JPWO2018056197A1 - Liquid cleaner - Google Patents

Abstract

The liquid detergent of the present invention comprises (A) component: nonionic surfactant, (B) component: anionic surfactant (but excluding higher fatty acid salt), and (C) component: the following general formula (c1) And B), the content of the component (B) is less than 50% by mass, and the mass ratio represented by the component (A) / (B) is less than 3. In the formula (c1), R31 to R33 each independently represent a hydrogen atom or an alkyl group having 1 to 3 carbon atoms, and R34 represents a hydrogen atom or an acetyl group.

Description

The present invention relates to liquid cleaners.
Priority is claimed on Japanese Patent Application No. 2016-185006, filed September 23, 2016, the content of which is incorporated herein by reference.

In recent years, with the increase in capacity and the like of washing machines, the frequency of washing with clothes and the like (to-be-washed objects) is increasing. Since the ratio of the to-be-washed matter with respect to the washing liquid is high in the nail-washing, the dirt concentration in the washing liquid tends to increase. Therefore, it is easy to cause recontamination that the dirt removed during cleaning adheres to the to-be-washed thing again.
Then, in order to improve the recontamination prevention property of a cleaning agent, the liquid cleaning agent which mix | blended the anionic surfactant is proposed (for example, patent document 1, 2).

JP, 2014-84432, A JP, 2015-1983859, A

By the way, when the sebum dirt etc. which are hard to fall adhere to a to-be-washed thing, a liquid detergent may be directly apply | coated and used for the dirt site | part of a to-be-washed thing.
However, when the proportion of the anionic surfactant in the liquid detergent is increased, the application detergency against stubborn stains such as mineral oil, machine oil, magic ink and the like may be lowered.

  The present invention has been made in view of the above circumstances, and it is an object of the present invention to provide a liquid cleaner which is excellent in anti-recontamination property and is also excellent in coating and cleaning properties.

The present invention has the following aspects.
[1] Component (A): nonionic surfactant, (B): anionic surfactant (but excluding higher fatty acid salt), and (C) component: represented by the following general formula (c1) A liquid detergent comprising an organic solvent, wherein the content of the component (B) is less than 50% by mass, and the mass ratio represented by the component (A) / (B) is less than 3.

In formula (c1), R ^{31 to} R ³³ each independently represent a hydrogen atom or an alkyl group having 1 to 3 carbon atoms, and R ³⁴ represents a hydrogen atom or an acetyl group.

[2] The liquid detergent according to [1], wherein the component (C) is 3-methoxy-3-methylbutanol.
[3] The component (A) contains two or more nonionic surfactants, and at least one of the two or more nonionic surfactants is an alkylene oxide adduct of a secondary alcohol or a branched chain. The liquid detergent according to [1] or [2], which is an alkylene oxide adduct of a primary alcohol.
[4] The liquid detergent according to [3], wherein the alkylene oxide adduct of the secondary alcohol is a compound represented by the following general formula (a2).
^{_{R 13 -O - [(EO)}} p / (PO) q] - (EO) r -H ··· (a2)
(In the formula (a2), R ¹³ is a hydrocarbon group having 6 to 22 carbon atoms derived from a secondary alcohol, EO represents an oxyethylene group, PO represents an oxypropylene group, and p is an average of EO It represents the number of repetitions, a number of 3 to 20, q represents the average number of repetitions of PO, is a number of 0 to 6, r represents the average number of repetitions of EO, and is a number of 0 to 20.)
[5] The liquid detergent according to [3] or [4], wherein the content of the alkylene oxide adduct of the secondary alcohol is 1 to 30% by mass.
[6] The liquid detergent according to [3], wherein the alkylene oxide adduct of the branched primary alcohol is a compound represented by the following general formula (a3).

  In formula (a3), EO represents an oxyethylene group, m represents an average number of repetition of EO, is a number of 3 to 10, and x and y each are a number of 1 to 7.

[7] The liquid detergent according to [3] or [6], wherein the content of the alkylene oxide adduct of the branched primary alcohol is 1 to 30% by mass.
[8] [1]-[7], wherein the component (B) contains one or more selected from the group consisting of linear alkyl benzene sulfonic acid or a salt thereof, and polyoxyalkylene alkyl ether sulfuric acid ester or a salt thereof The liquid detergent as described in any one.
[9] The component (B) contains linear alkyl benzene sulfonic acid or its salt (b1) and polyoxyalkylene alkyl ether sulfuric acid ester or its salt (b2), and is represented by (b2) / (b1) The liquid detergent as described in [8] whose mass ratio is 0.1-9.
[10] The liquid detergent according to any one of [1] to [9], wherein the content of the component (A) is 10 to 80% by mass.
[11] The liquid detergent according to any one of [1] to [10], wherein the content of the component (C) is 1 to 30% by mass.
[12] The liquid detergent according to any one of [1] to [11], wherein the total content of the components (A) and (B) is 15 to 80% by mass.
[13] The liquid detergent according to any one of [1] to [12], wherein the mass ratio represented by the (B) component / (C) component is 0.1 to 15.

  The liquid cleaning agent of the present invention is excellent in anti-soiling resistance and is also excellent in coating and cleaning properties.

Hereinafter, the present invention will be described in detail.
The liquid detergent of the present invention contains the following components (A), (B) and (C).
In the present invention, "ordinary cleaning" means that the object to be washed is cleaned with a washing machine or the like using a cleaning solution in which a liquid cleaning agent is dispersed in water, and "ordinary cleaning property" means that in normal cleaning. It is the washing power.
Further, "coating and cleaning" means that a liquid detergent is directly coated and washed on a material to be washed, and "coating and cleaning property" is the cleaning power in coating and cleaning.
Moreover, a "higher fatty acid salt" means a C8-C22 fatty acid salt.

<(A) component>
The component (A) is a nonionic surfactant. Component (A) may be produced by a conventional method, or a commercially available product may be used.
The nonionic surfactant may be any nonionic surfactant conventionally used in liquid detergents for clothing, etc. For example, alkylene oxide adducts such as polyoxyalkylene type nonionic surfactants, alkylphenols and higher amines Body, polyoxyethylene polyoxypropylene block copolymer, 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, alkylene of hydrogenated castor oil Oxide adducts, sugar fatty acid esters, N-alkyl polyhydroxy fatty acid amides, alkyl glycosides and the like can be mentioned. These nonionic surfactants may be used alone or in combination of two or more.

Among the above-mentioned nonionic surfactants, polyoxyalkylene type nonionic surfactants are preferable in view of viscosity and liquid stability.
As a polyoxyalkylene type nonionic surfactant, the compound (Hereinafter, it may be mentioned a "compound (a1).") Represented by the following general formula (a1) is mentioned.
R ¹¹ -X-[(EO) _s / (PO) _t ] -R ¹² (a1)

In formula (a1), R ¹¹ is a hydrocarbon group having 6 to 22 carbon atoms, X is a divalent linking group, R ¹² is a hydrogen atom, an alkyl group having 1 to 6 carbon atoms, or 2 to 2 carbon atoms 6 alkenyl groups, EO represents an oxyethylene group, PO represents an oxypropylene group, s represents an average repeat number of EO, is a number of 3 to 20, t represents an average repeat number of PO. , 0 to 6 numbers.

In the formula (a1), the carbon number of the hydrocarbon group of R ¹¹ is 6 to 22, preferably 8 to 22, and more preferably 10 to 18. The hydrocarbon group of R ¹¹ may be linear or branched, and may or may not have an unsaturated bond.
As -X-, -O-, -COO-, -CONH- and the like can be mentioned.
The carbon number of the alkyl group in R ¹² is 1 to 6, preferably 1 to 3.
The carbon number of the alkenyl group in R ¹² is 2 to 6, preferably 2 to 3.

-X- is -O -, - COO- or -CONH-, compound (a1) is a primary or secondary higher alcohols ^(R 11 -OH), higher fatty acid ^(R 11 -COOH) or higher It is obtained using fatty acid amide (R ¹¹ -CONH) as a raw material. ^{R 11} in these raw materials is the same as ^{R 11} in the formula (a1).

s is a number of 3 to 20 that represents the average number of repetitions of EO (that is, the average number of added moles of ethylene oxide), and is preferably 5 to 18. If the above upper limit is exceeded, the HLB value may become too high and the detergency against sebum may be reduced. If it is less than the said lower limit, there exists a possibility that deterioration of the raw material odor of (A) component itself may arise.
t is a number of 0 to 6 representing an average number of repetition of PO (i.e., an average number of moles of propylene oxide added), preferably 0 to 3. Above the upper limit, the liquid stability of the liquid detergent at high temperatures tends to decrease.

When t is 1 or more, that is, when the compound (a1) has EO and PO, the arrangement order of EO and PO may be mixed randomly or in block form regardless of the arrangement order of EO and PO. [(EO) _s / (PO) _t ] in the general formula (a1) means that EO and PO are mixed in a random or block shape. The addition method of ethylene oxide and propylene oxide is not particularly limited, and may be, for example, a random addition method or a block addition method. As a block addition method, for example, a method of adding propylene oxide after adding ethylene oxide, a method of adding ethylene oxide after adding propylene oxide, adding ethylene oxide, adding propylene oxide and further adding ethylene oxide The method to add etc. are mentioned.

The added mole number distribution of ethylene oxide or propylene oxide is not particularly limited.
The distribution of added moles tends to vary depending on the reaction method in producing the nonionic surfactant. For example, when ethylene oxide or propylene oxide is added to a hydrophobic base material using a common alkali catalyst such as sodium hydroxide or potassium hydroxide, the distribution of the molar number of ethylene oxide or propylene oxide added is relatively broad. Tend to be In addition, specific alkoxylations such as magnesium oxide to which metal ions such as Al ³⁺ , Ga ³⁺ , In ³⁺ , Tl ³⁺ , Co ³⁺ , Sc ³⁺ , La ³⁺ , and Mn ²⁺ are added as described in Japanese Patent Publication No. 6-15038. When ethylene oxide or propylene oxide is added to the hydrophobic base material by using a catalyst, the distribution of added moles of ethylene oxide or propylene oxide tends to be a relatively narrow distribution.

Especially as a compound (a1), the compound (for example, alcohol type nonionic surfactant) whose -X- is -O-, or -X- is -COO-, and R ¹² has 1 to 6 carbon atoms Compounds which are alkyl groups or alkenyl groups having 2 to 6 carbon atoms (e.g. fatty acid alkyl esters or fatty acid alkenyl esters) are preferred.

When -X- is -O-, the carbon number of R ¹¹ is preferably 10-22, more preferably 10-20, and still more preferably 10-18. R ¹² is preferably a hydrogen atom.

If -X- is ^-COO-, the carbon number of ^{R 11} is preferably 9 to 21, 11 to 21 is more preferable. R ¹² is preferably an alkyl group or an alkenyl group having 2 to 6 carbon atoms having 1 to 6 carbon atoms, more preferably an alkyl group having 1 to 3 carbon atoms.

  As a compound (a1) in which -X- is -O- or -COO-, for example, Diadol (trade name, C13 (C represents the number of carbon atoms, the same applies hereinafter)) manufactured by Mitsubishi Chemical Corporation, Shell Company 12 moles or 15 moles of ethylene oxide per mole of alcohol such as Neodol (trade name, a mixture of C12 and C13) and Sasol Safol 23 (trade name, a mixture of C12 and C13) Addition: 12 moles or 15 moles of ethylene oxide added to 1 mole of natural alcohol such as Procor & Gamble CO-1214 or CO-1270 (trade name); butene 3 7 moles of ethylene relative to 1 mole of C13 alcohol obtained by subjecting the C12 alkene obtained by quantification to the oxo method A product to which a hydroxide is added (trade name: Lutensol TO7, manufactured by BASF Corporation); a product to which 9 moles of ethylene oxide is added to 1 mol of C10 alcohol obtained by subjecting pentanol to a garbet reaction (trade name: Lutensol XP90 , BASF Corporation); 7 moles of ethylene oxide added to 1 mole of C10 alcohol obtained by subjecting pentanol to a garbet reaction (trade name: Lutensol XL70, manufactured by BASF); Those obtained by adding ethylene oxide equivalent to 6 moles to 1 mole of C10 alcohol obtained (trade name: Lutensol XA60, manufactured by BASF); 1 mole of secondary alcohol having 12 to 14 carbon atoms 9 mol equivalent or 15 mol equivalent A product obtained by adding tyrene oxide (trade name: Softanol 90, Softanol 150, manufactured by Nippon Shokubai Co., Ltd.); An alkoxylation catalyst is used to 1 mol of coconut fatty acid methyl (lauric acid / myristic acid = 8/2) What added ethylene oxide equivalent to 15 mol (polyoxyethylene coconut fatty-acid methyl ester (EO 15 mol)) etc. are mentioned.

As the compound (a1), among the above, compounds in which -X- is -COO-, R ¹² is an alkyl group having 1 to 6 carbon atoms, and t is 0, ie, a polyoxyethylene fatty acid alkyl ester Among them, polyoxyethylene fatty acid methyl ester (hereinafter sometimes referred to as MEE) in which R ¹² is a methyl group is particularly preferable.
By using polyoxyethylene fatty acid alkyl ester as the nonionic surfactant, the solubility of the liquid detergent in water is enhanced, and the detergency is improved. In addition, even if the content of the component (B) in the liquid detergent is increased, the viscosity does not significantly increase (gelation) and a concentrated liquid detergent having good fluidity can be obtained.
Polyoxyethylene fatty acid alkyl esters, in particular MEE, are nonionic surfactants in which the orientation of molecules is weak in aqueous solution systems and micelles are unstable. Therefore, it is presumed that the polyoxyethylene fatty acid alkyl ester does not cause gelation or the like at a high concentration, and the solubility in water can be enhanced even if one type alone is blended in a large amount in the liquid detergent. Therefore, when the liquid detergent containing the polyoxyethylene fatty acid alkyl ester is dispersed in water, the concentration of the polyoxyethylene fatty acid alkyl ester in the washing liquid quickly becomes uniform, and contacts the object to be washed at an arbitrary concentration from the initial stage of washing. Is considered to exert a high cleaning power.

  In the polyoxyethylene fatty acid alkyl ester, the narrow ratio indicating the distribution ratio of the compounds having different addition moles of ethylene oxide is preferably 20% by mass or more. The upper limit value of the narrow ratio is preferably substantially 80% by mass or less. The narrow ratio is more preferably 20 to 60% by mass. The higher the narrow ratio, the better the detergency. However, if the ratio is too high, the solution stability at low temperatures may be reduced, so the narrow ratio is more preferably 30 to 45% by mass.

  The narrow ratio of a polyoxyalkylene type nonionic surfactant such as polyoxyethylene fatty acid alkyl ester is a value determined by the following formula (S).

In the formula (S), S _max represents the number of added moles of alkylene oxide (value of s + t in the formula (a1)) in the alkylene oxide adduct which is most abundant in the polyoxyalkylene nonionic surfactant.
i represents the number of moles of alkylene oxide added.
Y i represents the proportion (% by mass) of the alkylene oxide adduct in which the addition mole number of the alkylene oxide present in the whole of the compound (a1) is i to the total mass of the compound (a1).

The narrow ratio can be controlled, for example, by the method for producing polyoxyethylene fatty acid alkyl ester.
The production method of the polyoxyethylene fatty acid alkyl ester is not particularly limited, but, for example, a method of addition polymerizing ethylene oxide to a fatty acid alkyl ester using a surface-modified composite metal oxide catalyst No. 2000-144179).
Preferred examples of the surface-modified composite metal oxide catalyst include metal ions (Al ³⁺ , Ga ³⁺ , In ³⁺ , Tl ³⁺ , Co ³⁺ which are surface-modified with, for example, a metal hydroxide or the like. , Complex metal oxide catalysts such as magnesium oxide to which Sc ³⁺ , La ³⁺ , Mn ²⁺ etc. are added, and catalysts of calcined hydrotalcites surface-modified with metal hydroxides and / or metal alkoxides etc. Can be mentioned.
In surface modification of the composite metal oxide catalyst, the ratio of metal hydroxide and / or metal alkoxide is preferably 0.5 to 10 parts by mass with respect to 100 parts by mass of the composite metal oxide, It is more preferable to set to 5 parts by mass.

  The method for producing the polyoxyethylene fatty acid alkyl ester is not limited to the method described above. For example, a polyoxyethylene fatty acid alkyl ester can be produced also by a method in which an alkylene oxide is added to a fatty acid alkyl ester by an alkoxylation catalyst prepared from a mixture of an alkaline earth metal compound and an oxy acid and the like. The above-mentioned alkoxylation catalyst is disclosed, for example, in Japanese Patent No. 049777609, International Publication No. 1993/004030, International Publication No. 2002/038269, International Publication No. 2012/028435, etc. For example, alkaline earth of carboxylic acid Examples thereof include alkoxylation catalysts prepared from a mixture of a metal salt and / or an alkaline earth metal salt of hydroxycarboxylic acid and sulfuric acid.

  By increasing the content of the component (A) in the liquid detergent, it is possible to wash the object with a small amount of the liquid detergent, and the container of the liquid detergent can be made compact. When the content of the component (A) in the liquid detergent is increased, the gelling region is small even at high concentration, and it is easy to mix, and as the component (A), a second alcohol obtained by adding ethylene oxide to the secondary alcohol Preferred are class alcohol ethoxylates (for example, softanol series manufactured by Nippon Shokubai Co., Ltd.) and MEE. Since these have a small gelled area even at high concentrations, gelation does not easily occur even if the content in the liquid detergent is increased.

As the component (A), one type may be used alone, or two or more types may be used in combination.
When the component (A) contains two or more types of nonionic surfactants, at least one of the two or more types of nonionic surfactants is a second component from the viewpoint of further improving the recontamination resistance and the coating cleaning properties. Alkylene oxide adducts of secondary alcohols or alkylene oxide adducts of branched primary alcohols are preferred. In particular, a combination of these adducts and a compound in which R ¹¹ in the formula (a1) is a linear hydrocarbon group is preferable, and a combination of these adducts and a polyoxyethylene fatty acid alkyl ester is more preferable, and these More preferred is a combination of an adduct and MEE.

Examples of alkylene oxide adducts of secondary alcohols include compounds represented by the following general formula (a2) (hereinafter sometimes referred to as "compound (a2)").
^{_{R 13 -O - [(EO)}} p / (PO) q] - (EO) r -H ··· (a2)

In formula (a2), R ¹³ is a hydrocarbon group having 6 to 22 carbon atoms derived from a secondary alcohol, EO represents an oxyethylene group, PO represents an oxypropylene group, and p is an average repetition of EO. It represents a number, is a number of 3 to 20, q represents an average number of repetitions of PO, is a number of 0 to 6, r represents an average number of repetitions of EO, and is a number of 0 to 20.

In the formula (a2), the carbon number of the hydrocarbon group of R ¹³ is 6 to 22, preferably 8 to 22, and more preferably 10 to 18.
R ¹³ is derived from a raw material alcohol (R ¹³ -OH), and the alcohol is a secondary alcohol.

p is a number of 3 to 20 representing an average number of repetition of EO (that is, an average added mole number of ethylene oxide), preferably 5 to 18.
q is a number of 0 to 6 that represents the average number of repetition of PO (that is, the average number of moles of propylene oxide added), preferably 0 to 3.
r is a number of 0 to 20 representing an average number of repetition of EO (that is, an average added mole number of ethylene oxide), and preferably 2 to 15.
When q is 1 or more, that is, when the compound (a2) has EO and PO, the arrangement order of EO and PO does not matter, and may be mixed randomly or in block. [(EO) _p / (PO) _q ] in general formula (a2) means that EO and PO are mixed in a random or block shape. The addition method of ethylene oxide and propylene oxide is not particularly limited, and examples thereof include the methods exemplified above in the description of compound (a1).

  Examples of the alkylene oxide adduct of a branched primary alcohol include a compound represented by the following general formula (a3) (hereinafter sometimes referred to as "compound (a3)").

  In formula (a3), EO represents an oxyethylene group, m represents an average number of repetition of EO, is a number of 3 to 10, and x and y each are a number of 1 to 7.

Examples of C _x H _{2x + 1} and C _y H _{2y + 1} in the formula (a3) include linear or branched alkyl groups, and both C _x H _{2x + 1} and C _y H _{2y + 1} are linear alkyl It is preferably a group. Preferred examples of C _x H _{2x + 1} and C _y H _{2y + 1} include a methyl group, an ethyl group, a propyl group, a butyl group, a pentyl group and a hexyl group. In particular, the combination of C _x H _{2x + 1} and C _y H _{2y + 1} is preferably a combination of ethyl and butyl or a combination of propyl and pentyl (in any combination, one is either May be).

  As the compound (a3), for example, one obtained by adding ethylene oxide to an alcohol (gerbet alcohol) obtained by a Garbett reaction can be used. For example, a branched primary alcohol obtained by treating a primary alcohol by a Gervet reaction can be used as the above-mentioned garbed alcohol. In the following description, the term "gerbet alcohol" means alcohol obtained by the garbet reaction. Here, "Gerbet reaction" refers to a reaction that "when primary alcohol is heated in the presence of metal sodium or metal potassium, causes bimolecular condensation to form a primary alcohol branched to the β position" See: "Large Organic Chemistry, Volume 2 Aliphatic Compounds I", supervised by Fujio Kotake, Asakura Shoten 1957). That is, the alcohol obtained by the Garbett reaction is represented by the following general formula (a4).

  In formula (a4), x and y each represent a number of 1 to 7.

  As the garbage alcohol, a branched primary alcohol having 8 to 12 carbon atoms is preferable. As such a garbage alcohol, a synthetic product may be used, or a commercially available product may be used. Examples of commercially available products include "ISOFOL12" (having 12 carbon atoms, x = 4 in the formula (a4), y = 6) manufactured by CONDEA.

  The content of the component (A) is preferably 10 to 80% by mass, more preferably 20 to 70% by mass, still more preferably 25 to 50% by mass, and further preferably 25 to 40% by mass with respect to the total mass of the liquid detergent. Particularly preferred. If the content of the component (A) is within the above range, it is easy to obtain a liquid detergent which is excellent in detergency against oily stains and excellent in liquid stability. In particular, if the content of the component (A) is equal to or more than the above lower limit value, high cleaning performance can be imparted to the liquid detergent. On the other hand, if content of (A) component is below the said upper limit, gelatinization will become difficult to occur and the stability of a liquid detergent will improve.

  When the component (A) contains a polyoxyethylene fatty acid alkyl ester, the content of the polyoxyethylene fatty acid alkyl ester is preferably 10 to 50% by mass, more preferably 15 to 50% by mass, based on the total mass of the liquid detergent. Preferably, 20 to 40% by mass is more preferable. If content of polyoxyethylene fatty acid alkyl ester is more than the above-mentioned lower limit, high washing performance can be exhibited. On the other hand, if content of polyoxyethylene fatty acid alkyl ester is below the said upper limit, film formation and gelatinization can be suppressed.

  When the component (A) contains an alkylene oxide adduct of a secondary alcohol, the content of the alkylene oxide adduct of the secondary alcohol is preferably 1 to 30% by mass with respect to the total mass of the liquid detergent, and 2 -20 mass% is more preferable, and 3-10 mass% is further more preferable. When the content of the alkylene oxide adduct of the secondary alcohol is equal to or more than the above lower limit value, high coating cleaning performance can be provided by the liquid detergent. On the other hand, when the content of the alkylene oxide adduct of the secondary alcohol is equal to or less than the above upper limit value, the increase in the viscosity of the liquid detergent can be further suppressed.

  When the component (A) contains an alkylene oxide adduct of a branched primary alcohol, the content of the alkylene oxide adduct of the branched primary alcohol is 1 to 30 based on the total mass of the liquid detergent. % By mass is preferable, 2 to 20% by mass is more preferable, and 3 to 10% by mass is more preferable. When the content of the alkylene oxide adduct of the branched primary alcohol is equal to or more than the above lower limit value, the liquid cleaning agent can impart high coating cleaning performance. On the other hand, if the content of the alkylene oxide adduct of the branched primary alcohol is less than or equal to the above upper limit, the increase in the viscosity of the liquid detergent can be further suppressed.

<(B) component>
The component (B) is an anionic surfactant (except for higher fatty acid salts). Component (B) may be produced by a conventional method, or a commercially available product may be used.
The anionic surfactant may be any anionic surfactant conventionally used for liquid detergents for clothing, etc. For example, linear alkyl benzene sulfonic acid or a salt thereof; α-olefin sulfonic acid or a salt thereof; Linear or branched alkyl sulfuric acid ester or salt thereof; polyoxyalkylene alkyl ether sulfuric acid ester or salt thereof; polyoxyalkylene alkenyl ether sulfuric acid ester or salt thereof; alkanesulfonic acid having alkyl group or salt thereof; Sulfo fatty acid esters or salts thereof; alkyl ether carboxylic acids or salts thereof, polyoxyalkylene ether carboxylic acids or salts thereof, alkyl amide ether carboxylic acids or salts thereof, alkenyl amide ether carboxylic acids or salts thereof, acyl amino carboxylic acids or salts thereof Etc. Carbo Acid type anionic surfactant; alkyl phosphate ester or salt thereof, polyoxyalkylene alkyl phosphate ester or salt thereof, polyoxyalkylene alkyl phenyl phosphate ester or salt thereof, glycerin fatty acid ester monophosphate ester or salt thereof or the like A phosphate ester type anionic surfactant etc. are mentioned.
Examples of the salt form of these anionic surfactants include alkali metal salts such as sodium and potassium; alkaline earth metal salts such as magnesium; and alkanolamine salts such as monoethanol ammonium and diethanol ammonium.

Among the above, as the linear alkylbenzene sulfonic acid or a salt thereof, a linear alkyl benzene sulfonic acid having 8 to 16 carbon atoms of a linear alkyl group or a salt thereof is preferable, and a linear alkyl group having 10 to 14 carbon atoms is preferable Particularly preferred are chain alkyl benzene sulfonic acids or salts thereof.
If the carbon number of the alkyl group is within the above range, the recontamination prevention can be improved. Examples of the alkyl group include decyl group, undecyl group, dodecyl group, tridecyl group and tetradecyl group.
A commercial item may be used as linear alkyl benzene sulfonic acid or its salt, and you may manufacture with a well-known synthetic method. As a known production method, it can be produced by a method of sulfonating alkylbenzene with sulfuric anhydride.

As an alpha-olefin sulfonic acid or its salt, a C10-C20 alpha-olefin sulfonic acid or its salt is preferable.
As an alkyl sulfate ester or its salt, a C10-C20 alkyl sulfate ester or its salt is preferable.

As a polyoxyalkylene alkyl ether sulfuric acid ester or a salt thereof, an alkyl ether sulfuric acid ester having a linear or branched alkyl group having 8 to 20 carbon atoms and having an average of 1 to 10 moles of ethylene oxide added or a salt thereof (I.e., polyoxyethylene alkyl ether sulfuric acid ester or a salt thereof) is preferable. In addition, any of alkylene oxides having 2 to 4 carbon atoms, or ethylene oxide and propylene oxide (molar ratio is ethylene oxide / propylene oxide = 0.1 / 9.9 to 9.9 / 0.1), the average is 0.5 to 0.5. Alkyl ether sulfuric acid ester having a linear or branched alkyl group having 8 to 20 carbon atoms or a salt thereof, to which 10 moles have been added is preferable.
The polyoxyalkylene alkyl ether sulfuric acid ester or a salt thereof is represented, for example, by the following general formula (b2).
R ²¹ -O-[(EO) _v / (PO) _w ] -SO ₃ ^- M ⁺ (B2)

In formula (b2), R ²¹ represents a linear or branched alkyl group having 8 to 20 carbon atoms, EO represents an oxyethylene group, PO represents an oxypropylene group, and v is an average repetition of EO. It represents a number, is a number of 0 or more, w represents an average number of repetitions of PO, is a number of 0 to 6, and 0 <v + w. M ⁺ is a counter cation.

The carbon number of R ²¹ is 8 to 20, preferably 10 to 20, and more preferably 12 to 14. Examples of R ²¹ include dodecyl, tridecyl and tetradecyl. Among these, dodecyl is preferable.
The average number of repetitions of EO is 0 or more, preferably 0.5 or more, and more preferably 1 or more. Moreover, 10 or less is preferable, 5 or less is more preferable, 3 or less is more preferable, and 1.5 or less is especially preferable.
0-3 are preferable and, as for the average repeating number of PO, 0 is more preferable.
Examples of M ⁺ include alkali metal ions such as sodium ion and potassium ion, alkaline earth metal ions such as magnesium ion, and cations derived from alkanolamines such as monoethanolamine and diethanolamine.
When v and w are 1 or more, that is, when the compound represented by the general formula (b2) has EO and PO, the arrangement order of EO and PO may be random, and may be mixed in block form. May be mixed. [(EO) _v / (PO) _w ] in the general formula (b2) means that EO and PO are mixed in a random or block shape. The addition method of ethylene oxide and propylene oxide is not particularly limited, and examples thereof include the methods exemplified above in the description of compound (a1).

Among the compounds represented by General Formula (b2), the polyoxyalkylene alkyl ether sulfuric acid ester or salt thereof particularly has a linear or branched alkyl group having 10 to 20 carbon atoms, and has an average of 1 to 10 moles It is preferable that (more preferably, 1 to 5 moles on average) of alkylene oxide be added.
By using a polyoxyalkylene alkyl ether sulfuric acid ester or a salt thereof as the component (B), denaturation of the enzyme by the anionic surfactant in the liquid detergent can be suppressed.
A commercial item may be used as polyoxyalkylene alkyl ether sulfuric acid ester or its salt, and you may manufacture with a well-known synthetic | combination method. As a known production method, polyoxyalkylene alkyl ether can be produced by a method of reacting sulfuric anhydride or a reaction of chlorosulfonic acid.

As polyoxyalkylene alkenyl ether sulfuric acid ester or a salt thereof, alkenyl ether sulfuric acid ester having a linear or branched alkenyl group having 8 to 20 carbon atoms and having an average of 1 to 10 moles of ethylene oxide added or a salt thereof (I.e., polyoxyethylene alkenyl ether sulfate or a salt thereof) is preferred. In addition, any of alkylene oxides having 2 to 4 carbon atoms, or ethylene oxide and propylene oxide (molar ratio is ethylene oxide / propylene oxide = 0.1 / 9.9 to 9.9 / 0.1), the average is 0.5 to 0.5. An alkenyl ether sulfuric acid ester having a linear or branched alkenyl group having 8 to 20 carbon atoms or a salt thereof to which 10 moles have been added is preferable.
The alkanesulfonic acid or a salt thereof includes alkanesulfonic acid having 10 to 20 carbon atoms or a salt thereof, preferably an alkanesulfonic acid having a carbon number of 14 to 17 or a salt thereof, and a secondary alkanesulfonic acid or a salt thereof Is particularly preferred.
As an alpha-sulfo fatty acid ester or its salt, a C10-C20 alpha-sulfo fatty acid ester salt is preferable.

These anionic surfactants are readily available in the market. Moreover, you may use what was synthesize | combined by the well-known method.
These anionic surfactants may be used alone or in combination of two or more.

  As the anionic surfactant, linear alkyl benzene sulfonic acid or a salt thereof, alkane sulfonic acid or a salt thereof, polyoxyalkylene alkyl ether sulfuric acid ester or a salt thereof (in particular, any of alkylene oxides having 2 to 4 carbon atoms, or ethylene oxide And propylene oxide (molar ratio of ethylene oxide / propylene oxide = 0.1 / 9.9 to 9.9 / 0.1), with an average of 0.5 to 10 moles added, linear or branched having 8 to 20 carbon atoms Alkyl ether sulfates having a linear alkyl group), polyoxyalkylene alkenyl ether sulfates or salts thereof (in particular, any of alkylene oxides having 2 to 4 carbon atoms, or ethylene oxide and propylene oxide (molar ratio is ethylene oxide / Propylene oxide = 0.1 / 9. An alkenyl ether sulfuric acid ester salt having a linear or branched alkenyl group having a carbon number of 8 to 20, to which an average of 0.5 to 10 moles of ̃9.9 / 0.1) is added, and an α-olefin sulfone At least one selected from the group consisting of an acid or a salt thereof is preferred. Among these, at least one selected from the group consisting of linear alkyl benzene sulfonic acid or a salt thereof, and polyoxyalkylene alkyl ether sulfuric acid ester or a salt thereof is more preferable.

  The content of the component (B) is less than 50% by mass, preferably 1 to 35% by mass, more preferably 3 to 25% by mass, and still more preferably 5 to 20% by mass, based on the total mass of the liquid detergent. 10 to 20% by mass is preferable. When the content of the component (B) is equal to or more than the above lower limit, the cleaning performance, particularly the application cleaning power, is further improved. On the other hand, if the content of the component (B) is less than the above upper limit value, the stability of the liquid detergent is improved.

  When the component (B) contains linear alkyl benzene sulfonic acid or its salt (b1) and polyoxyalkylene alkyl ether sulfate ester or its salt (b2), the mass ratio represented by (b2) / (b1) ((b)) Hereinafter, the “b2 / b1 ratio” is also preferably 0.1 to 9, more preferably 0.5 to 9, still more preferably 1.5 to 9, and particularly preferably 1 to 5. If the b2 / b1 ratio is equal to or more than the above lower limit value, the stability of the liquid detergent is further improved. On the other hand, if the b2 / b1 ratio is equal to or less than the above upper limit value, the recontamination prevention property is further improved.

  Further, the mass ratio represented by (A) component / (B) component (hereinafter also referred to as "A / B ratio") is less than 3, preferably 0.5 or more and less than 3, and 1 to 2.5. Is more preferable, and 1.5 to 2.5 is more preferable. When the A / B ratio is equal to or more than the above lower limit, the coating cleaning performance is further improved. On the other hand, if the A / B ratio is less than the above upper limit value, the recontamination prevention property and the normal washability are improved.

  Moreover, 15-80 mass% is preferable with respect to the total mass of a liquid detergent, and, as for the sum total of content of (A) component and (B) component, 30-70 mass% is more preferable, and 40-60 mass% is More preferable. If the sum total of content of (A) component and (B) component is more than the said lower limit, high application | coating cleaning performance can be exhibited. On the other hand, if the sum total of content of (A) component and (B) component is less than the said upper limit, film formation and gelatinization can be suppressed.

<(C) component>
The component (C) is an organic solvent represented by the following general formula (c1). Component (C) may be produced by a conventional method, or a commercially available product may be used.

In formula (c1), R ^{31 to} R ³³ each independently represent a hydrogen atom or an alkyl group having 1 to 3 carbon atoms, and R ³⁴ represents a hydrogen atom or an acetyl group.

As the component (C), 3-methoxybutanol, 3-methoxy-3-methylbutanol, 3-methoxy-3-ethylbutanol, 3-methoxy-3-propylbutanol, 3-methoxy-2-methylbutanol -3-methoxy-2-ethylbutanol, 3-methoxy-2-propylbutanol, 3-methoxy-1-methylbutanol, 3-methoxy-1-ethylbutanol, 3-methoxy-1-propylbutanol -, 3-methoxybutyl acetate, 3-methoxy-3-methylbutyl acetate, 3-methoxy-3-ethylbutyl acetate, 3-methoxy-3-propylbutyl acetate, 3-methoxy-2-methylbutyl acetate, 3 -Methoxy-2-ethyl butyl acetate, 3-methoxy-2-propyl butyl acetate, 3- Carboxymethyl-1-methyl-butyl acetate, 3-methoxy-1-ethyl butyl acetate, and 3-methoxy-1-propyl-butyl acetate. Among these, 3-methoxybutanol, 3-methoxy-3-methylbutanol, 3-methoxy-2-methylbutanol, 3-methoxy-1-methylbutanol and 3-methoxy-3-methylbutyl acetate are preferred, and 3-methoxy -3-Methyl butanol is more preferred.
As the component (C), one type may be used alone, or two or more types may be used in combination as appropriate.

  The content of the component (C) is preferably 1 to 30% by mass, more preferably 2 to 20% by mass, and still more preferably 3 to 10% by mass, with respect to the total mass of the liquid detergent. If content of (C) component is more than the said lower limit, gelatinization will be suppressed and the fluidity | liquidity of a liquid detergent will be easier to be maintained. In addition, coating and cleaning properties against ink stains are also improved. On the other hand, even if the content of the component (C) exceeds the above upper limit value, the flowability improving effect corresponding thereto can not be obtained, which is economically disadvantageous.

  Moreover, 0.1-15 are preferable, and, as for mass ratio (Hereafter, it is also mentioned "B / C ratio") represented by (B) component / (C) component, 1-10 are more preferable, and 2-5 are. More preferable. If B / C ratio is more than the said lower limit, high recontamination performance can be exhibited. On the other hand, if B / C ratio is below the said upper limit, high application | coating cleaning performance can be exhibited.

<Optional component>
The liquid detergent may contain components (optional components) other than the components (A), (B) and (C) as long as the effects of the present invention are not impaired.
The optional components include components generally used for liquid detergents, and examples thereof include water, higher fatty acids or salts thereof, cationic surfactants, amphoteric surfactants, component (C) and solvents other than water (other solvents (other solvents) ), Chelating agents, enzymes, hydrotropes (eg, polyethylene glycol, aromatic sulfonic acid or salts thereof), detersive builders, stabilizers, alkaline agents (eg, monoethanolamine, diethanolamine, triethanolamine etc.) Alkanolamines, etc.) Metal ion scavengers, texture improvers such as silicone, preservatives, fluorescent agents, dye transfer inhibitors, pearls, antioxidants, antibacterial agents, pigments or pigments generally used as colorants, emulsions Agents, perfumes, pH adjusters and the like.

(water)
The liquid detergent of the present invention preferably contains water as a solvent other than the component (C) from the viewpoint of ease of handling at the time of production, solubility in water at the time of use, and the like.
5-45 mass% is preferable with respect to the total mass of a liquid detergent, and, as for content of water, 10-40 mass% is more preferable. If the content of water is equal to or more than the above lower limit value, the fluidity and the stability can be favorably maintained. On the other hand, when the water content is equal to or less than the above upper limit value, the component (A), the component (B) and the component (C) can be contained in the liquid detergent in an optimum range.

(Higher fatty acids or their salts)
The higher fatty acid or the salt thereof is preferably a higher fatty acid having 10 to 20 carbon atoms or a salt thereof, such as caprylic acid, capric acid, lauric acid, myristic acid, palmitic acid, stearic acid, isostearic acid, hydroxystearic acid, Examples thereof include single fatty acids such as oleic acid and behenic acid or salts thereof, mixed fatty acids such as coconut oil fatty acids and beef tallow fatty acids or salts thereof.
Examples of salts of higher fatty acids include alkali metal salts such as sodium and potassium; alkaline earth metal salts such as magnesium; and alkanolamine salts such as monoethanol ammonium and diethanol ammonium.
These higher fatty acids or salts thereof may be used alone or in combination of two or more.

(Cationic surfactant)
The cationic surfactant may be any cationic surfactant conventionally used in liquid detergents for clothing, etc. For example, caprylic acid dimethylaminopropylamide, capric acid dimethylaminopropylamide, lauric acid dimethylamino Long-chain aliphatic amido alkyl tertiary amines or propylamino, propyl myristate dimethylaminopropylamide, palmitic acid dimethylaminopropylamide, stearic acid dimethylaminopropylamide, behenic acid dimethylaminopropylamide, oleic acid dimethylaminopropylamide, etc. Aliphatic ester alkyl tertiary amines such as palmitate ester propyldimethylamine, stearate ester propyldimethylamine or salts thereof; palmitic acid diethanolaminopropylamide, Stearic acid diethanol aminopropyl amide; alkyl trimethyl ammonium salts, dialkyl dimethyl ammonium salts, alkyl benzyl dimethyl ammonium salts, and quaternary compound such as an alkyl pyridinium salts.
Among these, long-chain aliphatic amidoalkyl tertiary amines or salts thereof are preferable, and caprylic acid dimethylaminopropylamide, caprylic acid dimethylaminopropylamide, lauric acid dimethylaminopropylamide, myristate dimethylaminopropylamide, palmitic acid dimethyl Aminopropylamide, stearic acid dimethylaminopropylamide, behenic acid dimethylaminopropylamide, oleic acid dimethylaminopropylamide or salts thereof are more preferred.
These cationic surfactants may be used alone or in combination of two or more.

(Ampholytic surfactant)
The amphoteric surfactant may be any amphoteric surfactant conventionally used in liquid detergents for clothing, etc. For example, alkylbetaine type, alkylamide betaine type, imidazoline type, alkylaminosulfonic acid type, Amphoteric surfactants such as alkylaminocarboxylic acid type, alkylamidocarboxylic acid type, amide amino acid type or phosphoric acid type can be mentioned.
These amphoteric surfactants may be used alone or in combination of two or more.

(Other solvents)
The other solvent may be any solvent conventionally used for liquid detergents for clothing, etc. For example, a C 2-4 monohydric alcohol, a C 2-4 polyhydric alcohol, glycol ether A system solvent is mentioned.
As a C2-C4 monohydric alcohol, ethanol, 1-propanol, 2-propanol, 1-butanol etc. are mentioned, for example.
As C2-C4 polyhydric alcohol, ethylene glycol, propylene glycol, butylene glycol, glycerol etc. are mentioned, for example.
As a glycol ether type solvent, General formula: R ^<41 >-(OR < ⁴² >) _uOH [In formula, R < ⁴¹ > is a C1-C6 alkyl group or a phenyl group. ^R42 is a C2-C4 alkylene group. u represents an average repeating number of ^{OR 42,} a number of 1-5. The compound represented by these is preferable, for example, ethylene glycol monobutyl ether, ethylene glycol monohexyl ether, ethylene glycol monophenyl ether, propylene glycol monophenyl ether, diethylene glycol monomethyl ether, diethylene glycol monobutyl ether and the like.

(Chelating agent)
The liquid detergent of the present invention may contain a chelating agent capable of chelating metal ions.
Chelating agents include organic chelating agents. Specifically, citric acid, lactic acid, tartaric acid, oxalic acid, malic acid, gluconic acid, nitrilotriacetic acid, iminodiacetic acid, ethylenediaminetetraacetic acid, diethylenetriaminepentaacetic acid, glycol ether Diamine tetraacetic acid, hydroxyethyl iminodiacetic acid, triethylene tetraamine hexaacetic acid, ethane-1,1-diphosphonic acid, ethane-1,1,2-triphosphonic acid, 1-hydroxyethane-1,1-diphosphonic acid, ethane Organic phosphonic acid derivatives such as hydroxy-1,1,2-triphosphonic acid, ethane-1,2-dicarboxy-1,2-diphosphonic acid, methanehydroxyphosphonic acid, aminotrimethylenephosphonic acid, ethylenediaminetetraxmethylenesulfonic acid Or salts thereof and the like. Among these, 1-hydroxyethane-1,1-diphosphonic acid and ethylenediaminetetraoxymethylenesulfonic acid are more preferable, and 1-hydroxyethane-1,1-diphosphonic acid is particularly preferable.

(enzyme)
If the liquid detergent contains an enzyme, the application cleaning property when the liquid detergent is directly applied to the object to be washed is further improved.
Examples of the enzyme include protease, amylase, lipase, cellulase, mannanase and the like.

As the protease, a protease having serine, histidine and aspartic acid in the molecule, such as serine protease, is preferable.
In general, preparations containing proteases (protease preparations) are commercially available. When preparing a liquid detergent, a protease is usually formulated using this protease preparation.
As a protease preparation, for example, trade names Savinase 16L, Savinase Ultra 16L, Savinase Ultra 16 XL, Everlase 16L Type EX, Everlase Ultra 16L, Esperase 8L, Alcalase 2.5L, Alcalase Ultra 2.5L, Licanase 2.5L available from Novozymes. Liquanase Ultra 2.5 L, Liquanase Ultra 2.5 XL, Coronase 48 L; trade names Purafect L, Purafect OX, Properase L available from Genencor, and the like.

As the amylase preparation, for example, trade name Termamyl 300L, trade name Ultramil 300L, Duramyl 300L, Stainzyme 12L, Stainzyme Plus 12L available from Novozymes; trade name Maxamyl available from Genencor, trade name Pululanase available from Amano Enzyme Co., Ltd. Amano; DB-250 available from Seikagaku Corporation, and the like.
As a lipase preparation, the brand name Lipex 100L, Lipolase 100L etc. which can be obtained from Novozymes are mentioned, for example.
As the cellulase preparation, for example, Carezyme 4500 L (trade name, manufactured by Novozymes), Carezyme Premium 4500 L (trade name, manufactured by Novozymes), Endolase 5000 L (trade name, manufactured by Novozymes), Cell Clean 4500 T (trade name, Novozymes) Company company).
Examples of mannanase preparations include, for example, trade name Mannaway 4L available from Novozymes.
The above enzymes may be used alone or in combination of two or more.

  The content of the enzyme is preferably 0.1 to 3% by mass based on the total mass of the liquid detergent as an enzyme preparation.

In addition, the sum total of content of (A) component, (B) component, and (C) component contained in a liquid detergent shall not exceed 100 mass% with respect to the total mass of a liquid detergent. When the liquid detergent contains water and optional components, the total content of (A) component, (B) component, (C) component, water and optional components contained in the liquid detergent is the total of the liquid detergent. It shall not exceed 100% by mass with respect to the mass.
In addition, the total content of all the components contained in the liquid detergent is 100% by mass.

<Manufacturing method>
The liquid detergent according to the present invention dissolves, for example, the components (A), (B) and (C), and optional components as needed, in water, and as necessary, adjusts the pH For example, it can manufacture by adjusting to predetermined | prescribed pH using a monoethanolamine, a diethanolamine, a triethanolamine, sodium hydroxide, potassium hydroxide etc.).

<PH>
5-9 are preferable and, as for pH at 25 degreeC of the liquid detergent of this invention, 6-8 are more preferable.
If the pH of the liquid detergent at 25 ° C. is within the above range, the storage stability of the liquid detergent is better maintained.
In the present invention, the pH of the liquid detergent is a liquid detergent adjusted to 25 ° C. and shows a value measured by a pH meter or the like.

<Function effect>
In the liquid cleaner of the present invention described above, by combining the components (A) and (B) and the component (C) in a specific mass ratio, the recontamination prevention property is excellent, and the coating and cleaning properties are also excellent. It is good. In addition, the liquid detergent of the present invention is generally good in terms of washability.
The liquid detergent of the present invention is suitable as a liquid detergent for clothes.

The method of using the liquid detergent is, for example, a method of putting the liquid detergent into the water together with the article to be washed in washing (usually washing), a liquid detergent aqueous solution prepared by previously dissolving the liquid detergent in water The method etc. which immerse a to-be-washed thing are mentioned. Alternatively, the liquid detergent may be applied directly to the object to be washed and left for a certain period of time, and then normal washing may be performed (application washing).
Examples of the material to be washed include, for example, textiles such as clothes, cloths, towels and sheets.
When the liquid detergent is dissolved in water and used, for example, it is preferable to dilute by 5 to 5000 times (volume basis).

As another aspect of the present invention,
Component (A): a nonionic surfactant comprising a compound represented by the following general formula (a1) and a compound represented by the following general formula (a2) or a compound represented by the following general formula (a3),
Component (B): An anionic surfactant (but excluding higher fatty acid salts)
Component (C): an organic solvent represented by the following general formula (c1),
water and,
If desired, a component acceptable as a liquid detergent
Contains
The content of the component (B) is less than 50% by mass with respect to the total mass of the liquid detergent,
The liquid detergent whose mass ratio represented by (A) component / (B) component is less than three.
R ¹¹ -X-[(EO) _s / (PO) _t ] -R ¹² (a1)
In formula (a1), R ¹¹ is a hydrocarbon group having 6 to 22 carbon atoms, X is a divalent linking group, R ¹² is a hydrogen atom, an alkyl group having 1 to 6 carbon atoms, or 2 carbon atoms EO represents an oxyethylene group, PO represents an oxypropylene group, s represents an average repeat number of EO, is a number of 3 to 20, and t represents an average repeat number of PO. Represents a number from 0 to 6.)
_{^{R 13 -O - [(EO)}} p / (PO) q] - (EO) r -H ··· (a2)
(In the formula (a2), R ¹³ is a hydrocarbon group having 6 to 22 carbon atoms derived from a secondary alcohol, EO represents an oxyethylene group, PO represents an oxypropylene group, and p is an average of EO It represents the number of repetitions, a number of 3 to 20, q represents the average number of repetitions of PO, is a number of 0 to 6, r represents the average number of repetitions of EO, and is a number of 0 to 20.)

  In formula (a3), EO represents an oxyethylene group, m represents an average number of repetition of EO, is a number of 3 to 10, and x and y each are a number of 1 to 7.

In formula (c1), R ^{31 to} R ³³ each independently represent a hydrogen atom or an alkyl group having 1 to 3 carbon atoms, and R ³⁴ represents a hydrogen atom or an acetyl group.

As another aspect of the present invention,
(A) Component: nonionic surfactant,
(B) Component: An anionic surfactant (but excluding higher fatty acid salts) containing linear alkyl benzene sulfonic acid or its salt (b1) and polyoxyalkylene alkyl ether sulfuric acid ester or its salt (b2)
Component (C): an organic solvent represented by the above general formula (c1),
water and,
If desired, a component acceptable as a liquid detergent
Contains
The content of the component (B) is less than 50% by mass with respect to the total mass of the liquid detergent,
The liquid detergent whose mass ratio represented by (A) component / (B) component is less than three.

As another aspect of the present invention,
(A) Component: nonionic surfactant,
Component (B): An anionic surfactant (but excluding higher fatty acid salts)
Component (C): selected from the group consisting of 3-methoxybutanol, 3-methoxy-3-methylbutanol, 3-methoxy-2-methylbutanol, 3-methoxy-1-methylbutanol, 3-methoxy-3-methylbutyl acetate One or more organic solvents
water and,
If desired, a component acceptable as a liquid detergent
Contains
The content of the component (B) is less than 50% by mass with respect to the total mass of the liquid detergent,
The liquid detergent whose mass ratio represented by (A) component / (B) component is less than three.

As another aspect of the present invention,
Component (A): a nonionic surfactant comprising a compound represented by the general formula (a1) and a compound represented by the general formula (a2) or a compound represented by the general formula (a3),
(B) Component: An anionic surfactant (but excluding higher fatty acid salts) containing linear alkyl benzene sulfonic acid or its salt (b1) and polyoxyalkylene alkyl ether sulfuric acid ester or its salt (b2)
Component (C): selected from the group consisting of 3-methoxybutanol, 3-methoxy-3-methylbutanol, 3-methoxy-2-methylbutanol, 3-methoxy-1-methylbutanol, 3-methoxy-3-methylbutyl acetate One or more organic solvents
water and,
If desired, a component acceptable as a liquid detergent
Contains
The content of the component (B) is less than 50% by mass with respect to the total mass of the liquid detergent,
The liquid detergent whose mass ratio represented by (A) component / (B) component is less than three.

As another aspect of the present invention,
Component (A): a polyoxyethylene fatty acid methyl ester in which -X- is -COO-, R ¹² is a methyl group, and t is 0 in the general formula (a1), and the general formula (a2) A nonionic surfactant comprising a compound represented by the formula: or a compound represented by the above general formula (a3);
(B) Component: An anionic surfactant (but excluding higher fatty acid salts) containing linear alkyl benzene sulfonic acid or its salt (b1) and polyoxyalkylene alkyl ether sulfuric acid ester or its salt (b2)
Component (C): an organic solvent containing 3-methoxy-3-methylbutanol
water and,
If desired, a component acceptable as a liquid detergent
Contains
The content of the component (B) is less than 50% by mass with respect to the total mass of the liquid detergent,
The liquid detergent whose mass ratio represented by (A) component / (B) component is less than three.

As another aspect of the present invention,
(A) Component: nonionic surfactant,
Component (B): An anionic surfactant (but excluding higher fatty acid salts)
Component (C): an organic solvent represented by the above general formula (c1),
water and,
If desired, a component acceptable as a liquid detergent
Contains
The content of the component (A) is 10 to 80% by mass, the content of the component (B) is less than 50% by mass, and the content of the component (C) is 1 with respect to the total mass of the liquid detergent And 30% by mass, and the total content of each component does not exceed 100% by mass,
The liquid detergent whose mass ratio represented by (A) component / (B) component is less than three.

As another aspect of the present invention,
(A) Component: nonionic surfactant,
Component (B): An anionic surfactant (but excluding higher fatty acid salts)
Component (C): an organic solvent represented by the above general formula (c1),
water and,
If desired, a component acceptable as a liquid detergent
Contains
The content of the component (A) is 25 to 50% by mass, the content of the component (B) is 1 to 35% by mass, and the content of the component (C) is relative to the total mass of the liquid detergent 3 to 10% by mass, and the total content of each component does not exceed 100% by mass,
The liquid detergent whose mass ratio represented by (A) component / (B) component is 1-2.5.

As another aspect of the present invention,
(A) Component: nonionic surfactant,
Component (B): An anionic surfactant (but excluding higher fatty acid salts)
Component (C): an organic solvent represented by the above general formula (c1),
water and,
If desired, a component acceptable as a liquid detergent
Contains
The content of the component (A) is 10 to 80% by mass, the content of the component (B) is less than 50% by mass, and the content of the component (C) is 1 with respect to the total mass of the liquid detergent The total content of the components (A) and (B) is 15 to 80% by mass, and the total content of the respective components does not exceed 100% by mass,
The liquid detergent whose mass ratio represented by (A) component / (B) component is less than three.

As another aspect of the present invention,
(A) Component: nonionic surfactant,
Component (B): An anionic surfactant (but excluding higher fatty acid salts)
Component (C): an organic solvent represented by the above general formula (c1),
water and,
If desired, a component acceptable as a liquid detergent
Contains
The content of the component (A) is 10 to 80% by mass, the content of the component (B) is less than 50% by mass, and the content of the component (C) is 1 with respect to the total mass of the liquid detergent And 30% by mass, and the total content of each component does not exceed 100% by mass,
The liquid detergent whose mass ratio represented by (A) component / (B) component is less than 3, and mass ratio represented by (B) component / (C) component is 0.1-15.

As another aspect of the present invention,
(A) Component: nonionic surfactant,
Component (B): An anionic surfactant (but excluding higher fatty acid salts)
Component (C): an organic solvent represented by the above general formula (c1),
water and,
If desired, a component acceptable as a liquid detergent
Contains
The content of the component (A) is 10 to 80% by mass, the content of the component (B) is less than 50% by mass, and the content of the component (C) is 1 with respect to the total mass of the liquid detergent The total content of the components (A) and (B) is 15 to 80% by mass, and the total content of the respective components does not exceed 100% by mass,
The liquid detergent whose mass ratio represented by (A) component / (B) component is less than 3, and mass ratio represented by (B) component / (C) component is 0.1-15.

As another aspect of the present invention,
(A) Component: nonionic surfactant,
Component (B): An anionic surfactant (but excluding higher fatty acid salts)
Component (C): an organic solvent represented by the above general formula (c1),
water and,
If desired, a component acceptable as a liquid detergent
Contains
The content of the component (A) is 25 to 50% by mass, the content of the component (B) is 1 to 35% by mass, and the content of the component (C) is relative to the total mass of the liquid detergent It is 3 to 10% by mass, the total of the contents of the components (A) and (B) is 30 to 70% by mass, and the total of the contents of the respective components does not exceed 100% by mass,
The liquid detergent whose mass ratio represented by (A) component / (B) component is 1-2.5, and mass ratio represented by (B) component / (C) component is 2-5.

As another aspect of the present invention,
Component (A): a nonionic surfactant comprising a compound represented by the general formula (a1) and a compound represented by the general formula (a2) or a compound represented by the general formula (a3),
(B) Component: An anionic surfactant (but excluding higher fatty acid salts) containing linear alkyl benzene sulfonic acid or its salt (b1) and polyoxyalkylene alkyl ether sulfuric acid ester or its salt (b2)
Component (C): selected from the group consisting of 3-methoxybutanol, 3-methoxy-3-methylbutanol, 3-methoxy-2-methylbutanol, 3-methoxy-1-methylbutanol, 3-methoxy-3-methylbutyl acetate One or more organic solvents
water and,
If desired, a component acceptable as a liquid detergent
Contains
The content of the component (A) is 10 to 80% by mass, the content of the component (B) is less than 50% by mass, and the content of the component (C) is 1 with respect to the total mass of the liquid detergent And 30% by mass, and the total content of each component does not exceed 100% by mass,
The liquid detergent whose mass ratio represented by (A) component / (B) component is less than three.

As another aspect of the present invention,
Component (A): a nonionic surfactant comprising a compound represented by the general formula (a1) and a compound represented by the general formula (a2) or a compound represented by the general formula (a3),
(B) Component: An anionic surfactant (but excluding higher fatty acid salts) containing linear alkyl benzene sulfonic acid or its salt (b1) and polyoxyalkylene alkyl ether sulfuric acid ester or its salt (b2)
Component (C): selected from the group consisting of 3-methoxybutanol, 3-methoxy-3-methylbutanol, 3-methoxy-2-methylbutanol, 3-methoxy-1-methylbutanol, 3-methoxy-3-methylbutyl acetate One or more organic solvents
water and,
If desired, a component acceptable as a liquid detergent
Contains
The content of the component (A) is 25 to 50% by mass, the content of the component (B) is 1 to 35% by mass, and the content of the component (C) is relative to the total mass of the liquid detergent 3 to 10% by mass, and the total content of each component does not exceed 100% by mass,
The liquid detergent whose mass ratio represented by (A) component / (B) component is 1-2.5.

As another aspect of the present invention,
Component (A): a nonionic surfactant comprising a compound represented by the general formula (a1) and a compound represented by the general formula (a2) or a compound represented by the general formula (a3),
(B) Component: An anionic surfactant (but excluding higher fatty acid salts) containing linear alkyl benzene sulfonic acid or its salt (b1) and polyoxyalkylene alkyl ether sulfuric acid ester or its salt (b2)
Component (C): selected from the group consisting of 3-methoxybutanol, 3-methoxy-3-methylbutanol, 3-methoxy-2-methylbutanol, 3-methoxy-1-methylbutanol, 3-methoxy-3-methylbutyl acetate One or more organic solvents
water and,
If desired, a component acceptable as a liquid detergent
Contains
The content of the component (A) is 10 to 80% by mass, the content of the component (B) is less than 50% by mass, and the content of the component (C) is 1 with respect to the total mass of the liquid detergent The total content of the components (A) and (B) is 15 to 80% by mass, and the total content of the respective components does not exceed 100% by mass,
The liquid detergent whose mass ratio represented by (A) component / (B) component is less than three.

As another aspect of the present invention,
Component (A): a nonionic surfactant comprising a compound represented by the general formula (a1) and a compound represented by the general formula (a2) or a compound represented by the general formula (a3),
(B) Component: An anionic surfactant (but excluding higher fatty acid salts) containing linear alkyl benzene sulfonic acid or its salt (b1) and polyoxyalkylene alkyl ether sulfuric acid ester or its salt (b2)
Component (C): selected from the group consisting of 3-methoxybutanol, 3-methoxy-3-methylbutanol, 3-methoxy-2-methylbutanol, 3-methoxy-1-methylbutanol, 3-methoxy-3-methylbutyl acetate One or more organic solvents
water and,
If desired, a component acceptable as a liquid detergent
Contains
The content of the component (A) is 10 to 80% by mass, the content of the component (B) is less than 50% by mass, and the content of the component (C) is 1 with respect to the total mass of the liquid detergent And 30% by mass, and the total content of each component does not exceed 100% by mass,
The mass ratio represented by (A) component / (B) component is less than 3, and the mass ratio represented by (B) component / (C) component is 0.1 to 15, (b2) / ( The liquid detergent whose mass ratio represented by b1) is 0.1-9.

As another aspect of the present invention,
Component (A): a nonionic surfactant comprising a compound represented by the general formula (a1) and a compound represented by the general formula (a2) or a compound represented by the general formula (a3),
(B) Component: An anionic surfactant (but excluding higher fatty acid salts) containing linear alkyl benzene sulfonic acid or its salt (b1) and polyoxyalkylene alkyl ether sulfuric acid ester or its salt (b2)
Component (C): selected from the group consisting of 3-methoxybutanol, 3-methoxy-3-methylbutanol, 3-methoxy-2-methylbutanol, 3-methoxy-1-methylbutanol, 3-methoxy-3-methylbutyl acetate One or more organic solvents
water and,
If desired, a component acceptable as a liquid detergent
Contains
The content of the component (A) is 10 to 80% by mass, the content of the component (B) is less than 50% by mass, and the content of the component (C) is 1 with respect to the total mass of the liquid detergent The total content of the components (A) and (B) is 15 to 80% by mass, and the total content of the respective components does not exceed 100% by mass,
The mass ratio represented by (A) component / (B) component is less than 3, and the mass ratio represented by (B) component / (C) component is 0.1 to 15, (b2) / ( The liquid detergent whose mass ratio represented by b1) is 0.1-9.

As another aspect of the present invention,
Component (A): a polyoxyethylene fatty acid methyl ester in which -X- is -COO-, R ¹² is a methyl group, and t is 0 in the general formula (a1), and the general formula (a2) A nonionic surfactant comprising a compound represented by the formula: or a compound represented by the above general formula (a3);
(B) Component: An anionic surfactant (but excluding higher fatty acid salts) containing linear alkyl benzene sulfonic acid or its salt (b1) and polyoxyalkylene alkyl ether sulfuric acid ester or its salt (b2)
Component (C): an organic solvent containing 3-methoxy-3-methylbutanol
water and,
If desired, a component acceptable as a liquid detergent
Contains
The content of the component (A) is 25 to 50% by mass, the content of the component (B) is 1 to 35% by mass, and the content of the component (C) is relative to the total mass of the liquid detergent It is 3 to 10% by mass, the total of the contents of the components (A) and (B) is 30 to 70% by mass, and the total of the contents of the respective components does not exceed 100% by mass,
The mass ratio represented by (A) component / (B) component is 1 to 2.5, and the mass ratio represented by (B) component / (C) component is 2 to 5, (b2) / The liquid detergent whose mass ratio represented by (b1) is 0.5-9.

  Hereinafter, the present invention will be described in detail by way of examples, but the present invention is not limited by the following description. In addition, the compounding quantity of the component used in each case is a pure part conversion value unless there is particular notice.

"Used raw materials"
The following compounds were used as the component (A).
A-1: A mixture of methyl ethylene carbonate (a mixture of methyl laurate / methyl myristate = 8/2 by mass ratio) and ethylene oxide equivalent to 15 moles using an alkoxylation catalyst (polyoxyethylene fatty acid methyl) Ester (MEE)). In the above general formula (a1), R ¹¹ = a linear alkyl group having 11 carbon atoms and a linear alkyl group having 13 carbon atoms, R ¹² = methyl group, -X- is -COO-, s = 15 , T = 0, narrow rate 33%. Those synthesized by the following synthesis method.
A-2: A secondary alcohol having 12 to 14 carbon atoms, to which 7 moles of ethylene oxide are added (manufactured by Nippon Shokubai Co., Ltd., trade name “Softanol 70”). In the above general formula (a2), R ¹³ = a branched alkyl group having 12 to 14 carbon atoms, p = 7, q = 0, r = 0.
A-3: C12 alcohol obtained by subjecting C12 alkene obtained by trimerizing butene to the oxo method to which 10 moles of ethylene oxide is added (C13 oxo alcohol ethoxylate), (manufactured by BASF AG) , Brand name "Lutensol TO10"). In the above general formula (a3), x + y = 11, m = 10.
A-4: natural alcohol having 12 and 14 carbon atoms (primary alcohol) added with 15 moles of ethylene oxide (polyoxyethylene alkyl ether (LMAO)). Those synthesized by the following synthesis method.

(Method of synthesizing A-1)
A-1 was synthesized according to the synthesis method described in JP-A-2000-144179 as follows.
Firing an alumina and magnesium hydroxide (made by Kyowa Chemical Industry Co., Ltd., trade name “Kyoward 300”) having a composition of 2.5MgO · Al ₂ O ₃ · wH ₂ O at 600 ° C. for 1 hour in a nitrogen atmosphere Thus, a calcined alumina / magnesium hydroxide (unmodified) catalyst was obtained. An autoclave is charged with 2.2 g of a calcined alumina / magnesium hydroxide (unmodified) catalyst, 2.9 mL of a 0.5 N potassium hydroxide ethanol solution, 280 g of lauric acid methyl ester, and 70 g of myristic acid methyl ester in a 4 L autoclave. The catalyst was reformed inside. Next, after replacing the inside of the autoclave with nitrogen, 1052 g of ethylene oxide was introduced while maintaining the temperature at 180 ° C. and the pressure at 0.3 MPa, and reaction was carried out while stirring.
The resulting reaction solution was cooled to 80 ° C., 159 g of water and 5 g of activated clay and 5 g of diatomaceous earth as a filter aid were added and mixed, and then the catalyst was separated by filtration to obtain A-1.

The narrow ratio of A-1 was measured by the following procedure.
Under the following measurement conditions, the distribution of ethylene oxide adducts different in addition mole number of ethylene oxide was measured, and the narrow ratio (mass%) was calculated by the above-mentioned numerical formula (S).
[Conditions for measuring distribution of ethylene oxide adducts by HPLC]
-Device: LC-6A (manufactured by Shimadzu Corporation).
Detector: SPD-10A.
-Measurement wavelength: 220 nm.
Column: Zorbax C8 (manufactured by Du Pont Co., Ltd.).
Mobile phase: acetonitrile / water = 60/40 (volume ratio).
Flow rate: 1 mL / min.
Temperature: 20 ° C.

(Method of synthesizing A-4)
861.2 g of CO-1214 (trade name) manufactured by Procter & Gamble Co., Ltd. and 2.0 g of a 30% by mass aqueous solution of NaOH were charged in a pressure resistant reaction vessel, and the inside of the reaction vessel was purged with nitrogen. Next, after dehydrating at a temperature of 100 ° C. and a pressure of 2.0 kPa or less for 30 minutes, the temperature was raised to 160 ° C. Then, 760.6 g of ethylene oxide (gaseous) was gradually added to the reaction solution while stirring the reaction solution. At this time, ethylene oxide was added by a blow-in tube while controlling the addition rate so that the reaction temperature did not exceed 180 ° C.
After completion of the addition of ethylene oxide, the mixture was aged for 30 minutes at a temperature of 180 ° C. and a pressure of 0.3 MPa or less, and then unreacted ethylene oxide was distilled off for 10 minutes at a temperature of 180 ° C. and a pressure of 6.0 kPa or less.
Next, after cooling the temperature to 100 ° C. or less, 70% by mass p-toluenesulfonic acid is added to neutralize so that the pH of a 1% by mass aqueous solution of the reaction product becomes about 7, to obtain A-4. The

The compounds shown below were used as the component (B).
-B-1: Linear alkyl benzene sulfonic acid (LAS), (The Lion Corporation make, brand name "Lipon LH-200").
B-2: Polyoxyalkylene alkyl ether sulfate (AES), (a mixture of sodium polyoxyethylene lauryl ether sulfate and sodium polyoxyethylene myristyl ether sulfate, average added mole number of EO: 1).

The compound shown below was used as (C) component.
C-1: 3-methoxy-3-methylbutanol (manufactured by Kuraray Co., Ltd., trade name "Solfit"). In the above general formula (c1), R ³¹ = methyl group, R ³² = hydrogen atom, R ³³ = hydrogen atom, R ³⁴ = hydrogen atom.

The following compounds were used as optional components.
-Yuzu fatty acid: manufactured by NOF Corporation, trade name "coconut fatty acid".
-Ethanol (water-miscible organic solvent): manufactured by Japan Alcohol Sales Co., Ltd., trade name "specific alcohol 95 degree synthesis".
-PPG4000: polyoxypropylene glyceryl ether (Mitsui Chemical Co., Ltd. make, brand name "Actocol T-4000", mass mean molecular weight 4000).
PTSH: para-toluenesulfonic acid (manufactured by Kyowa Hakko Kogyo Co., Ltd., trade name "PTS acid").
Sodium lactate (enzyme stabilizer): manufactured by Kanto Chemical Co., Ltd., trade name "sodium lactate".
MGDA: methylglycine diacetate trisodium (BASF company, trade name "Trilon M Liquid").
Calcium chloride (enzyme stabilizer): manufactured by Kanto Chemical Co., Ltd., trade name "calcium chloride".
-Sodium benzoate (preservative): manufactured by Toagosei Co., Ltd., trade name "sodium benzoate".
-Perfume (flavoring agent): Perfume composition A described in Tables 11 to 18 of JP-A-2002-146399.
SR agent: soil release polymer (manufactured by Clariant Japan Co., Ltd., trade name "TexCare SRN-170C", weight average molecular weight: 2000 to 3000, pH (5% by mass aqueous solution at 20 ° C): 4, viscosity (20 ° C): 300 mPa · s). TexCare SRN-170C is a 70% by weight aqueous solution of TexCare SRN-100 (trade name: manufactured by Clariant Japan, weight average molecular weight: 2000 to 3000) under the trade name.
HP-20: ethylene oxide adduct of polyethyleneimine (manufactured by BASF, trade name "Sokalan HP20").
Sodium hydroxide: manufactured by Tsurumi Soda Co., Ltd., trade name "sodium hydroxide".
-Dichrosan (antibacterial agent): 4,4'-dichloro-2-hydroxydiphenyl ether (manufactured by BASF, trade name "Tinosan HP100").
Alcalase (enzyme): manufactured by Novozymes, trade name "Alcalase 2.5 L".
-Dye (coloring agent): made by Tsubaki Kasei Co., Ltd., trade name "Green No. 3".
MEA (alkaline agent): monoethanolamine (manufactured by Nippon Shokubai Co., Ltd., trade name "Monoethanolamine").
Purified water: manufactured by Kanto Chemical Co., Ltd.

"Examples 1 to 9, Comparative Examples 1 and 2"
<Preparation of Liquid Detergent>
Sodium hydroxide after adding and mixing (A) component, (B) component, (C) component and optional components (excluding sodium hydroxide and MEA) according to the composition shown in Tables 1 and 2 The pH of the mixture at 25 ° C. was adjusted to 7 using and MEA to prepare a liquid detergent. In addition, the pH meter (Toa DK company product name "HM-30G") was used for the measurement of pH.
With respect to the liquid detergents of the respective examples obtained, the recontamination prevention property, the application cleaning property and the normal cleaning property were evaluated as follows. The results are shown in Tables 1 and 2.

<Evaluation>
(Evaluation of recontamination prevention)
Using the liquid detergent of each example, the washing process shown below was repeated three times in the order of washing, rinsing and drying steps. In addition, the following cotton cloth, polyester (PE) cloth, a wet artificial soiling cloth, and a skin shirt were used as a to-be-washed thing.
Cotton cloth: 5 pieces of 5 cm x 5 cm cotton knitwear (made by Tanigami Store) as a recontamination judgment cloth.
PE cloth: 5 sheets of 5 x 5 cm of polyester tropical (made by Tanigami Store) as a recontamination judgment cloth.
Wet artificial contaminating cloth: Contaminated cloth manufactured by Japan Foundation for the Laundry Science (28.3% oleic acid, 15.6% triolein, 12.2% cholesterol oleate, 2.5% liquid paraffin, 2.5% squalene, cholesterol 20 pieces of cloth with a stain of composition of 1.6%, gelatin 7.0%, mud 29.8%, carbon black 0.5% (mass ratio).
Skin shirt: A BVD skin shirt (LL size, manufactured by Fujibo Holdings Inc.) is finely cut (about 3 cm × 3 cm).

Cleaning process:
In a Terg-o-tometer (manufactured by UNITED STATES TESTING Co., Ltd.), 900 mL of 3 ° DH hard water at 25 ° C. was added, 0.6 g of the liquid detergent of each example was added thereto, and then the to-be-washed matter was placed. Thereafter, the bath ratio was adjusted to 20 times with 3 ° DH hard water, and washed at 120 rpm and 25 ° C. for 10 minutes.

Rinse process:
The washed material was dewatered for 1 minute, and then 900 mL of 3 ° DH hard water at 25 ° C. was added, followed by rinsing at 120 rpm and 25 ° C. for 3 minutes. This operation (dehydration, rinse) was repeated twice. In the second time, a predetermined amount of softener was added to 900 mL of 3 ° DH hard water at 25 ° C. for rinsing. As a softener, room-dried Soflan (manufactured by Lion Corporation) was used.

Drying process:
After the rinsed material was dewatered for 1 minute, only the recontamination test cloth (cotton cloth) was taken out, sandwiched with filter paper, and dried with an iron.
Separately, only the recontamination test cloth (PE cloth) was taken out, sandwiched by filter paper, and dried with an iron.

The reflectance (Z value) of the recontamination test cloth (cotton cloth) before and after the laundry treatment is measured using a spectral color difference meter (product name "SE200" manufactured by Nippon Denshoku Kogyo Co., Ltd.), and ΔZ is calculated from the following formula. The Similarly, the reflectance (Z value) of the recontamination determination cloth (PE cloth) before and after the laundry treatment was measured, and ΔZ was determined from the following equation.
Δ Z = (Z value before laundry treatment)-(Z value after laundry treatment)

The average value of five sheets was determined for ΔZ in the cotton cloth recontamination determination cloth, and the recontamination prevention property to the cotton cloth by the liquid cleaning agent was evaluated based on the following criteria. In the case of ◎ or 、, it was judged that the recontamination prevention property to cotton was good.
◎: ΔZ (average value) is less than 5.
○: ΔZ (average value) is 5 or more and less than 7.
Δ: ΔZ (average value) is 7 or more and less than 9.
X: ΔZ (average value) is 9 or more.

Similarly, an average value of five sheets was determined for ΔZ in the recontamination determination fabric of PE fabric, and the recontamination prevention property to the PE fabric by the liquid cleaning agent was evaluated based on the following criteria. In the case of ◎ or 、, it was judged that the recontamination prevention property to PE cloth was good.
◎: ΔZ (average value) is less than 3.
○: ΔZ (average value) is 3 or more and less than 4.
Δ: ΔZ (average value) is 4 or more and less than 5.
X: ΔZ (average value) is 5 or more.

(Evaluation of Detergency: Coating and Cleaning for Ink Contamination)
Ten pieces of cotton cloth (cotton knitted fabric, manufactured by Tanigami Store) cut into 5 cm × 5 cm are used as evaluation cloths, and coated with an oil-based ink of oil-based ballpoint pen (manufactured by ZEBRA, trade name "Clip-on-Slim oil-based ballpoint pen") An ink-contaminated cloth with oil-based ink stains was produced. At this time, an oil-based ink was applied to the center of a cotton cloth so as to form a circle having a diameter of 2 cm.
The ink stain was cleaned with the liquid cleaner of each example in the following procedure.

Apply 0.05 mL of the liquid detergent of each example to oil-based ink stain attached to the ink stain and leave it for 3 minutes, and then use a washing liquid in which 6 mL of the liquid detergent of each example is dissolved in 15 L of water And washed by the following washing method.
A Terg-O-Tometer (manufactured by UNITED STATES TESTING) was used as a cleaning tester. The liquid detergent of each example is coated and left for 3 minutes, and the 10 pieces of the ink-contaminated cloth and the washing liquid are put in a washing tester, adjusted to a bath ratio of 30 times, 120 rpm, 15 ° C for 10 minutes It was washed. Next, transfer to a two-tank washing machine (Mitsubishi Electric Co., Ltd., part number “CW-C30A1-H1”), dewater for 1 minute, rinse in 30 liters of tap water (15 ° C., 4 ° DH) for 3 minutes, and air-dry did.
The reflectance of the evaluation cloth not stained with oil ink, the ink stain cloth before washing, and the ink stain cloth after washing is measured with a color difference meter (product name "SE200" manufactured by Nippon Denshoku Kogyo Co., Ltd.) It measured and the cleaning rate (%) was computed from following formula (1).
Cleaning rate (%) = {(K / S of ink fouling before cleaning-K / S of ink fouling after cleaning) / (K / S of ink fouling before cleaning-evaluation cloth K / S)} × 100 (1)
However, K / S is a value determined by the formula: (1-R / 100) ² / (2R / 100), and R is an evaluation cloth, an ink stain before cleaning, or an ink stain after cleaning The reflectance (%) of

The cleaning rate (%) was calculated for 10 sheets of the ink-contaminated cloth, the average value was determined, and the application cleaning property to ink contamination was evaluated based on the following criteria. In the case of ◎ or 、, it was judged that the coating cleaning properties were good.
◎: The cleaning rate (average value) is 40% or more.
○: The cleaning rate (average value) is 35% or more and less than 40%.
Δ: The cleaning rate (average value) is 30% or more and less than 35%.
X: The cleaning rate (average value) is less than 30%.

(Evaluation of detergency: Regular cleanability for lipstick stains)
As a stain for evaluation of detergency, a lipstick (lipstick), which is a typical example of oily complex stains that are difficult to remove, was used. Lipstick (made by Shiseido Co., Ltd., trade name "Makiage moisture rouge color on type red") is transferred to the finger, and it is applied to the surface of 10 pieces of PE cloth (polyester tropical, manufactured by Tanigami Store), and lipstick is applied. A smeared lipstick smear was prepared. At this time, a lipstick was applied to the center of the PE cloth so as to form a circle having a diameter of 3 cm.
The lipstick soiled cloth was washed by the following washing method using a washing liquid in which 6 mL of the liquid detergent of each example was dissolved in 15 L of water.

A Terg-O-Tometer (manufactured by UNITED STATES TESTING) was used as a cleaning tester. Ten pieces of the lipstick soiling cloth, the washing knitted cloth and the washing liquid were put in a washing tester, adjusted to a bath ratio of 30 times, and washed at 120 rpm and 15 ° C. for 20 minutes. Next, transfer to a two-tank washing machine (Mitsubishi Electric Co., Ltd., part number “CW-C30A1-H1”), dewater for 1 minute, rinse in 30 liters of tap water (15 ° C., 4 ° DH) for 3 minutes, and air-dry did.
The lipstick stain before washing and the lipstick stain after washing are each measured with a color difference meter (product name "SE200" manufactured by Nippon Denshoku Kogyo Co., Ltd.) and washed according to the following formula 2) The percentage (%) was calculated.
Washing rate (%) = {(a value of lipstick dirty cloth before washing − a value of lipstick dirty cloth after washing) / a value of lipstick dirty cloth before washing} × 100 ・ ・ ・(2)

The wash rate (%) was calculated for 10 lipstick stains, the average value was determined, and the normal washability for lipstick stains was evaluated based on the following criteria. In the case of 、 or 洗浄, it was judged that the washability was usually good.
◎: The cleaning rate (average value) is 60% or more.
○: The cleaning rate (average value) is 50% or more and less than 60%.
Δ: The cleaning rate (average value) is 40% or more and less than 50%.
X: The cleaning rate (average value) is less than 40%.

In Tables 1 and 2, "balance" is the blending amount (mass%) of water (purified water) required to make 100 mass% in the whole liquid detergent.
Moreover, "A + B" is the sum total of content of (A) component and (B) component in a liquid detergent. "A / B ratio" is a mass ratio represented by (A) component / (B) component. The “B / C ratio” is a mass ratio represented by (B) component / (C) component. The "B-2 / B-1 ratio" is a mass ratio represented by B-2 / B-1.

As is clear from Table 1, the liquid detergents of the respective examples were excellent in anti-soiling resistance and also excellent in coating and cleaning properties. Moreover, the liquid detergent of each Example was excellent also in the normal washability compared with the liquid detergent of Comparative Examples 1 and 2.
On the other hand, as apparent from Table 2, the liquid detergent of Comparative Example 1 having an A / B ratio of 5.00 was inferior in anti-soiling resistance.
The liquid detergent of Comparative Example 2 not containing the component (C) was inferior in coating and cleaning properties.

  The liquid cleaning agent of the present invention is excellent in anti-soiling resistance and is also excellent in coating and cleaning properties.

Claims (3)

(A) Component: nonionic surfactant,
Component (B): An anionic surfactant (but excluding higher fatty acid salts)
Component (C): an organic solvent represented by the following general formula (c1),
Contains
The content of component (B) is less than 50% by mass,
The liquid detergent whose mass ratio represented by (A) component / (B) component is less than three.

(In formula (c1), R ^{31 to} R ³³ each independently represent a hydrogen atom or an alkyl group having 1 to 3 carbon atoms, and R ³⁴ represents a hydrogen atom or an acetyl group.)   The liquid detergent according to claim 1, wherein the component (C) is 3-methoxy-3-methylbutanol.   The component (A) contains two or more nonionic surfactants, and at least one of the two or more nonionic surfactants is an alkylene oxide adduct of a secondary alcohol or a branched primary. The liquid detergent according to claim 1 or 2, which is an alkylene oxide adduct of alcohol.