JP2000234099A - Liquid detergent composition - Google Patents

Abstract

PROBLEM TO BE SOLVED: To obtain a liquid detergent composition which is easily soluble even in low-temperature water and has a high detergency by incorporating at least one terminal-blocked nonionic surfactant, an alkanolamine, and a hydrophilic organic compound having at least two hydroxyl groups into the same. SOLUTION: This composition contains 15-60 wt.% at least one surfactant selected from among terminal-blocked nonionic surfactants represented by formulas I and II, 1-25 wt.% alkanoloamine represented by formula II (e.g. diethanolamine), and 0.1-30 wt.% hydrophilic organic compound having at least two hydroxyl groups (e.g. ethylene glycol). In the formulas, R1 and R8 are each a 6-22C hydrocarbon group; R2 and R4 are each 1-20C alkyl or alkenyl; R5 is 1-4C hydroxyalkyl; R6 and R7 are each H, 1-4C hydroxyalkyl or the like; AO is 3-8C oxyalkylene; EO is oxyethylene (the distribution of number of moles of EO added satisfies the degree of narrowness of formula IV); Yi is an ethylene oxide adduct; 0<=m<=15; 0<n<=40 provided m+n is 2-50; 0<s<=15; and 0<t<=40 provided s+t is 2-50.

Description

DETAILED DESCRIPTION OF THE INVENTION

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a high-concentration liquid detergent composition having good solubility even at a low water temperature and 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)
Detergent containers have been reduced in size, and with this, concentration of the detergent composition has become an issue. 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. Furthermore, in the case of performing washing at a designated time (reservation course, etc.) with an automatic washing machine in winter, gelation occurs due to contact between the detergent composition and low-temperature water in the liquid detergent charging section, and the detergent composition becomes sufficient. There is a concern that a problem such as remaining undissolved in the liquid detergent input portion without melting may occur.

Although it is effective to add an alkali component to improve the cleaning power, inorganic salts such as phosphates and carbonates have low solubility in a liquid cleaning composition, so that the cleaning power is improved. When a sufficient amount is added, the inorganic salt cannot be completely dissolved, so that the inorganic salt that cannot be completely dissolved must be dispersed and stabilized, but there has been a problem that a high technology is required.

[0005] On the other hand, as nonionic surfactants to be blended in the detergent composition, 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.

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). A liquid detergent composition using a fatty acid polyoxyalkylene alkyl ether produced by the method described in JP-A-4-279552 (JP-A-5-202381,
JP-A-5-222396, JP-A-9-25598
No. 8) is disclosed. However, fatty acid polyoxyalkylene alkyl ethers synthesized with these catalysts have a remarkably wide addition mole distribution of alkylene oxide, so that unreacted raw material ester odor remains or the addition mole number of alkylene oxide is high (or low). The components have an adverse effect on detergency and rinsing properties, and it has been difficult to put them into practical use in detergent compositions. In order to overcome these disadvantages, a method for synthesizing a fatty acid polyoxyalkylene alkyl ether having a narrow addition molar distribution of an alkylene oxide is disclosed in JP-A-8-169860 and JP-A-8-169860.
No. 169,861. A method of synthesizing a fatty acid polyoxyalkylene alkyl ether having a narrow addition molar distribution of alkylene oxide using this method, followed by filtration, and a method using the present activator in a liquid detergent composition (Japanese Patent Application Laid-Open No. 10-7620) ) Is disclosed, but the performance when used as a high-concentration liquid detergent is not sufficient.

[0007]

SUMMARY OF THE INVENTION An object of the present invention is to provide a concentrated liquid detergent composition which has good solubility even at a low water temperature and high detergency.

[0008]

Means for Solving the Problems The present inventors have conducted intensive studies to solve the above-mentioned problems, and as a result, have found that a specific end-blocking nonionic surfactant, an alkanolamine and a hydrophilic organic compound having two or more hydroxyl groups are available. The present inventors have found that a liquid detergent composition containing a compound as an essential component achieves the object of the present invention, and have completed the present invention.

That is, the present invention relates to (A) one or more compounds selected from terminal-blocking nonionic surfactant compounds represented by the following general formulas (I) and (II): It comprises, as essential components, at least one selected from alkanolamines represented by the general formula (III) and (C) at least one selected from hydrophilic organic compounds having two or more hydroxyl groups. And a liquid detergent composition. 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 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 n _max : ethylene oxide adduct having the highest content (when m is not 0, an 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 4) (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 R ⁵ —N—R ⁶ .R ⁷ (III) (wherein, R ⁵ is a hydroxyalkyl group having 1 to 4 carbon atoms,
R ⁶ and R ^{7 each} represent a hydrogen atom, a hydroxyalkyl group having 1 to 4 carbon atoms or an alkyl group having 1 to 4 carbon atoms)

In the liquid detergent composition of the present invention, the hydrophilic organic compound (C) is preferably a compound represented by the following general formula (IV). ^{_{HO- (R 8 O) c -}} (R 9 O) d - in _{(R 10 O) e -H (} IV) ( wherein, c, d, e each a number of 0 or ^{more, R} 8 O,
R ⁹ O and R ¹⁰ O each represent an oxyethylene group or an oxypropylene group, and the compound has a weight-average molecular weight of 400 to 6000. Furthermore, in the liquid detergent composition of the present invention, the component (A) Is preferably 2% by weight or less.

[0011]

BEST MODE FOR CARRYING OUT THE INVENTION Hereinafter, the present invention will be described in detail.
As the component (A) in the present invention, at least one selected from the terminal-blocking nonionic surfactants represented by the general formulas (I) and (II) is used.

In the terminal-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 include 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 oxyalkylene block, or may be randomly added. May be. Also, from the viewpoint of detergency, foam performance and biodegradability, the number of carbon atoms is 3 to
The oxyalkylene group of 8 is particularly preferably an oxypropylene group or an oxybutylene group having 3 or 4 carbon atoms.

The average number of moles 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) must have an addition oxide distribution of ethylene oxide satisfying 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. Numerical expression (1) representing the narrowness is, for example, assuming that the component having the largest content is an ethylene oxide addition (intermediate) body having an addition mole number of 9 (n _max = 9),
Components added mole number 7-11 means that accounts for at least 50 wt% of the total _{(Y 7 + Y 8 + Y} 9 + Y 10 + Y 11 ≧ 50 wt%). This calculation does not include the weight of the component to which ethylene oxide is not added. That is,
When n _max is 1 or 2, the narrowness formulas are (Y ₁ + Y ₂ + Y ₃ ) and (Y ₁ + Y ₂ + Y ₃ + Y ₄ ), respectively.
Shall be

Specific examples of the end-blocking nonionic surfactant represented by the general formula (I) are as follows. In the case where 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 terminal-blocking nonionic surfactant represented by the general formula (II), R ³ is the same as R ¹ in the general formula (I), and R ⁴ is R ² in the general formula (I). Is the same as AO and EO are represented by the general formula (I)
And s and t are the same as AO and EO in
It is the same as m and n in General formula (I) except that it is not.

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. Formula (2) representing the above-mentioned narrowness is obtained by measuring the chromatographic conditions shown in the examples. For example, if the component having the highest content is detected in a retention time of 10 minutes, 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, v _max
If is less than 4 minutes, the narrowness equation is from 0 minutes to v
_max + represents 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 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 (V) is used. —Al composite metal oxide. aMgO.Al ₂ O ₃ .bH ₂ O (V) The compound represented by the general formula (V) is alumina / magnesium hydroxide such as aluminum hydroxide / magnesium hydroxide coprecipitate. In the general formula (V), a and b
Is a positive number and is not particularly limited, but a is suitably 1 to 5, preferably 2 to 4, particularly preferably 2.2 to 3.5, and b is 0 to 20, preferably 0. To 15, particularly preferably 0 to 12. Further, the compound represented by the general formula (V) is calcined at 200 to 1000 ° C, preferably 300 to 950 ° C, particularly preferably 400 to 800 ° C, and the calcining time is usually 30 to 400 minutes, preferably 3 to 400 minutes.
The time is from 0 to 300 minutes, particularly preferably from 60 to 250 minutes. The reason for limiting the firing temperature in this manner is that 200
If the temperature is lower than 100 ° C., the activity of the catalyst becomes insufficient. If the temperature is higher than 1000 ° C., the crystal structure changes and the catalytic activity decreases rapidly.

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 metal ion-added magnesium oxide. Examples of the metal ion-added magnesium oxide include Al ³⁺ , Ga ³⁺ ,
Zr ⁴⁺ , Ti ⁴⁺ , In ³⁺ , Tl ³⁺ , Co ³⁺ ,
It is preferable to add one or more metal ions selected from the group consisting of Ni ³⁺ , Sc ³⁺ , La ³⁺ , Fe ³⁺ , Cu ²⁺ and Mn ²⁺ . The amount of metal ions added to magnesium oxide is 0.1 to
It is in the range of 40% by weight, preferably 0.5 to 20% by weight.

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 subjected to the steps of evaporation to dryness, pulverization, and calcination to 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. Is precipitated at the same time as a hydroxide, and the catalyst particles are produced by filtration → drying → crushing → calcination. 3) Deposition method: An aqueous solution containing added metal ions is added to the dispersion liquid in which the magnesium oxide particles are dispersed, and a hydroxide of the added metal is deposited and deposited on the surface of the magnesium oxide particles, followed by filtration, drying, and firing.

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 (VI). ^{_{[Mg 2+ 1-x Al 3+}} x (OH) 2] x + [(A p-) x / p · qH 2 O] x- (VI) above general formula ^{(IV), A p-} is, C
^{_{O 3 2-, SO 4 2-,}} OH -, NO 3 -, Fe (C
_N) ^{6 3-} or _CH 3 COO ^- it is. x is a positive number and is not particularly limited, but is generally 0 <x ≦ 0.33, preferably 0.25 ≦ x ≦ 0.3. Although not particularly limited, p is suitably 1 to 5, preferably 2 to 4, particularly preferably 2.2 to 3.5, and q is 0 to 0.
10, preferably 0-8, particularly preferably 0-5. 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 an alkali metal hydroxide such as sodium hydroxide or potassium hydroxide, or an alkaline earth metal hydroxide 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.

[0032] 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 end-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 an alkylene oxide having 3 to 8 carbon atoms are mixed in advance and added to a fatty acid alkyl ester, a terminal-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, more preferably 1% by weight or less.

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 propylene 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.

In the present invention, the compounding amount of the component (A) is 15 to 60% by weight, preferably 20 to 50% by weight in the liquid detergent composition. If the amount is too small, sufficient cleaning power cannot be obtained. On the other hand, if the amount is too large, the low-temperature solubility becomes extremely poor.

The liquid detergent composition of the present invention contains, as an essential component (B), at least one selected from the alkanolamines represented by the general formula (III). Among the alkanolamines represented by the general formula (III), R ⁶ is a hydroxyalkyl group having 2 to 3 carbon atoms, R ⁶ is a hydrogen atom or a hydroxyalkyl group having 2 to 3 carbon atoms, and R ⁷ is a hydrogen atom or a carbon atom. Preferred are compounds having an alkyl group of Formulas 1 to 4. For example, monoethanolamine, diethanolamine, monomethylmonoethanolamine, monomethyldiethanolamine, dimethylmonoethanolamine, monoethyldiethanolamine and monobutyldiethanolamine are mentioned. Among them, preferred alkanolamines are monoethanolamine, diethanolamine and monomethylamine from the viewpoint of detergency. Diethanolamine and dimethylmonoethanolamine are exemplified. These alkanolamines can be used alone or in combination of two or more.

The compounding amount of the alkanolamine (B) is 1 to 25% by weight, preferably 2 to 20% by weight, particularly preferably 3 to 20% by weight in the liquid detergent composition. If the amount is less than 1% by weight, the detergency is insufficient. If the amount is more than 25% by weight, no particular improvement is observed, which is economically undesirable.

The liquid detergent composition of the present invention contains, as an essential component (C), at least one selected from hydrophilic organic compounds having two or more hydroxyl groups. As the component (C), ethylene glycol, propylene glycol,
Low molecular glycols such as hexylene glycol can be mentioned, but when these are used alone, a relatively large amount is required, so that they are used in combination with a hydrophilic organic compound represented by the following general formula (IV). Is preferred. ^{_{HO- (R 8 O) c -}} (R 9 O) d - in _{(R 10 O) e -H (} IV) ( wherein, c, d, e each a number of 0 or ^{more, R} 8 O,
R ⁹ O and R ¹⁰ O each represent an oxyethylene group or an oxypropylene group, and the compound has a weight average molecular weight of 400 to 6000.) The hydrophilic organic compound represented by the general formula (IV) is a single compound. It is effective even when used in

When the weight average molecular weight of the hydrophilic organic compound represented by the general formula (IV) is more than 6000, the storage stability of the liquid detergent composition is deteriorated due to the decrease in water solubility, and the hydrophilic organic compound precipitates from the composition. There is a problem. On the other hand, if the weight average molecular weight is smaller than 400, no improvement in solubility at low water temperature is observed. Examples of the component (C) include polyethylene glycol, polypropylene glycol, and a block copolymer of ethylene oxide and propylene oxide (a so-called pluronic type polymer), but are not limited thereto as long as the above effects are satisfied. .

The amount of component (C) is from 0.1 to 30% by weight, preferably from 1 to 25% by weight, based on the liquid detergent composition. If the amount is less than 0.1% by weight, the solubility at low water temperature is not improved, and a gel is formed. Even if the amount is more than 30% by weight, no special effect is observed, which is not economically preferable.

To the cleaning composition of the present invention, various surfactants and additives conventionally used in liquid cleaning compositions may be added as long as the effects of the present invention are not impaired. good. Examples of the component that can be added include an anionic surfactant and a nonionic surfactant other than the component (A).

Examples of the nonionic surfactant excluding the component (A) include alkylene oxide (preferably ethylene oxide) adducts such as higher alcohols, alkylphenols, higher fatty acids and higher amines, polyoxyethylene polyoxypropylene block copolymers, and the like. Fatty acid alkanolamine, fatty acid alkanolamide, polyhydric alcohol fatty acid ester or alkylene oxide adduct thereof, polyhydric alcohol fatty acid ether, alkyl (or alkenyl) amine oxide, hydrogenated castor oil alkylene oxide adduct, sugar fatty acid ester, N-alkyl Examples include polyhydroxy fatty acid amides and alkyl glycosides. Of these, polyoxyethylene alkyl ethers having 10 to 14 carbon atoms in the alkyl group and 3 to 20 average addition moles of ethylene oxide are preferred.

These nonionic surfactants may be used alone or in combination of two or more, and preferably 0.5 to 30% by weight in the detergent composition according to the purpose. %, More preferably 1 to 25% by weight.

Examples of the anionic surfactant include (1)
Carboxylic acid types such as higher fatty acid salts, alkyl ether carboxylate salts, polyoxyalkylene alkyl ether carboxylate salts, alkyl (or alkenyl) amide ether carboxylate salts, acylamino carboxylate salts, etc., (2) higher alcohol sulfate salts, Polyoxyalkylene higher alcohol sulfate, alkyl phenyl ether sulfate, polyoxyalkylene alkyl phenyl ether sulfate, glycerin fatty acid ester monosulfate, etc., (3) alkyl sulfonate, α-olefin Sulfonates, linear alkylbenzene sulfonates, α-sulfofatty acid ester salts, sulfonic acid types such as dialkyl sulfosuccinates,
(4) Phosphate ester-type anion interfaces such as alkyl phosphate ester salts, polyoxyalkylene alkyl phosphate ester salts, alkylphenyl phosphate ester salts, polyoxyalkylene alkylphenyl phosphate ester salts, and glycerin fatty acid ester monophosphate ester salts Activators and the like. Among these, a fatty acid alkali metal salt having an alkyl group having 14 to 24 carbon atoms, a linear alkyl sulfate having an alkyl group having an average carbon number of 10 to 20, an α-alkyl group having an alkyl group having an average carbon number of 10 to 20 Sulfo fatty acid ester alkali metal salts and the like are preferred.

These anionic surfactants may be used alone or in combination of two or more, and preferably 0.5 to 30% by weight in the detergent composition according to the purpose. %, More preferably 1 to 25% by weight.

As other components, a solubilizing agent such as ethanol, a dye, a fragrance and the like can also be blended.

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. Oxides such as ethers, aliphatic oxides, terpene oxides, aldehydes such as aliphatic aldehydes, terpene aldehydes, aliphatic cyclic aldehydes, thioaldehydes, aromatic aldehydes, aliphatic ketones, terpene ketones, and aliphatic cyclics Ketones, non-benzene-based aromatic ketones, ketones such as aromatic ketones, acetals, ketals, phenols, phenol ethers, fatty acids,
Terpene carboxylic acids, aliphatic cyclic carboxylic acids, acids such as aromatic carboxylic acids, acid amides, aliphatic lactones,
Lactones such as macrocyclic lactone, terpene lactone, aliphatic cyclic lactone, aromatic lactone, aliphatic ester, furan carboxylic acid ester, aliphatic cyclic carboxylic acid ester, cyclohexyl carboxylic acid ester, terpene carboxylic acid ester, aromatic Esters such as aromatic carboxylic acid esters, nitro musks, nitriles, amines,
Mix and use one or more of synthetic fragrances such as pyridines, quinolines, pyrroles, indole and other nitrogen-containing compounds and natural fragrances from animals and plants, and compounded fragrances including natural fragrances and / or synthetic fragrances can do. For example, "Synthetic Fragrance Chemistry and Product Knowledge" written by Motoichi Indo, published by Kagaku Kogyo Nippo, 1996
N. J. Published by Steffen Arctander “P”
erfumeand Flavor Chemical
s "and the like can be used.

Specific examples of main flavors 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, amyl cinamic aldehyde dimethyl acetal, amyl valerianate, amyl salicylate, isoamyl acetate, isoamyl salicylate, auranthiol, acetyl eugenol, vacdanol, benzyl acetate, benzyl alcohol, Benzyl salicylate, bergamyl acetate, bornyl acetate, butyl butyrate, pt-butylcyclohexanol, pt-butyl Clohexyl acetate, o-
t-butylcyclohexanol, tert-butylcyclohexyl acetate, benzaldehyde, benzylformate, caryophyllene, cashmeren, carvone,
Cedroambar, Cedrol Acetate, Cedrol, Celestride, Cinnamic Alcohol, Cinnamic Aldehyde, Cisjasmon, Citral, Citral Dimethyl Acetal, Citrasal, Citronellal,
Citronellol, citronellyl acetate, citronellyl formate, citronellyl nitrile, Shikurasetto, cyclamen aldehyde, Shikurapuroppu, Caron, coumarin, cinnamyl acetate, [delta]-C ₆ -C
₁₃ lactone, dimethylbenzylcarbinol, dihydrojasmon, dihydrolinalool, dihydromyrcenol, dimetol, dimyrcetol, diphenyloxide, ethylvanillin, eugenol, fluitate,
Fen chill alcohol, phenylethyl phenylacetate, Garakusorido, _{γ-C 6 ~ 13} lactone, alpha-pinene, beta-pinene, limonene, myrcene, beta-caryophyllene, geraniol, geranyl acetate, geranyl formate, geranyl nitrile, Hedion, ocean propanal , Heliotropin, cis-3-hexenol,
cis-3-hexenyl acetate, cis-3-hexenyl salicylate, hexylcinamic aldehyde, hexyl salicylate, hyacinth dimethyl acetal, hydrotropic alcohol, hydroxycitronellal, indole, ionone, isobornyl acetate, isocyclo Citral, IsoE Super, Isoeugenol, Isononyl Acetate, Isobutylquinoline, Jasmar, Jasmolactone, Jasmophylan, Koabon, Rigstral, Lilial, Lime Oxide, Linalool, Linalool Oxide, Linalyl Acetate, Lilal, Manzanate, Mayol, Mensa Neil acetate, mensonate, methyl anthranilate, methyl eugenol, menthol, α
-Methylionone, β-methylionone, γ-methylionone, methylisoeugenol, methyl lavender ketone, methyl salicylate, mugealdehyde, mugol, musk TM-II, musk 781, musk C ₁₄ , muscone, civetone, cyclopentadecanone,
Cyclohexadecenone, cyclopentadecanolide, ambrettolide, cyclohexadecanolide, 10-oxahexadecanolide, 11-oxahexadecanolide, 1
2-oxahexadecanolide, ethylene brush rate,
Ethylene dodecandioate, oxahexadecene-2
-One, 14-methyl-hexadecenolide, 14-methyl-hexadecanolide, musk ketone, musk tibetin, nopyr alcohol, nopyr acetate, neryl acetate, nerol, methyl phenyl acetate, mirac aldehyde, neobergamate, oakmos No.
1. Oribbon, oxyphenylone, paracresyl methyl ether, pentalid, phenylethyl alcohol, phenylethyl acetate, rubafuran, rosephenone, rose oxide, sandaloa, sandera, Santarex, styrilyl acetate, styrilyl propionate , Terpineol, terpinyl acetate, tetrahydrolinalool, tetrahydrolinalyl acetate, tetrahydrogeraniol, tetrahydrogeranyl acetate, tonalid, traseolide, tripral, thymol, crocodile, verdox, yayala, anise oil, bay oil, bored 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, Hinoki oil, Jasmine oil,
Lavandin oil, lavender oil, lemon oil, lemongrass oil, lime oil, neroli oil, oak moss oil, okotia oil,
Patchouli oil, peppermint oil, perilla oil, petitgren oil, pine oil, rose oil, rosemary oil, camphor oil, fragrance 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, yuzu oil, benzoin, peruvian balsam, true balsam, tuberose oil, musk tincture, castorium tincture, civet tincture, ambergris tincture, absolute oak moss, etc. It is.

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 fragrance is not limited to the fragrance described in the examples.

[0053]

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, “%” is “% by weight”. A production example of the terminal-blocking nonionic surfactant used in this example is shown below.

Production Example 1 Alumina / magnesium hydroxide having a chemical composition of 2.5 MgO.Al ₂ O ₃ .nH ₂ O (Kyowa Chemical Industry Co., Ltd.)
(Kyoward 300) was fired at 700 ° C. for 3 hours in a nitrogen atmosphere to obtain 14 g of fired alumina / magnesium hydroxide. 1.2 g of calcined alumina / magnesium hydroxide (unmodified) catalyst, 1.3 g of 5% methanol solution of potassium hydroxide, and 350 g of methyl laurate
g 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, and while maintaining the temperature at 180 ° C. and the pressure at 3 atm, ethylene oxide 648 was used.
g 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 for 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 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 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.
, 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 According to Example 1 of JP-A-4-279552,
11 g of an MgO catalyst to which ions were added and 350 g of methyl laurate were placed in a 4 liter autoclave, and the inside of the autoclave was replaced with nitrogen. Then, the temperature was raised, and while maintaining the temperature at 180 ° C. and the pressure at 3 atm, 648 g of ethylene oxide Was introduced and reacted with stirring. The average number of moles of ethylene oxide added to the obtained polyoxyethylene methyl ether laurate is 9.0, the narrowness is 35%, and the content of polyethylene glycol is 0.4%.
Met. This was designated as Sample F, and the results are shown in Tables 1 and 2.
Shown in

[0063]

[Table 1]

[0064]

[Table 2] PEG molecular weight refers to weight average molecular weight

Examples and Comparative Examples The liquid detergent compositions shown in Table 3 were prepared, and their performance was evaluated by the following evaluation methods. The results are shown in Table 3.

1) Low Water Temperature Solubility Evaluation One liter of tap water at 5 ° C. was placed in a 1 liter glass beaker, and this was gently stirred with a magnetic stirrer. 1 g of the liquid detergent composition was fractionated and dropped therein. The state of dissolution in tap water was evaluated as follows. ：: Slowly disperses and dissolves uniformly within 1 minute △: Dissolution takes time but dissolves uniformly within 5 minutes ×: Gelled as it is dropped in water and elapses for 5 minutes Leaves a drop after

2) Evaluation of Detergency Terg-O-Tome of US Testing, USA
ter was used as a washing tester, and a wet-type artificial soil cloth (5c
m × 5 cm), 10 pieces, sebum cloth and clean knitted cloth, adjust the bath ratio to 30 times, 120 rpm at 15 ° C.
Washed for 0 minutes. The washing solution used is 900 mL with a detergent concentration of 0.067%, and the rinsing is performed with 900 ml of water.
Minutes. The water used was 3 ° DH. The detergency was calculated according to the following formula and evaluated according to the following criteria. Detergency (%) = (K / S of contaminated cloth−K / of cleaning cloth)
S) / (K / S of contaminated cloth−K / S of uncontaminated cloth) × 100
Here, K / S = (1−R / 100) ² / (2R / 10
0), R represents reflectance (%). The cleaning cloth is a contaminated cloth after cleaning, and the non-contaminated cloth is a cloth before artificial stain is attached. ◎: Detergency according to the above formula is 90% or more ○: Detergency is 80 to 90% △: Detergency is 70 to 80% ×: Detergency is less than 70%

[0068]

[Effect of the present invention] The liquid detergent composition of the present invention comprises:
By blending the components (A), (B) and (C) as essential components, for example, even in winter, problems such as gelation due to contact with low-temperature water and remaining undissolved are eliminated, and high cleaning is achieved. Have power. The liquid detergent composition of the present invention can be used for washing clothes and the like.

[0069]

[Table 3]

The composition of the perfume A for the detergent composition is as follows. Linalool 7 parts Citronellol 5 parts Lilyal 10 parts Methyldihydrojasmonate 10 parts Jasmacyclene 5 parts Hexylcinnamic aldehyde 12 parts Galaxolide 50 dipropylene glycol 10 parts Methylionone 7 parts Geraniol 3 parts Phenylethyl alcohol 10 parts Tonalid 10 parts Santalex 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 Dimethylbenzyl carvinyl acetate 10 parts Methyl naphthyl ketone 2 parts Phenylethyl isobutyrate 10 parts Piconia 5 parts Raspberry ketone 0.5 parts Damacenone 0.5 parts Phenylethyl Seteto 3-oxa-hexa decene-2-one 6.5 parts of Peach aldehyde 2 parts fur balsam 2 parts orange oil 3 parts

[0071]

[Table 4]

The composition of the perfume B for the above-mentioned detergent composition is as follows. Orange oil 10 parts Linalool 15 parts Linalyl acetate 10 parts Triplar 1 part Citronellol 8 parts Lemon oil 10 parts Lavender oil 5 parts Bakudanol 5 parts Kashmeran 3 parts Phenylethyl alcohol 25 parts Heliotropin 8 parts Dimethylbenzylcarbyl acetate 15 parts Raspberry ketone 2. 5 parts Benzyl acetate 5 parts Methyl dihydrojasmonate 11 parts Geranium oil 4 parts Lillal 8 parts Nerol 2 parts Geraniol 3 parts Citronellyl acetate 4 parts Tonalide 7 parts Belldox 5 parts Lutenex 9 parts Clove oil 3.5 parts Okemos absolute 1 part Geranyl acetate 5 parts Styralyl acetate 3 parts Benzyl benzoate 10 parts Octylaldehyde 0.7 parts Undecylenic aldehyde 1.3 parts

──────────────────────────────────────────────────続 き Continued on the front page (51) Int.Cl. ⁷ Identification symbol FI theme coat ゛ (Reference) C11D 3/37 C11D 3/37

Claims (3)

[Claims] (A) The following general formulas (I) and (II)
And at least one compound selected from the group consisting of terminal-blocking nonionic surfactants represented by the following formula (B):
And at least one selected from among alkanolamines represented by formula (I) and one or more selected from (C) hydrophilic organic compounds having two or more hydroxyl groups as essential components. Liquid detergent composition. 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 n _max : ethylene oxide adduct having the highest content (when m is not 0, an 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 R ⁵ —N—R ⁶ .R ⁷ (III) (wherein, R ⁵ is a hydroxyalkyl group having 1 to 4 carbon atoms,
R ⁶ and R ^{7 each} represent a hydrogen atom, a hydroxyalkyl group having 1 to 4 carbon atoms or an alkyl group having 1 to 4 carbon atoms) 2. The liquid detergent composition according to claim 1, wherein the hydrophilic organic compound (C) is a compound represented by the following general formula (IV). _{^{HO- (R 8 O) c -}} (R 9 O) d - in _{(R 10 O) e -H (} IV) ( wherein, c, d, e each a number of 0 or ^{more, R} 8 O,
R ⁹ O and R ¹⁰ O each represent an oxyethylene group or an oxypropylene group, and the weight-average molecular weight of the compound is 400 to 6000) 3. The fatty acid alkyl ester content in the component (A) is 2% by weight or less.
Or the liquid detergent composition according to 2. [0001]