a small amount of detergent. For example, in the case of the above-described liquid detergent composition, a concentrated detergent in which the concentration of a nonionic surfactant that is a washing component is increased is required. In other words, by adding a nonionic surfactant at a high concentration, the amount of the liquid detergent composition used for one washing can be reduced, and even if the detergent container is downsized, it can be washed as many times as it is now. (For example, even if the detergent container is halved, if the amount used per wash is halved, it can be washed the same number of times).
However, in general, surfactants are known to form high-viscosity high-order association structures such as hexagonal liquid crystals and lyotropic liquid crystals typified by lamellar liquid crystals in a high concentration region. The primary alcohol alkoxylate which is a surfactant tends to form a highly viscous liquid crystal phase in a considerably wide concentration range. Therefore, when a concentrated detergent is prepared using a primary alcohol alkoxylate, the liquid stability is poor and precipitation and gelation are likely to occur. For this reason, it is difficult to stably mix a detergency improving agent such as an enzyme, and the dissolution rate when put into a washing bath during washing is slow, so that a sufficient washing effect cannot be obtained.
In order to improve liquid stability and the like for such problems, a method of blending a hydrotrope agent or the like is known (for example, Patent Document 1). However, in order to obtain a concentrated detergent with higher concentration, it is necessary to increase the concentration of hydrotrope in addition to the concentration of primary alcohol alkoxylate. Difficult to do. Although the hydrotrope agent has a solubility improving effect, it does not affect the cleaning power at all, so that such a composition cannot provide a sufficient cleaning power.
Even if it is the same alcohol ethoxylate, the secondary alcohol ethoxylate is known as a nonionic surfactant that is less likely to precipitate and gel than the primary alcohol alkoxylate. However, even when a secondary alcohol ethoxylate is used, if the blending amount exceeds 50% by mass, it is difficult to ensure sufficient stability as a composition, and the same problem as described above occurs. .

On the other hand, the importance of products that are friendly to the global environment is the same for household electric washing machines, and new models that are friendly to the global environment have been put on the market one after another using technologies such as energy saving, water saving, and power saving. In these washing machines, the washing method (mechanical force) is devised so that washing with less energy is possible, or washing with a smaller amount of water is possible. However, in such a washing method, the load applied to the clothing is large, and the finished feeling becomes worse after washing. For this reason, there is an increasing demand for detergents for clothing that can give a good finish after washing. For example, Patent Document 2 discloses a detergent composition containing a flexibility-imparting component such as a long-chain amine or a cationic surfactant. Is disclosed.
In recent years, with the increase in size of washing machines and the spread of water-saving washing machines, there are many cases where clothes are stuffed and washed under conditions of less water. However, when washing is performed under such conditions, the stains removed by washing again adhere to the clothing, and the problem of re-contamination is likely to occur. In order to solve such a problem, it is known that an anti-staining effect can be obtained when an anionic surfactant such as a linear alkylbenzene sulfonate is added to the cleaning composition.

JP 2005-23123 A JP 2009-73915 A

However, a liquid detergent composition containing an alcohol alkoxylate as a main base, a flexibility-imparting component such as a long-chain amine and a cationic surfactant, and an anionic surfactant used for preventing recontamination When these two components are blended, the flexibility imparting performance and the recontamination preventing performance may not be sufficiently exhibited, or the storage stability of the liquid detergent composition may be lowered. This is presumably because precipitation is likely to occur due to electrostatic interaction between the two components. In particular, in the case of a concentrated detergent containing 40% by mass or more of alcohol alkoxylate, precipitation of these components is likely to occur, and it becomes more difficult to ensure storage stability.
The present invention has been made in view of the above circumstances, and contains a high concentration of a nonionic surfactant alcohol alkoxylate, storage stability, solubility in water, detergency, recontamination prevention performance and An object is to provide a liquid detergent composition for clothing that is also excellent in flexibility imparting performance.

As a result of intensive studies, the present inventors formulated a specific amount of a specific nonionic surfactant, a specific tertiary amine compound, a specific anionic surfactant, and a specific solvent. Thus, the present invention has been completed.
The present invention for solving the aforementioned problems ^is, in _{^{R 1 -O (R 2 O)}} n H [ wherein, ^{R 1} is a hydrocarbon group having a carbon number of 10 to 22 derived from a primary alcohol, ^{R 2} is carbon It is a C2-C4 alkylene group, n represents an average addition mole number and is 5-20. The compound represented by] (A-1), and ^{R 1 '-O (R 2'} O) n 'H [ in the formula, ^{R 1'} is a hydrocarbon having a carbon number of 10 to 22 derived from a secondary alcohol R ² ′ is an alkylene group having 2 to 4 carbon atoms, and n ′ represents an average added mole number and is 10 to 16. Nonionic surfactant (A) selected from the group consisting of the compound (A-2) represented by the formula:
R ⁶ —N (R ⁷ ) (R ⁸ ) [wherein R ⁶ is a hydrocarbon group having 7 to 27 carbon atoms which may have a linking group, and R ⁷ and R ⁸ are each independently , An alkyl group having 1 to 4 carbon atoms, a hydroxyalkyl group having 1 to 4 carbon atoms, or (R ⁹ O) _p H [wherein R ⁹ is an alkylene group having 2 to 4 carbon atoms, and p is an average addition The number of moles is 1 to 25. ]. 0.1 to 10% by mass of a compound (B) selected from the group consisting of a tertiary amine compound represented by the formula:
1 to 20% by mass of an anionic surfactant (C) having SO ₃ group or SO ₄ group,
Monohydric alcohol having 2 to 4 carbon atoms, a polyhydric alcohol, and ^R 11 from 2 to 4 carbon atoms ^{- (OR} ₁₂₎ in l OH ^{[wherein, R 11} is an alkyl group or a phenyl group having 1 to 6 carbon atoms, R ¹² represents an alkylene group having 2 to 4 carbon atoms, and 1 represents an average added mole number and is 1 to 5. A solvent (D) selected from the group consisting of glycol ether solvents represented by the formula:
In the component (A), before asked compound and (A-1), prior to hear compound (A-2) the ratio (mass ratio) of (A-1) / (A -2) = 90 / 10-0 / 100,
The ratio (mass ratio) of the component (B) and the component (C) is (C) / (B) = 1/1 to 10/1.

  According to the present invention, a nonionic surfactant alcohol alkoxylate is contained in a high concentration, and is excellent in storage stability, solubility in water, detergency, recontamination prevention performance and flexibility imparting performance. A liquid detergent composition can be provided.

  The liquid cleaning composition for clothing of the present invention (hereinafter sometimes referred to as a liquid cleaning composition) contains the following components (A) to (D).

<(A) component>
The component (A) is a nonionic surfactant represented by R ¹ —O (R ² O) _n H.
The component (A) is an alcohol alkoxylate in which an alkylene oxide having 2 to 4 carbon atoms is added to an alcohol (R ¹ —OH) at an average addition mole number n, and is also referred to as polyoxyethylene alkyl ether. The component (A) is blended mainly for the purpose of imparting detergency to the liquid detergent composition of the present invention.
In the formula, R ¹ is a hydrocarbon group having 10 to 22 carbon atoms. When the carbon number is 10 or more, the detergency against sebum stains is improved, and when it is 22 or less, solubility and liquid stability are improved. 10-20 are preferable and, as for carbon number of this hydrocarbon group, 10-18 are more preferable. The hydrocarbon group is preferably an aliphatic hydrocarbon group (a hydrocarbon group having no aromaticity). The hydrocarbon group may or may not have an unsaturated bond. The hydrocarbon group is preferably linear or branched.
R ¹ may be a single chain length or a mixture of a plurality of chain lengths.
R ¹ is derived from a raw material alcohol (R ¹ —OH), and examples of the alcohol include alcohols derived from natural fats and oils such as coconut oil, palm oil, and beef tallow, and synthetic alcohols derived from petroleum.

R ² is an alkylene group having 2 to 4 carbon atoms, preferably an ethylene group or a propylene group. Among them, it is preferable that R ² is an ethylene group because foaming during washing is good and inexpensive.
n represents the average added mole number of alkylene oxide. n is 5-20, 8-18 are preferable and 10-16 are especially preferable. When n is within this range, it exhibits excellent detergency against sebum dirt. Further, when n is 5 or more, it is possible to further prevent odor degradation. On the other hand, when n exceeds 20, HLB (Hydrophile-Lipophile Balance) becomes too high, and the detergency with respect to sebum dirt decreases.

In the component (A), the addition mole number distribution of the alkylene oxide is not particularly limited. The distribution varies depending on the reaction method during the production of component (A). For example, when ethylene oxide is added to a hydrophobic raw material using a general alkali catalyst such as sodium hydroxide or potassium hydroxide. , Tend to have a relatively wide distribution. Also, specific alkoxylation such as magnesium oxide to which metal ions such as Al ³⁺ , Ga ³⁺ , In ³⁺ , Tl ³⁺ , Co ³⁺ , Sc ³⁺ , La ³⁺ , Mn ^{2+ and the} like described in Japanese Patent Publication No. 6-15038 are added. When ethylene oxide is added to a hydrophobic group raw material using a catalyst, the distribution tends to be relatively narrow.

In the liquid detergent composition of the present invention, as the component (A), only one type may be used alone, or a plurality of types may be used in combination.
In the liquid detergent composition of the present invention, the blending amount of the component (A) needs to be 40 to 75% by mass with respect to the total mass of the liquid detergent composition. When the blending amount is 40% by mass or more, a high cleaning power can be given to the liquid detergent composition, and the amount of the liquid detergent composition used can be reduced. On the other hand, if it exceeds 75% by mass, gelation tends to occur, and the storage stability and solubility are lowered.
The blending amount is preferably 45% by mass or more, more preferably 50% by mass or more, and further preferably more than 50% by mass. The blending amount is preferably 70% by mass or less, and more preferably 65% by mass or less.

In the present invention, in component (A), R ¹ is a hydrocarbon group derived from a primary alcohol (A-1) (hereinafter referred to as component (A-1)), and R ^1. Is a ratio (mass ratio) with the compound (A-2) (hereinafter referred to as component (A-2)), which is a hydrocarbon group derived from a secondary alcohol, (A-1) / (A-2) = 90/10 to 0/100. That is, the component (A) includes the component (A-2) as an essential component, and may optionally include the component (A-1). When the component (A-1) is included, the ratio is (A- It is necessary to be 10% by mass or less based on the total of 1) component and (A-2) component. When the proportion of the component (A-1) is too high, gelation is likely to occur, and storage stability and solubility in water are deteriorated.
(A-1) / (A-2) is preferably 80/20 to 0/100, particularly preferably 70/30 to 0/100.

In the liquid detergent composition of the present invention, the blending amounts of the component (A-1) and the component (A-2) are the total blending amount as the component (A) and (A-1) / (A-2). May be any amount that satisfies the above ranges.
The compounding amount of the component (A-1) is preferably 0 to 67.5% by mass, more preferably 0 to 56% by mass, and 0 to 45.5% by mass with respect to the total mass of the liquid detergent composition. Further preferred.
(A-2) As for the compounding quantity of a component, 4-75 mass% is preferable with respect to the total mass of a liquid detergent composition, 9-70 mass% is more preferable, 15-65 mass% is further more preferable.

Specific examples of the component (A-1) include 12 to 15 moles of ethylene oxide with respect to an alcohol such as a product manufactured by Shell: trade name Neodol (C12 / C13) and a product manufactured by Sasol: Safol23 (C12 / C13). Added product, manufactured by P & G: Products obtained by adding 9, 12, and 15 moles of ethylene oxide to natural alcohols such as trade names CO-1214 and CO-1270.
Specific examples of the component (A-2) include a secondary alcohol having 12 to 14 carbon atoms added with 9, 12 and 15 moles of ethylene oxide (Nippon Shokubai Co., Ltd., Softanol 90, 120). And 150).
As the component (A-1) and the component (A-2), one type may be used alone, or two or more types may be used in combination.

<(B) component>
The component (B) is a compound selected from the group consisting of tertiary amine compounds represented by R ⁶ —N (R ⁷ ) (R ⁸ ) and salts thereof.
The component (B) is blended mainly for the purpose of imparting flexibility imparting performance to clothing such as cotton and polyester to the liquid detergent composition of the present invention.
In the formula, R ⁶ is a hydrocarbon group having 7 to 27 carbon atoms which may have a linking group. The carbon number is preferably 7-25. In addition, when this hydrocarbon group has a coupling group, the carbon number contained in a coupling group is not contained in the carbon number of a hydrocarbon group.
The hydrocarbon group is preferably an aliphatic hydrocarbon group. The hydrocarbon group may or may not have an unsaturated bond. The hydrocarbon group is preferably linear or branched.
Here, the phrase “the hydrocarbon group has a linking group” means that the linking group is interposed between carbon atoms in the hydrocarbon group.
Examples of the linking group that the hydrocarbon group may have include an amide group (—CO—NH—), an ester group (—CO—O—), an ether group (—O—), and the like.
R ⁷ and R ⁸ are each independently an alkyl group having 1 to 4 carbon atoms, a hydroxyalkyl group having 1 to 4 carbon atoms, or (R ⁹ O) _p H [wherein R ⁹ is 2 to 4 carbon atoms. And p represents an average added mole number and is 1 to 25. ].
The alkyl group, hydroxyalkyl group (alkanol group) in R ⁷ and R ^8, and the alkylene group in R ⁹ may each be linear or branched.
R ⁹ is preferably an ethylene group or a propylene group, and particularly preferably an ethylene group.

The tertiary amine compound represented by R ⁶ —N (R ⁷ ) (R ⁸ ) may be used as it is or as a salt. Specific examples of the salt include an acid salt obtained by neutralizing the tertiary amine compound with an acid. Examples of the acid used for neutralization include hydrochloric acid, sulfuric acid, nitric acid, phosphoric acid, glycolic acid, lactic acid, citric acid, polyacrylic acid, paratoluenesulfonic acid, cumenesulfonic acid, and the like. Two or more types may be used in combination.

  The component (B) is particularly preferably at least one selected from the group consisting of tertiary amine compounds represented by the following general formula (b-1) or (b-2) and salts thereof.

［式中、Ｒ^６１は炭素数７〜２３の炭化水素基であり、Ｒ^６２は炭素数１〜４のアルキレン基であり、Ｒ^７及びＲ^８はそれぞれ前記と同じである。］

[Wherein R ⁶¹ is a hydrocarbon group having 7 to 23 carbon atoms, R ⁶² is an alkylene group having 1 to 4 carbon atoms, and R ⁷ and R ⁸ are the same as defined above. ]

In the formula, the hydrocarbon group in R ⁶¹ is a hydrocarbon group having 7 to 23 carbon atoms, and the carbon number is preferably 7 to 21. The hydrocarbon group is preferably an aliphatic hydrocarbon group. The hydrocarbon group may or may not have an unsaturated bond. The hydrocarbon group is preferably linear or branched.
The alkylene group for R ⁶² may be linear or branched.

［式中、Ｒ^６３は炭素数１１〜２３の炭化水素基であり、Ｒ^６４は炭素数１〜４のアルキレン基であり、Ｒ^７及びＲ^８はそれぞれ前記と同じである。］

[Wherein R ⁶³ is a hydrocarbon group having 11 to 23 carbon atoms, R ⁶⁴ is an alkylene group having 1 to 4 carbon atoms, and R ⁷ and R ⁸ are the same as defined above. ]

In the formula, the hydrocarbon group in R ⁶³ is a hydrocarbon group having 11 to 23 carbon atoms, and the carbon number is preferably 12 to 20. The hydrocarbon group is preferably an aliphatic hydrocarbon group. The hydrocarbon group may or may not have an unsaturated bond. The hydrocarbon group is preferably linear or branched.
The alkylene group for R ⁶⁴ may be linear or branched.

Specific examples of the tertiary amine compound represented by the formula (b-1) include caprylic acid dimethylaminopropylamide, capric acid dimethylaminopropylamide, lauric acid dimethylaminopropylamide, myristic acid dimethylaminopropylamide, palmitic acid. Long-chain aliphatic amide dialkyl tertiary amines such as dimethylaminopropylamide, stearic acid dimethylaminopropylamide, behenic acid dimethylaminopropylamide, oleic acid dimethylaminopropylamide; palmitic acid diethanolaminopropylamide, stearic acid diethanolaminopropylamide Long chain aliphatic amide dialkanol tertiary amines, and the like.
Specific examples of the tertiary amine compound represented by the formula (b-2) include aliphatic ester dialkyl tertiary amines such as palmitate ester propyldimethylamine and stearate ester propyldimethylamine.
Among these, a tertiary amine compound represented by the formula (b-1) or a salt thereof is preferable, and caprylic acid dimethylaminopropylamide, capric acid dimethylaminopropylamide, lauric acid dimethylaminopropylamide, myristic acid dimethylaminopropyl. Amides, dimethylaminopropylamide palmitate, dimethylaminopropylamide stearate, dimethylaminopropylamide behenate, dimethylaminopropylamide oleate or salts thereof are particularly preferred.

  In addition to the tertiary amine compound represented by the formula (b-1) or (b-2) and a salt thereof, specific examples of the tertiary amine compound that can be used as the component (B) include lauryldimethylamine, myristyldimethylamine. Palm alkyl dimethylamine, palmityl dimethyl amine, beef tallow alkyl dimethyl amine, cured beef tallow alkyl dimethyl amine, stearyl dimethyl amine, stearyl diethanol amine, polyoxyethylene cured beef tallow alkyl amine (product name: ETHOMEEN HT / 14) Etc.).

(B) A commercially available thing may be used for a component and you may synthesize | combine by a well-known method.
For example, when the production method of the component (B) is described by taking a long-chain aliphatic amidoalkyl tertiary amine such as the tertiary amine compound represented by the formula (b-1) as an example, for example, fatty acid or fatty acid Derivatives (fatty acid lower alkyl esters, animal / vegetable oils and fats) and dialkyl (or alkanol) aminoalkylamine are subjected to a condensation reaction, and then unreacted dialkyl (or alkanol) aminoalkylamine is reduced in pressure or nitrogen blown. The target compound is obtained by distilling off.
Here, as the fatty acid or fatty acid derivative, caprylic acid, capric acid, lauric acid, myristic acid, palmitic acid, stearic acid, oleic acid, behenic acid, erucic acid, 12-hydroxystearic acid, coconut oil fatty acid, cottonseed oil fatty acid, Specific examples include corn oil fatty acid, beef tallow fatty acid, palm kernel oil fatty acid, soybean oil fatty acid, flaxseed oil fatty acid, castor oil fatty acid, olive oil fatty acid and other vegetable oils or animal oil fatty acids, or their methyl esters, ethyl esters, glycerides, etc. Among them, caprylic acid, capric acid, lauric acid, myristic acid, palmitic acid, stearic acid, oleic acid, behenic acid and the like are particularly preferable. These fatty acids or fatty acid derivatives may be used alone or in combination of two or more.
Specific examples of the dialkyl (or alkanol) aminoalkylamine include dimethylaminopropylamine, dimethylaminoethylamine, diethylaminopropylamine, diethylaminoethylamine, etc. Among them, dimethylaminopropylamine is particularly preferable.
The amount of dialkyl (or alkanol) aminoalkylamine used in the production of the long-chain aliphatic amidoalkyl tertiary amine is preferably 0.9 to 2.0 times the moles of the fatty acid or derivative thereof, and is 1.0 to A 1.5-fold mole is particularly preferred. The reaction temperature is usually 100 to 220 ° C, preferably 150 to 200 ° C. If the reaction temperature is less than 100 ° C., the reaction becomes too slow, and if it exceeds 220 ° C., the resulting tertiary amine may be markedly colored.
The production conditions other than those described above for the long-chain aliphatic amidoalkyl tertiary amine can be appropriately changed. The pressure during the reaction may be normal pressure or reduced pressure, and may be introduced by blowing an inert gas such as nitrogen during the reaction. Is possible.
Also, when using fatty acids, acid catalysts such as sulfuric acid and p-toluenesulfonic acid, and when using fatty acid derivatives, alkaline catalysts such as sodium methylate, caustic potash and caustic soda can be used for a short time at a low reaction temperature. The reaction can proceed efficiently.
Further, when the obtained tertiary amine is a long-chain amine having a high melting point, it is preferably molded into a flake shape or a pellet shape after the reaction in order to improve handling properties, or in an organic solvent such as ethanol. It is preferable to dissolve and make it liquid.
Specific examples of the commercially available component (B) include Kachinal MPAS-R manufactured by Toho Chemical Co., Ltd.

As the component (B), only one type may be used alone, or a plurality of types may be used in combination.
In the liquid detergent composition of the present invention, the blending amount of the component (B) is 0.1 to 10% by mass, and 0.5 to 5% by mass with respect to the total mass of the liquid detergent composition. preferable. When the content of the component (B) is 0.1% by mass or more, sufficient flexibility imparting performance can be obtained. Moreover, even if it mixes more than (B) component more than 10 mass%, the improvement effect of the softness | flexibility provision property corresponding to it is not seen, but it becomes economically disadvantageous.

<(C) component>
The component (C) is an anionic surfactant having an SO ₃ group or an SO ₄ group.
Component (C) is blended mainly for the purpose of imparting recontamination preventing performance to the liquid detergent composition of the present invention.
(C) It does not specifically limit as a component, A well-known thing can be utilized.
Specific examples of the component (C) include linear alkylbenzene sulfonic acid or a salt thereof; α-olefin sulfonate; linear or branched alkyl sulfate ester salt; alkyl ether sulfate ester salt or alkenyl ether sulfate ester salt; Alkane sulfonate having a group; α-sulfo fatty acid ester salt and the like.
Examples of these salts include alkali metal salts such as sodium and potassium, alkaline earth metal salts such as magnesium, and alkanolamine salts such as monoethanolamine and diethanolamine.
Among these, as the linear alkylbenzene sulfonic acid or a salt thereof, one having 8 to 16 carbon atoms in the linear alkyl group is preferable, and one having 10 to 14 carbon atoms is particularly preferable.
The α-olefin sulfonate is preferably one having 10 to 20 carbon atoms.
As the alkyl sulfate ester salt, those having 10 to 20 carbon atoms are preferable.
The alkyl ether sulfate ester salt or alkenyl ether sulfate ester salt has a linear or branched alkyl group or alkenyl group having 10 to 20 carbon atoms, and an average of 1 to 10 moles of ethylene oxide added thereto (ie, Polyoxyethylene alkyl ether sulfate ester salt or polyoxyethylene alkenyl ether sulfate ester salt) is preferable.
The carbon number of the alkane sulfonate is 10 to 20, preferably 14 to 17, and the secondary alkane sulfonate is particularly preferable.
The α-sulfo fatty acid ester salt is preferably one having 10 to 20 carbon atoms.
These components (C) can be easily obtained on the market. Moreover, you may synthesize | combine by a well-known method.
As component (C), among the above, at least one selected from the group consisting of linear alkylbenzene sulfonic acid or a salt thereof, alkane sulfonate, polyoxyethylene alkyl ether sulfate, and α-olefin sulfonate. Species are preferred.

As the component (C), only one type may be used alone, or a plurality of types may be used in combination.
In the liquid detergent composition of the present invention, the amount of component (C) is 1 to 20% by mass, preferably 1 to 10% by mass, based on the total mass of the liquid detergent composition. When the content of the component (C) is 1% by mass or more, sufficient recontamination prevention performance can be obtained. Moreover, if content of (C) component is 20 mass% or less, the liquid stability of this composition will improve.

By blending the component (B) and the component (C) at a specific ratio, it is possible to improve both the anti-recontamination performance and improve the flexibility imparting performance for clothing, particularly clothing made of hydrophobic fibers such as polyester. it can.
In the liquid detergent composition of the present invention, the ratio (mass ratio) of the component (B) and the component (C) is (C) / (B) = 1/1 to 10/1, and 1.05 / 1. ~ 5/1 is preferred. When the ratio of the component (C) is too low, not only the effect of preventing recontamination by the component (C) can be sufficiently obtained, but also it cannot be stably blended as a liquid detergent composition. On the other hand, when the ratio of the component (B) is too low, a sufficient flexibility imparting effect by the component (B) cannot be obtained.
The reason for the above effect is not clear, but the hydrophobicity of the component (B), which is a softening component, is probably increased by forming a complex in the water when the component (B) and the component (C) are washed. This is presumed to be due to the high adsorptivity on the hydrophobic fiber surface.

<(D) component>
Component (D), a monohydric alcohol having 2 to 4 carbon atoms, a polyhydric alcohol, and ^R 11 from 2 to 4 carbon atoms ^- in ^(OR ₁₂₎ l OH ^{[wherein, R 11} is an alkyl group having 1 to 6 carbon atoms Or it is a phenyl group, R < ¹² > is a C2-C4 alkylene group, l represents an average addition mole number, and is 1-5. ] A solvent selected from the group consisting of glycol ether solvents represented by glycol ether solvents.
Examples of the monohydric alcohol having 2 to 4 carbon atoms include ethanol, 1-propanol, 2-propanol, 1-butanol and the like.
Examples of the polyhydric alcohol having 2 to 4 carbon atoms include ethylene glycol, propylene glycol, butylene glycol, glycerin and the like.
Examples of the glycol ether solvent represented by the formula R ¹¹ — (OR ¹² ) ₁ OH include ethylene glycol monobutyl ether, diethylene glycol monobutyl ether, ethylene glycol monohexyl ether, ethylene glycol monophenyl ether, propylene glycol monophenyl ether, and diethylene glycol. A monomethyl ether etc. are mentioned.
Of these, monohydric alcohols and polyhydric alcohols are preferred, with ethanol and propylene glycol being particularly preferred, because of their mild odor and availability of raw materials.
In the liquid detergent composition of the present invention, as the component (D), only one type may be used alone, or a plurality of types may be used in combination.

  In the liquid detergent composition of the present invention, the blending amount of the component (D) is 3 to 20 mass%, preferably 4 to 15 mass%, preferably 5 to 12 based on the total mass of the liquid detergent composition. The mass% is more preferable. If content of (D) component is 3 mass% or more, the liquid fluidity | liquidity of this composition will become favorable, it does not gelatinize and can be used as a washing | cleaning agent. Even if it mixes more than 20 mass%, the liquid fluid improvement effect corresponding to it is not seen, but it becomes economically disadvantageous.

The liquid detergent composition of the present invention contains the above components (A) to (D) as essential components, and may be composed of only the components (A) to (D). Components other than the components (A) to (D) may be contained. The other components are not particularly limited, and can include components usually used in a liquid cleaning composition for clothing.
For example, the liquid detergent composition of the present invention preferably further contains water in view of ease of preparation of the liquid detergent composition, solubility in water as the detergent composition, storage stability, and the like. In the liquid cleaning composition of the present invention, the water content is preferably 0 to 59% by mass, more preferably 10 to 49% by mass, based on the total mass of the liquid cleaning composition. preferable.

Moreover, the liquid cleaning composition of this invention can contain surfactant other than (A) component and (C) component.
Examples of the surfactant include a nonionic surfactant other than the component (A), an anionic surfactant other than the component (C), a cationic surfactant, and an amphoteric surfactant.
Examples of nonionic surfactants other than the component (A) include fatty acid alkyl ester alkoxylates such as fatty acid methyl ester ethoxylates (alkylene oxide adducts of fatty acid alkyl esters), alkylenes such as alkylphenols, higher fatty acids, and higher amines. Oxide adduct, polyoxyethylene polyoxypropylene 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, hydrogenated castor oil Alkylene oxide adducts, sugar fatty acid esters, N-alkyl polyhydroxy fatty acid amides, alkyl glycosides, and the like.
Examples of anionic surfactants other than the component (C) include higher fatty acid salts, alkyl ether carboxylates, polyoxyalkylene ether carboxylates, alkyl (or alkenyl) amide ether carboxylates, acylaminocarboxylic acids. Phosphate-type anionic surface activity such as carboxylic acid type such as salt, alkyl phosphate ester salt, polyoxyalkylene alkyl phosphate salt, polyoxyalkylene alkylphenyl phosphate salt, glycerin fatty acid ester monophosphate ester salt Agents and the like.
Examples of cationic surfactants include alkyltrimethylammonium salts, dialkyldimethylammonium salts, alkylbenzyldimethylammonium salts, and alkylpyridinium salt cationic surfactants.
Examples of amphoteric surfactants include alkyl betaine type, alkyl amide betaine type, imidazoline type, alkyl amino sulfone type, alkyl amino carboxylic acid type, alkyl amide carboxylic acid type, amide amino acid type, phosphoric acid type amphoteric surfactant. Is mentioned.

In addition, triethylene glycol, tetraethylene glycol, glycols such as polyethylene glycol having an average molecular weight of about 200 to 5000, paratoluenesulfonic acid, benzoate (also has an effect as a preservative), a viscosity reducing agent such as urea, A solubilizer can be contained, for example, 0.01 to 15% by mass.
Moreover, 0.1-20 mass% of metal ion sequestering agents, such as malonic acid, a succinic acid, malic acid, diglycolic acid, tartaric acid, a citric acid, can be included.
Moreover, 0.01-2 mass% of antioxidants, such as butylhydroxytoluene, distyrenation cresol, sodium sulfite, and sodium hydrogensulfite, can be included, for example.
Moreover, antiseptic | preservatives, such as Rohm and House company made caisson CG (brand name), can be contained, for example, 0.001-1 mass%.

In addition, for the purpose of improving detergency and stability, an alkali builder such as texture improver, alkanolamine such as monoethanolamine, diethanolamine, triethanolamine, N-methyl-diethanolamine, N, N-dimethylmonoethanolamine , PH adjusters, hydrotropes, fluorescent agents, enzymes, dye transfer inhibitors, anti-staining agents that do not fall under component (C) (eg, polyvinylpyrrolidone, carboxymethylcellulose, etc.), pearl agents, soil release agents, etc. be able to.
As the texture improver, FZ-3707, FZ-3504, BY16-205, FZ-3760, FZ-3705, BY16-209, FZ-3710, SF8417, BY16-849, BY16 manufactured by Toray Dow Corning Co., Ltd. -850, BY16-879B, BY16-892, FZ3501, FZ-3785, BY16-872, BY16-213, BY16-203, BY16-898, BY16-890, BY16-878, BY16-891, BY16-893, FZ -3789, BY16-880, SF8428, FZ-3704, BY16-606, CF1188HV, SH3748, SH3794, SH3772M, SH3775M, SF8410, SH8700, BY22-008, BY22-012, SILWET L-7001, SILWET L-7002, SILWET L-7602, SILWET L-7604, SILWET FZ-2104, SILWET FZ-2120, SILWET FZ-2161, SILWET FZ-2162, SILWET FZ-2164, SILWET FZ-217 SILWET FZ-F1-009-01, ABN SILWET FZ-F1-009-02, ABN SILWET FZ-F1-009-03, ABN SILWET FZ-F1-009-05, ABN SILWET FZ-F1-009-0WZIL -F1-009-11, ABN SILWET FZ-F1-009-13, ABN SILWET FZ-F1-009-54, ABN SILWET FZ-22-22, Modified silicones such as X-20-8010B, KF352A, KF6008, KF615A, KF6012, KF6016, KF6017 manufactured by Koshi Chemical Industry Co., Ltd .; TSF4450, TSF4452 and TSF4445 manufactured by GE Toshiba Silicone Co., Ltd. The modified silicone can be used in an amount of 0.1 to 3% by mass in the liquid detergent composition.

In addition to the above, flavoring agents, coloring agents, emulsifying agents, extracts of natural products, and the like can also be included for the purpose of improving the added value of goods.
As a flavoring agent, as a typical example, the fragrance composition described in JP-A-2002-146399 and JP-A-2009-108248 can be used, and the preferred blending amount is 0.1 to 2 mass. %.
Colorants include general-purpose dyes and pigments such as Acid Red 138, Polar Red RLS, Acid Yellow 203, Acid Blue 9, Blue No. 1, Blue No. 205, Green No. 3, and Turquoise P-GR (all trade names) For example, about 0.00005 to 0.005 mass%.
Examples of the emulsion include polystyrene emulsion and polyvinyl acetate emulsion, and usually an emulsion having a solid content of 30 to 50% by mass is suitably used. As a specific example, polystyrene emulsion (Syden Chemical Co., Ltd. (trade name) Cybinol RPX-196 PE-3, solid content 40% by mass) and the like can be contained in an amount of 0.01 to 0.5% by mass.
Examples of extracts such as natural products include Inuenju, Uwaurushi, Echinacea, Koganebana, Yellowfin, Ouren, Allspice, Oregano, Enju, Chamomile, Honeysuckle, Clara, Keigai, Kay, Bay bay, Honoki, Burdock, Comfrey, Jasho, Waremokou, Peonies, Ginger, Solidago, Elderberry, Sage, Mistletoe, Prunus, Thyme, Prunus, Clove, Satsuma Mandarin, Tea Tree, Barberry, Dokudami, Nanten, Nyuko, Yorigusa, Shirogaya, Bow Fu, Dutch Hyu, Mountain, Gray , Murasakitagayasan, yamahakka, cypress, yamajiso, eucalyptus, lavender, rose, rosemary, balun, cedar, gilead balsamno , Ringworm, kochia, Polygonum aviculare, Jingyou, Liquidambar formosana, Adenophortriphylla, Yamabishi, cayratia japonica, licorice, include plant extracts such as St. John's wort, these example, can include about 0-0.5 wt%.

In the liquid detergent composition of the present invention, the pH at 25 ° C. is preferably 4 to 9, and more preferably 4 to 8. When the pH is 4 to 9, it is possible to maintain good stability over time even when the liquid detergent composition is stored for a long period of time.
The pH can be adjusted with a pH adjuster. Examples of the pH adjuster include inorganic acids such as hydrochloric acid, sulfuric acid and phosphoric acid; organic acids such as polyvalent carboxylic acids and hydroxycarboxylic acids; sodium hydroxide, potassium hydroxide, alkanolamine and ammonia. Among these, sulfuric acid, sodium hydroxide, potassium hydroxide, and alkanolamine are preferable, and sulfuric acid and sodium hydroxide are preferable from the viewpoint of the temporal stability of the liquid detergent composition.
A pH adjuster may be used individually by 1 type, and may use 2 or more types together. For example, when controlled by adding a certain amount of sulfuric acid, sodium hydroxide or the like, an inorganic acid (preferably hydrochloric acid or sulfuric acid) or potassium hydroxide can be further added for fine adjustment of pH.
In the present specification, the pH of the liquid detergent composition (controlled at 25 ° C.) indicates a value measured by a pH meter (product name: HM-30G, manufactured by Toa DKK Corporation).

  The liquid detergent composition of the present invention can be manufactured based on a conventional method, for example, by mixing the above-described components. At this time, it is preferable to add water as a liquid medium.

The liquid detergent composition of the present invention can be used in the same manner as the usual method for using the liquid detergent composition for clothing. That is, a method in which the liquid detergent composition is poured into the water together with the laundry at the time of washing, a method in which the liquid detergent composition is directly applied to mud stains and sebum stains, a liquid detergent composition previously dissolved in water and clothing. And the like. Also preferred is a method in which the liquid detergent composition is applied to the laundry and then allowed to stand as appropriate, followed by normal washing using a normal laundry solution.
In that case, the usage-amount of the liquid cleaning composition of this invention can be made smaller than the usage-amount of the conventional liquid cleaning composition.

The present invention will be described more specifically with reference to examples. However, the present invention is not limited to these.
< Reference Examples 1-2, Examples 3-14, Reference Examples 15-16, Examples 17-19 , Comparative Examples 1-9>
A liquid detergent composition having the composition shown in Table 1 was prepared by the following procedure.
(A) component and (D) component were put into a 500 mL beaker, and it stirred sufficiently with the magnetic stirrer (made by MITAMURA KOGYO INC.). Subsequently, while adding other components (component (B), component (C), common additive component) and stirring, purified water was added so that the total amount became 98 parts by mass, and further stirred. After adding a suitable amount of pH adjusting agent (sodium hydroxide or sulfuric acid) so that the pH at 25 ° C. is 7.0, purified water is added so that the total amount becomes 100 parts by mass, and a liquid detergent composition Got.
In Table 1, the unit of the blending amount of each component is “mass%”. Table 1 shows the blending amount (mass%) of the component (A) in the liquid detergent composition and the ratio of blending amounts of the components (A-1) and (A-2) (A-1 / A). -2) and the ratio (C / D) of the blending amounts of component (B) and component (C).
The following evaluation was performed about the obtained liquid detergent composition. The results are also shown in Table 1.

<Evaluation of initial appearance>
The beaker (capacity 500 mL) containing the liquid cleaning composition 500 g prepared by the above procedure was tilted, and about 100 mL of the contents were taken out into a transparent glass bottle (wide-mouth standard bottle PS-NO.11).
At this time, it was determined that the liquid detergent composition taken out into the glass bottle had fluidity, and the liquid detergent composition that could not be taken out had no fluidity.
Moreover, the external appearance of the liquid detergent composition taken out to the glass bottle was observed visually.
From these results, the initial appearance of each liquid detergent composition was evaluated according to the following criteria.
○: fluid and transparent and uniform in appearance.
X: No fluidity (cannot be taken out into a glass bottle) Or, although it has fluidity, it is turbid in appearance and has floating and sediment.

<Evaluation of solubility>
Put 400 mL of ion-exchanged water at 25 ° C. into a 500 mL tall beaker and stir (500 rpm) using a magnetic stirrer (MITAMURA KOGYO INC.), And drop 0.1 mL of the liquid detergent composition using a poly dropper. Then, the time (dissolution time) until the liquid detergent composition was completely dissolved was visually measured.
From the measured dissolution time, the solubility of each liquid detergent composition was evaluated according to the following criteria.
A: Less than 30 seconds.
○: 30 seconds or more and less than 60 seconds.
Δ: 60 seconds or more and less than 120 seconds.
X: 120 seconds or more.

<Evaluation of sebum detergency>
About the liquid detergent composition determined to have fluidity in the evaluation of the initial appearance, the sebum detergency was evaluated by the following procedure.
10 sheets of polyester cloth (tropical) rubbed with sebum stains on the face cut into 20 cm square and 4 sheets of commercially available T-shirts (100% cotton, manufactured by BVD Corporation) It was put into a washing machine (manufactured by Mitsubishi Electric Corporation, “CW-C30A1 type”).
Next, 10 g of the liquid detergent composition is added to about 30 L of tap water at 25 ° C., washed with a standard water flow (10 minutes), dehydrated (1 minute), and rinsed with a standard water flow (repeated twice, 5 times each) ) And dehydration (1 minute) were sequentially performed.
A polyester cloth not rubbed with sebum stain was used as an uncontaminated cloth, a polyester cloth before washing treatment was used as a contaminated cloth, and a polyester cloth after washing treatment was used as a washing cloth. For each of the unstained cloth, the contaminated cloth and the cleaning cloth, the Z value (reflectance) is measured with a spectroscopic color difference meter (manufactured by Nippon Denshoku Industries Co., Ltd., “SE2000”). ) Was calculated.

From the determined washing rate (%) (average value of 10 sheets subjected to washing at the same time), the cleaning ability of the liquid detergent composition against sebum stain was evaluated according to the following criteria.
A: The cleaning rate is 70% or more.
○: The cleaning rate is 60% or more and less than 70%.
Δ: The cleaning rate is 50% or more and less than 60%.
X: The cleaning rate is less than 50%.

<Evaluation of flexibility>
About the liquid detergent composition determined to have fluidity in the evaluation of the initial appearance, the flexibility (flexibility imparting effect) was evaluated by the following procedure.
Into a two-tank washing machine (Mitsubishi Electric Co., Ltd., CW-C30A1 type), 30L of tap water and 10g of a liquid detergent composition are put, and there are 5 pieces of polyester cloth (tropical) cut into a 20cm square size. Six sheets of commercially available T-shirts (100% cotton, manufactured by BVD Corporation) were added, washed for 10 minutes, dehydrated for 1 minute, rinsed for 5 minutes, and dehydrated for 1 minute. The tap water used was adjusted to a temperature of 25 ° C. The polyester fabric treated in the washing operation was shaded and dried for 12 hours. The dried polyester cloth was left in a constant temperature and humidity room at 25 ° C. and 65% RH for 2 days. This was used as a test cloth, and its softness was compared with a control cloth by a panelist (5 persons) and scored according to the following criteria. As a control cloth, nonionic surfactant (alcohol ethoxylate (a-1 in Table 1) obtained by adding an average of 15 moles of ethylene oxide per mole to a natural alcohol CO-1270 manufactured by P & G) A polyester cloth treated with the same washing operation as above was used as a composition.
1 point: Equivalent to the control cloth.
2 points: Slightly softer than the control cloth.
3 points: Softer than the control cloth.
4 points: considerably softer than the control cloth.
5 points: Very softer than the control fabric.
From the average value of the scoring results of five panelists, flexibility was evaluated according to the following criteria.
：: 4 points or more, ○: flat 3.5 points or more and less than 4 points, Δ: 3 points or more and less than 3.5 points, ×: less than 3 points.

<Evaluation of recontamination prevention>
About the liquid detergent composition determined to have fluidity in the evaluation of the initial appearance, the recontamination prevention property was evaluated by the following procedure.
In a cleaning bath of Terg-O-Tometer (manufactured by UNITED STATES TESTING), 900 mL of tap water and 0.3 g of cleaning solution were added and stirred at 120 rpm for 3 minutes, and then one piece of oil stain cloth (5 × 5 cm), red soil stain One paste cloth (5 × 5 cm) and two white polyester tropical cloths (5 × 5 cm) were added and washed for 10 minutes (25 ° C.). Thereafter, the cleaning solution was removed by emptying the colander, and the test cloth (oil soil cloth, red soil soil cloth, white polyester tropical cloth) was dehydrated for 1 minute in a dewatering tank of a 2-tank washing machine. Further, it was rinsed for 3 minutes in a Terg-O-Tomometer bath containing 900 mL of tap water, and the test cloth was dehydrated for 1 minute in a dewatering tank of a 2-tank washing machine (CW-C30A1 type, manufactured by Mitsubishi Electric Corporation). Similarly, after repeating the operations of rinsing (3 minutes) and dehydration (1 minute), the white polyester tropical cloth was dried to measure the reflectance, and the difference from the reflectance before washing was determined as the degree of recontamination (ΔZ). Calculated as From the value of ΔZ, the anti-recontamination property was evaluated according to the following criteria.
A: ΔZ is 3 or less, O: ΔZ is more than 3 and 6 or less, Δ: ΔZ is more than 6 and less than 9, X: ΔZ is more than 9.

<Evaluation of storage stability>
The storage stability of the liquid detergent composition determined to have fluidity in the initial appearance evaluation was evaluated according to the following procedure.
100 mL of the liquid detergent composition was placed in a transparent glass bottle (wide-mouth bottle PS-NO.11), sealed with the lid closed, and placed in a thermostatic bath at -5 ° C in this state and stored for 1 month. Then, it took out from the thermostat, and the external appearance of the contents was observed visually at room temperature (25 degreeC) within 1 minute, and it evaluated by the following reference | standard.
○: Appearance was transparent and uniform.
Δ: Precipitation or gelation was observed, but the appearance became transparent and uniform when immersed in a 40 ° C. hot water bath for 1 hour.
X: Precipitation or gelation was observed, and the appearance did not become transparent and uniform even when immersed in a hot water bath at 40 ° C. for 1 hour.

As shown in the results of Table 1, the liquid detergent compositions of Reference Examples 1-2, Examples 3-14, Reference Examples 15-16, and Examples 17-19 are well balanced and good in all evaluation items. Results were obtained. In particular, the liquid detergent compositions of Examples 13 and 14 and Reference Example 16 exhibited excellent initial appearance and storage stability even though the blending amount of the component (A) exceeded 50% by mass and dissolved. The property was also good.
On the other hand, Comparative Example 1 in which A-1 / A-2 is 94/6, Comparative Example 3 in which A-1 / A-2 is 100/0, Comparative Example 6 in which the amount of component (D) is 2% by mass, Comparative Example 8 in which the blending amount of the component (A) was 76% by mass was poor in initial appearance and solubility, and could not be evaluated thereafter. Further, Comparative Example 2 in which the blending amount of component (A) is 30% by mass has low sebum detergency, and Comparative Example 4 in which component (B) is not blended and Comparative Example 9 in which C / B is 12/1 are flexible. The nature was bad. Further, Comparative Example 5 in which the component (C) is not blended has poor recontamination preventing property and poor flexibility, and Comparative Example 7 having C / B of 0.5 / 1 has flexibility and recontamination preventing property. And storage stability was poor.

Each code | symbol in Table 1 shows the following.
<(A) component>
[(A-1) component]
(A-1): An average equivalent of 15 moles relative to natural alcohol CO-1270 (trade name, primary alcohol having 12 to 16 carbon atoms (C12 / C14 / C16 = 71/28/1)) manufactured by P & G. Added with ethylene oxide.
(A-2): An average equivalent of 15 moles relative to natural alcohol CO-1214 (trade name, primary alcohol having 12 to 16 carbon atoms (C12 / C14 / C16 = 68/26/8)) manufactured by P & G. Added with ethylene oxide.
(A-3): An average of 12 moles of ethylene oxide added to natural alcohol CO-1270 manufactured by P & G.
(A-4): A product obtained by adding an average of 9 moles of ethylene oxide to P & G natural alcohol CO-1270.

Said (a-1)-(a-4) was synthesize | combined in the following procedures, respectively.
Synthesis of (a-1):
224.4 g of natural alcohol CO-1270 manufactured by P & G, and 2.0 g of 30% NaOH aqueous solution were collected in a pressure-resistant reaction vessel, and the inside of the vessel was purged with nitrogen. Next, after dehydrating for 30 minutes at a temperature of 100 ° C. and a pressure of 2.0 kPa or less, the temperature was raised to 160 ° C. While stirring the alcohol, 760.4 g of ethylene oxide (gaseous) was gradually added to the alcohol liquid using a blowing tube while adjusting the addition rate so that the reaction temperature did not exceed 180 ° C.
After completion of the addition of ethylene oxide, aging was performed at a temperature of 180 ° C. and a pressure of 0.3 MPa or less for 30 minutes, and unreacted ethylene oxide was distilled off at a temperature of 180 ° C. and a pressure of 6.0 kPa or less for 10 minutes.
Next, after cooling the temperature to 100 ° C. or lower, 70% p-toluenesulfonic acid was added to neutralize so that the pH of the 1% aqueous solution of the reaction was about 7, to obtain (a-1). .

Synthesis of (a-2):
Synthesis was performed in the same manner as (a-1) except that 224.4 g of natural alcohol CO-1214 manufactured by P & G was used instead of natural alcohol CO-1270, and 760.6 g of ethylene oxide was used.
Synthesis of (a-3):
The compound was synthesized in the same manner as (a-1) except that 610.2 g of ethylene oxide was used.
Synthesis of (a-4):
The compound was synthesized in the same manner as (a-1) except that 457.2 g of ethylene oxide was used.

[(A-2) component]
(A-5): Softanol 70 (trade name, polyoxyethylene alkyl ether obtained by adding ethylene oxide (EO) to secondary alcohol having 12 to 14 carbon atoms with an average addition mole number of 7 mol, manufactured by Nippon Shokubai Co., Ltd. ).
(A-6): Softanol 90 (trade name, polyoxyethylene alkyl ether obtained by adding ethylene oxide (EO) to a secondary alcohol having 12 to 14 carbon atoms with an average addition mole number of 9 mol, manufactured by Nippon Shokubai Co., Ltd. ).
(A-7): Softanol 120 (trade name, polyoxyethylene alkyl ether obtained by adding ethylene oxide (EO) to a secondary alcohol having 12 to 14 carbon atoms with an average addition mole number of 12 mol, manufactured by Nippon Shokubai Co., Ltd. ).
(A-8): Softanol 150 (trade name, polyoxyethylene alkyl ether obtained by adding ethylene oxide (EO) to secondary alcohol having 12 to 14 carbon atoms with an average addition mole number of 15 mol, manufactured by Nippon Shokubai Co., Ltd. ).

<(B) component>
(B-1): Kachinal MPAS-R (trade name, fatty acid (C16 / C18) dimethylaminopropylamide, stearic acid / palmitic acid mass ratio = 7/3) manufactured by Toho Chemical Co., Ltd.
(B-2): C ₁₇ H ₃₅ CONH (CH ₂ ) ₃ N (CH ₃ ) ₂ , amidopropyldimethylamine stearate; synthetic product.

Said (b-2) was synthesize | combined in the following procedures.
A 1 liter four-necked flask equipped with a flow condenser was charged with 360 g of stearic acid (molecular weight 284) and heated to 80 ° C. to melt the stearic acid. After performing nitrogen substitution twice, the temperature was raised to 150 ° C., and 123 g of dimethylaminopropylamine (molecular weight 102) (molar ratio to stearic acid: 0.95) was added dropwise over 1 hour. Next, after maintaining at 150 to 160 ° C. for 1 hour, the temperature was raised to 185 ° C. over 1 hour, and 45 g of dimethylaminopropylamine was further added dropwise over 1 hour. After completion of the dropping, the temperature was maintained at 185 to 190 ° C. and aged for 7 hours to distill off by-product water out of the system. Further, the pressure was reduced (4.0 kPa) while maintaining at 170 to 190 ° C., and the mixture was left for 1 hour to distill off unreacted dimethylaminopropylamine to obtain (b-2).

<(C) component>
(C-1): Raipon LH-200 (trade name, linear alkylbenzene sulfonic acid (LAS), carbon number 10-14, average molecular weight 322, manufactured by Lion Corporation).
(C-2): HOSTAPUR SAS30A (trade name, secondary sodium alkanesulfonate (SAS), manufactured by Clariant Japan).
(C-3): Sodium polyoxyethylene alkyl ether sulfate (AES) (synthetic product, carbon number 12-13, average addition mole number of EO 2 mol, raw material alcohol: Neodol 23 (trade name, manufactured by Shell Chemicals)) .

(C-3) was synthesized by the following procedure.
In a 4 liter autoclave, Neodol 23 alcohol [trade name, manufactured by Shell Chemicals; C12, 13 alcohol (mixture with a mass ratio of 1/1 C12 alcohol to C13 alcohol), branching ratio 20% by mass 400 g and potassium hydroxide catalyst 0.8 g were charged, the inside of the autoclave was purged with nitrogen, and the temperature was raised while stirring. Thereafter, 272 g of ethylene oxide was introduced while maintaining a temperature of 180 ° C. and a pressure of 0.3 mPa, to obtain a reaction product having an average added mole number of ethylene oxide of 2.
Next, 280 g of the alcohol ethoxylate obtained above was placed in a 500 mL flask equipped with a stirrer, and after nitrogen substitution, 67 g of liquid sulfuric anhydride (sulfan) was slowly added dropwise while maintaining the reaction temperature at 40 ° C. After completion of dropping, stirring was continued for 1 hour (sulfation reaction) to obtain polyoxyethylene alkyl ether sulfuric acid. Furthermore, (c-3) was obtained by neutralizing this with sodium hydroxide aqueous solution.

<(D) component>
(D-1): Ethanol (trade name, specific alcohol 95 degree synthesis, manufactured by Nippon Alcohol Sales Co., Ltd.).
(D-2): Propylene glycol (manufactured by BASF).

<Common additive component a>
Sodium benzoate: 0.5% by mass
Citric acid: 0.2% by mass,
Paratoluenesulfonic acid: 2.0% by mass
Coconut fatty acid: 1.0% by mass
Polyethylene glycol: 1.0% by mass,
Isothiazolone solution: 0.01% by mass,
Fragrance: 1.0% by mass
Water (purified water): Balance (amount for making the total amount of the liquid detergent composition 100% by mass).

Details of each component included in the common additive component a are as follows.
Sodium benzoate: manufactured by Toagosei Co., Ltd., trade name “Sodium benzoate”.
Citric acid: trade name “Liquid Citric Acid”, manufactured by Yushi Co., Ltd.
Paratoluenesulfonic acid: Kyowa Hakko Kogyo Co., Ltd., trade name “PTS acid”.
Coconut fatty acid: NOF Corporation, trade name “Zushi fatty acid”.
Polyethylene glycol: Product name “PEG # 1000”, manufactured by Lion Corporation.
Isothiazolone solution: manufactured by Rohm and Haas, trade name “Caisson CG”, 5-chloro-2-methyl-4-isothiazolin-3-one / 2-methyl-4-isothiazolin-3-one / magnesium salt / water Liquid mixture.
Perfume: Perfume component a described in JP-A-2009-108248.
The details of sodium hydroxide and sulfuric acid used as pH adjusters are as follows.
Sodium hydroxide: manufactured by Tsurumi Soda Co., Ltd.
Sulfuric acid: Toho Zinc Co., Ltd.

Claims (1)

R ¹ —O (R ² O) _n H [wherein R ¹ is a hydrocarbon group having 10 to 22 carbon atoms derived from a primary alcohol , and R ² is an alkylene group having 2 to 4 carbon atoms. , N represents the average added mole number and is 5-20. The compound represented by] (A-1), and ^{R 1 '-O (R 2'} O) n 'H [ in the formula, ^{R 1'} is a hydrocarbon having a carbon number of 10 to 22 derived from a secondary alcohol R ² ′ is an alkylene group having 2 to 4 carbon atoms, and n ′ represents an average added mole number and is 10 to 16. Nonionic surfactant (A) selected from the group consisting of the compound (A-2) represented by the formula:
R ⁶ —N (R ⁷ ) (R ⁸ ) [wherein R ⁶ is a hydrocarbon group having 7 to 27 carbon atoms which may have a linking group, and R ⁷ and R ⁸ are each independently , An alkyl group having 1 to 4 carbon atoms, a hydroxyalkyl group having 1 to 4 carbon atoms, or (R ⁹ O) _p H [wherein R ⁹ is an alkylene group having 2 to 4 carbon atoms, and p is an average addition The number of moles is 1 to 25. ]. 0.1 to 10% by mass of a compound (B) selected from the group consisting of a tertiary amine compound represented by the formula:
1 to 20% by mass of an anionic surfactant (C) having SO ₃ group or SO ₄ group,
Monohydric alcohol having 2 to 4 carbon atoms, a polyhydric alcohol, and ^R 11 from 2 to 4 carbon atoms ^{- (OR} ₁₂₎ in l OH ^{[wherein, R 11} is an alkyl group or a phenyl group having 1 to 6 carbon atoms, R ¹² represents an alkylene group having 2 to 4 carbon atoms, and 1 represents an average added mole number and is 1 to 5. A solvent (D) selected from the group consisting of glycol ether solvents represented by the formula:
In the component (A), before asked compound and (A-1), prior to hear compound (A-2) the ratio (mass ratio) of (A-1) / (A -2) = 90 / 10-0 / 100,
A liquid detergent composition for clothing, wherein the ratio (mass ratio) of the component (B) to the component (C) is (C) / (B) = 1/1 to 10/1.