JP2000192099A - Liquid detergent composition - Google Patents

Abstract

PROBLEM TO BE SOLVED: To obtain a concentrated detergent composition which does not form a gel film on the liquid surface even when left standing in an open container by incorporating an end-blocked nonionic surfactant with a hydrophilic organic compound having a plurality of OH groups and oxygen. SOLUTION: The end-blocked nonionic surfactant used is at least either of compounds represented by formulae I and II. In the formulae, R1 and R3 are each a 6-22C hydrocarbon group; R2 and R4 are each a 1-20C alkyl or an alkenyl; AO is a 3-8C oxyalkylene; EO is oxyethylene, 0<m; s<=15; 0, n, t<=40; m+n and s+t are each 2-50; AD and ED units in formula II form a random addition product; and the distribution of the number of moles of BO added in formula I and the distribution of the number of moles of AO and EO added in formula II should satisfy the narrowness relationships of formulae III and IV, respectively. In the formulae, i is a positive integer; Yi is the amount (wt.%) of an EO adduct with an addition mole number of i; nmax is the number of moles of an EO adduct contained in the largest amount; j is the retention time (min); Yj is the amount (wt.%) of the component with a retention time of j; and vmax is the retention time (min) when the component contained in the largest amount is detected.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a concentrated liquid detergent composition which does not form a film due to gelation of the liquid surface even when left in an open container and has high detergency.

[0002]

2. Description of the Related Art Conventionally, liquid detergents for clothing have been mainly composed of a nonionic surfactant as a main base material, a combination of a nonionic surfactant and an anionic surfactant, and an anionic surfactant. There are those used as base materials. In recent years, with the aim of saving resources and reducing the burden on the environment (reducing the amount of waste)
As the size of the detergent container has been reduced, the concentration of the detergent composition has been a problem. Among these types of liquid detergents, those having a nonionic surfactant as a main base material are hardly affected by calcium ions in the washing solution,
There is an advantage that the cleaning performance does not decrease even at a relatively high calcium hardness. For this reason, those using a nonionic surfactant as a main base material can maintain the cleaning performance without blending a chelate builder component in the cleaning composition, and concentrate the cleaning composition. Is a valid type.

[0003] However, it has been considered that a general nonionic surfactant forms a gel in a specific concentration region, that is, about 20 to 70% by weight, and loses fluidity, so that it is considered difficult to concentrate the surfactant. Further, there is a problem that a film is formed in an open system. That is, a film is formed during storage, causing problems such as clogging of the cleaning agent container, difficulty in removing the cleaning agent from the container, and solidification of the film adhered to the outlet of the container, making the container unsightly. Further, when performing washing at a designated time (such as a reservation course) with an automatic washing machine, there is a problem that a film is formed in the liquid detergent charging portion and adheres to the wall of the charging portion.

On the other hand, as a nonionic surfactant to be incorporated in a detergent composition, polyoxyalkylene alkyl ethers, polyoxyalkylene alkyl allyl ethers, alkyl glycosides, and the like are generally used. In recent years, ester-type nonionic surfactants have been used. The development of fatty acid polyoxyalkylene alkyl ethers as surfactants has been promoted.

[0005] 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 mole distribution of alkylene oxide, so that the odor of the unreacted raw material ester remains or the addition mole number of the 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 JP-A-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 the performance of this composition is not always satisfactory.

[0009]

DISCLOSURE OF THE INVENTION The present invention relates to a method for forming a film by gelation of the liquid surface using an ester type nonionic surfactant fatty acid polyoxyalkylene alkyl ether even when left in an open container. It is another object of the present invention to provide a concentrated liquid detergent composition having high detergency.

[0010]

Means for Solving the Problems As a result of intensive studies, the present inventors have found that a specific end-blocking nonionic surfactant, a hydrophilic organic compound having two or more hydroxyl groups, and an enzyme are combined. It has been found that a liquid detergent composition has solved the above-mentioned problems, and has 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), and (B) two or more kinds of surfactants. The present invention relates to a liquid detergent composition comprising: a hydrophilic organic compound having a hydroxyl group; and (C) an enzyme.

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 ≦ 15 n: average addition mole number of ethylene oxide,
0 <n ≦ 40 m + n: a number of 2 to 50, and it is essential that the additional molar distribution of EO satisfies the narrowness condition represented by the following formula (1).

[0014]

(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 : a hydrocarbon group having 6 to 22 carbon atoms which may contain a substituent R ⁴ : an alkyl or alkenyl group having 1 to 20 carbon atoms AO: an oxyalkylene group having 3 to 8 carbon atoms EO: oxyethylene group s: average addition mole number of alkylene oxide, 0 <s ≦ 15 t: average addition mole number of ethylene oxide,
0 <t ≦ 40 s + t: a number of 2 to 50, 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.

[0018]

(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 highest content is subjected to high performance liquid chromatography (In minutes))]

In the liquid detergent composition of the present invention, (B) the hydrophilic organic compound having two or more hydroxyl groups is preferably a compound represented by the following general formula (III).

HO-[(EO) _x , (PO) _y ] -H (III)

(Wherein, EO: oxyethylene group, PO: oxypropylene group, x and y are numbers not less than 0, and the number is such that the weight average molecular weight of the compound is in the range of 200 to 8000, and x and y are the same.) Are both numbers exceeding 0, EO and PO may be block addition or random addition.)

Further, in the liquid detergent composition of the present invention, the fatty acid alkyl ester content in the component (A) is 2
It is preferable that the content be not more than weight%.

[0024]

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 end-blocking nonionic surfactant represented by the above 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, each 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 15, preferably in the range of 0 to 5;
A range of 5 is preferred. On the other hand, the average addition mole number n of ethylene oxide is in a range satisfying 0 <n ≦ 40, preferably in a range of 3 to 40, and more preferably in a range of 5 to 30. When the average number of added moles n exceeds 40, handling properties are reduced and biodegradability is also deteriorated. Further, m + n needs to be in the range of 2 to 50. When m + n is less than 2, many components to which ethylene oxide (or alkylene oxide and ethylene oxide) has not been added remain, which adversely affects detergency, rinsing properties and odor. Also,
If m + n exceeds 50, the handleability will deteriorate and the biodegradability will also deteriorate.

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 (5) 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 (5) methyl ether, polyoxypropylene (7) polyoxyethylene (25) methyl ether, and the like, but are not limited thereto.

In the end-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.

The end-blocking nonionic surfactant represented by the general formula (II) must have a final product satisfying 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), a terminal-blocking nonionic surfactant, may be synthesized or prepared by any method, and the production method 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.

As the catalyst to be used, a surface-modified composite metal oxide catalyst is exemplified. 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 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 can be 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 a metal ion-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, then evaporated to dryness, pulverized and fired.
Obtain catalyst particles.

2) Coprecipitation method: A magnesium salt aqueous solution such as a magnesium nitrate aqueous solution and an aqueous solution containing added metal ions such as an aluminum nitrate aqueous solution are mixed, 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 a 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 with 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 -z Al ³⁺ _z (OH) ₂ ] ^{z +} [(A ^p− ) _{z / p} · qH ₂ O] ^z− (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. z is a positive number and is not particularly limited, but is usually 0 <z ≦ 0.33, preferably 0.25 ≦
Let z ≦ 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 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 and 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 component 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 catalyst, the product contains about 0.3 to 5% by weight of 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 usually 15 to 60% by weight, preferably 20 to 50% by weight, particularly preferably 25 to 45% by weight in the liquid detergent composition. Outside this range, good detergency cannot be obtained.

The component (B) in the present invention is a hydrophilic organic compound having two or more hydroxyl groups. The component (B) prevents a high concentration of nonionic surfactant from being further concentrated at the interface with air when the liquid detergent composition is exposed to the air, thereby preventing gelation and formation of a film. Has an action.

Specific examples of the component (B) include so-called low molecular weight glycols such as ethylene glycol, propylene glycol, and hexylene glycol, and compounds represented by the above formula (III). . Among these, the compound represented by the above general formula (III) is preferable. When a low-molecular glycol is used alone, a relatively large amount is required. Therefore, it is preferable to use the low-molecular glycol together with the compound represented by the general formula (III).

The compound represented by the above general formula (III) has a weight average molecular weight in the range of 200 to 8000, preferably 400 to 6000. If the molecular weight is too large, not only can the film formation not be prevented, but also the storage stability of the liquid detergent composition is poor due to a decrease in water solubility,
There are problems such as precipitation from the composition. Specific examples thereof include polyethylene oxide which is a polymer of ethylene oxide, polypropylene oxide which is a polymer of propylene oxide, and a so-called pluronic type polymer which is a block copolymer of ethylene oxide and propylene oxide.

As the component (B), one type may be used alone, or two or more types may be used in combination.
It is 1 to 30% by weight, preferably 1 to 30% by weight. By blending the component (B) within this range, a film is not formed, the film does not come out of the container, the film solid adheres to the outlet, and it becomes unsightly, and the liquid detergent in the automatic washing machine is introduced. There is no problem such as adhesion to the inside of the unit.

The component (C) in the present invention is an enzyme.
The component (C) has a function of decomposing components such as protein stains, sebum stains, and starch stains derived from food to improve the detergency.

The enzymes include protease, lipase,
Examples include amylase, isoamylase, cellulase, isovertase, pectinase, lactase, glucose oxidase, lysozyme, glucose isomerase, and the like. Among these, proteases are preferred from the viewpoint of efficiently decomposing proteins such as skin-derived keratin contained in dirt adhering to clothing and improving detergency.

As the component (C), one type may be used alone, or two or more types may be used in combination.
The range is from 0.5 to 3% by weight, preferably from 0.1 to 1.5% by weight, particularly preferably from 0.3 to 1% by weight. It is preferable to mix the component (C) in this range because the dirt component is efficiently decomposed. If the amount is too small, the dirt component cannot be completely decomposed, and if it is too large, it is not economically preferable.

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

Such optional components include anionic surfactants, amphoteric surfactants, nonionic surfactants other than the component (A), chelating agents, ultraviolet absorbers, dyes, fragrances,
Examples include antioxidants, preservatives, solvents such as ethanol and isopropanol, and pH adjusters.

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, 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, absolute oak moss, fabal sam, 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 is preferably used as a liquid detergent for clothing, but is not limited thereto.

[0072]

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, “%”, “parts”, and “molecular weight” are “% by weight”, “parts by weight”, and “weight average molecular weight”, respectively.

A production example of the terminal-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. In addition, the ethylene oxide addition molar distribution, unreacted fatty acid ester content, polyethylene glycol (PEG) content and 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 molecular weight of PEG) Gel filtration chromatography was performed under the following conditions to determine the molecular weight of PEG. 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 the temperature at tm, 956 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 15.0, the narrowness was 65%, and the content of polyethylene glycol was 1.5%. 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 The above magnesium alumina hydroxide / 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.
, 1440 g of ethylene oxide was introduced and reacted while stirring. The resulting polyoxyethylene methyl ether laurate had an average ethylene oxide addition mole number of 20.0, a narrowness of 65%, and a polyethylene glycol content of 2.0%. 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 720 g of ethylene oxide, and reacted while stirring. When a small amount of this intermediate was extracted and analyzed, the average number of moles of ethylene oxide added was 10.0 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 1.1%. 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 was calculated by measuring the ethylene oxide addition molar distribution of the ethylene oxide addition intermediate in lauric acid polyoxypropylene polyoxyethylene methyl ether as described above. 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 1080 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 15.0. The narrowness was 65% and the content of polyalkylene glycol was 1.7%. 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.

[0083]

Table 1 Structural formula Narrowness sample A C ₁₁ H ₂₃ CO (EO) ₉ OCH ₃ 70% Sample B C ₁₃ H ₂₇ CO (EO) ₁₅ OCH ₃ 65% Sample C C ₁₁ H ₂₃ CO (EO) ₂₀ OCH ₃ 65% sample _{D C 11 H 23 CO (PO} ) (EO) 10 OCH 3 70% sample _{E C 11 H 23 CO [(} PO) 2, (EO) 15] 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

[0084]

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.

Examples 1 to 11 and Comparative Examples 1 to 3 Liquid detergent compositions shown in Tables 3 and 4 were prepared, and their performance was evaluated by the following test methods. The results are shown in the table. In addition, the compounding quantity in a table | surface is a weight%.

(Method of Evaluating Prevention of Film Formation) 5 g of the liquid detergent composition was weighed and placed in a petri dish having a diameter of 5 cm, allowed to stand indoors, and the ability of the opening device to prevent film formation on the liquid surface was determined according to the following criteria. A: No film formation was observed even after 3 days. ：: No film formation was observed even after 24 hours. Δ: A film is formed between 1 and 24 hours. ×: A film is formed in about 15 minutes.

(Method for Evaluating Detergency) US Testi, USA
ng Co., Ltd. Terg-O-Tometer was used as a washing tester, and 10 wet artificial soiling cloths (5 cm × 5 cm) obtained from the Washing Science Association as soiling cloths,
A sebum cloth and a clean knitted cloth were put in, the bath ratio was adjusted to 30 times, and washed at 120 rpm at 25 ° C. for 10 minutes. The washing liquid used was 900 mL with a detergent concentration of 0.067%, and the rinsing was performed with 900 mL of water for 3 minutes. Water used is 3 ゜ DH
It was made. The detergency was calculated according to the following equation (3), and the detergency was evaluated according to the following criteria. In addition, evaluation was performed by the average value of 10 test artificial soil cloths.

Cleaning power (%) = (K / S of contaminated cloth−K / S of cleaning cloth) / (K / S of contaminated cloth−K / S of uncontaminated cloth) × 100 (3)

Here, K / S = {1- (R / 100)} ² /
(2R / 100) (R is reflectance (%) measured by an ELREPHO reflectometer manufactured by Carl Zeiss).
Further, the cleaning cloth is a contaminated cloth after cleaning, and the non-contaminated cloth is a cloth before the artificial dirt is attached.

Detergency Evaluation Criteria A: Detergency is 90% or more. ：: Detergency is 80% or more and less than 90%. Δ: Detergency is 70% or more and less than 80%. X: Detergency is less than 70%.

[0091]

[Table 3] Example 1 2 3 4 5 6 7 8 [Composition] (A) Component Sample A 35 25 Sample B 35 30 Sample C 35 40 Sample D 35 Sample E 35 (B) Component b-1 5 10 10 b -2 10 5 b-35 b-55 b-55 55 b-65 55 (C) component c-1 0.5 0.5 0.5 c-2 0.5 0.5 c-3 0.6 0.6 0.6 Others ethanol 44 44 4 4 4 4 Perfume A 0.2 0.2 0.2 0.2 0.2 Perfume B 0.2 0.2 0.2 Purified water Remaining Remaining Remaining Remaining Remaining Remaining Remaining Remaining Remaining [Evaluation results] Prevention of film formation ◎ ○ ○ ◎ ◎ ◎ ◎ ◎ ◎ Cleaning power ○ ◎ ○ ○ ○ ◎ ○ ○

[0092]

Example 4 Comparative Example 9 10 11 1 2 3 [Composition] (A) Component Sample A 20 20 Sample B 35 Sample C 25 35 Sample D 10 Sample E 15 20 Sample F 35 (B) Component b-2 10 b-35 b-45 55 b-55 (C) component c-1 0.5 0.5 c-2 0.5 0.5 c-3 0.6 Other ethanol 44 44 44 44 Perfume A 0.2 0.2 Perfume B 0.2 0.2 0.2 0.2 Purification Water Remaining Remaining Remaining Remaining Remaining Remaining Remaining [Evaluation result] Prevention of film formation ○ ◎ ◎ △ × ○ Cleaning power ○ ○ ◎ △ ○ △

The abbreviations of the components (B) and (C) in Tables 3 and 4 and the composition of the fragrance are shown below. (B) hydrophilic organic compound of component b-1: propylene glycol b-2: hexylene glycol b-3: polyethylene glycol # 400 (molecular weight 40)
0) b-4: polyethylene glycol # 1000 (molecular weight 1)
000) b-5: polyethylene glycol # 6000 (molecular weight 6)
000) b-6: polypropylene glycol (molecular weight 800)

(C) Component enzyme c-1: Protease, trade name "Everlase 1"
6L ", Novo Nordisk c-2: Protease, trade name" Savinase 1
6L ", manufactured by Novo Nordisk c-3: Protease, trade name" Maxapem 30 "
L ", manufactured by Genencor

Composition of Perfume Perfume A 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 parts 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 Kashmelane 1 part Benzyl acetate 2 parts Octanol 1 part Dimethylbenzyl Carvinyl acetate 10 parts Methyl naphthyl ketone 2 parts Phenylethyl isobutyrate 10 parts Piconia 5 parts Raspberry ketone 0.5 Damascenone 0.5 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

Perfume B Linalool 10 parts Citronellol 5 parts Lilyal 10 parts Methyldihydrojasmonate 10 parts Jasmacyclene 5 parts Hexylcinnamic aldehyde 12 parts Pentalid 8 parts Eugenol 2 parts Methylionone 7 parts Geraniol 3 parts Phenylethyl alcohol 10 parts Muscon 0.5 parts 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 part Dimethylbenzyl car Vinyl acetate 10 parts Methyl naphthyl ketone 2 parts Phenylethyl isobutyrate 10 parts Piconia 5 parts Raspberry ketone 0.5 parts Damacenone .5 parts 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

As is clear from Tables 3 and 4, the liquid detergent compositions of the present invention (Examples 1 to 11) are excellent in the effect of preventing film formation and the detergency. On the other hand, when any of these is lacking (Comparative Examples 1 to 3), it can be seen that the effect of preventing film formation or the detergency is poor.

[0098]

The liquid detergent composition of the present invention does not form a film due to gelation of the liquid surface even when left in an open container, and has a high detergency. Therefore, it is suitable for washing clothes and the like. Used.

 ──────────────────────────────────────────────────続 き Continuation of the front page (72) Inventor Meiko Sakaki 3-7-7 Honjo, Sumida-ku, Tokyo Lion F-term (reference) 4H003 AC12 BA12 DA01 EB04 EB34 EB36 EC01 EC02 ED02 ED28 ED29 FA35

Claims (3)

[Claims] 1. A hydrophilic compound having (A) one or more kinds of terminal-blocking nonionic surfactants represented by the following general formulas (I) and (II), and (B) two or more hydroxyl groups. A liquid detergent composition comprising a lipophilic organic compound and (C) an enzyme. 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 ≦ 15 n: average of ethylene oxide The number of moles added,
0 <n ≦ 40 m + n: a number of 2 to 50, and it is essential that the additional molar distribution of EO satisfies the narrowness condition 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 ≦ 15 t: average addition mole number of ethylene oxide
0 <t ≦ 40 s + t: a number of 2 to 50, 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. (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)] 2. The liquid detergent composition according to claim 1, wherein (B) the hydrophilic organic compound having two or more hydroxyl groups is a compound represented by the following general formula (III). HO-[(EO) _x , (PO) _y ] -H (III) (wherein, EO: an oxyethylene group, PO: an oxypropylene group, x and y are numbers of 0 or more, and the weight average molecular weight of the compound is EO and PO may be block addition or random addition when x and y are numbers exceeding 0 in the range of 200 to 8000. 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.