JP2009144002A - Liquid detergent composition - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a liquid detergent composition which contains one surfactant in a large amount singly, which excels in detergency and a softness imparting effect and which does not cause gelling on the liquid surface even in low temperatures, and hardly forms a film. <P>SOLUTION: The liquid detergent composition contains 50-70 mass% of an alkylene oxide addition product (A) represented by general formula (I) (wherein R<SP>1</SP>is a 9-13C straight chain or branched chain alkyl group or alkenyl group; R<SP>2</SP>is a 2-4C alkylene group; R<SP>3</SP>is a 1-3C alkyl group; and n indicates an average addition moles of alkylene oxide and is 5-30), an amidoamine compound (B) and an anionic surfactant (C). <P>COPYRIGHT: (C)2009,JPO&INPIT

Description

  The present invention relates to a liquid detergent composition.

In recent years, in the field of cleaning agents, as methods for reducing the burden on the environment, it has been proposed to reduce the amount of the cleaning composition used or to reduce the size of the container in which the cleaning composition is stored. ing.
Among them, a so-called “concentrated type” having a high surfactant concentration has been developed as a liquid detergent composition. As a specific example, a liquid detergent composition for clothing comprising a specific nonionic surfactant and a polyoxyalkyleneamine has been proposed (see Patent Document 1).

On the other hand, for example, in liquid detergent compositions for clothing, in order to reduce the labor of housework, in addition to appealing “detergency”, “improving flexibility” was also proposed. The thing which mix | blended the component (flexibility provision component) to provide is proposed.
Conventionally, polymers such as quaternary ammonium salt type cationic surfactants and silicones have been mainly used as flexibility-imparting components (see, for example, Patent Document 2).
JP 2005-171195 A Japanese Patent Laid-Open No. 09-255988

General-purpose surfactants such as polyoxyethylene alkyl ether used as a cleaning component in a liquid cleaning composition have a markedly increased viscosity (gelation) as the surfactant concentration increases. In addition, since the range of the surfactant concentration causing the gelation is wide, a concentrated type liquid detergent composition containing such a general-purpose surfactant in a large amount (for example, 50% by mass or more) alone. It is difficult to manufacture.
Although Patent Document 1 describes a liquid detergent composition containing 5 to 80% by mass of a surfactant, it is essential to use two specific surfactants together. The composition does not contain a large amount of the surfactant alone.

Further, in the concentrated type liquid detergent composition, there is a problem that a film is easily formed by gelation of the liquid detergent composition itself on the liquid surface of the liquid detergent composition, particularly at a low temperature in winter. is there.
Such a problem is likely to occur even in a liquid detergent composition in which a flexibility imparting component such as a quaternary ammonium salt type cationic surfactant or an amidoamine compound is blended. Depending on the use situation of the liquid detergent composition, Since the film is formed at an automatic loading port of a washing machine for use, there is a concern that it may lead to consumer complaints.

  The present invention has been made in view of the above circumstances, and contains a single surfactant in a large amount, is excellent in detergency and flexibility imparting effect, and does not gel on the liquid surface even at low temperatures. It is an object of the present invention to provide a liquid detergent composition in which a film is hardly formed.

As a result of intensive studies, the present inventors have completed the present invention by using a combination of a specific nonionic surfactant, a specific flexibility-imparting component, and an anionic surfactant.
That is, the liquid detergent composition of the present invention comprises 50 to 70% by mass of an alkylene oxide adduct (A) represented by the following general formula (I), an amidoamine compound (B), and an anionic surfactant (C). It is characterized by containing.

［式（Ｉ）中、Ｒ^１は炭素数９〜１３の直鎖状もしくは分岐鎖状のアルキル基又はアルケニル基であり、Ｒ^２は炭素数２〜４のアルキレン基であり、Ｒ^３は炭素数１〜３のアルキル基であり；ｎはアルキレンオキサイドの平均付加モル数を示し、５〜３０である。］

[In Formula (I), R ¹ is a linear or branched alkyl group or alkenyl group having 9 to 13 carbon atoms, R ² is an alkylene group having 2 to 4 carbon atoms, and R ³ is carbon. N represents an alkyl group having 1 to 3; n represents an average number of added moles of alkylene oxide, and is 5 to 30. ]

  In the liquid detergent composition of the present invention, the anionic surfactant (C) preferably contains a polyoxyethylene alkyl ether sulfate (C1) represented by the following general formula (II).

［式（ＩＩ）中、Ｒ^４は炭素数６〜２４の直鎖状もしくは分岐鎖状のアルキル基又はアルケニル基であり；ｎ_１はエチレンオキサイドの平均付加モル数を示し、１〜６である。Ｍはアルカリ金属原子、アルカリ土類金属原子、アルカノールアミン又はアンモニウムである。ただし、当該（Ｃ１）成分を構成する全エチレンオキサイド付加体中に質量を基準として最も多く存在するエチレンオキサイド付加体のエチレンオキサイドの付加モル数を「ｎ_１ｍａｘ」とした際、全エチレンオキサイド付加体に対する、エチレンオキサイドの付加モル数が（ｎ_１ｍａｘ−１）とｎ_１ｍａｘと（ｎ_１ｍａｘ＋１）のエチレンオキサイド付加体の合計の割合が５５質量％以上である。］

[In the formula (II), R ⁴ represents a linear or branched alkyl group or alkenyl group having 6 to 24 carbon atoms; n ₁ represents the average number of moles of ethylene oxide added and is 1 to 6; . M is an alkali metal atom, an alkaline earth metal atom, an alkanolamine or ammonium. However, when the number of moles of ethylene oxide added in the ethylene oxide adduct existing most in the total ethylene oxide adduct constituting the component (C1) is “n _1max ”, the total ethylene oxide adduct The total proportion of the ethylene oxide adducts having an addition mole number of ethylene oxide of (n _1max −1), n _1max and (n _1max +1) is 55% by mass or more. ]

  In this specification, the “concentrated type” liquid detergent composition means that the total surfactant concentration in the liquid detergent composition is high, and the surfactant concentration is in the liquid detergent composition. , 50% by mass or more, preferably 55% by mass or more.

  According to the present invention, a liquid detergent containing a large amount of a surfactant alone, excellent in detergency and flexibility, and hardly forming a film without gelation on the liquid surface even at low temperatures. A composition can be provided.

≪Liquid detergent composition≫
The liquid detergent composition of the present invention comprises 50 to 70% by mass of an alkylene oxide adduct (A) (hereinafter referred to as component (A)) represented by the general formula (I), an amidoamine compound (B) ( (Hereinafter referred to as “component (B)”) and an anionic surfactant (C) (hereinafter referred to as “component (C)”).

<(A) component>
In the present invention, the component (A) is an alkylene oxide adduct represented by the general formula (I).
By using the component (A), the liquid detergent composition of the present invention does not cause gelation even if it contains a high concentration of surfactant, and contains a large amount of surfactant alone. be able to.
Here, “a single surfactant is contained in a large amount” means that the surfactant is contained alone in an amount of 50% by mass or more in the liquid detergent composition.
Moreover, the liquid detergent composition of this invention is excellent in the solubility to water by containing this (A) component, and becomes easy to obtain high detergency. Furthermore, even if a high concentration of surfactant is contained, the viscosity does not remarkably increase (gelation), and a concentrated liquid detergent composition having good fluidity can be produced.

In the general formula (1), R ¹ is a linear or branched alkyl group having 9 to 13 carbon atoms, or a linear or branched alkenyl group having 9 to 13 carbon atoms.
In R ¹ , the carbon number of the alkyl group and the alkenyl group is preferably 10 to 13 carbon atoms, more preferably 11 to 13 carbon atoms, respectively, from the viewpoint of improving detergency and preventing gelation.
R ² is an alkylene group having 2 to 4 carbon atoms, preferably an alkylene group having 2 to 3 carbon atoms, and more preferably an ethylene group. In the component (A), R ² may be a single alkylene group, or two or more alkylene groups may be mixed.
R ³ is an alkyl group having 1 to 3 carbon atoms, preferably a methyl group.
n shows the average addition mole number of alkylene oxide, and is 5-30. Preferably, it is 12 to 18 from the viewpoint of improvement in detergency and liquid stability of the liquid detergent composition (particularly stability at low temperatures with time).

In the component (A), the narrow ratio indicating the proportion of the distribution of alkylene oxide adducts having different numbers of added moles of alkylene oxide is preferably 20% by mass or more, and the upper limit is substantially 80% by mass. % Or less is preferable. The narrow ratio is more preferably 20 to 60% by mass, and 30 to 45% by mass is more preferable because the temporal stability at low temperature is improved.
The higher the narrow rate, the better the cleaning power. Moreover, it becomes easy to obtain the liquid detergent composition with few raw material odors of surfactant as the said narrow rate is 20 mass% or more, especially 30 mass% or more. This is because, after the production of the component (A), the fatty acid ester which is the raw material of the component (A) coexisting with the component (A) and the alkylene oxide adduct of n = 1 and 2 in the general formula (I) are reduced. This is probably because of this.

  Here, the “narrow ratio” in the present specification means that represented by the following formula (S) indicating the distribution ratio of alkylene oxide adducts having different numbers of added moles of alkylene oxide.

［式中、ｎ_ｍａｘは全体のアルキレンオキサイド付加体中に最も多く存在するアルキレンオキサイド付加体のアルキレンオキサイドの付加モル数を示す。ｉはアルキレンオキサイドの付加モル数を示す。Ｙｉは全体のアルキレンオキサイド付加体中に存在するアルキレンオキサイドの付加モル数がｉであるアルキレンオキサイド付加体の割合（質量％）を示す。］

[ _Wherein n _max represents the number of added moles of alkylene oxide of the alkylene oxide adduct most present in the entire alkylene oxide adduct. i represents the number of added moles of alkylene oxide. Yi represents the proportion (mass%) of the alkylene oxide adduct having an added mole number of alkylene oxide present in the entire alkylene oxide adduct. ]

The narrow rate can be controlled by, for example, the method for producing the component (A).
The method for producing the component (A) is not particularly limited. For example, a method in which ethylene oxide is addition-polymerized to a fatty acid alkyl ester using a surface-modified composite metal oxide catalyst (JP 2000-2000-A). 144194179)).
As a suitable example of such a surface-modified composite metal oxide catalyst, specifically, metal ions (Al ³⁺ , Ga ³⁺ , In ³⁺ , Tl ³⁺ , surface-modified with a metal hydroxide or the like, Co ³⁺ , Sc ³⁺ , La ³⁺ , Mn ^2+, etc.) and a composite metal oxide catalyst such as magnesium oxide, and a hydrotalcite fired product whose surface is modified with a metal hydroxide and / or metal alkoxide Such as a catalyst.
Further, in the surface modification of the composite metal oxide catalyst, the mixing ratio of the composite metal oxide and the metal hydroxide and / or metal alkoxide is changed to metal hydroxide with respect to 100 parts by mass of the composite metal oxide. The ratio of the product and / or metal alkoxide is preferably 0.5 to 10 parts by mass, and more preferably 1 to 5 parts by mass.

The component (A) used in the present invention has a molecular group with no hydrophilic group at the end of the molecule (end-capped type) and a highly polar carbonyl group in the molecule.
As a result, the component (A) is a nonionic surfactant in which the orientation of molecules in an aqueous solution system is weak and the micelle is unstable, so that gelation or the like does not occur at a high concentration, and a large amount of one kind alone. It is presumed that it can be incorporated into a liquid detergent composition. Moreover, it is estimated that the solubility to water improves. Furthermore, it is thought that it contributes to good fluidity at a high concentration. Therefore, after the component (A) is introduced into the water in the washing machine tub, the concentration of the component (A) in the washing liquid becomes uniform quickly and can contact the article to be washed at a predetermined concentration from the initial stage of washing. Therefore, it is considered that high detergency can be obtained.

(A) A component can be used 1 type or in mixture of 2 or more types.
(A) Content of a component is 50-70 mass% in a liquid detergent composition, and it is preferable that it is 51-65 mass%.
When the content of the component (A) is 50% by mass or more, preferably 51% by mass or more, good detergency can be obtained. Further, a concentrated liquid detergent composition containing a high concentration of surfactant is obtained. Moreover, the effectiveness (commercial value) as a concentrated type liquid detergent composition becomes high.
When the content of the component (A) is 70% by mass or less, preferably 65% by mass or less, the liquid detergent composition does not gel on the liquid surface even at low temperatures, and a film is hardly formed.

<(B) component>
In the present invention, the component (B) is an amidoamine compound.
By using the component (B), a flexibility imparting effect can be obtained. Further, unlike a flexibility imparting component such as a quaternary ammonium salt type cationic surfactant, the liquid detergent composition does not gel on the liquid surface at a low temperature, and an effect that makes it difficult to form a film (hereinafter, “ It is sometimes referred to as “the effect of suppressing film formation”).

In the present invention, the “amidoamine compound” includes a compound in which at least one hydrogen atom of ammonia NH ₃ is substituted with an organic group containing an amide group (—NH—C (═O) —). The organic group preferably contains a long-chain hydrocarbon group (preferably having 7 or more carbon atoms). Further, the amidoamine compound may be any of primary amine, secondary amine, tertiary amine or a salt thereof.
Preferable examples of such component (B) include tertiary amines represented by the following general formula (b-1) or salts thereof (B1) (hereinafter referred to as (B1) component). When the component (B1) is used, the effect of imparting flexibility and the effect of suppressing film formation are further improved.

［式（ｂ−１）中、Ｒ^５は置換基を含んでいてもよい炭素数７〜２３の炭化水素基であり、Ｒ^６は炭素数１〜４の直鎖状もしくは分岐鎖状のアルキレン基であり；Ｒ^７およびＲ^８はそれぞれ独立して炭素数１〜４の直鎖状もしくは分岐鎖状のアルキル基、炭素数１〜４の直鎖状もしくは分岐鎖状のヒドロキシアルキル基、又は−（ＣＨ_２ＣＨ_２Ｏ）ｎ_２−Ｈ（ただし、ｎ_２はエチレンオキサイドの付加モル数を示し、１〜２５である。）である。］

[In Formula (b-1), R ⁵ is a hydrocarbon group having 7 to 23 carbon atoms which may contain a substituent, and R ⁶ is a linear or branched alkylene having 1 to 4 carbon atoms. Each of R ⁷ and R ⁸ is independently a linear or branched alkyl group having 1 to 4 carbon atoms, a linear or branched hydroxyalkyl group having 1 to 4 carbon atoms, or — (CH ₂ CH ₂ O) n ₂ —H (where n ₂ represents the number of moles of ethylene oxide added and is 1 to 25). ]

In the formula (b-1), R ⁵ is a hydrocarbon group having 7 to 23 carbon atoms which may contain a substituent, and may be linear or branched and saturated. Or unsaturated.
R ⁵ is a hydrocarbon group having 7 to 23 carbon atoms, preferably a hydrocarbon group having 7 to 21 carbon atoms. For example, a C7-23 linear or branched alkyl group or a C7-23 linear or branched alkenyl group can be mentioned.

R ⁶ is a linear or branched alkylene group having 1 to 4 carbon atoms, preferably a propylene group.
R ⁷ and R ⁸ are each independently a linear or branched alkyl group having 1 to 4 carbon atoms, a linear or branched hydroxyalkyl group having 1 to 4 carbon atoms, or-( CH ₂ CH ₂ O) n ₂ —H (where n ₂ is the number of moles of ethylene oxide added and is 1 to 25), and in particular, a linear or branched chain having 1 to 4 carbon atoms. The alkyl group is preferably.

Preferred specific examples of the component (B1) include caprylic acid dimethylaminopropylamide, capric acid dimethylaminopropylamide, lauric acid dimethylaminopropylamide, myristic acid dimethylaminopropylamide, palmitic acid dimethylaminopropylamide, dimethyl stearate. Long chain aliphatic amide alkyl tertiary amines such as aminopropylamide, behenic acid dimethylaminopropylamide, oleic acid dimethylaminopropylamide, or salts thereof; palmitic acid diethanolaminopropylamide, stearic acid diethanolaminopropylamide, and the like.
Among them, caprylic acid dimethylaminopropylamide, capric acid dimethylaminopropylamide, lauric acid dimethylaminopropylamide, myristic acid dimethylaminopropylamide, palmitic acid dimethylaminopropylamide, stearic acid dimethylaminopropylamide, behenic acid dimethylaminopropyl Amides, oleic acid dimethylaminopropylamide or salts thereof are particularly preferred.

The production example of the component (B1) will be described using “long-chain aliphatic amidoalkyl tertiary amine” in the above-exemplified compounds. For example, fatty acids or fatty acid lower alkyl esters, animal and vegetable oils and fats, etc. A fatty acid derivative and a dialkyl (or alkanol) aminoalkylamine are subjected to a condensation reaction, and then unreacted dialkyl (or alkanol) aminoalkylamine is distilled off under reduced pressure or nitrogen blowing.
Here, as the fatty acid or fatty acid derivative, caprylic acid, capric acid, lauric acid, myristic acid, palmitic acid, stearic acid, oleic acid, behenic acid, erucic acid, 12-hydroxystearic acid, coconut oil fatty acid, cottonseed oil fatty acid, Specific examples include corn oil fatty acid, beef tallow fatty acid, palm kernel oil fatty acid, soybean oil fatty acid, linseed oil fatty acid, castor oil fatty acid, olive oil fatty acid and other vegetable oils or animal oil fatty acids, or methyl esters, ethyl esters, glycerides, etc. Among them, caprylic acid, capric acid, lauric acid, myristic acid, palmitic acid, stearic acid, oleic acid, behenic acid and the like are particularly preferable.
These fatty acids or fatty acid derivatives may be used alone or in combination of two or more.

  Specific examples of the “dialkyl (or alkanol) aminoalkylamine” include dimethylaminopropylamine, dimethylaminoethylamine, diethylaminopropylamine, diethylaminoethylamine and the like, and dimethylaminopropylamine is particularly preferable.

In addition, the amount of dialkyl (or alkanol) aminoalkylamine used in the production of the long-chain aliphatic amidoalkyl tertiary amine is preferably 0.9 to 2.0 moles relative to the fatty acid or derivative thereof. 0 to 1.5 times mole is particularly preferable.
It is preferable that reaction temperature is 100-220 degreeC normally, More preferably, it is 150-200 degreeC. When the reaction temperature is 100 ° C. or higher, the reaction does not become too slow, and when it is 220 ° C. or lower, coloring of the resulting tertiary amine is suppressed.
The production conditions other than those described above for the long-chain aliphatic amidoalkyl tertiary amine can be appropriately changed. The pressure during the reaction may be normal pressure or reduced pressure, and an inert gas such as nitrogen may be used during the reaction. It is also possible to introduce it by blowing.

In addition, when a fatty acid is used, an acid catalyst such as sulfuric acid or p-toluenesulfonic acid; when a fatty acid derivative is used, an alkaline catalyst such as sodium methylate, caustic potash or caustic soda can be used at a low reaction temperature for a short time. The reaction can proceed more efficiently.
In addition, when the obtained component (B1) is a long-chain amine having a high melting point, it is preferably formed into a flake shape or a pellet shape after the reaction in order to improve handling properties, or an organic solvent such as ethanol. It is preferable to dissolve it in a liquid state.

Specific examples of the component (B1) include those using a tertiary amine as it is, and acid salts obtained by neutralizing the tertiary amine with an acid.
Examples of the acid used for neutralization include hydrochloric acid, sulfuric acid, nitric acid, phosphoric acid, glycolic acid, lactic acid, citric acid, polyacrylic acid, paratoluenesulfonic acid, cumenesulfonic acid, and the like. Two or more types may be used in combination.

  Specific examples of the commercially available component (B1) include Kachinal MPAS-R (trade name) manufactured by Toho Chemical Co., Ltd.

(B) A component can be used 1 type or in mixture of 2 or more types.
The content of the component (B) is preferably 0.1 to 5% by mass in the liquid detergent composition, more preferably 0.2 to 4% by mass, and 1 to 4% by mass. More preferably.
When the content of the component (B) is 0.1% by mass or more, the flexibility imparting effect is more easily obtained. When the content of the component (B) is 5% by mass or less, the liquid detergent composition does not gel on the liquid surface even at low temperatures, and a film is hardly formed. Moreover, it becomes easy to take a blending balance with other components.

<(C) component>
In the present invention, the component (C) is an anionic surfactant.
By using the component (C), the liquid detergent composition does not gel on the liquid surface at a low temperature, and an effect that it is difficult to form a film (an effect of suppressing film formation) is obtained.

Examples of the component (C) include the following anionic surfactants (1) to (4).
(1) Carboxylic acid types such as higher fatty acid salts, alkyl ether carboxylates, polyoxyalkylene ether carboxylates, alkyl amide ether carboxylates, alkenyl amide ether carboxylates, and acylaminocarboxylates.
(2) Sulfuric ester types such as higher alcohol sulfates, polyoxyalkylene higher alcohol sulfates, alkylphenyl ether sulfates, polyoxyalkylene alkylphenyl ether sulfates, glycerin fatty acid esters monosulfate.
(3) Sulfonic acid types such as alkyl sulfonates, α-olefin sulfonates, linear alkylbenzene sulfonates, α-sulfo fatty acid ester salts, and dialkyl sulfosuccinates.
(4) Phosphate ester types such as alkyl phosphate ester salts, polyoxyalkylene alkyl phosphate ester salts, polyoxyalkylene alkyl phenyl phosphate ester salts, and glycerin fatty acid ester monophosphate ester salts.

  Among the above, as the component (C), since the gelation on the liquid surface of the liquid detergent composition at a low temperature is further suppressed, the polyoxyethylene alkyl ether sulfate represented by the following general formula (II) It preferably contains an ester salt (C1) (hereinafter referred to as component (C1)).

［式（ＩＩ）中、Ｒ^４は炭素数６〜２４の直鎖状もしくは分岐鎖状のアルキル基又はアルケニル基であり；ｎ_１はエチレンオキサイドの平均付加モル数を示し、１〜６である。Ｍはアルカリ金属原子、アルカリ土類金属原子、アルカノールアミン又はアンモニウムである。ただし、当該（Ｃ１）成分を構成する全エチレンオキサイド付加体中に質量を基準として最も多く存在するエチレンオキサイド付加体のエチレンオキサイドの付加モル数を「ｎ_１ｍａｘ」とした際、全エチレンオキサイド付加体に対する、エチレンオキサイドの付加モル数が（ｎ_１ｍａｘ−１）とｎ_１ｍａｘと（ｎ_１ｍａｘ＋１）のエチレンオキサイド付加体の合計の割合が５５質量％以上である。］

[In the formula (II), R ⁴ represents a linear or branched alkyl group or alkenyl group having 6 to 24 carbon atoms; n ₁ represents the average number of moles of ethylene oxide added and is 1 to 6; . M is an alkali metal atom, an alkaline earth metal atom, an alkanolamine or ammonium. However, when the number of moles of ethylene oxide added in the ethylene oxide adduct existing most in the total ethylene oxide adduct constituting the component (C1) is “n _1max ”, the total ethylene oxide adduct The total proportion of the ethylene oxide adducts having an addition mole number of ethylene oxide of (n _1max −1), n _1max and (n _1max +1) is 55% by mass or more. ]

In the formula (II), R ⁴ is a linear or branched alkyl group having 6 to 24 carbon atoms, or a linear or branched alkenyl group having 6 to 24 carbon atoms.
R ⁴ has 6 to 24 carbon atoms, preferably 10 to 18 carbon atoms. When the number of carbon atoms is 6 or more, the effect of suppressing film formation is further improved. On the other hand, when the carbon number is 24 or less, the solubility of the component (C1) itself is improved, precipitation during storage is suppressed, and stability over time is improved.
Further, the alkyl group or alkenyl group in R ⁴ is preferably a primary or secondary alkyl group, or a primary or secondary alkenyl group. Preferable specific examples include hexyl group, octyl group, decyl group, dodecyl group, myristyl group, palmityl group, stearyl group, oleyl group, aralkyl group, behenyl group and the like.
These alkyl groups or alkenyl groups may be used singly or in combination, and may be derived from natural raw materials or synthesized. For example, commercially available Dovanox (registered trademark), Diadol (registered trademark), Neodol (registered trademark), primary alcohol such as Saffol (registered trademark), natural alcohol such as palm oil higher alcohol, softanol (registered) Those derived from secondary alcohols such as trademark) are very suitable.

In the formula (II), _{n 1} represents an average addition mole number of ethylene oxide, from 1 to 6, 1 to 3 are preferred.
However, when the number of moles of ethylene oxide added in the ethylene oxide adduct existing most in the total ethylene oxide adduct constituting the component (C1) is “n _1max ”, the total ethylene oxide adduct The total proportion of the ethylene oxide adducts of (n _1max -1), n _1max, and (n _1max +1) with respect to the number of moles of ethylene oxide added is 55 mass% or more, and is in the range of 55 to 75 mass%. It is preferable. Within the above range, the effect of suppressing film formation is more easily obtained.

M is an alkali metal atom, an alkaline earth metal atom, an alkanolamine or ammonium.
Specific examples include alkali metal atoms such as sodium, potassium and lithium; alkaline earth metal atoms such as calcium and magnesium; alkanolamines such as monoethanolamine, diethanolamine and triethanolamine; ammonium and the like. It may be single or mixed. Especially, as M, an alkali metal atom is preferable and sodium is especially preferable.

The component (C1) can be produced, for example, as follows.
Polyoxyethylene alkyl ether (alcohol ethoxylate) is obtained by adding ethylene oxide to a higher alcohol, preferably a higher alcohol selected from the following (a) to (e). As a catalyst used when adding ethylene oxide, for example, a composite metal oxide Lewis acid sintered solid catalyst composed of Al / Mg / Mn described in Japanese Patent No. 3312883 is preferable. Thereby, the thing with a narrow addition mole number distribution of ethylene oxide is obtained.
Next, the obtained polyoxyethylene alkyl ether is sulfonated or sulfated with sulfone and neutralized to produce the component (C1).

(A) Product name, Neodol 23 (branch rate: 20% by mass), manufactured by Shell Chemicals. This is produced from an n-olefin by a modified oxo method and rectified.
(B) C13 alcohol obtained from butene trimer by oxo method (branch rate: 100% by mass).
c) A higher alcohol (branch rate: 100% by mass) obtained from a medium chain alcohol by a garvet reaction.
(D) Product name Safol 23 (branch rate: 50% by mass) manufactured by Sasol. In this method, an olefin obtained from the gasification of coal is obtained by obtaining an alcohol by the oxo method and further hydrogenating it.
(E) Natural higher alcohol synthesized from natural fats and oils (branching rate: 0% by mass).
The “branch rate” indicates the ratio (mass%) of the higher alcohol having a branched chain to the total higher alcohol.

(C) component can be used 1 type or in mixture of 2 or more types.
(C) It is preferable that it is 0.5-10 mass% in content of a liquid detergent composition, and, as for content of a component, it is more preferable that it is 1-5 mass%.
When the content of the component (C) is 0.5% by mass or more, an effect that the liquid detergent composition does not gel on the liquid surface even when the temperature is low and the film is hardly formed can be easily obtained. On the other hand, when the content of the component (C) is 10% by mass or less, the effect of suppressing film formation can be sufficiently obtained. Moreover, it becomes easy to take a blending balance with other components.

In the present invention, the effect of suppressing the formation of the film obtained by using the component (C) is particularly prominent when the component (B) is used as a flexibility-imparting component.
The reason why such an effect can be obtained is not clear, but in the washing liquid in which the liquid detergent composition is dissolved in water, the (B) component and the (C) component interact electrostatically, It is presumed that the phase state when the components blended in the liquid detergent composition are mixed changes compared to the phase state when the component (C) is lacking.

<Optional component>
In addition to the components (A) to (C), other components can be appropriately blended in the liquid detergent composition of the present invention as necessary.

(Surfactant)
In the liquid detergent composition of the present invention, surfactants other than the components (A) to (C) may be blended depending on the use, and nonionic surfactants, amphoteric surfactants, etc. may be used. it can.
Nonionic surfactants include alcohol ethoxylates obtained by adding ethylene oxide to long chain alcohols, alkylphenols, alkylene oxide adducts such as higher fatty acids or higher amines, polyoxyethylene polyoxypropylene block copolymers, fatty acid alkanolamines, fatty acid alkanolamides, Polyhydric alcohol fatty acid ester or its alkylene oxide adduct, polyhydric alcohol fatty acid ether, alkylamine oxide, alkenylamine oxide, alkylene oxide adduct of hydrogenated castor oil, sugar fatty acid ester, N-alkyl polyhydroxy fatty acid amide, alkyl glycoside, etc. Is mentioned.
Examples of amphoteric surfactants include alkylbetaine type, alkylamide betaine type, imidazoline type, alkylaminosulfone type, alkylaminocarboxylic acid type, alkylamidecarboxylic acid type, amide amino acid type or phosphoric acid type amphoteric surfactant. Can be mentioned.

(Organic solvent)
In the liquid detergent composition of the present invention, alcohols such as ethanol, 1-propanol, 2-propanol and 1-butanol; glycols such as propylene glycol, butylene glycol and hexylene glycol; diethylene glycol and triethylene glycol , Tetraethylene glycol, polyethylene glycol having a weight average molecular weight of about 200, polyethylene glycol having a weight average molecular weight of about 400, polyglycols such as dipropylene glycol; water miscibility such as alkyl ethers such as diethylene glycol monomethyl ether and diethylene glycol dimethyl ether The organic solvent can be used. The content of the organic solvent is preferably 0.1 to 15% by mass in the liquid detergent composition.

(silicone)
In the liquid detergent composition of the present invention, CF1188HV, SH3748, SH3749, SH3772M, SH3775M, SF8410, SH8700, BY22-008, BY22-012, SILWET L-7001, SILWET manufactured by Toray Dow Corning Co., Ltd. L-7002, SILWET L-7602, SILWET L-7604, SILWET FZ-2104, SILWET FZ-2120, SILWET FZ-2161, SILWET FZ-2162, SILWET FZ-2164, SILWET FZ-2171, ABN F SILET 009-01, ABN SILWET FZ-F1-009-02, ABN SILWET FZ-F1-009-03, ABN SILWET FZ-F1-009 05, ABN SILWET FZ-F1-009-09, ABN SILWET FZ-F1-009-11, ABN SILWET FZ-F1-009-13, ABN SILWET FZ-F1-009-54, ABN SILWET FZ-22-22;
X-20-8010B, KF352A, KF6008, KF615A, KF6012, KF6016, KF6017 manufactured by Shin-Etsu Chemical Co., Ltd .;
Polyether-modified silicones such as TSF4450, TSF4452, and TSF4445 (above, trade names) manufactured by GE Toshiba Silicone can be used. The content of the polyether-modified silicone is preferably 0.1 to 3% by mass in the liquid detergent composition.

Further, in the liquid detergent composition of the present invention, it is possible to use paratoluenesulfonic acid, benzoate (which also has an effect as a preservative), a thinning agent or solubilizer such as urea. The content of the thinning agent or solubilizing agent is preferably 0.01 to 30% by mass in the liquid detergent composition.
In the liquid detergent composition of the present invention, metal ion scavengers such as malonic acid, succinic acid, malic acid, diglycolic acid, tartaric acid and citric acid can be used. The content of the metal ion scavenger is preferably 0.1 to 20% by mass in the liquid detergent composition.
In the liquid detergent composition of the present invention, an antioxidant such as butylhydroxytoluene, distyrenated cresol, sodium sulfite, sodium hydrogen sulfite and the like can be used. The content of the antioxidant is preferably 0.01 to 2% by mass in the liquid detergent composition.
In the liquid detergent composition of the present invention, an antiseptic such as Caisson CG (trade name) manufactured by Rohm and House may be used. It is preferable that content of the said preservative is 0.001-1 mass% in a liquid detergent composition.

Further, in the liquid detergent composition of the present invention, enzymes (proteases, lipases, cellulases, etc.), texture improvers, alkali builders such as alkanolamines, dibutylhydroxytoluene (BHT) for the purpose of improving washing performance and stability. ) And the like, pH adjusters, hydrotropes, fluorescent agents, dye transfer inhibitors, recontamination inhibitors, pearl agents, soil release agents, and the like can be used.
In addition, for the purpose of improving the added value of goods, a coloring agent, an emulsifying agent, and a fragrance for aroma can be included.
Colorants include general-purpose dyes and pigments such as Acid Red 138, Polar Red RLS, Acid Yellow 203, Acid Blue 9, Blue No. 1, Blue No. 205, Green No. 3, and Turquoise P-GR (all trade names) Can be used. The content of the colorant is preferably 0.00005 to 0.005% by mass in the liquid detergent composition.
Examples of the emulsifying agent include polystyrene emulsion and polyvinyl acetate emulsion, and usually an emulsion having a solid content of 30 to 50% by mass is suitably used. As a specific example, polystyrene emulsion (manufactured by Seiden Chemical Co., Ltd., trade name: Cybinol RPX-196 PE-3, solid content 40% by mass) and the like can be used. The content of the emulsifying agent is preferably 0.01 to 0.5% by mass in the liquid detergent composition.
As a fragrance | flavor, the fragrance | flavor component as described in Unexamined-Japanese-Patent No. 2002-146399 is mentioned. It is preferable that content of the said fragrance | flavor is 0.01-2 mass% in a liquid detergent composition.

  In the liquid detergent composition according to the present invention, the content of water is preferably 10 to 50% by mass, more preferably 20 to 40% by mass in the liquid detergent composition. If it is this range, it will become easy to obtain a stable liquid detergent composition as "concentration type".

In the liquid detergent composition according to the present invention, the pH adjuster includes inorganic acids such as hydrochloric acid, sulfuric acid and phosphoric acid; organic acids such as polyvalent carboxylic acids and hydroxycarboxylic acids; sodium hydroxide and potassium hydroxide , Alkanolamine, ammonia and the like, and sulfuric acid, sodium hydroxide, potassium hydroxide and alkanolamine are preferable from the viewpoint of the temporal stability of the liquid detergent composition.
A pH adjuster can be used 1 type or in mixture of 2 or more types.
The pH adjuster is appropriately added in an amount that adjusts the pH of the liquid detergent composition at 25 ° C., preferably to pH 4-9.

The pH of the liquid detergent composition of the present invention is preferably 4 to 9 at 25 ° C., more preferably 4 to 8. When the pH is 4 to 9, it is possible to maintain good stability over time even when the liquid detergent composition is stored for a long period of time.
The adjustment of the pH can be controlled, for example, by adding a certain amount of sulfuric acid, sodium hydroxide or the like. Further, an inorganic acid (preferably hydrochloric acid or sulfuric acid) or potassium hydroxide can be further added for fine adjustment of pH.
In the present invention, the pH of the liquid detergent composition (controlled at 25 ° C.) indicates a value measured by a pH meter (product name: HM-30G, manufactured by Toa DKK Co., Ltd.) or the like.

The liquid detergent composition of the present invention can be produced based on a conventional method, preferably using water as a solvent.
The usage method is a normal usage method, that is, a method in which the liquid detergent composition of the present invention (product of the present invention) is poured into water together with the laundry during washing, and the product of the present invention is directly applied to mud and sebum soil. And a method of immersing clothing by dissolving the product of the present invention in water in advance. Also preferred is a method in which the product of the present invention is applied to the laundry and then allowed to stand as appropriate, followed by normal washing using a normal laundry solution. In that case, the usage-amount of this invention product can be decreased to substantially half or less rather than the usage-amount of the conventional liquid detergent composition.

According to the present invention, a liquid detergent containing a large amount of a surfactant alone, excellent in detergency and flexibility, and hardly forming a film without gelation on the liquid surface even at low temperatures. A composition can be provided.
The liquid detergent composition of the present invention is particularly suitable for clothing.

  Hereinafter, the present invention will be described in more detail with reference to examples, but the present invention is not limited to these examples. “%” Means “% by mass” unless otherwise specified.

≪Manufacture of liquid detergent composition≫
Liquid detergent compositions having the compositions shown in Tables 1 and 2 were produced as follows according to a conventional method.
First, the component (A) was placed in a cylindrical glass bottle (diameter 50 mm, height 100 mm) containing a 2 cm stir bar. Next, the mixed solution of arbitrary components was put, and the stirring bar was stirred at 400 rpm. Next, component (B) was added and stirred, and then component (C) was sequentially added and stirred and mixed. Thereafter, purified water is added so that the total amount (the total amount is 100 parts by mass) is 95 parts by mass, and after stirring and mixing, the pH is adjusted, and ethanol is added so that the total amount becomes 100% by mass. In addition, a liquid detergent composition was produced.
The pH was adjusted by adding an appropriate amount of a pH adjuster (sodium hydroxide or sulfuric acid) so that the pH of the liquid cleaning composition at 7.0 was 7.0.
In addition, the unit of the compounding amount in Tables 1 and 2 is mass%, and indicates a pure equivalent amount.
Below, the measuring method of the narrow rate of (A) component and the component shown in the table | surface are demonstrated.

<Method for Measuring Narrow Rate of Component (A)>
The distribution of ethylene oxide adducts with different numbers of moles of ethylene oxide was measured under the following measurement conditions. And the narrow rate (mass%) of (A) component was computed based on the said Numerical formula (S).
[Conditions for measuring the distribution of ethylene oxide adducts by HPLC]
Apparatus: LC-6A (manufactured by Shimadzu Corporation)
Detector: SPD-10A
Measurement wavelength: 220 nm
Column: Zorbax C8 (manufactured by Du Pont)
Mobile phase: acetonitrile / water = 60/40 (volume ratio)
Flow rate: 1 mL / min
Temperature: 20 ° C

<Description of components shown in the table>.
-(A) component A-1: a mixture of C ₁₁ H ₂₃ CO (OC ₂ H ₄ ) ₁₅ OCH ₃ and C ₁₃ H ₂₇ CO (OC ₂ H ₄ ) ₁₅ OCH ₃ in a mass ratio of 8/2, Narrow ratio 33% by mass; synthetic product.
_{A-2: C 11 H 23} CO (OC 2 H 4) 15 OCH 3, narrow ratio 37 wt%; synthetic.
A-3 (comparative product): C ₁₂ H ₂₅ O (C ₂ H ₄ O) ₁₅ H, narrow ratio 30% by mass; synthetic product.

However, for A-1, a synthetic product produced according to the synthesis method described in JP 2000-144179 A (corresponding to sample D) was used. That is, alumina hydroxide / magnesium hydroxide (product name: Kyoward 300, manufactured by Kyowa Chemical Industry Co., Ltd.) having a chemical composition of 2.5 MgO.Al ₂ O ₃ .nH ₂ O, at 600 ° C. for 1 hour in a nitrogen atmosphere Calcined alumina hydroxide / magnesium (unmodified) catalyst 2.2 g obtained by calcining under pressure, 2.9 mL of 0.5 N potassium hydroxide ethanol solution, 280 g of lauric acid methyl ester and myristic acid methyl ester 70 g was charged into a 4 liter autoclave and the catalyst was reformed in the autoclave. Subsequently, after replacing the inside of the autoclave with nitrogen, the temperature was raised, and while maintaining the temperature at 180 ° C. and the pressure at 3 atm, 1052 g of ethylene oxide was introduced and reacted while stirring.
Further, the reaction solution was cooled to 80 ° C., 159 g of water and 5 g of activated clay and diatomaceous earth as filter aids were added respectively, and then the catalyst was filtered off to obtain A-1.
In addition, A-1 with a narrow rate of 33% by mass was obtained by controlling the amount of alkali added to the catalyst.

A-2 was produced in the same manner as the synthesis method of A-1, except that 350 g of lauric acid methyl ester was used and 1079 g of ethylene oxide was introduced in the synthesis method of A-1.
In addition, A-2 with a narrow rate of 37% by mass was obtained by controlling the amount of alkali added to the catalyst.

A-3 (comparative product) was synthesized as follows.
186 g of lauryl alcohol and 2.0 g of 30% by mass NaOH aqueous solution were respectively collected in a pressure-resistant reaction vessel, and the inside of the vessel was purged with nitrogen.
Next, after dehydrating for 30 minutes at a temperature of 100 ° C. and a pressure of 2.0 kPa or less, the temperature was raised to 160 ° C. While stirring the alcohol, 660 g of ethylene oxide (gaseous) was gradually added to the alcohol liquid while adjusting the addition rate so that the reaction temperature did not exceed 180 ° C. using a blowing tube.
After completion of the addition of ethylene oxide, aging was performed at a temperature of 180 ° C. and a pressure of 0.3 MPa or less for 30 minutes, and then unreacted ethylene oxide was distilled off at a temperature of 180 ° C. and a pressure of 6.0 kPa or less for 10 minutes.
Next, after cooling the temperature to 100 ° C. or lower, p-toluenesulfonic acid (70% by mass aqueous solution) was added to neutralize so that the pH of the 1% by mass aqueous solution of the reaction was about 7, and A- 3 (comparative product) was obtained.
In addition, in A-1, A-2, and A-3, the narrow ratio measured the distribution of ethylene oxide adducts in which the number of moles of ethylene oxide added in the obtained synthetic product is different by the method for measuring the narrow ratio. And calculated.

(B) Component B-1: C _{m ′} H _{2m ′ + 1} CONH (CH ₂ ) ₃ N (CH ₃ ) ₂ (mixture of 3/7 by mass ratio of m ′ = 15 and m ′ = 17), Product name “Katinal MPAS-R” manufactured by Toho Chemical Co., Ltd.
_{B-2: C 17 H 35} CONH (CH 2) 3 N (CH 3) 2, dimethylaminopropyl amide stearic acid; synthetic.

B-2 was synthesized as follows.
In a 1 liter four-necked flask equipped with a reflux condenser, 360 g of stearic acid (molecular weight 284) was charged and heated to 80 ° C. to melt the stearic acid. After performing nitrogen substitution twice, the temperature was raised to 150 ° C., and 123 g of dimethylaminopropylamine (molecular weight 102) (molar ratio to stearic acid: 0.95) was added dropwise over 1 hour.
Next, after maintaining at 150 to 160 ° C. for 1 hour, the temperature was raised to 185 ° C. over 1 hour, and 45 g of dimethylaminopropylamine was added dropwise over 1 hour.
After completion of the dropping, the temperature was maintained at 185 to 190 ° C. and aged for 7 hours to distill off by-product water out of the system. Further, the pressure was reduced (4.0 kPa) while maintaining at 170 to 190 ° C., and the mixture was allowed to stand for 1 hour, whereby unreacted dimethylaminopropylamine was distilled off to obtain B-2.
The conversion rate of stearic acid calculated from the acid value was 99.6%.

-(C) component C-1: Polyoxyethylene alkyl (carbon number 12) ether ether sulfate (AES) (average addition mole number of ethylene oxide 2); synthetic product.

C-1 was synthesized as follows.
Into a 4 L autoclave, 400 g of lauryl alcohol and 0.8 g of potassium hydroxide catalyst were charged, the inside of the autoclave was purged with nitrogen, and the temperature was increased while stirring. Thereafter, 54 g of ethylene oxide was introduced while maintaining a temperature of 180 ° C. and a pressure of 0.3 mPa, to obtain a reaction product having an average added mole number of ethylene oxide of 2.
Next, 274 g of the alcohol ethoxylate obtained above was placed in a 500 mL flask equipped with a stirrer, and after nitrogen substitution, 81 g of liquid sulfuric anhydride (sulfan) was slowly added dropwise while maintaining the reaction temperature at 40 ° C. After completion of the dropping, stirring was continued for 1 hour (sulfation reaction) to obtain polyoxyethylene alkyl ether sulfuric acid. Furthermore, C-1 was obtained by neutralizing this with sodium hydroxide aqueous solution.

  C-2: Polyoxyethylene alkyl (carbon number 12) sodium ether sulfate (NRES) (average addition mole number of ethylene oxide 2); synthetic product.

C-2 was synthesized as follows.
In a 4 L autoclave, 400 g of lauryl alcohol and 0.4 g of a composite metal oxide Lewis acid sintered solid catalyst composed of Al / Mg / Mn were charged, and the autoclave was purged with nitrogen and heated with stirring. . Thereafter, 54 g of ethylene oxide was introduced while maintaining the temperature at 180 ° C. and the pressure at 0.3 mPa, to obtain a reaction product.
Next, 274 g of the alcohol ethoxylate obtained above was placed in a 500 mL flask equipped with a stirrer, and after nitrogen substitution, 81 g of liquid sulfuric anhydride (sulfan) was slowly added dropwise while maintaining the reaction temperature at 40 ° C. After completion of the dropwise addition, stirring was continued for 1 hour to obtain the desired polyoxyethylene alkyl ether sulfuric acid. Furthermore, C-2 was obtained by neutralizing this with sodium hydroxide aqueous solution.

  C-3: linear alkyl (C11-15) sodium benzenesulfonate (LAS), manufactured by Lion Corporation, trade name “Lypon LS-250”.

Optional component POE silicone: Toray Dow Corning Co., Ltd., trade name “SH3375M”.
Ethanol: Product name “95 vol% synthetic ethanol” manufactured by NEDO.
p-Toluenesulfonic acid: manufactured by Kyowa Hakko Kogyo Co., Ltd.
Citric acid 3Na dihydrate: Made by Miles (USA), trade name “Sodium citrate”.
Benzoic acid Na: manufactured by Toagosei Co., Ltd., trade name “sodium benzoate”.
Fragrance composition: Fragrance composition A described in Tables 11 to 18 of JP-A No. 2002-146399.
Dye: Product name “Blue No. 1” manufactured by Hatake Kasei Co., Ltd.
Caisson CG: manufactured by Rohm and Haas.
Sodium hydroxide: manufactured by Tsurumi Soda Co., Ltd.
Sulfuric acid: Toho Zinc Co., Ltd.

≪Evaluation method≫
About the obtained liquid cleaning composition, it evaluated by the method and evaluation criteria shown below, and the result was written together in Table 1,2.

<Evaluation of flexibility imparting effect>
Seven commercially available T-shirts (100% cotton, manufactured by BVD) were placed in a two-tank washing machine (trade name: CW-C30A1, manufactured by Mitsubishi Electric Corporation), and the liquid detergent composition of each example was added to 30 L of tap water. An aqueous solution in which 15 mL of the product is dissolved is put in the two-tank washing machine, washed with a weak water flow for 10 minutes, washed for 1 minute, rinsed (repeated twice, 5 minutes each) and dehydrated for 1 minute as one step. A washing operation was performed. The temperature of the tap water used was adjusted to 25 ° C.
The T-shirt treated in the first washing operation was shaded and dried for 12 hours. Thereafter, the T-shirt was left in a constant temperature and humidity chamber at 25 ° C. and a humidity of 65% RH for 2 days. The T-shirt which gave the above process was used for evaluation of the softness | flexibility provision effect as test cloth.
In the above washing operation, 30 mL of a 20% by mass aqueous solution of a nonionic surfactant (an alcohol ethoxylate added with an average of 15 mol of ethylene oxide per mol of lauryl alcohol) was used as a liquid detergent composition in the same manner as described above. The T-shirt treated was used as an evaluation control cloth.
The evaluation of the flexibility-imparting effect was performed by performing one-pair comparison with the evaluation control cloth according to the following evaluation criteria by sensory means and obtaining an average value of 10 professional panelists. The average value was rounded off to the first decimal place and 3 or more points were regarded as acceptable levels.
(Evaluation criteria)
3 points: Felt softer than the control fabric.
2 points: felt slightly softer than the control cloth.
1 point: equivalent to the control cloth.

<Evaluation of gelation prevention at low temperature>
15 g of the liquid detergent composition of each example is collected in a 20 mL cup, left in a constant temperature room at 5 ° C. for 1 day, and the appearance (gelation degree) of the liquid detergent composition after 1 day is observed. According to the following evaluation criteria, The anti-gelling property at low temperature was evaluated.
(Evaluation criteria)
A: No gelation was observed at all.
○: Partial gelation was observed.
Δ: About half of the gel was formed.
X: The whole was gelatinized.

<Evaluation of cleaning power>
(1) Washing treatment method A 100th cotton plain weave cloth (uncontaminated cloth) cut into a 10 cm square was rubbed with sebum dirt on the face, and 10 pieces of sebum dirt cloth were prepared for each evaluation. A total of 2 kg of the sebum-stained cloth for a total amount of 2 kg and a commercially available T-shirt (100% cotton, manufactured by BVD) were combined with a fully automatic washing machine (trade name: NA-F802P, Matsushita Electric Industrial Co., Ltd.) ) Made).
Then, according to the bath ratio of 30 times, 15 mL of the liquid detergent composition of each example was dissolved in 30 L of tap water (hardness 3 ° DH) at 20 ° C., rinsed for 10 minutes, dehydrated for 1 minute, and rinsed (repeated twice) , Each for 5 minutes) and dehydration for 1 minute were performed as a single step.
(2) Detergency evaluation method The reflectance of the sebum-soiled cloth treated in the washing operation 1 step was measured with a color difference meter (trade name: SE200 type, manufactured by Nippon Denshoku Co., Ltd.), and the washing rate (%). Was calculated by the following formula.
Washing rate (%) = (K / S of sebum soiled cloth before washing process−K / S of sebum soiled cloth after washing process) / (K / S of sebum soiled cloth before washing process) −K of unsoiled cloth / S) × 100
Here, in the formula, K / S = (1−R / 100) ² / (2R / 100). However, R shows a reflectance (%).
The cleaning power was evaluated according to the following evaluation criteria using the cleaning rate (%) calculated by the above formula. The cleaning rate (%) was an average value of 10 sebum-stained cloths.
(Evaluation criteria)
A: The cleaning rate was 70% or more.
○: The cleaning rate was 65% or more and less than 70%.
Δ: The cleaning rate was 60% or more and less than 65%.
X: The cleaning rate was less than 60%.

As is clear from the results of Tables 1 and 2, the liquid detergent compositions of Examples 1 to 11 according to the present invention have good flexibility-imparting effects, anti-gelling properties at low temperatures, and detergency. I was able to confirm.
In addition, it was confirmed that the liquid detergent composition of Example 7 using NRES corresponding to the component (C1) as the component (C) was particularly excellent in anti-gelling property at low temperatures.

On the other hand, the liquid detergent composition of Comparative Example 1 in which the content of the component (A) exceeds 70% by mass has poor gelation prevention properties at low temperatures, and the content of the component (A) is less than 50% by mass. It was confirmed that the liquid detergent compositions of Examples 2 and 3 were inferior in detergency.
Moreover, it was confirmed that the liquid detergent composition of Comparative Example 4 using a comparative product different from the component (A) according to the present invention has poor gelation preventing properties at low temperatures.
Further, the liquid detergent composition of Comparative Example 5 lacking the component (B) has a poor flexibility-imparting effect, and the liquid detergent composition of Comparative Example 6 lacking the component (C) has an anti-gelling property at low temperatures. Was confirmed to be bad.

Claims (2)

A liquid detergent comprising 50 to 70% by mass of an alkylene oxide adduct (A) represented by the following general formula (I), an amidoamine compound (B), and an anionic surfactant (C) Composition.

[In Formula (I), R ¹ is a linear or branched alkyl group or alkenyl group having 9 to 13 carbon atoms, R ² is an alkylene group having 2 to 4 carbon atoms, and R ³ is carbon. N represents an alkyl group having 1 to 3; n represents an average number of added moles of alkylene oxide, and is 5 to 30. ] The liquid detergent composition of Claim 1 in which the said anionic surfactant (C) contains the polyoxyethylene alkyl ether sulfate ester salt (C1) represented by the following general formula (II).

[In the formula (II), R ⁴ represents a linear or branched alkyl group or alkenyl group having 6 to 24 carbon atoms; n ₁ represents the average number of moles of ethylene oxide added and is 1 to 6; . M is an alkali metal atom, an alkaline earth metal atom, an alkanolamine or ammonium. However, when the number of moles of ethylene oxide added in the ethylene oxide adduct that is the most present in the total ethylene oxide adduct constituting the component (C1) is “n _1max ”, the total ethylene oxide adduct The total proportion of the ethylene oxide adducts having an addition mole number of ethylene oxide of (n _1max −1), n _1max and (n _1max +1) is 55% by mass or more. ]