JP2011137111A - Liquid detergent composition for clothing - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a liquid detergent composition for clothing that has excellent detergency and resoiling preventing performance, and has good liquid stability, moreover has a whitening preventing effect on cloths comprised of Tencel fiber. <P>SOLUTION: The liquid detergent composition for clothing includes a nonionic surfactant (A) represented by R<SP>1</SP>-O(EO)<SB>m</SB>-(PO)<SB>n</SB>-H, a compound (B) selected from a tertiary amine compound represented by R<SP>2</SP>-N(R<SP>3</SP>)(R<SP>4</SP>) and their salts, anionic surfactant (C) having SO<SB>3</SB>or SO<SB>4</SB>group, and specified solvent (D), wherein the compounding amount of component (A) is 40-75 mass%, the compounding amount of component (B) is 1-10 mass%, the compounding amount of component (C) is 1-20 mass%, the compounding ratio of component (B) and (C) is (C)/(B)=1/1 to 10/1, and the compounding amount of component (D) is 3-25 mass%, moreover, inclusion of a specified silicone compound (E) therein is desirable. <P>COPYRIGHT: (C)2011,JPO&INPIT

Description

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

In recent years, the importance of development and sales of products that are friendly to the global environment has increased, and products that are friendly to the global environment are also demanded in the daily necessities field. 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 cleaning composition that exhibits high cleaning performance with a small amount of detergent. For example, in the case of a liquid detergent composition having a surfactant as a main base, a concentrated detergent having an increased surfactant concentration is required.
On the other hand, with regard to household electric washing machines, 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 feeling after washing, and a detergent composition containing a softening ingredient 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 2003-206500 A JP 2005-23123 A

However, even when a softening component such as a long-chain amine or a cationic surfactant is added to the liquid detergent composition, it is water-saving for fibers such as tencel that are weak against friction when wet. When stuffed and washed with a type washing machine, the fiber surface becomes fuzzy, and the part appears whitened due to diffuse reflection of light (hereinafter sometimes referred to as whitening), and the texture after drying becomes poor. It is easy to produce.
Furthermore, when an anionic surfactant is also added to prevent re-contamination, these performances may not be sufficiently exhibited, or the stability of the liquid detergent composition after storage may be lowered. This is presumably because precipitation is likely to occur due to electrostatic interaction between the two components.
The present invention has been made in view of the above circumstances, and has excellent detergency, re-contamination prevention performance, good liquid stability, and also has a whitening prevention effect on clothing made of tencel fibers. An object is to provide a liquid detergent composition.

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 that solves the above problems is R ¹ —O (EO) _m — (PO) _n —H [wherein R ¹ is an alkyl group having 10 to 20 carbon atoms or an alkenyl group having 10 to 20 carbon atoms. EO represents ethylene oxide and PO represents propylene oxide. m and n represent an average added mole number, m is 5-20, and n is 1-4. A nonionic surfactant (A) represented by
R ² —N (R ³ ) (R ⁴ ) [wherein R ² is a hydrocarbon group having 7 to 27 carbon atoms which may have a linking group, and R ³ and R ⁴ are each independently , An alkyl group having 1 to 4 carbon atoms, a hydroxyalkyl group having 1 to 4 carbon atoms, or (R ⁵ O) _p H [wherein R ⁵ is an alkylene group having 2 to 4 carbon atoms, and p is an average addition The number of moles is 1 to 25. ]. A compound (B) selected from the group consisting of a tertiary amine compound and a salt thereof, an anionic surfactant (C) having an SO ₃ group or an SO ₄ group, and 2 to 4 carbon atoms Monohydric alcohol, polyhydric alcohol having 2 to 4 carbon atoms and R ^6- (OR ⁷ ) ₁ OH [wherein R ⁶ is an alkyl group having 1 to ⁶ carbon atoms or a phenyl group, and R ⁷ is carbon number. 1 to 5 represents an average added mole number. And a solvent (D) selected from the group consisting of glycol ether solvents represented by:
(A) The compounding quantity of component is 40-75 mass%, (B) The compounding quantity of component is 1-10 mass%, (C) The compounding quantity of component is 1-20 mass%, (C The mixing ratio (mass ratio) of the component (B) and the component (B) is (C) / (B) = 1/1 to 10/1, and the blending amount of the component (D) is 3 to 25% by mass. A cleaning composition for liquid clothing.

  Furthermore, 0.1-5 mass% of 1 or more types of silicone compounds (E) chosen from an amino modification silicone compound, a carboxy modification silicone compound, and a polyether modification silicone compound are contained, and the mixture ratio (B) with said (B) component ( The mass ratio is preferably (B) / (E) = 1/1 to 100/1.

  According to the present invention, a liquid detergent for clothing having excellent detergency and anti-recontamination performance, good liquid stability, and having whitening-preventing effect on clothing made of Tencel (registered trademark). A 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 (EO) _m — (PO) _n —H. In the formula, R ¹ is an alkyl group having 10 to 20 carbon atoms or an alkenyl group having 10 to 20 carbon atoms. When the number of carbon atoms is within the above range, the detergency and gelation resistance are excellent. The alkyl group and alkenyl group each preferably have 12 to 18 carbon atoms, and more preferably 12 to 14 carbon atoms.
Each of the alkyl group and the alkenyl group is preferably linear or branched. 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.

EO represents ethylene oxide and PO represents propylene oxide. m and n represent the average addition mole number of ethylene oxide and propylene oxide, respectively. m is 5-20, and 5-18 are preferable. When m is within this range, the cleaning power of the resulting liquid cleaning composition, particularly the cleaning power against sebum dirt, is improved.
n is 1-4, and 1-3 are more preferable. When n is within the range, good foaming property at the time of rinsing and prevention of gelation of the liquid detergent composition can be obtained.
As an addition method of EO and PO, for example, random addition or EO may be added, PO may be added, and vice versa. In particular, from the viewpoint of good rinsability in washing with a fully automatic washing machine, those having an EO chain at the end, such as EO and PO, and then EO, are preferred.

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 (B). 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.

The component (A) is blended mainly for the purpose of imparting detergency to the liquid detergent composition of the present invention.
Among these, the compounding quantity of (A) component is 40-75 mass% with respect to the total mass of this liquid detergent composition, 45-70 mass% is more preferable, 50-65 mass% is further preferable. (A) When the compounding quantity of a component is 50 mass% or more, even if it is a small usage-amount, a high cleaning power can be given to a liquid detergent composition. On the other hand, when it exceeds 75 mass%, the viscosity of the composition becomes high, and the usability becomes poor, such as being difficult to pour into a measuring cup. In addition, gelation is likely to occur, the component (B) or the component (C) cannot be stably blended, and the stability as a liquid detergent composition is lowered.

<(B) component>
The component (B) is a compound selected from the group consisting of tertiary amine compounds represented by R ² —N (R ³ ) (R ⁴ ) and salts thereof.
(B) A component is mix | blended mainly for providing the softness | flexibility provision performance to the clothing which consists of cotton, polyester, an acryl, etc. to the liquid detergent composition of this invention.
In the formula, R ² 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 ³ and R ⁴ are each independently an alkyl group having 1 to 4 carbon atoms, a hydroxyalkyl group having 1 to 4 carbon atoms, or (R ⁵ O) _p H [wherein R ⁵ has 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 ³ and R ^4, and the alkylene group in R ⁵ may each be linear or branched.
R ⁵ is preferably an ethylene group or a propylene group, and particularly preferably an ethylene group.

The tertiary amine compound represented by R ² —N (R ³ ) (R ⁴ ) 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^２１は炭素数７〜２３の炭化水素基であり、Ｒ^２２は炭素数１〜４のアルキレン基であり、Ｒ^３及びＲ^４はそれぞれ前記と同じである。］
式中、Ｒ^２１における炭化水素基は、炭素数７〜２３の炭化水素基であり、該炭素数は、７〜２１が好ましい。該炭化水素基は、脂肪族炭化水素基であることが好ましい。該炭化水素基は、不飽和結合を有してよく、有さなくてもよい。該炭化水素基は、直鎖状又は分岐鎖状であることが好ましい。
Ｒ^２２におけるアルキレン基は、直鎖状であってもよく、分岐鎖状であってもよい。

[Wherein R ²¹ is a hydrocarbon group having 7 to ²³ carbon atoms, R ²² is an alkylene group having 1 to 4 carbon atoms, and R ³ and R ⁴ are the same as defined above. ]
In the formula, the hydrocarbon group in R ²¹ 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 ²² may be linear or branched.

［式中、Ｒ^２３は炭素数１１〜２３の炭化水素基であり、Ｒ^２４は炭素数１〜４のアルキレン基であり、Ｒ^３及びＲ^４はそれぞれ前記と同じである。］

[Wherein R ²³ is a hydrocarbon group having 11 to ²³ carbon atoms, R ²⁴ is an alkylene group having 1 to 4 carbon atoms, and R ³ and R ⁴ are the same as defined above. ]

In the formula, the hydrocarbon group in R ²³ 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 ²⁴ 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 dimethylamine, beef tallow alkyl dimethylamine, cured beef tallow alkyl dimethylamine, stearyl dimethylamine, stearyl diethanolamine, polyoxyethylene cured beef tallow alkylamine (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 amount of component (B) is 1 to 10% by mass, preferably 2 to 7% by mass, based on the total mass of the liquid detergent composition. When the content of the component (B) is 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.
In particular, when the blending amount of the component (B) in the liquid detergent composition is in the range of 1 to 10% by mass, the whitening prevention effect for clothing made of tencel fibers is exhibited. It is known that clothes made of tencel fibers become hard when wet, and the fibers become fluffy like split ends due to friction received by washing, and the portions appear whitened by diffuse reflection of light. Although the reason of the whitening prevention effect expression with respect to the clothing consisting of the tencel fiber of the liquid detergent composition of the present invention is not clear, the component (A), which is the main cleaning agent, probably has excellent rinsing properties and remains on the fiber surface. Because it is difficult, it can be rinsed efficiently even in washing with a small amount of water, such as a water-saving washing machine, and the component (B), which is a softening agent, is efficiently adsorbed, and fluff due to friction between clothes during washing and rinsing It is presumed that

<(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 2 to 15% 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, the improvement of the re-contamination prevention performance and the improvement of the flexibility imparting performance to the clothing, in particular, the clothing made of hydrophobic fibers such as acrylic and polyester, Can be compatible.
In the liquid detergent composition of the present invention, the blending 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 preferable. 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 6 of 2 to 4 carbon atoms - ^(OR ₇₎ in l OH [wherein, ^{R 6} is an alkyl group having 1 to 6 carbon atoms or phenyl group, R ⁷ is an alkylene group having 2 to 4 carbon atoms, l is 1 to 5 represent the average addition mole number. ] 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 ^6- (OR ⁷ ) 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 particular, it is preferable to use a combination of ethanol and propylene glycol or diethylene glycol monobutyl ether, or a combination of propylene glycol and diethylene glycol monobutyl ether from the viewpoints of fragrance and storage stability of the detergent composition.

  In the liquid detergent composition of the present invention, the blending amount of the component (D) is 3 to 25% by mass with respect to the total mass of the liquid detergent composition, preferably 4 to 23% by mass, and 5 to 20%. 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 blending more than 25% by mass, the liquid fluidity improvement effect corresponding to it is not seen, which is disadvantageous economically.

The composition of the present invention contains the components (A) to (D) as essential components, and may be composed of only the components (A) to (D). If necessary, (A) Components other than the component (D) may be contained.
The liquid detergent composition of the present invention may further contain a silicone compound (E) selected from amino-modified silicone compounds, carboxy-modified silicone compounds, and polyether-modified silicone compounds (hereinafter referred to as “component (E)”). preferable. Thereby, the whitening prevention effect with respect to the clothing which consists of a tencel fiber further improves. In particular, when all of the components (A) to (E) are blended, an excellent whitening prevention effect is exerted on clothing made of tencel fibers even under harsh washing conditions such as when a large amount of clothing is packed at once. .

<(E) component>
The component (E) is a silicone compound selected from amino-modified silicone compounds, carboxy-modified silicone compounds, and polyether-modified silicone compounds.
The component (E) is blended mainly for the purpose of improving the slipperiness of clothes comprising tencel fibers to the liquid detergent composition of the present invention and improving the whitening prevention effect by washing.
The amino-modified silicone is not particularly limited as long as it has an amino group as a functional group. Moreover, as long as an amino group is introduced, there is no problem even if another functional group is introduced.
Specific examples of commercially available amino-modified silicone compounds include BY16-871, BY16-853U, FZ-3705, SF8417, BY16-849, FZ-3785, BY16-890, manufactured by Toray Dow Corning Co., Ltd. BY16-208, BY16-893, FZ-3789, BY16-878, BY16-891 and the like can be mentioned.

The carboxy-modified silicone is not particularly limited as long as it has a carboxyl group as a functional group. Moreover, as long as the carboxyl group is introduced, there is no problem even if other functional groups are introduced.
Specific examples of commercially available carboxyl-modified silicone compounds include BY16-880 manufactured by Toray Dow Corning Co., Ltd.
The polyether-modified silicone is not particularly limited as long as it has a polyether group such as polyethylene oxide or polypropylene oxide as a functional group. Moreover, as long as polyether groups such as polyethylene oxide and polypropylene oxide are introduced, there is no problem even if other functional groups are introduced.
Of these, polyether-modified silicones represented by the following general formula (S-1) are preferred.

In said general formula (S-1), R < ⁶ > is a hydrogen atom or a C1-C4 linear or branched alkylene group. If the number of carbon atoms of the alkylene group is within the above range, it is easy to synthesize industrially. R ⁷ is any one of a linear or branched alkyl group having 1 to 4 carbon atoms, a linear or branched alkenyl group having 2 to 4 carbon atoms, or a hydrogen atom. When the carbon number of the alkyl group or alkenyl group is within the above range, the silicone compound has good fluidity and is easy to handle. Y represents a polyoxyalkylene group. The order of each structural unit to which a and b are attached may be different, a is an integer of 10 to 10000, and b is an integer of 1 to 1000. If the integer of a and b is in the said range, it is excellent in the whitening prevention effect with respect to the clothing which consists of a tencel fiber.

  Specific examples of commercially available polyether-modified silicone compounds include SH3772M, SH3775M, SH3749, SF8410, SH8700, BY22-008, SF8421, and SILWET L-7001, SILWET L-7002 manufactured by Toray Dow Corning Co., Ltd. , SILWET L-7602, SILWET L-7604, SILWET FZ-2104, SILWET FZ-2164, SILWET FZ-2171, ABN SILWET FZ-F1-009, ABN SILWET FZ-F1-009-05, ABN ZILF 009-09, ABN SILWET FZ-F1-009-54, ABN SILWET FZ-2222, Shin-Etsu Chemical KF352A, KF 6008, KF615A, KF6016, KF6017, TSF4450, TSF4452 manufactured by GE Toshiba Silicone Corporation, and the like.

(E) A component may be used individually by 1 type and may be used in combination of multiple types.
In the liquid detergent composition of the present invention, the blending amount of the component (E) is 0.1 to 5% by mass, and 0.2 to 3% by mass with respect to the total weight of the liquid detergent composition. preferable. If content of (E) component is 0.1 mass% or more, sufficient whitening prevention effect with respect to the clothing consisting of a tencel fiber will be acquired. Moreover, even if it mixes more than (E) component more than 5 mass%, the improvement effect of whitening prevention corresponding to it is not seen, but it becomes economically disadvantageous.

By blending the component (B) and the component (E) at a specific ratio, an excellent whitening prevention effect is expressed for clothing made of tencel fibers when a large amount of clothing is packed and washed at once.
In the liquid detergent composition of the present invention, the blending ratio (mass ratio) of the component (B) and the component (E) is (B) / (E) = 1/1 to 100/1, 30/1 is preferred. When the ratio of the component (B) is too low, a sufficient whitening prevention effect cannot be obtained sufficiently for clothing made of tencel fibers. On the other hand, if the ratio of the component (E) is too low, a sufficient whitening prevention effect for clothing made of tencel fibers cannot be obtained when a large amount of clothing is packed and washed at once.
Although it is not clear why the above effect is achieved, the silicone compound (E) is likely to be applied to clothing made of tencel fibers by forming a complex in water when the component (B) and the component (E) are washed. This is presumably because the friction between the fibers in the washing process is reduced because it effectively exhibits adsorptivity and imparts slipperiness.

The liquid detergent composition of the present invention contains the above components (A) to (C) as essential components, and may be composed of only the components (A) to (C). Components other than the components (A) to (C) 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 detergent composition of the present invention, the water content is preferably 0 to 55 mass%, more preferably 10 to 40 mass%, based on the total mass of the liquid detergent 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 alkylphenols, higher fatty acids, higher fatty acid alkyl esters, polyoxyethylene alkyl ethers, polyoxyethylene polyoxypropylene block copolymers, polyhydric alcohol fatty acid esters or the like Examples include alkylene oxide adducts, polyhydric alcohol fatty acid ethers, alkyl (or alkenyl) amine oxides, hydrogenated castor oil alkylene oxide adducts, sugar fatty acid esters, and alkyl glycosides.

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, glycols such as triethylene glycol, tetraethylene glycol, polyethylene glycol having an average molecular weight of about 200 to 5000, paratoluenesulfonic acid, cumene sulfonate, benzoate (also has an effect as a preservative), urea and the like A thinning agent and 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, preservatives, such as Rohm and Haas company made caisson CG (brand name), can be contained, for example, 0.001-1 mass%.

    Further, for the purpose of improving detergency and stability, etc., alkali builders such as monoethanolamine, diethanolamine, triethanolamine, N-methyl-diethanolamine, N, N-dimethylmonoethanolamine, etc., pH adjusters , Hydrotropes, fluorescent agents, enzymes, dye transfer inhibitors, anti-staining agents (for example, polyvinylpyrrolidone, carboxymethyl cellulose, etc.), pearl agents, soil release agents, and the like.

As the enzyme, an enzyme conventionally blended in a detergent composition for clothing can be used, and examples thereof include protease, amylase, lipase, cellulase, mannanase and the like.
Specific examples of proteases include trade names such as Savinase 16L, Savinase Ultra 16L, Savinase Ultra 16XL, Everlase 16L Type 2.5, Erase Ultra L, Elarse Ultra L, Esperase 2.5L, Esperase Ultra L 2.5L, Liquanase Ultra 2.5L, Liquanase Ultra 2.5XL, Coronase 48L, trade names available from Genencor, Inc., Purefect L, Purefect OX, Properase L, and the like.
Specific examples of amylase include trade names such as Termamyl 300L, Termamyl Ultra 300L, Duramyl 300L, Stainzyme 12L, and trade name Max available from Genencore, Inc. Name pullulanase Amano, trade name DB-250 available from Seikagaku Corporation.

Specific examples of the lipase include trade names Lipex 100L and Lipolase 100L available from Novozymes as lipase preparations.
Specific examples of cellulase include trade names Endolase 5000L, Celluzyme 0.4L, Carzyme 4500L, and the like, which are available from Novozymes as cellulase preparations.
Specific examples of mannanase include Mannaway 4L, a trade name available from Novozymes as a mannanase preparation.
The said enzyme may be used individually by 1 type, and may use 2 or more types together.
Moreover, the said enzyme can contain 0.1-3 mass%, for example.

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 representative example, a fragrance composition described in JP-A No. 2002-146399 and JP-A No. 2009-108248 can be used, and a preferable blending amount is 0.1 to 3 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. 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 can include, for example, about 0.0001 to 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. Furthermore, since the liquid detergent composition of this invention is excellent in rinse property, even if it reduces the rinse process performed twice in the standard course of a normal fully automatic washing machine to 1 time, favorable rinse property is shown.

The present invention will be described more specifically with reference to examples. However, the present invention is not limited to these.
<Examples 1 to 21 and Comparative Examples 1 to 8>
Liquid detergent compositions having the compositions shown in Tables 1 and 2 were prepared by the following procedure.
When the (A) component, the (D) component, and the (E) component were contained in a 500 mL beaker, the (E) component was added and sufficiently stirred with a magnetic stirrer (manufactured by MITAMURA KOGYO INC.). Subsequently, while adding other components (component (C), component (D), 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 and Table 2, the unit of the blending amount of each component is “mass%”. Tables 1 and 2 show the ratio (C / B) of the blending amounts of component (B) and component (C) in the liquid detergent composition, and Table 2 shows components (B) and (E). The blending ratio (B / E) is also shown.
The following evaluation was performed about the obtained liquid detergent composition. The results are also shown in Tables 1 and 2.

<Evaluation of initial appearance>
Tilt the beaker (capacity 500 mL) containing 500 g of the liquid detergent composition prepared in the above procedure diagonally (horizontal and beaker sides are up to about 30 degrees), and transfer about 100 mL of the contents to a transparent glass bottle (wide-mouth standard bottle PS -The operation of taking out to NO.11) was performed.
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 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 pieces of cotton cloth (cotton plain weave cloth, 100 count) rubbed with sebum stains on the face cut into a 20 cm square size and a commercially available T-shirt (100% cotton, manufactured by BVD Corp.) 4 The sheet was put into an electric washing machine (manufactured by Mitsubishi Electric Corporation, “CW-C30A1 type”).
Next, a liquid detergent composition is added at a rate of 10 mL to about 30 L of tap water at 25 ° C., washed with a standard water stream (10 minutes), dehydrated (1 minute), rinsed with a standard water stream (3 minutes), A washing operation for sequentially performing dehydration (1 minute) was performed.
A cotton cloth not rubbed with sebum stain was used as an uncontaminated cloth, a cotton cloth before the cleaning treatment as a contamination cloth, and a cotton cloth after the cleaning treatment as a cleaning 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.
5 pieces of acrylic jersey cloth cut into 20cm square size, dark blue blouse (Tencel 100%), T-shirt (100% cotton) and cotton towel to adjust the weight so that the total amount of cloth is 3kg (100% cotton) is put into a drum-type washing machine (Matsushita Electric Industrial Co., Ltd., National NA-VR1100 type), 12.5 g of the liquid detergent composition is put into the detergent inlet, and washing is performed on the Omakase course. It was. After the washing, the acrylic jersey cloth was shaded and dried for 12 hours. The dried acrylic jersey 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, 25 g of a 20% aqueous solution of a nonionic surfactant (obtained by adding 15 mol of ethylene oxide to natural alcohol (C12 / C14 = 7/3)) Acrylic jersey cloth treated by the same washing operation was used.
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, ○: 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 a liquid cleaning composition were added and stirred at 120 rpm for 3 minutes, and then an oil stain cloth (5 × 5 cm) 1 A sheet of red soil dirt 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). The white polyester tropical cloth was dried and the reflectance was measured, and the difference from the reflectance before washing was calculated as the recontamination degree (ΔZ). 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 9 or less, and X: ΔZ is more than 9.

<Evaluation of whitening prevention A: Evaluation of normal washing for clothing made of Tencel fiber>
About the liquid detergent composition determined to have fluidity in the evaluation of the initial appearance, the whitening prevention performance was evaluated by the following procedure.
The blouse which was washed by repeating the washing operation of the above <Evaluation of Flexibility> 5 times was left in a constant temperature and humidity room at 25 ° C. and humidity 65% RH. One day later, the panelists (5 persons) compared the whitening degree of the blouse with that of a new article (control article) that was not washed, and scored according to the following criteria.
1 point: looks very white compared to the control product 2 points: looks whiter compared to the target product 3 points: looks whiter than the target product, but there is no problem Degree 4 points: It appears to be slightly whitened compared to the control product 5 points: Whitening is not felt compared to the target product (equivalent to the control product)
From the average value of the scoring results of five panelists, the comfort of the clothes after washing was evaluated according to the following criteria.
◎: 4 points or more, ○: 3.5 points or more and less than 4 points, △: 3 points or more and less than 3.5 points, ×: less than 3 points

<Evaluation of whitening prevention B: Evaluation at the time of stuffing washing for clothing made of Tencel fiber>
About the liquid detergent composition determined to have fluidity in the evaluation of the initial appearance, the whitening prevention performance was evaluated by the following procedure.
5 pieces of acrylic jersey cloth cut to 20cm square, dark blue blouse (100% Tencel), T-shirt (100% cotton) and cotton towel to adjust the weight so that the total amount of cloth is 6kg (100% cotton) was put into a drum-type washing machine (National NA-VR1100, manufactured by Matsushita Electric Industrial Co., Ltd.), 25 g of the liquid detergent composition was put into the detergent inlet, and washing was carried out on an automatic course. The blouse that was washed 5 times was left in a constant temperature and humidity chamber at 25 ° C. and a humidity of 65% RH. One day later, the panelists (5 persons) compared the whitening degree of the blouse with that of a new article (control article) that was not washed, and scored according to the following criteria.
1 point: looks very white compared to the control product 2 points: looks whiter compared to the target product 3 points: looks whiter than the target product, but there is no problem Degree 4 points: It appears to be slightly whitened compared to the control product 5 points: Whitening is not felt compared to the target product (equivalent to the control product)
From the average value of the scoring results of five panelists, the clothes were evaluated as whitening prevention B after washing according to the following criteria.
◎: 4 points or more, ○: 3.5 points or more and less than 4 points, △: 3 points or more and less than 3.5 points, ×: less than 3 points

<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 40 ° C. hot water bath for 1 hour.

As shown in the results of Tables 1 and 2, the liquid detergent composition of the present invention had good liquid stability and good results in both initial appearance and storage stability. In addition, good results were obtained with good balance in all evaluation items of whitening prevention, flexibility and anti-recontamination prevention of washed clothes made of tencel fibers.
On the other hand, Comparative Example 6 in which the blending amount of component (A) was 77% by mass and Comparative Example 5 in which the blending amount of component (E) was 2% by mass were poor in initial appearance, and could not be evaluated thereafter. Further, Comparative Example 1 in which the blending amount of the component (A) was 20% by mass was inferior in cleaning power. Moreover, the comparative example 2 which mix | blended the nonionic surfactant which does not correspond to (A) component of this invention was bad in the detergency, and the whitening prevention effect and the storage stability were also inferior. Moreover, the comparative example 3 which is not mix | blending (B) component was inferior in the softness | flexibility and the whitening prevention effect. Moreover, the comparative example 4 which does not mix | blend (C) component has bad recontamination prevention property, and the comparative example 7 whose C / B is 12/1 was inferior in the softness | flexibility and the whitening prevention effect. Further, Comparative Example 8 having a C / B of 0.2 / 1 was inferior in flexibility, recontamination prevention and storage stability.
Furthermore, as shown in the results of Table 2, the liquid detergent composition of the present invention had good liquid stability and good results in both initial appearance and storage stability. In addition, good results were obtained with good balance in all evaluation items of whitening prevention, softness, anti-recontamination property of clothes consisting of washed tencel fibers, especially when a large amount of clothes were packed and washed at once. Moreover, the result which was excellent in the whitening prevention effect of the clothing which consists of the washed tencel fiber was obtained.

Each code | symbol in Table 1 and Table 2 shows the following.
<(A) component>
(A-1): Nonionic surfactant obtained by randomly adding 16 mol of ethylene oxide and 2 mol of propylene oxide to natural alcohol (C12 / C14 = 7/3) (a-2): Natural alcohol Nonionic surfactant obtained by adding 14 mol of ethylene oxide to (C12 / C14 = 7/3) and then adding 1 mol of propylene oxide (a-3): natural alcohol (C12 / C14 = 7/3) Nonionic surfactant (a-4) obtained by randomly adding 4 mol of ethylene oxide and 2 mol of propylene oxide and then adding 12 mol of ethylene oxide: natural alcohol (C12 / 4 moles of ethylene oxide and 2 moles of propylene oxide were randomly added to C14 = 7/3) Nonionic surfactant obtained by adding ethylene oxide (a-5 (comparative product)): Nonion obtained by adding 7 mol of ethylene oxide to natural alcohol (C12 / C14 = 7/3) Surfactant.

In addition, each (A) component was prepared as follows, respectively.
Preparation of (a-1):
224.4 g of “CO-1270” manufactured by P & G and 2.0 g of 30% by mass 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, 704 g of ethylene oxide (gaseous) and 116 g of propylene oxide were gradually added to the alcohol solution while adjusting the addition rate so that the reaction temperature did not exceed 180 ° C. using a blowing tube. I let you.
After the addition of ethylene oxide and propylene oxide, after aging for 30 minutes at a temperature of 180 ° C. and a pressure of 0.3 MPa or less, unreacted ethylene oxide and propylene oxide are distilled off at a temperature of 180 ° C. and a pressure of 6.0 kPa or less for 10 minutes. did.
Next, after cooling the temperature to 100 ° C. or lower, 70% by mass p-toluenesulfonic acid is added to neutralize so that the pH of the 1% by mass aqueous solution of the reaction product is about 7, and (a-1) Got.

Preparation of (a-2):
224.4 g of “CO-1270” manufactured by P & G and 2.0 g of 30% by mass 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, 616 g of ethylene oxide (gaseous) was gradually added to the alcohol solution while adjusting the addition rate so that the reaction temperature did not exceed 180 ° C. using a blowing tube. Next, 58 g of propylene oxide was introduced and further reacted.
After completion of the addition, after aging at a temperature of 180 ° C. and a pressure of 0.3 MPa or less for 30 minutes, unreacted ethylene oxide and propylene oxide were 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 less, 70% by mass p-toluenesulfonic acid is added to neutralize so that the pH of the 1% by mass aqueous solution of the reaction is about 7, and (a-2) Got.

Preparation of (a-3):
224.4 g of “CO-1270” manufactured by P & G and 2.0 g of 30% by mass 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, 176 g of ethylene oxide (gaseous) and 116 g of propylene oxide were gradually added to the alcohol solution while adjusting the addition rate so that the reaction temperature did not exceed 180 ° C. using a blowing tube. I let you. Next, 526 g of ethylene oxide (gaseous) was introduced and further reacted.
After completion of the addition, after aging at a temperature of 180 ° C. and a pressure of 0.3 MPa or less for 30 minutes, unreacted ethylene oxide and propylene oxide were 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 less, 70% by mass p-toluenesulfonic acid was added to neutralize so that the pH of the 1% by mass aqueous solution of the reaction product was about 7, and (a-3) Got.

Preparation of (a-4):
224.4 g of “CO-1270” manufactured by P & G and 2.0 g of 30% by mass 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, 176 g of ethylene oxide (gaseous) and 116 g of propylene oxide were gradually added to the alcohol solution while adjusting the addition rate so that the reaction temperature did not exceed 180 ° C. using a blowing tube. I let you. Next, 440 g of ethylene oxide (gaseous) was introduced and further reacted.
After completion of the addition, after aging at a temperature of 180 ° C. and a pressure of 0.3 MPa or less for 30 minutes, unreacted ethylene oxide and propylene oxide were 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% by mass p-toluenesulfonic acid is added to neutralize so that the pH of the 1% by mass aqueous solution of the reaction product is about 7, and (a-4) Got.

Preparation of (a-5):
224.4 g of “CO-1270” manufactured by P & G and 2.0 g of 30% by mass 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. Next, while stirring the reaction solution, 354.7 g of ethylene oxide (gaseous) was gradually added to the reaction solution. At this time, it added, adjusting the addition rate so that reaction temperature might not exceed 180 degreeC using the blowing tube.
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 then 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% by mass p-toluenesulfonic acid was added to neutralize so that the pH of the 1% by mass aqueous solution of the reaction product was about 7, and (a-5) Got.

<(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, while maintaining the temperature at 170 to 190 ° C., the pressure was reduced (4.0 kPa), and the mixture was allowed to stand for 1 hour, whereby unreacted dimethylaminopropylamine was distilled off 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)) .

Said (c-3) was synthesize | combined in the following procedures.
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 (Asahi Glass Co., Ltd. trade name, propylene glycol).
(D-3): Diethylene glycol monobutyl ether (trade name, butyl diglycol manufactured by Nippon Emulsifier Co., Ltd.).

<(E) component>
(E-1) Amino-modified silicone (trade name, SZ8417 manufactured by Toray Dow Corning Co., Ltd.)
(E-2) Polyether-modified silicone (trade name, SH3775M manufactured by Toray Dow Corning Co., Ltd.)
(E-3) Polyether-modified silicone, a silicone compound represented by the following general formula (S-2) was used (a = 210, b = 9, R ⁶ = C ₃ H ₆ , Y =-(OC ₂ H ₄ ) ₁₀ −, R ⁷ = CH ₃ ). This was synthesized by the following method.

An organohydrogenpolysiloxane (α = 210, β = 9) represented by the following general formula (S-3) in a 1 L four-necked flask equipped with a stirrer, a condenser, a thermometer, and a nitrogen insertion port 100 g, 50 g of isopropyl alcohol, 29 g of a polyoxyalkylene compound (γ = 10, Z = CH ₃ ) represented by the following general formula (S-4), 0.2 g of platinum catalyst for addition reaction, 2% by mass of sodium acetate The isopropyl alcohol solution 0.3g was thrown in, and these were made to react at 90 degreeC by nitrogen atmosphere for 3 hours. After completion of the reaction, the solvent was distilled off under reduced pressure to obtain the above (e-3).

<Common additive component a>
Citric acid: 0.1% by mass,
P-toluenesulfonic acid: 3.0% by mass,
Coconut fatty acid: 1.0% by mass
Monoethanolamine: 2.8% by mass,
Fragrance: 1.4% by mass
Dye (Green No. 3): 0.0001% by mass,
Water (purified water): Balance (amount to make 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.
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”.
Monoethanolamine: manufactured by Nippon Shokubai Co., Ltd.
Perfume: Perfume component a described in JP-A-2009-108248.
Green No. 3 (pigment): Product name “Green No. 3” manufactured by Sakai Kasei Co., Ltd.
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 (2)

R ¹ —O (EO) _m — (PO) _n —H [wherein R ¹ is an alkyl group having 10 to 20 carbon atoms or an alkenyl group having 10 to 20 carbon atoms, EO is ethylene oxide, and PO is propylene. Oxide is shown. m and n represent an average added mole number, m is 5-20, and n is 1-4. A nonionic surfactant (A) represented by
R ² —N (R ³ ) (R ⁴ ) [wherein R ² is a hydrocarbon group having 7 to 27 carbon atoms which may have a linking group, and R ³ and R ⁴ are each independently , An alkyl group having 1 to 4 carbon atoms, a hydroxyalkyl group having 1 to 4 carbon atoms, or (R ⁵ O) _p H [wherein R ⁵ is an alkylene group having 2 to 4 carbon atoms, and p is an average addition The number of moles is 1 to 25. ]. A compound (B) selected from the group consisting of a tertiary amine compound represented by the formula:
An anionic surfactant (C) having a SO ₃ group or a SO ₄ group;
A monohydric alcohol having 2 to 4 carbon atoms, a polyhydric alcohol having 2 to 4 carbon atoms and R ⁶ — (OR ⁷ ) ₁ OH [wherein R ⁶ is an alkyl group having 1 to ⁶ carbon atoms or a phenyl group, R ⁷ represents an alkylene group having 2 to 4 carbon atoms, and 1 represents an average added mole number and is 1 to 5. And a solvent (D) selected from the group consisting of glycol ether solvents represented by:
(A) The compounding quantity of component is 40-75 mass%, (B) The compounding quantity of component is 1-10 mass%, (C) The compounding quantity of component is 1-20 mass%, (C ) Component and (D) component (C) / (B) = 1/1 to 10/1,
(D) The cleaning composition for liquid clothing characterized by the compounding quantity of a component being 3-25 mass%.   0.1-5 mass% of 1 or more types of silicone compounds (E) chosen from an amino modification silicone compound, a carboxy modification silicone compound, and a polyether modification silicone compound are contained, and the compounding ratio (mass ratio) with the said (B) component ) Is (B) / (E) = 1/1 to 100/1, the cleaning composition for liquid clothing according to claim 1.