JP2000186296A - Liquid detergent composition - Google Patents

Abstract

PROBLEM TO BE SOLVED: To obtain a composition excellent in softness and rinsing properties by blending specified end-blocked nonionic surfactant(s), a specified anionic surfactant containing SO3 or SO4 groups, and a specified cationic surfactant. SOLUTION: Nonionic surfactants of formula I and formula II, and a cationinc surfactant of formula III are used for the composition. In formula I and formula II, R1 and R3 are each a (substituted) 6-22C hydrocarbon group; R2 and R4 are each a 1-20C alkyl, or alkenyl: AO is at least one kind of 3-8C oxyalkylene; the distribution of the number of EO molecules added in formula I satisfies formula IV (wherein Yi is the wt.% of an EO adduct of which the number of EO molecules added is i; and nmax is the number of EO molecules added of an adduct having a highest content); and the distribution of the number of AO and EO molecules added in formula II satisfies formula V [wherein j is a retention time (min); Yj is the wt.% of a component having a retention time of j; and vmax is a retention time (min) detected when the component with a highest content is subjected to high speed liquid chromatography]. In formula III, R5 is a (substituted or divided) 6-24C hydrocarbon group; R6 to R8 are each a 1-3C alkyl, or hydroxyalkyl; and X is halogeno, or a monoalkylsulfuric acid group containing a 1-3C alkyl group.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

The present invention relates to a liquid detergent composition having excellent flexibility and rinsing properties.

[0002]

2. Description of the Related Art As nonionic surfactants incorporated in detergent compositions, polyoxyalkylene alkyl ethers, polyoxyalkylene alkyl allyl ethers, alkyl glycosides and the like are generally used. The development of fatty acid polyoxyalkylene alkyl ethers as surfactants has been promoted.

[0003] Fatty acid polyoxyalkylene alkyl ethers are said to be less irritating to the skin than alcohol-based alkylene oxide adducts, and polyoxyalkylene alkyl allyl ethers, which are considered to have a large effect on the environment. Is extremely superior in biodegradability compared to
It also has the advantage.

As a method for synthesizing a fatty acid polyoxyalkylene alkyl ether, a two-stage reaction method in which a polyoxyalkylene alkyl ether or a fatty acid polyoxyalkylene ether is synthesized and then esterified, or an alkylene oxide is directly added to the fatty acid alkyl ester. There is a one-step reaction method. The former reaction requires two steps of addition of an alkylene oxide and transesterification, and has the disadvantage that a large amount of by-products such as diesters and polyalkylene glycols are generated. The latter one-step reaction has been developed to solve this problem. As a characteristic catalyst, for example, magnesium oxide added with metal ions (Japanese Unexamined Patent Publication No.
No. 279552) and calcined hydrotalcite (Japanese Unexamined Patent Publication No. Hei 4-505449). As a composition containing a fatty acid polyoxyalkylene alkyl ether produced by the method described in JP-A-4-279552, a liquid detergent composition is disclosed in JP-A-5-2023.
No. 81, JP-A-5-222396, JP-A-9
-255988.

However, the fatty acid polyoxyalkylene alkyl ether synthesized with the above-mentioned catalyst has an extremely wide addition molar distribution of alkylene oxide, so that the odor of the unreacted raw material ester remains or the number of added moles of alkylene oxide decreases. High (or low) components have a detrimental effect on detergency and rinsing properties, making practical application to detergent compositions difficult.

A method for synthesizing a fatty acid polyoxyalkylene alkyl ether having a narrow addition molar distribution of alkylene oxide which can overcome these disadvantages is disclosed in Japanese Patent Application Laid-Open No. 8-1.
Japanese Patent Application Laid-Open No. 69860/1996 and Japanese Patent Application Laid-Open No. 8-169861 / 1994. A method of synthesizing a fatty acid polyoxyalkylene alkyl ether having a narrow addition molar distribution of an alkylene oxide using this method, followed by filtration, and a method using the activator thereof in a liquid detergent composition (Japanese Patent Application Laid-Open No.
No. 7620), but this composition does not exhibit flexibility.

[0007] Further, in detergents for delicate fiber materials such as sweaters and blouses such as wool, silk, acrylic and polyester, so-called light detergents,
It is preferable to neutralize the product itself and to impart flexibility simultaneously with washing. In such a case, a composition in which a nonionic surfactant is used as a main component and an anionic surfactant and a cationic surfactant are appropriately combined is disclosed in JP-A-56-1981.
JP-A-152898, JP-A-56-152899, JP-A-61-97396, JP-A-62-70
No. 498, etc. However, even in these compositions, there is no description about a fatty acid polyoxyalkylene alkyl ether having insufficient rinsing properties and a narrow addition molar distribution of alkylene oxide.

[0008]

SUMMARY OF THE INVENTION An object of the present invention is to provide a liquid detergent composition having excellent flexibility and rinsing properties.

[0009]

Means for Solving the Problems As a result of extensive studies, the present inventors have found that (A) a specific end-blocking nonionic surfactant and (B) an anionic interface having an SO ₃ group or an SO ₄ group. The present inventors have found that a liquid detergent composition comprising a combination of an activator and (C) a specific cationic surfactant solves the above problem, and have completed the present invention.

That is, the present invention relates to (A) one or more kinds of terminal-blocking nonionic surfactants represented by the following general formulas (I) and (II), (B) an SO ₃ group or S
The present invention relates to a liquid detergent composition comprising an anionic surfactant having an O ₄ group and (C) a cationic surfactant represented by the following general formula (III).

R ¹ CO— (AO) _m — (EO) _n —OR ² (I)

Wherein R ^{1 is} a hydrocarbon group having 6 to 22 carbon atoms which may contain a substituent R ^{2 is} an alkyl or alkenyl group having 1 to 20 carbon atoms AO is an oxyalkylene group having 3 to 8 carbon atoms EO: oxyethylene group m: average addition mole number of alkylene oxide, 0 ≦ m ≦ 10 n: average addition mole number of ethylene oxide,
5 ≦ n ≦ 30 m + n: a number of 7 to 30, and it is essential that the additional molar distribution of EO satisfies the narrowness condition represented by the following formula (1).

[0013]

(Equation 3)

(Wherein, i: a positive integer, Y _i : an ethylene oxide adduct having an addition mole number of i (an ethylene oxide addition intermediate when m is not 0)
% By weight of _nmax : ethylene oxide adduct having the highest content (when m is not 0, ethylene oxide adduct)
Is the number of moles of addition, and represents a positive integer.)]

R ³ CO — [(AO) _s , (EO) _t ] —OR ⁴ (II)

Wherein R ^{3 is} a hydrocarbon group having 6 to 22 carbon atoms which may contain a substituent R ^{4 is} an alkyl or alkenyl group having 1 to 20 carbon atoms AO is an oxyalkylene group having 3 to 8 carbon atoms EO: oxyethylene group s: average addition mole number of alkylene oxide, 0 <s ≦ 10 t: average addition mole number of ethylene oxide,
5 ≦ t ≦ 30 s + t: a number of 7 to 30, and AO and EO are random additions, and the mixed addition molar distribution of AO and EO satisfies the narrowness condition represented by the following formula (2) It is essential.

[0017]

(Equation 4)

(Wherein, j: retention time (minutes), Y _j : weight% of the component having the retention time j, v _max : retention time detected when the component having the largest content is subjected to high performance liquid chromatography. (In minutes))]

[0019]

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(Wherein, R ⁵ : a hydrocarbon group having 6 to 24 carbon atoms which may contain a substituent and may be separated by a linking group; R ^{6 to} R ⁸ : an alkyl group having 1 to 3 carbon atoms or Hydroxyalkyl group X: represents a halogen or a monoalkyl sulfate group having an alkyl group having 1 to 3 carbon atoms)

Further, the liquid detergent composition of the present invention preferably further contains a polyether-modified silicone.

Further, the liquid detergent composition of the present invention comprises:
It is preferable that the fatty acid alkyl ester content in the component (A) be 2% by weight or less.

[0023]

DETAILED DESCRIPTION OF THE INVENTION The component (A) in the present invention is at least one selected from the terminal-blocking nonionic surfactants represented by the above general formulas (I) and (II).

In the terminal-blocking nonionic surfactant represented by the general formula (I), R ¹ is a hydrocarbon group having 6 to 22 carbon atoms, and has ^{1 to} 16 carbon atoms. Alkyl or alkenyl groups are particularly preferred. The hydrocarbon group R ¹ may be linear or branched, saturated or unsaturated, and may optionally contain a substituent such as a hydroxyl group. Among them, R ¹ is preferably a decyl group, a lauryl group, a myristyl group, a palmityl group, an oleyl group, an alkyl group derived from coconut oil fatty acid, or an alkyl group derived from tallow fatty acid.

R ² in the general formula (I) is an alkyl or alkenyl group having 1 to 20 carbon atoms,
It is preferably an alkyl or alkenyl group having 1 to 10 carbon atoms, particularly preferably an alkyl or alkenyl group having 1 to 4 carbon atoms. R ² may be linear or branched, and may be saturated or unsaturated. Among them, R ² is preferably a methyl group, an ethyl group, a propyl group, a butyl group or the like.

AO is at least one selected from oxyalkylene groups having 3 to 8 carbon atoms. In the case of two or more types, AO may be divided into a plurality of blocks in the alkylene oxide block, or may be randomly added. May be.
Further, from the viewpoint of detergency, foam performance and biodegradability, the number of carbon atoms is 3
As the oxyalkylene group having 8 to 8, an oxypropylene group or an oxybutylene group having 3 or 4 carbon atoms is particularly preferable.

The average addition mole number m of the alkylene oxide having 3 to 8 carbon atoms is in the range of 0 to 10, preferably in the range of 0 to 5, and when foaming is sufficient, it is 1 to 3 from the viewpoint of stability.
A range of 5 is preferred. On the other hand, the average addition mole number n of ethylene oxide is in the range of 5 to 30, preferably 7 to 30.
It is in the range of 20, more preferably in the range of 7 to 15. When the average number of added moles n exceeds 30, the handleability decreases, and the biodegradability also deteriorates. Further, m + n needs to be in the range of 7-30. When m + n is less than 7, short components of ethylene oxide (or alkylene oxide and ethylene oxide) remain, which adversely affects the flexibility of clothing. Further, when m + n exceeds 30, the handleability decreases and the biodegradability also deteriorates.

The terminal-blocking nonionic surfactant represented by the general formula (I) is essential that the addition molar distribution of ethylene oxide satisfies the narrowness condition represented by the above formula (1). However, the narrowness is more preferably 65% by weight or more, and particularly preferably 70% by weight or more. Formula (1) representing the above-mentioned narrowness is obtained from, for example, the case where the component having the largest content is an ethylene oxide addition (intermediate) body having an addition mole number of 9 (n _max = 9). Occupies 50% by weight or more of the whole (Y ₇ + Y ₈ + Y ₉ + Y ₁₀ + Y ₁₁ ≧ 50% by weight). This calculation does not include the weight of the component to which ethylene oxide is not added. That is, n _max is 1
Or 2, the narrowness equations are (Y ₁ + Y ₂ + Y
₃ ) and (Y ₁ + Y ₂ + Y ₃ + Y ₄ ).

Specific examples of the end-blocking nonionic surfactant represented by the general formula (I) are as follows. When m = 0, polyoxyethylene (7) methyl ether decanoate and polylaurate are exemplified. Oxyethylene (12) methyl ether, polyoxyethylene (9) ethyl laurate, polyoxyethylene (20) butyl ether laurate, polyoxyethylene (15) methyl ether myristate, polyoxyethylene palmitate (1)
8) Ethyl ether, coconut oil fatty acid polyoxyethylene (15) methyl ether, oleic acid polyoxyethylene (25) methyl ether, and the like, when m is not 0, examples are polyoxypropylene (2) polyoxyethylene decanoate. (10) methyl ether, polyoxypropylene (3) polyoxyethylene (7) methyl ether, laurate polyoxypropylene (3) polyoxyethylene (15) methyl ether, polyoxybutylene laurate (2) polyoxy Ethylene (10) ethyl ether, polyoxypropylene laurate (5)
Polyoxyethylene (20) butyl ether, polyoxypropylene myristate (5) polyoxyethylene (10) methyl ether, polyoxybutylene palmitate (4) polyoxyethylene (18) ethyl ether, coconut oil fatty acid polyoxypropylene (2) ) Polyoxyethylene (7) methyl ether, polyoxypropylene (5) polyoxyethylene (15) methyl ether oleate, and the like, but are not limited thereto.

In the terminal-blocking nonionic surfactant represented by the above general formula (II), R ³ is the same as R ¹ in the general formula (I), and R ⁴ is the same as R ¹ in the general formula (I).
^Same as ² . AO and EO are the same as AO and EO in the general formula (I), and s and t are the same as m and n in the general formula (I) except that s is not 0.

In the non-blocking nonionic surfactant represented by the general formula (II), it is essential that the final product satisfies the narrowness condition represented by the above formula (2). The narrowness is more preferably 65% by weight or more, and particularly preferably 70% by weight or more. The expression (2) representing the narrowness is obtained when the component having the largest content is detected in a retention time of 10 minutes when the measurement is performed under the chromatographic conditions shown in the examples, and the retention time is from 6 minutes to 14 minutes. Means that the total amount of the components contained therein accounts for 50% by weight or more of the whole. However, if v _max is less than 4 minutes, the expression for the degree of narrowness is 0 min to v _max +
It shall represent the total amount of components having a retention time of up to 4 minutes.

The component (A), the terminal-blocking nonionic surfactant, may be synthesized or prepared by any method, and the production method thereof is not particularly limited. It is preferable that ethylene oxide or ethylene oxide and alkylene oxide be addition-polymerized to the fatty acid alkyl ester.

Examples of the catalyst to be used include a surface-modified composite metal oxide catalyst. As the composite metal oxide catalyst, for example, first, a Mg compound obtained by calcining a compound represented by the following general formula (IV) is used. —Al composite metal oxide.

AMgO.Al ₂ O ₃ .bH ₂ O (IV)

The compound represented by the above general formula (IV) is alumina / magnesium hydroxide such as aluminum hydroxide / magnesium hydroxide coprecipitate. In the general formula (IV), a and b are positive numbers and are not particularly limited, but a is 1 to 5, preferably 2 to 4, and particularly preferably 2.2 to 2.
It is suitably 3.5 and b is 0-20, preferably 0-15, particularly preferably 0-12. The firing of the compound represented by the general formula (IV) is 200 to 1000.
° C, preferably 300 to 950 ° C, particularly preferably 40 ° C.
The reaction is carried out at 0 to 800 ° C., and the calcination time is usually 30 to 400 minutes, preferably 30 to 300 minutes, particularly preferably 60 to 300 minutes.
~ 250 minutes. The reason for limiting the calcination temperature in this way is that if the temperature is lower than 200 ° C., the activity of the catalyst becomes insufficient. If the temperature is higher than 1000 ° C., the crystal structure changes, and the catalyst activity rapidly increases. It is because it falls to.

In particular, when alumina / magnesium hydroxide is used as the composite metal oxide, a large catalyst surface area is obtained, and the reaction activity in the addition polymerization of ethylene oxide or ethylene oxide and alkylene oxide to the fatty acid alkyl ester. Is much higher than other composite metal oxides. That is, as a composite metal oxide,
The use of alumina / magnesium hydroxide is industrially advantageous because it allows a predetermined addition polymerization reaction to be efficiently achieved and the catalyst can be easily separated after the reaction.

Next, examples of the composite metal oxide catalyst include metal oxide-added magnesium oxide. Al ³⁺ , Ga ³⁺ , Zr
⁴⁺ , Ti4 ⁺ , In3 ⁺ , Tl3 ⁺ , Co3 ⁺ , Ni3 ⁺ , S
It is preferable to add one or more metal ions selected from the group consisting of c ³⁺ , La ³⁺ , Fe ³⁺ , Cu ²⁺ and Mn ²⁺ . The amount of metal ions added to the magnesium oxide is in the range of 0.1 to 40% by weight, preferably 0.5 to 20% by weight in the composite metal oxide.

A method for producing magnesium oxide with added metal ions is described in Japanese Patent Application Laid-Open No. 1-164437. However, as described below, the added metal ions are precipitated from an aqueous solution containing the added metal ions to form a metal. It is desirable to produce ionized magnesium oxide particles.

1) Impregnation method: MgO particles are added to an aqueous solution containing added metal ions, such as an aqueous solution of aluminum nitrate, mixed, and then evaporated to dryness, crushed, and fired.
Obtain catalyst particles.

2) Coprecipitation method: A magnesium salt aqueous solution such as an aqueous solution of magnesium nitrate is mixed with an aqueous solution containing added metal ions such as an aqueous solution of aluminum nitrate, and a precipitant such as ammonia is added thereto. And the added metal are simultaneously precipitated as hydroxide, and the catalyst particles are produced by filtration → drying → pulverization → calcination.

3) Deposition method: An aqueous solution containing added metal ions is added to a dispersion in which magnesium oxide particles are dispersed,
A hydroxide of the added metal is precipitated and deposited on the surface of the magnesium oxide particles, and is filtered, dried and fired.

When the catalyst is produced by a precipitation method such as the above-mentioned coprecipitation method or deposition method, unnecessary anions present in the catalyst slurry after the precipitation treatment can be removed by an ion exchange resin, whereby the filtration can be carried out. The subsequent washing step can be omitted or simplified. The firing treatment can be performed in the same manner as in the case of the Mg-Al composite metal oxide.

The composite metal oxide catalyst further includes a calcined product of hydrotalcite represented by the following general formula (V).

[Mg 2 ⁺ _{1 -x} Al ³⁺ _x (OH) ₂ ] ^{x +} [(A ^p− ) _{x / p} · qH ₂ O] ^x− (V)

In the above general formula (V), A ^{p-
_{O 3 2-, SO 4 2-,}} OH -, NO 3 -, Fe (CN) 6 3- or C
H ₃ COO ^- is. x is a positive number and is not particularly limited, but is usually 0 <x ≦ 0.33, preferably 0.25 ≦
Let x ≦ 0.3. Although not particularly limited, p is 1
-5, preferably 2-4, particularly preferably 2.2-3.
Suitably, q is 0 to 10, preferably 0.
To 8, particularly preferably 0 to 5. Hydrotalcite may be a natural product or a synthetic product prepared by coprecipitation or the like. The firing treatment can be performed in the same manner as in the case of the Mg-Al composite metal oxide.

The above-mentioned composite metal oxide catalyst is surface-modified with a metal hydroxide to obtain a modified composite metal oxide catalyst. By performing the surface modification in this way, in the production of the component (A), the added molar distribution of ethylene oxide or the mixed added molar distribution of ethylene oxide and alkylene oxide is narrowed to improve the quality, and the residual amount is not improved. The amount of the reactive fatty acid alkyl ester can be reduced.

A method for modifying a composite metal oxide is disclosed in
No. 169861. More specifically, a method in which the composite metal oxide is modified with a metal hydroxide and / or metal alkoxide of an alkali metal or an alkaline earth metal and then used as a reaction catalyst, In the above, the composite metal oxide and the metal hydroxide and / or metal alkoxide are mixed with the raw material fatty acid alkyl ester, and the surface of the composite metal oxide is modified in the reaction system. Or a method in which ethylene oxide and alkylene oxide are added to carry out the reaction. The former method is not particularly limited, but after spraying an aqueous solution or alcohol solution of metal hydroxide and / or metal alkoxide on the composite metal oxide,
Drying or baking is preferred. In the latter method, the order of adding the composite metal oxide and the metal hydroxide and / or metal alkoxide to the fatty acid alkyl ester as the raw material does not need to be particularly limited. At this time, it is also preferable to add a metal hydroxide and / or a metal alkoxide as a lower alcohol solution from the viewpoint of more uniformly and more selectively partially poisoning the acid surface of the catalyst.

The metal hydroxide is preferably a hydroxide of an alkali metal such as sodium hydroxide or potassium hydroxide, or a hydroxide of an alkaline earth metal such as calcium hydroxide or magnesium hydroxide. As the metal alkoxide, alkoxides of alkali metals such as sodium alkoxide and potassium alkoxide, and alkoxides of alkaline earth metals such as magnesium alkoxide are preferable. still,
The amount of the metal hydroxide and / or metal alkoxide used for modifying the composite metal oxide is in the range of 0.5 to 10% by weight, preferably 1 to 5% by weight based on the composite metal oxide. Is appropriate. Thus, the metal hydroxide and / or
The reason for limiting the amount of the metal alkoxide is that if the amount is less than 0.5% by weight, a sufficient reforming effect cannot be obtained. If the amount is more than 10% by weight, the catalytic activity is inhibited,
After all, sufficient activity cannot be obtained.

The starting materials used for producing the component (A) in the direct insertion reaction are fatty acid alkyl esters and ethylene oxide (or ethylene oxide and alkylene oxide). The fatty acid alkyl ester may be one kind or a mixture of two or more kinds.

The alkoxylation reaction in the method for producing the component (A) can be easily carried out under ordinary operating means and reaction conditions.

The reaction temperature in the alkoxylation reaction is in the range of 80 to 230 ° C., preferably 120 to 200 ° C., particularly preferably 120 to 180 ° C. The reason for defining the temperature in this manner is that if the temperature is lower than 80 ° C., the catalyst shows little activity, and if the temperature is higher than 230 ° C., an expensive apparatus is required, and the colored or reacted alkylene oxide chain is required. This is because decomposition occurs. The reaction pressure is
Usually, the pressure is suitably 0 to 20 atm, preferably 2 to 8 atm, particularly preferably 2 to 6 atm. The reason why the air pressure is defined in this way is that if it is higher than 20 atm, it is difficult to ensure safety.

The amount of the catalyst used is in the range of 0.01 to 20% by weight, preferably 0.05 to 10% by weight, particularly preferably 0.1 to 5% by weight, based on the amount of the fatty acid alkyl ester. Is appropriate. The reason for limiting the use amount in this way is that if the amount is less than 0.01% by weight, it takes a long time until the reaction is completed. If the amount is more than 20% by weight, the heat removal ability of the apparatus exceeds the limit. This is because it becomes difficult to maintain the reaction temperature or the product loss increases when the catalyst is removed after the reaction.

As an example of the method for producing the component (A), a fatty acid alkyl ester and a modified composite metal oxide catalyst are charged into an autoclave, degassed and dehydrated, and then subjected to a nitrogen atmosphere at a predetermined temperature. The reaction is carried out under pressure conditions by introducing ethylene oxide or ethylene oxide and alkylene oxide. The method of separating the catalyst is not particularly limited, but after the reaction is completed, after cooling the reaction product, for example, water is added to reduce the viscosity, and a diatomaceous earth, a cellulose resin, a filter aid such as activated clay is added. And a method of filtering off the catalyst.

In the case of the direct insertion reaction using a catalyst as described above, the terminal-blocking nonionic surfactant represented by the above general formula (I) (when m = 0) can be obtained by using only ethylene oxide. When ethylene oxide is added to the obtained fatty acid alkyl ester and then alkylene oxide having 3 to 8 carbon atoms is added, the end-blocking nonionic surfactant represented by the above general formula (I) (m is not 0) Case) is obtained. On the other hand, if ethylene oxide and alkylene oxide having 3 to 8 carbon atoms are mixed in advance and added to the fatty acid alkyl ester, the end-blocking nonionic surfactant represented by the above general formula (II) can be obtained. .

When the component (A) in the present invention satisfies the above-mentioned narrowness condition, not only the detergency and the foaming performance are remarkably improved, but also the unreacted unreacted components remaining when a direct insertion reaction is carried out. Odors derived from fatty acid alkyl esters are reduced. In the present invention, the content of the unreacted fatty acid alkyl ester in the component (A) is preferably 2% by weight or less,
It is more preferably at most 1% by weight.

When a direct insertion reaction is carried out using the above-mentioned catalyst, the product contains about 0.3 to 5% by weight of a polyalkylene glycol (weight average molecular weight of tens of thousands to hundreds of thousands). The polyalkylene glycol includes polyethylene glycol when ethylene oxide is added, and includes polyoxyethylene polyoxyalkylene copolymer when ethylene oxide and alkylene oxide are added. In the case of the cleaning composition of the present invention, the content of the polyalkylene glycol is preferably 3% by weight or less, more preferably 2% by weight or less, and particularly preferably 0.1 to 2% by weight. preferable. Polyalkylene glycol is described in, for example, JP-A-9-2
If filtration is performed by the method described in Japanese Patent Application Laid-Open No. 62456, the method described in Japanese Patent Application Laid-Open No. 10-7620, or the like, the catalyst can be removed simultaneously.

The amount of the component (A) is 10 to 50% by weight, preferably 15 to 40% by weight in the liquid detergent composition.
It is. When the amount of the component (A) is less than 10% by weight, the detergency is insufficient. On the other hand, when it exceeds 50% by weight, the viscosity of the composition increases, which is not preferable in terms of usability.

The component (B) in the present invention is an anionic surfactant having an SO ₃ group or an SO ₄ group, and may be used alone or in combination of two or more.

Specific examples of the component (B) are shown below. 1) an alkylbenzene sulfonate having an alkyl group having 8 to 16 carbon atoms 2) an alkyl sulfate having 10 to 20 carbon atoms 3) an olefin sulfonate having 10 to 20 carbon atoms 4) an alkanesulfonic acid having 10 to 20 carbon atoms Salt 5) Alkyl ether sulfate or alkenyl ether sulfate having a linear or branched alkyl group or alkenyl group having 10 to 20 carbon atoms and having an average of 0.5 to 8 mol of ethylene oxide added thereto 6) Carbon number With an average of 0.1 to 10 to 20 alkyl groups.
Polyoxyethylene alkyl phenyl ether sulfate to which 5 to 8 mol of ethylene oxide is added 7) α-sulfo fatty acid ester salt having an alkyl group having 10 to 20 carbon atoms

Examples of these salts include alkali metal salts such as sodium and potassium, alkaline earth metal salts such as magnesium, ammonium salts, alkanolamine salts and the like.

In the present invention, among these, a linear alkylbenzene sulfonate having an alkyl group having 8 to 16 carbon atoms is preferable.

The component (C) in the present invention is a cationic surfactant represented by the above general formula (III), and may be used alone or in combination of two or more.

In the cationic surfactant represented by the above general formula (III), R ⁵ is a hydrocarbon group having 6 to 24 carbon atoms. The hydrocarbon group R ⁵ may be linear or branched, saturated or unsaturated, and may optionally contain a substituent such as a hydroxyl group. Further, the hydrocarbon group R ⁵ may have a linking group such as an ester group, an amide group or an ether group in its chain. As R ⁵ , specifically, an alkyl group having 6 to 24 carbon atoms, an alkenyl group or a β-hydroxyalkyl group, or an alkyl group having 6 to 24 carbon atoms separated by an ester group, an amide group or an ether group, or Alkenyl groups are mentioned, and among them, those having 12 to 24 carbon atoms are particularly preferable.

R ^{6 to} R ⁸ are preferably a methyl group or an ethyl group, and X is preferably a halogen such as chlorine.

Specific examples of the cationic surfactant (C) are shown in the following formulas (VI) to (VII).

[0066]

Embedded image

[0067]

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The mixing ratio of the anionic surfactant (B) and the cationic surfactant (C) used in the present invention is a molar ratio, (B) / (C) = 30/70.
６０60/40, preferably 40/60 to 55/45. When the ratio is less than 30/70, yellowing of the article to be washed is caused, and when it exceeds 60/40, the flexibility is deteriorated.

The total amount of the components (B) and (C) is in the range of 1 to 15% by weight, preferably 2 to 10% by weight in the liquid detergent composition. If the amount is less than 1% by weight, sufficient flexibility cannot be exerted. On the other hand, if the amount exceeds 15% by weight, the viscosity of the composition sharply rises, which is not preferable because it causes problems in use.

In the present invention, a polyether-modified silicone may be further added to the liquid detergent composition in order to impart an effect of imparting slipperiness to clothing. The polyether-modified silicone is obtained by modifying a silicone by introducing a polyether as a hydrophilic group. For example, a water-soluble polyether-modified silicone represented by the following general formula (VIII) is preferably used.

[0071]

Embedded image

[0072] _{(wherein, Y: -C e H 2e -O-} (C f H
_2f O) _g a substituent represented by _g c, d: an integer e: an integer of 1 to 4 f: an integer of 2 to 4 g: an integer of 1 or more M: represents a hydrogen or an alkyl group)

Here, c is in the range of 3 to 100, and d is 1 to
A range of 100 is preferred. G is preferably in the range of 1 to 20.

The polyether-modified silicone preferably has a 1% by weight aqueous solution having a cloud point of 5 to 70 ° C., preferably 10 to 60 ° C., and more preferably 20 to 50 ° C. As such a silicone, for example, a product name “SH374” manufactured by Dow Corning Toray Silicone Co., Ltd.
9 ”(cloud point 32 ° C.),“ SH3746 ”(cloud point 46
° C), “SH8700” (cloud point 28 ° C), Nippon Unicar Co., Ltd. product name “FZ2120” (cloud point 26 ° C),
“FZ7002” (cloud point 40 ° C), Shin-Etsu Chemical Co., Ltd.
Trade name “KF351A” (cloud point 65 ° C.).

The blending amount of the polyether-modified silicone is 0.1 to 5% by weight, preferably 0.2 to 3% by weight in the liquid detergent composition. This compounding amount is 0.1
If the amount is less than 5% by weight, the slipperiness of the garment is insufficient, and if it exceeds 5% by weight, not only is it not economically favorable, but also the viscosity of the composition increases, which is not preferable in terms of usability.

The liquid detergent composition of the present invention contains the above-mentioned components as essential components. However, if necessary, the following optional components can be blended as long as the effects of the present invention are not impaired.

Examples of such optional components include amphoteric surfactants, nonionic surfactants other than component (A), chelating agents, ultraviolet absorbers, fragrances, antioxidants, preservatives, ethanol and 2-propanol. Solvents and the like. The method for producing the liquid detergent composition of the present invention is not particularly limited, but citric acid, sodium citrate, sulfuric acid, sodium hydroxide, alkanolamine, and the like can be used as the pH adjuster.

Examples of the fragrance include hydrocarbons such as aliphatic hydrocarbons, terpene hydrocarbons and aromatic hydrocarbons, alcohols such as aliphatic alcohols, terpene alcohols and aromatic alcohols, aliphatic ethers and aromatic ethers. Such as ethers, aliphatic oxides, terpene oxides, etc., aliphatic aldehydes, terpene aldehydes, aliphatic cyclic aldehydes, thioaldehydes, aromatic aldehydes, etc., aliphatic ketones, terpene ketones, and fats Ketones such as aromatic cyclic ketones, non-benzene aromatic ketones, aromatic ketones, acetals, ketals, phenols, phenol ethers, fatty acids, terpene carboxylic acids, aliphatic cyclic carboxylic acids, aromatic carboxylic acids, etc. Acids, acid amides, aliphatic lactones, macrocyclic lactones Lactones such as terpene lactones, aliphatic cyclic lactones, aromatic lactones, aliphatic esters, furan carboxylic esters, aliphatic cyclic carboxylic esters, cyclohexyl carboxylic esters, terpene carboxylic esters, aromatic carboxylic esters And synthetic fragrances such as nitrogen-containing compounds such as esters, nitromusks, nitriles, amines, pyridines, quinolines, pyrroles, indole and the like, and natural fragrances from animals and plants, and compounded fragrances containing natural fragrances and / or synthetic fragrances , Or a mixture of two or more. For example, synthetic fragrances are described in “Synthetic fragrance chemistry and product knowledge”, written by Motoichi Indo, published by Kagaku Kogyo Nippo, 1996; J. Perfume and Flavor Chemicals, published by Stefan Arctander (Perf)
Ume and Flavor Chemical
s)) and the like. As the natural fragrance, the fragrance described in “Encyclopedia of Fragrance” edited by the Japan Fragrance Association can be used.

Specific names of the main fragrances include aldehydes C ₆ -C ₁₂ , anisaldehyde, acetal R, acetophenone, acetylsedrene, adoxal, allyl amyl glycolate, allyl cyclohexane propionate, α-damascon, β-damascon, δ-damascon, ambroxane, amylcinamic aldehyde,
Amylcinnamic aldehyde dimethyl acetal, amyl valerinate, amyl salicylate, isoamyl acetate, isoamyl salicylate, auran thiol, acetyl eugenol, bacdanol, benzyl acetate, benzyl alcohol, benzyl salicylate, bergamyl acetate, bornyl acetate, butyl butyrate, p -T-butylcyclohexanol,
pt-butylcyclohexyl acetate, ot-butylcyclohexanol, ot-butylcyclohexyl acetate, benzaldehyde, benzylformate, caryophyllene, cashmeren, carvone, sedroambar, cetyl acetate, cedrol, celestrid, cinamic Alcohol, cinnamic aldehyde, cis jasmon, citral, citral dimethyl acetal, citrasal, citronellal, citronellol, citronellyl acetate, citronellyl formate, citronellyl nitrile, cyclaset, cyclamenaldehyde, cyclaprop, caron, coumarin, cinnamyl acetate , Δ-C ₆ -C ₁₃ lactone,
Dimethylbenzylcarbinol, dihydrojasmon,
Dihydro linalool, dihydromyrcenol, Jimetoru, Jimirusetoru, diphenyl oxide, Echiruwanirin, eugenol, Furuiteto, Fen chill alcohol, phenylethyl phenylacetate, Garakusorido, γ-C ₆ ~C ₁₃ lactone, alpha-pinene, beta-pinene, limonene , Myrcene, β-caryophyllene, geraniol, geranyl acetate, geranyl formate,
Geranyl nitrile, hedion, helional, heliotropin, cis-3-hexenol, cis-3-hexenyl acetate, cis-3-hexenyl salicylate, hexylcinnamic aldehyde, hexyl salicylate, hyacinthium dimethyl acetal, hydrotropic alcohol, Hydroxycitronellal,
Indole, ionone, isobornyl acetate, isocyclocitral, iso-E super, isoeugenol, isononyl acetate, isobutylquinoline, jasmar, jasmolactone, jasmophylan, coabon, rigstral, lilial, lime oxide, linalool, linalool oxide , Linalyl acetate, lilal, manzanate, mayol, menthanyl acetate, menthone, methyl anthranilate, methyl eugenol, menthol, α-methyl ionone, β-methyl ionone, γ-methyl ionone, methyl iso eugenol, methyl lavender ketone, methyl salicylate, muguet aldehydes, Mugoru, musk TM-II, musk 781, musk C _14, muscone, civetone, Shikuropentade Non, cyclohexadecen cyclohexenone, cyclopentadecanolide, Ann Bled chloride, cyclohexanol deca laver de, 10-oxa-hexadecanol laver de,
11-oxahexadecanolide, 12-oxahexadecanolide, ethylene brassate, ethylene dodecandioate, oxahexadecen-2-one, 14-methyl-hexadecenolide, 14-methyl-hexadecanolide, musk ketone, musktivetine, nopyr Alcohol, nopyr acetate, neryl acetate, nerol,
Methyl phenyl acetate, mirac aldehyde, neobergamate, oakmoss no. 1, Oribund, oxyphenylone, p-cresyl methyl ether, pentalid, phenylethyl alcohol, phenylethyl acetate, lubafuran, damacenone, raspberry ketone,
Dimethylbenzylcarbyl acetate, jasmacyclene, methyl naphthyl ketone, rosephenone, rose oxide, sandaroa, sandella, santalex, styryl acetate, styraryl propionate, terpineol, terpinyl acetate, tetrahydrolinalool, tetrahydro Linalyl acetate,
Tetrahydrogeraniol, tetrahydrogeranyl acetate, tonalid, traseolide, tripral,
Thymol, crocodile, veldox, yarayara, anise oil, bay oil, boad rose oil, cananga oil, cardamom oil, cassia oil, cedarwood oil, orange oil, mandarin oil, tangerine oil, basil oil, nutmeg oil, citronella oil, clove oil , Coriander oil, elemi oil, eucalyptus oil, fennel oil, galvanum oil, geranium oil,
Hiba oil, Cypress oil, Jasmine oil, Lavandin oil, Lavender oil, Lemon oil, Lemongrass oil, Lime oil, Neroli oil, Oak moss oil, Ocotia oil, Patchouli oil, Peppermint oil, Perilla oil, Petitgren oil, Pine oil, Rose Oil, rosemary oil, camphor oil, aromatic oil, clary sage oil, sandalwood oil, spearmint oil, spike lavender oil, star anise oil, thyme oil, tonka bean tincture, turpentine oil, crocodile bean tincture, vetiver oil, ylang ylang oil , Grapefruit oil, citron oil, benzoin,
Peruvian sam, true balsam, tuberose oil, oak moss absolute, fam balsam, musk tincture, castorium tincture, civet tincture, ambergris tincture and the like.

Further, diethyl phthalate, dipropylene glycol, benzyl benzoate, isopropyl myristate, hercoline, isopentane, orange terpene and the like can be used as a solvent or a retaining agent for the fragrance.

The liquid detergent composition of the present invention has a pH of 6.
Since it is adjusted to 0 to 7.5 and has excellent flexibility and rinsing properties, it is preferably used as a light detergent for delicate fiber materials such as sweaters and blouses such as wool, silk, acrylic and polyester.

[0082]

Next, the present invention will be described in more detail by way of examples, which should not be construed as limiting the present invention. In the following examples, “%” and “part” are “% by weight” and “part by weight”, respectively.

A production example of the end-blocking nonionic surfactant used in the examples is shown below.

Production Example 1 Alumina / magnesium hydroxide having a chemical composition of 2.5 MgO.Al ₂ O ₃ .nH ₂ O (manufactured by Kyowa Chemical Industry Co., Ltd.)
25 g of Kyoward 300) were fired at 700 ° C. for 3 hours in a nitrogen atmosphere to obtain 14 g of fired alumina / magnesium hydroxide. 1.2 g of a calcined alumina / magnesium hydroxide (unmodified) catalyst, 1.3 g of a 5% methanol solution of potassium hydroxide, and 350 g of methyl laurate in 4 parts
A liter autoclave was charged, and the catalyst was reformed in the autoclave. Next, after the inside of the autoclave was replaced with nitrogen, the temperature was raised, and the temperature was set to 180 ° C. and the pressure was set to 3
While maintaining atm, 648 g of ethylene oxide was introduced and reacted with stirring. The resulting polyoxyethylene methyl ether laurate had an average ethylene oxide addition mole number of 9.0, a narrowness of 70%, and a polyethylene glycol content of 0.5%. Further, the reaction solution was cooled to 80 ° C., and 120 g of water and 5 g each of activated clay and diatomaceous earth were added as filter aids, and then the catalyst was separated by filtration. The content of polyethylene glycol after filtration was 0.2% or less. This was designated as Sample A, and the results are shown in Tables 1 and 2. The narrowness was calculated by measuring the molar distribution of ethylene oxide addition of the obtained polyoxyethylene methyl ether laurate. The ethylene oxide addition molar distribution, unreacted fatty acid ester content, polyethylene glycol (PEG) content and weight average molecular weight were measured by the following methods.

(Method for Measuring Ethylene Oxide Addition Molar Distribution and Unreacted Fatty Acid Ester Amount) High-performance liquid chromatography was performed under the following conditions to determine ethylene oxide addition molar distribution and unreacted fatty acid ester content. Apparatus: LC-6A (manufactured by Shimadzu Corporation) Detector: SPD-10A (manufactured by Shimadzu Corporation) Measurement wavelength: 220 nm Column: Zorbax C8 (4.6 mm in diameter x 0.25 m in length; Du Pont ( Mobile phase: acetonitrile / water = 60/40 (volume ratio) Flow rate: 1 mL / min Temperature: 20 ° C.

(Method of measuring PEG content) Gel filtration chromatography was performed under the following conditions to determine the PEG content. Apparatus: LC-6A (manufactured by Shimadzu Corporation) Detector: RID-6A (manufactured by Shimadzu Corporation) Column: Asahi Pack GS-310 (7.6 mm in diameter)
× length 0.5 m; manufactured by Showa Denko KK Mobile phase: acetonitrile / water = 45/55 (volume ratio) Flow rate: 1 mL / min Temperature: 30 ° C.

(Method for measuring weight average molecular weight of PEG) Gel filtration chromatography was performed under the following conditions,
Was determined. Apparatus: LC-6A (manufactured by Shimadzu Corporation) Detector: RID-10A (manufactured by Shimadzu Corporation) Column: Asahi Pack GF-510HQ (diameter 7.6)
mm × length 0.3 m; manufactured by Showa Denko KK Mobile phase: water Flow rate: 1 mL / min Temperature: 30 ° C.

Production Example 2 1.2 g of the calcined alumina / magnesium hydroxide (unmodified) catalyst obtained in Production Example 1, 0.12 g of a 40% aqueous potassium hydroxide solution, and 350 g of methyl myristate were placed in a 4-liter autoclave. The charge and the reforming of the catalyst were performed in an autoclave. Next, after the inside of the autoclave was replaced with nitrogen, the temperature was raised, the temperature was set to 180 ° C., and the pressure was set to 3a.
While maintaining at tm, 765 g of ethylene oxide was introduced and reacted with stirring. The average number of moles of ethylene oxide added to the obtained myristic acid polyoxyethylene methyl ether was 12.0, the narrowness was 65%, and the content of polyethylene glycol was 1.3%. Furthermore,
When the catalyst was separated by filtration in the same manner as in Sample A, the content of polyethylene glycol after filtration was 0.2% or less. This was designated as Sample B, and the results are shown in Tables 1 and 2.

Production Example 3 Alumina / magnesium hydroxide (Kyoward 3)
00) in a nitrogen atmosphere at 600 ° C. for 1 hour, 2.2 g of a calcined alumina / magnesium hydroxide (unmodified) catalyst, 2.9 mL of 0.5 N potassium hydroxide in ethanol, and laurin 350 g of methyl acid was charged into a 4-liter autoclave, and the catalyst was reformed in the autoclave. Next, after the inside of the autoclave was replaced with nitrogen, the temperature was raised, the temperature was set to 180 ° C., and the pressure was set to 3 atm.
While maintaining the above, 1080 g of ethylene oxide was introduced and reacted with stirring. The resulting polyoxyethylene methyl ether laurate had an average ethylene oxide addition mole number of 15.0, a narrowness of 65%, and a polyethylene glycol content of 1.5%. Further, when the catalyst was separated by filtration in the same manner as in Sample A, the content of polyethylene glycol after filtration was 0.2% or less. This was designated as Sample C, and the results are shown in Tables 1 and 2.

Production Example 4 1.4 g of the calcined alumina / magnesium hydroxide (unmodified) catalyst obtained in Production Example 1, 0.14 g of a 40% aqueous potassium hydroxide solution, and 350 g of methyl laurate were placed in a 4-liter autoclave. The charge and the reforming of the catalyst were performed in an autoclave. Next, after the inside of the autoclave was replaced with nitrogen, the temperature was raised, the temperature was set to 180 ° C., and the pressure was set to 3 at.
m, while introducing 648 g of ethylene oxide, and reacted while stirring. When a small amount of this intermediate was extracted and analyzed, the average ethylene oxide addition mole number was 9.0 and the narrowness was 70%. Subsequently, 95 g of propylene oxide was introduced and reacted while stirring. The average propylene oxide addition mole number of the obtained polyoxypropylene polyoxyethylene methyl ether laurate was 1.0, and the content of polyalkylene glycol was 1.0%. Further, when the catalyst was separated by filtration in the same manner as in Sample A, the content of polyalkylene glycol after filtration was 0.2% or less. This was designated as Sample D, and the results are shown in Tables 1 and 2. The narrowness is
As described above, the molar distribution was calculated by measuring the ethylene oxide addition molar distribution of the ethylene oxide addition intermediate in polyoxypropylene polyoxyethylene methyl ether laurate. The ethylene oxide addition molar distribution and unreacted fatty acid ester content were calculated by performing the same high performance liquid chromatography measurement as in Production Example 1, and the content of polyalkylene glycol (PAG) was determined by gel filtration chromatography as in Production Example 1. It was calculated by performing measurements.

Production Example 5 1.4 g of the calcined alumina / magnesium hydroxide (unmodified) catalyst obtained in Production Example 1, 0.14 g of a 40% aqueous potassium hydroxide solution, and 350 g of methyl laurate were placed in a 4-liter autoclave. The charge and the reforming of the catalyst were performed in an autoclave. Next, after the inside of the autoclave was replaced with nitrogen, the temperature was raised, the temperature was set to 180 ° C., and the pressure was set to 3 at.
m, a mixture of 864 g of ethylene oxide and 190 g of propylene oxide, which had been mixed in advance, was introduced and reacted while stirring. The obtained polyoxypropylene polyoxyethylene methyl ether laurate is obtained by random polymerization of ethylene oxide and propylene oxide, and has an average propylene oxide addition mole number of 2.0 and an average ethylene oxide addition mole number of 12.0. The narrowness was 65% and the content of polyalkylene glycol was 1.5%. Further, when the catalyst was separated by filtration in the same manner as in Sample A, the content of polyalkylene glycol after filtration was 0.2% or less. This was designated as Sample E, and the results are shown in Tables 1 and 2. The narrowness was calculated from the obtained polyoxypropylene polyoxyethylene methyl ether laurate by the same high performance liquid chromatography measurement as in Production Example 1 and according to the above mathematical formula (2).

Production Example 6 A 4-liter autoclave was charged with 11 g of an Al ion-added MgO catalyst prepared according to the method described in JP-A-4-279552 and 350 g of methyl laurate, and the inside of the autoclave was replaced with nitrogen. While maintaining the temperature at 180 ° C. and the pressure at 3 atm, 648 g of ethylene oxide was introduced and reacted while stirring.
The resulting polyoxyethylene methyl ether laurate has an average ethylene oxide addition mole number of 9.0, a narrowness of 35%, and a polyethylene glycol content of 0.4.
%Met. This was designated as Sample F, and the results are shown in Tables 1 and 2.

[0093]

[Table 1] Structural formula Narrow degree sample A C ₁₁ H ₂₃ CO (EO) ₉ OCH ₃ 70% Sample B C ₁₃ H ₂₇ CO (EO) ₁₂ OCH ₃ 65% Sample C C ₁₁ H ₂₃ CO (EO) ₁₅ OCH ₃ 65% sample _{D C 11 H 23 CO (PO} ) (EO) 9 OCH 3 70% sample _{E C 11 H 23 CO [(} PO) 2, (EO) 12] OCH 3 65% sample F C ₁₁ H ₂₃ CO (EO) ₉ OCH ₃ 35% PO is an oxypropylene group, EO is an oxyethylene group

[0094]

Table 2 Fatty acid ester content PAG (PEG) content PEG molecular weight Sample A 0% 0.2% or less About 70,000 Sample B 0% 0.2% or less About 80,000 Sample C 0% 0.2% or less About 100,000 Sample D 0 % 0.2% or less-Sample E 0% 0.2% or less- Sample F 3% 0.4% Approx. 70000 PEG molecular weight refers to weight average molecular weight

Examples 1 to 20 and Comparative Examples 1 to 4 The liquid detergent compositions shown in Tables 3 and 4 were prepared and evaluated for flexibility, rinsing properties and slip properties by the following test methods. The results are shown in the table. In addition, the compounding quantity in a table | surface is a weight%, and pH adjusted the composition to 7.

(Measurement Method of pH) The pH of the stock solution (temperature: 25 ± 1 ° C.) of the liquid detergent composition was measured in accordance with the pH test method of the general test method based on cosmetic raw materials.

(Evaluation Method of Flexibility and Slipperiness for Synthetic Fiber) In a small reversing washing machine of about 10 L, 13 g of the liquid detergent composition was dissolved in 5 L of tap water at 25 ° C., and the bath ratio was 5%.
An acrylic jersey cloth was put so as to be 0 times, washed for 10 minutes, dehydrated so as to have a water content of 100%, rinsed twice with 5 L of 25 ° C tap water, and then dried in the shade.
Let dry for hours. This washing operation was repeated 5 times on the same acrylic jersey cloth, and then left in a constant temperature and humidity room at 25 ° C. and 65% RH for 2 days, and this was used as a test cloth for evaluation.
As a control for evaluation, a 20% aqueous solution of a nonionic surfactant (alcohol ethoxylate to which an average of 15 moles of ethylene oxide was added per mole of lauryl alcohol) was used as a composition, and the above-described washing and drying treatment was performed. And A pair of the test cloth is compared with the control cloth,
The flexibility and slipperiness were evaluated by five expert panelists according to the following evaluation criteria. In addition, the evaluation result showed the average value of five specialized panelists.

Flexibility ：: Very softer than control cloth ：: Sufficiently softer than control cloth △: Slightly softer than control cloth ×: Equal to or less than control cloth

Slipperability ：: Very slippery than control cloth ○: Slipperily than control cloth △: Slightly slippery than control cloth ×: Equal to or less than control cloth

(Evaluation method for rinsing properties) Using a two-tub washing machine, dissolve 40 g of the liquid detergent composition in 30 L of tap water at 25 ° C, and put an acrylic jersey and a cotton towel so that the bath ratio becomes 50 times. After putting 300 g and washing for 10 minutes, it was dehydrated so that the water content became 100%. Then, at 25 ° C
Was rinsed with 30 L of tap water for 3 minutes, dehydrated in the same manner as above, and then rinsed again with the same conditions. After the completion of the second rinsing, the amount of foam remaining on the liquid surface was determined according to the following criteria, and the rinsing property was evaluated.

◎: Almost no bubbles, and the liquid surface is transparent. ：: Bubbles of less than 3 mm remain in less than １ ／ of the liquid surface. △ to Δ: Bubbles of 3 mm or more in 〜 to less than half of the liquid surface. Remains: Bubbles of 3 mm or more remain on half or more of the liquid surface. X: Bubbles of 3 mm or more remain on the entire surface.

[0102]

[Table 3]

[0103]

[Table 4]

Abbreviations other than the component (A) in Tables 3 and 4 are shown below. (B) Component anionic surfactant b-1: Alkyl (C ₁₀ -C ₁₄ ) sodium benzenesulfonate (weight average molecular weight (hereinafter abbreviated as Mw) 34
4) b-2: α-olefin (C ₁₄ ) sodium sulfonate (Mw 308) b-3: Sodium polyoxyethylene alkyl (C ₁₃ ) ether sulfate (average number of moles of ethylene oxide added =
3, Mw436)

Component (C) Cationic Surfactant c-1: Mono-long-chain alkyl (C ₁₈ ) trimethylammonium chloride (Mw 348) c-2: Cationic surfactant (Mw 391) represented by the following formula (IX) )

[0106]

Embedded image

Polyether-modified silicone d-1: SH3749 (cloud point of 1% aqueous solution 32 ° C., Dow Corning Toray Silicone Co., Ltd.) d-2: SH8700 (cloud point of 1% aqueous solution 28 ° C., Dow Corning Toray) Silicone Co., Ltd.)

Fragrance-1 (composition) 10 parts of linalool 10 parts of citronellol 10 parts of liliar 10 parts of methyldihydrojasmonate 10 parts of jasmacyclene 5 parts of hexylcinnamic aldehyde 12 parts of pentalid 8 parts of eugenol 7 parts of methylionone 3 parts of geraniol 3 parts of phenylethyl Alcohol 10 parts Muscon 0.5 part Santalinol 5 parts Santalex TNK 3 parts Belt Fix 2 parts Ionone 2 parts Linalyl acetate 2 parts Terpineol 1.5 parts Heliotropin 1 part Ambroxane 1 part Kashmeran 1 part Benzyl acetate 2 parts Octanol 1 Parts Dimethylbenzylcarbinyl acetate 10 parts Methylnaphthyl ketone 2 parts Phenylethylisobutyrate 10 parts Piconia 5 parts Raspberry ketone 0.5 part Masenon 0.5 part of ethylene brassylate 4.5 parts phenylethyl acetate 3-oxa-hexa decene-2-one 6.5 parts of Peach aldehyde 2 parts fur balsam 2 parts orange oil 3 parts

Fragrance-2 (composition) Linalool 7 parts Citronellol 5 parts Lilyal 10 parts Methyldihydrojasmonate 10 parts Jasmacyclene 5 parts Hexylcinnamic aldehyde 12 parts Galaxolide 50% dipropylene glycol solution 10 parts Methylionone 7 parts Geraniol 3 Part Phenylethyl alcohol 10 parts Tonalid 10 parts Santarex TNK 3 parts Belt Fix 2 parts Bertenex 2 parts Linalyl acetate 2 parts Terpineol 1.5 parts Heliotropin 1 part Ambroxane 1 part Kashmeran 1 part Benzyl acetate 2 parts Octanol 1 part Dimethyl Benzyl carvinyl acetate 10 parts Methyl naphthyl ketone 2 parts Phenylethyl isobutyrate 10 parts Piconia 5 parts Raspberry ketone 0.5 part Damacenone 0.5 parts Phenylethyl acetate 3 parts Oxahexadecene-2-one 6.5 parts Peachaldehyde 2 parts Farbal sam 2 parts Orange oil 3 parts

As is clear from Tables 3 and 4, the liquid detergent compositions of the present invention (Examples 1 to 15) are excellent in flexibility and rinsing properties. Further, the liquid detergent composition of the present invention containing a polyether-modified silicone (Examples 16 to 20)
Has excellent sliding properties in addition to flexibility and rinsing properties. It can be seen that when any of these is lacking (Comparative Examples 1 to 4), the flexibility and the slipperiness are inferior.

[0111]

As described above, the liquid detergent composition of the present invention is excellent in flexibility and rinsing properties. Therefore, it can be used as a light detergent for delicate fiber materials such as sweaters and blouses of wool, silk, acrylic and polyester. It is preferably used.

──────────────────────────────────────────────────の Continued on the front page (51) Int.Cl. ⁷ Identification symbol FI theme coat ゛ (Reference) C11D 3/37 C11D 3/37 17/08 17/08 (72) Inventor Meiko Sakaki, Sumida-ku, Tokyo 1-7-3 Lion No. Lion F-term (reference) 4H003 AB14 AB15 AB19 AB21 AB27 AB31 AB32 AC08 AC23 AE05 AE06 BA12 DA01 EB37 FA22 FA23

Claims (3)

[Claims] (A) one or more end-blocking nonionic surfactants represented by the following general formulas (I) and (II), and (B) an SO ₃ group or an SO ₄ group. A liquid detergent composition comprising: an anionic surfactant having the formula (C) and a cationic surfactant represented by the following general formula (III). R ¹ CO— (AO) _m — (EO) _n —OR ² (I) wherein R ^{1 is} a hydrocarbon group having 6 to 22 carbon atoms which may contain a substituent R ² : a hydrocarbon group having 1 to 20 carbon atoms Alkyl or alkenyl group AO: at least one selected from oxyalkylene groups having 3 to 8 carbon atoms EO: oxyethylene group m: average addition mole number of alkylene oxide, 0 ≦ m ≦ 10 n: average of ethylene oxide The number of moles added,
5 ≦ n ≦ 30 m + n: a number of 7 to 30, and it is essential that the additional molar distribution of EO satisfies the condition of narrowness represented by the following formula (1). (Equation 1) (Wherein, i: a positive integer, Y _i : an ethylene oxide adduct having an addition mole number of i (an ethylene oxide addition intermediate when m is not 0)
% By weight of _nmax : ethylene oxide adduct having the highest content (when m is not 0, ethylene oxide adduct)
A of addition mole number, positive represents an ^{integer)] R 3 CO - [(} AO) s, (EO) t] -OR 4 (II) [ wherein, R ^3: carbon atoms, which may contain a substituent 6 to 22 hydrocarbon groups R ⁴ : alkyl or alkenyl group having 1 to 20 carbon atoms AO: at least one selected from oxyalkylene groups having 3 to 8 carbon atoms EO: oxyethylene group s: average addition of alkylene oxide 0 <s ≦ 10 t: average addition mole number of ethylene oxide
5 ≦ t ≦ 30 s + t: a number from 7 to 30, and AO and EO are random additions, and the mixed addition molar distribution of AO and EO satisfies the narrowness condition represented by the following equation (2) It is essential. (Equation 2) (Wherein, j: retention time (minutes) Y _j : weight% of the component with retention time j v _max : retention time (minutes) detected when the component with the highest content is subjected to high performance liquid chromatography Is shown)] (Wherein, R ⁵ : a hydrocarbon group having 6 to 24 carbon atoms which may contain a substituent and may be separated by a linking group; R ^{6 to} R ⁸ : an alkyl group or a hydroxyalkyl group having 1 to 3 carbon atoms) X: represents a halogen or a monoalkyl sulfate group having an alkyl group having 1 to 3 carbon atoms) 2. The liquid detergent composition according to claim 1, further comprising a polyether-modified silicone. 3. The liquid detergent composition according to claim 1, wherein the fatty acid alkyl ester content in the component (A) is 2% by weight or less.