JP5764654B2 - Liquid cleaning agent - Google Patents

Description

The present invention relates to a liquid cleaning agent.
This application is based on Japanese Patent Application No. 2011-102349 filed in Japan on April 28, 2011, Japanese Patent Application No. 2011-111607, and Japanese Patent Application No. 2011-111458 filed in Japan on May 18, 2011. Claims priority and incorporates the contents here.

Washing of tableware or cooking utensils is usually performed while pouring a liquid detergent for kitchen onto a sponge. Liquid detergents for kitchens are required to have high detergency, foaming and foaming properties (foam amount, foaming speed) against oil stains attached to tableware or cooking utensils.
In order to improve the detergency, foaming, and foaming properties of oil stains, conventional liquid detergents for kitchens have been effective in cleaning with anionic surfactants, nonionic surfactants, amphoteric surfactants, etc. The ingredients are combined in an appropriate combination.
For example, a liquid detergent containing a specific polyoxyethylene alkyl ether sulfate ester salt and an amine oxide surfactant has been proposed (see Patent Documents 1 and 2).
For example, a liquid detergent containing a specific polyoxyalkylene alkyl ether sulfate ester salt, an amine oxide type surfactant, a hydrotrope agent, an organic solvent, and 2-ethylhexyl monoglyceryl ether has been proposed ( (See Patent Document 3).

JP 2008-156589 A JP 2008-156590 A JP 2010-13579 A

However, since the surface of tableware or the like is covered with foam while the tableware or the like is being cleaned using a sponge, it is difficult to confirm the removal of dirt during cleaning with a conventional liquid cleaning agent.
For this reason, it is not possible to confirm that the dirt has been removed from the dishes, etc., after the rinsing has been completed. There is a problem that you have to start over. Simply using a low-foaming detergent makes it difficult to obtain satisfaction with the removal of dishes such as dishes due to insufficient foaming or slow foaming.
In addition, when the amount of foam has decreased while washing dishes or cooking utensils, etc., or when washing dishes with a large amount of oil attached, add a liquid detergent to the sponge. Cleaning is performed.
However, when washing tableware with a large amount of oil attached, the conventional liquid detergent containing polyoxyethylene alkyl ether sulfate ester salt and amine oxide type surfactant has foaming properties (foam amount). , Foaming speed) is insufficient. In addition, when a large amount of liquid detergent is added to the sponge and the amount of use increases, there is a problem that the rinsing property (no null-sticking, no bubbles) is deteriorated. In particular, when the liquid cleaning agent poured into the sponge directly adheres to the tableware or the like, it takes time and effort to eliminate the feeling of nulliness from the tableware or the like due to rinsing.
In addition, liquid detergents containing polyoxyalkylene alkyl ether sulfates and amine oxide surfactants have excellent detergency and foaming properties, but they are nullified due to the influence of the surfactant from the hand skin by rinsing. There is a problem that it takes time, and it takes time and effort, and the amount of water used increases. In particular, such a problem becomes conspicuous when a large amount of liquid detergent is added to the sponge and the amount of use increases.
In the invention described in Patent Document 3, although the reduction of nulls at the time of washing dishes and the like is attempted by blending 2-ethylhexyl monoglyceryl ether, the effect of reducing the nulls is insufficient.
The present invention has been made in view of the above circumstances, and a liquid cleaning agent that can realize that the dirt has been removed even if tableware or the like is covered with foam during cleaning while maintaining foaming power. The issue is to provide.
Another object of the present invention is to provide a liquid detergent that is excellent in both foaming properties and rinsing properties even when cleaning dishes or the like to which dirt having a large amount of oil adheres.
Moreover, this invention makes it a subject to provide the liquid cleaning agent which has the outstanding washing | cleaning performance and the nullification of the hand skin at the time of washing | cleaning tableware etc. was suppressed.

The combination of a straight-chain alcohol ethoxy sulfate and an amine oxide type semipolar surfactant or amphoteric surfactant can improve detergency and foaming. It is covered with foam and can only be confirmed after the dirt has been removed. On the other hand, in such a combination of surfactants, if the amount of the surfactant is increased in order to improve the removal of dirt, the rinsing properties (goodness of foaming and non-nullness) become inferior. When the amount of the surfactant is reduced in order to suppress the amount of foam in the interior, there is a problem that foaming is delayed.
As a result of intensive studies, the present inventors have found that an anionic surfactant having a specific structure from among branched-chain compounds that are generally difficult to form an association state and are suitable components for low foaming compositions. By using together with other cleaning ingredients at a specified blending ratio, tableware and other items are covered with foam during cleaning while maintaining foaming power (ease of foaming and foam volume). However, the present inventors have found that the feeling of friction between the sponge and the tableware can be changed to realize that the dirt has been removed from the tableware, and the present invention has been completed.
In addition, the inventors have generally found that an anionic surfactant having a specific structure and a non-ionic surfactant among the branched compounds that are difficult to form an association state and are suitable components for low foaming compositions. The combination with an ionic surfactant is selected, and the present invention is completed by finding that the above-mentioned problems can be solved by using a combination of a cleaning component other than these and the anionic surfactant at a predetermined blending ratio. It came to do.
In addition, the present inventors generally select an anionic surfactant having a specific structure from among branched-chain compounds that are difficult to form an association state and are suitable components for low foaming compositions. It has been found that the above-mentioned problems can be solved by selecting and using a cleaning component other than this and a specific alkyl glyceryl ether in combination, and the present invention has been completed.

  That is, one aspect of the liquid detergent of the present invention contains a compound (a) represented by the following general formula (a1), and at least one of an amphoteric surfactant and a semipolar surfactant (b), The mass ratio represented by (a) component / (b) component is 0.5-6.

［式中、ｘとｙはそれぞれ１〜７の整数であり、ｘ＋ｙ＝８である。ＰＯはオキシプロピレン基、ＥＯはオキシエチレン基を表す。ｐはＰＯの平均繰返し数、ｑはＥＯの平均繰返し数を表し、ｐ＋ｑは１〜１０である。Ｍはアルカリ金属、アルカリ土類金属、アンモニウム又はアルカノールアミンを表す。］
また、ｐ＋ｑは０〜１０でもよい。

[Wherein, x and y are each an integer of 1 to 7, and x + y = 8. PO represents an oxypropylene group, and EO represents an oxyethylene group. p represents the average number of repetitions of PO, q represents the average number of repetitions of EO, and p + q is 1 to 10. M represents an alkali metal, alkaline earth metal, ammonium or alkanolamine. ]
Moreover, 0-10 may be sufficient as p + q.

In one aspect of the liquid detergent of the present invention, the fatty acid monoethanolamide compound (c), the compound (d) represented by the following general formula (d1), and the compound (f) represented by the following general formula (f1) It is preferable to further contain a compound selected from:
Also, a combination of two or more compounds selected from the fatty acid monoethanolamide compound (c), the compound (d) represented by the following general formula (d1), and the compound (f) represented by the following general formula (f1) It may be used.

［式（ｄ１）中、ｉとｊはそれぞれ１〜６の整数であり、６≦ｉ＋ｊ≦１２である。ＰＯはオキシプロピレン基、ＥＯはオキシエチレン基を表す。ｓはＰＯの平均繰返し数、ｔはＥＯの平均繰返し数を表し、ｓ＋ｔは６〜１２である。］

[In the formula (d1), i and j are each an integer of 1 to 6, and 6 ≦ i + j ≦ 12. PO represents an oxypropylene group, and EO represents an oxyethylene group. s represents the average number of repetitions of PO, t represents the average number of repetitions of EO, and s + t is 6-12. ]

［式中、Ｒ^１は炭素数６〜１４の直鎖状もしくは分岐鎖状のアルキル基、又は炭素数６〜１４の直鎖状もしくは分岐鎖状のアルケニル基を表す。ｎは平均繰返し数を表し、１〜４の数である。］
本発明の液体洗浄剤においては、［（ａ）成分＋（ｂ）成分］／（ｄ）成分で表される質量比が２〜１５であることが好ましい。
本発明の液体洗浄剤においては、［（ａ）成分＋（ｂ）成分］／（ｆ）成分で表される質量比が３〜１６０であることが好ましい。

[Wherein, R ¹ represents a linear or branched alkyl group having 6 to 14 carbon atoms, or a linear or branched alkenyl group having 6 to 14 carbon atoms. n represents the average number of repetitions and is a number of 1 to 4. ]
In the liquid cleaning agent of the present invention, the mass ratio represented by [(a) component + (b) component] / (d) component is preferably 2-15.
In the liquid detergent of this invention, it is preferable that mass ratio represented by [(a) component + (b) component] / (f) component is 3-160.

According to the liquid cleaning agent of the present invention, it is possible to realize that the dirt has been removed while maintaining the foaming power, even if dishes and the like are covered with foam during cleaning.
Furthermore, according to the present invention, it is possible to provide a liquid detergent that is excellent in both foaming properties and rinsing properties even when cleaning tableware or the like to which dirt having a large amount of oil adheres.
Moreover, according to this invention, it can provide the liquid cleaning agent which has the outstanding washing | cleaning performance and the nullification of the hand skin at the time of washing | cleaning tableware etc. was suppressed.

One aspect of the liquid detergent of the present invention contains the compound (a) represented by the general formula (a1) and at least one of an amphoteric surfactant and a semipolar surfactant (b).
Hereinafter, these components are also referred to as component (a) and component (b), respectively.
Moreover, the liquid cleaning agent of this invention may contain the compound (d) represented by the said general formula (d1) further.
Moreover, the liquid cleaning agent of this invention may contain the compound (f) represented by the said general formula (f1) further.
The liquid detergent of the present invention can be suitably used as a hard surface detergent. Here, the “hard surface” means a surface made of a hard material such as pottery, porcelain, glass, hard plastic, metal, painted metal, or tile. Specific examples thereof include tableware, cooking utensils, toilet bowls, window glass, vehicle glass, glasses, transparent plastic, mirrors; bathtubs, bathroom walls and floors, sinks, washstands, and the like. Especially, the liquid cleaning agent of this invention can be utilized especially suitably as cleaning agents for kitchens, such as tableware and cooking utensils.

<Compound (a)>
In the liquid detergent of the present invention, compound (a) is an anionic surfactant having a branched alkyl group represented by the following general formula (a1).
By containing the component (a), excellent foaming properties (foam amount, foaming speed) and rinsing properties are mainly imparted.
By using a combination of the component (a), the component (b) and the component (d), which will be described later, mainly with respect to dirt with a large amount of oil, excellent foaming properties (foam amount, foaming speed) Rinsing properties (no nulliness, no bubbles) can be obtained. Moreover, a high cleaning effect against oil stains can be obtained.
By using a combination of the component (a), the component (b) and the component (f), which will be described later, nulling of the hand skin when cleaning tableware or the like is suppressed.

［式中、ｘとｙはそれぞれ１〜７の整数であり、ｘ＋ｙ＝８である。ＰＯはオキシプロピレン基、ＥＯはオキシエチレン基を表す。ｐはＰＯの平均繰返し数、ｑはＥＯの平均繰返し数を表し、ｐ＋ｑは１〜１０である。Ｍはアルカリ金属、アルカリ土類金属、アンモニウム又はアルカノールアミンを表す。］

[Wherein, x and y are each an integer of 1 to 7, and x + y = 8. PO represents an oxypropylene group, and EO represents an oxyethylene group. p represents the average number of repetitions of PO, q represents the average number of repetitions of EO, and p + q is 1 to 10. M represents an alkali metal, alkaline earth metal, ammonium or alkanolamine. ]

In the formula (a1), x and y are each an integer of 1 to 7, and x + y = 8. By being x + y = 8, it becomes possible to actually feel that the dirt has been removed even if the dishes and the like are covered with foam during washing (a feeling of being washed is given). Further, when x + y = 8, both foaming properties and rinsing properties are improved. Moreover, it becomes easy to suppress the nullification of the hand skin at the time of washing tableware etc.
_{Examples of} C _x H _{2x + 1} and C _y H _{2y + 1} include a linear alkyl group or a branched alkyl group, respectively. In view of the balance between rinsing properties and rinsing properties, a linear alkyl group is preferred. Among them, C _x H _{2x + 1} and C _y H _{2y + 1} are particularly preferably a combination of a propyl group and a pentyl group (one of x and y is 3 and the other is 5).

In the formula (a1), PO represents an oxypropylene group, EO represents an oxyethylene group, p represents the average number of repetitions of PO, and q represents the average number of repetitions of EO.
p + q is 1 to 10, preferably 1 or more as a lower limit, and particularly preferably 3 or more. Further, the upper limit is preferably 5 or less, particularly preferably 4 or less. The upper limit value and the lower limit value can be arbitrarily combined. More specifically, p + q is preferably 1 to 5, and particularly preferably 3 to 4.
p + q may be 0-10. When p + q is 0 to 10, the detergency is excellent and the foaming property is good. Moreover, the low temperature stability of the liquid detergent is further improved.
In addition, when p + q is in the range of 1 to 10 described above, and in combination with the component (b) described later, when dirt is removed from the dishes, even during washing, the sponge and the dishes Friction is generated during the cleaning, and it is easy to obtain a washed feeling. In addition, the rinsing properties (goodness of foaming, no nulliness) are good. Furthermore, the detergency increases and bubbles are easily formed.
Moreover, when p + q is the range of said 1-10, it becomes easy to suppress the nullification of a hand skin. In addition, the detergency is excellent, and the foaming properties and rinsing properties are good.
Since component (a) has a high ability to lower dynamic interfacial tension, component (a) has a high diffusion speed in the cleaning liquid. Accordingly, the components (a) and (b) do not stay for a long time between the sponge and tableware. For this reason, when oil stains are removed while cleaning dishes with a sponge containing a liquid cleaning agent, a feeling of friction between the sponge and the dishes will be felt. . Thereby, even if dishes and the like are covered with foam during washing, it is considered that the dirt can be felt.
q is preferably from 1 to 10, and more preferably from 1 to 5.
p is preferably from 0 to 9, and more preferably from 0 to 4, from the viewpoints of washed feeling, foaming, and foaming properties, and from the balance between foaming properties and rinsing properties.
When PO and EO are mixed, the arrangement state of PO and EO is not particularly limited, and may be mixed in a random manner or in a block shape.
p and q represent the “average” number of repetitions of PO and EO, respectively. That is, the compound represented by the formula (a1) is an aggregate of molecules (including molecules having no PO or EO) having different numbers of repetitions of PO and EO. Further, it may be an assembly of molecules having different combinations of C _x H _{2x + 1} and C _y H _{2y + 1} .

In the formula (a1), M is an alkali metal, alkaline earth metal, ammonium or alkanolamine, and (C _x H _{2x + 1} ) (C _y H _{2y + 1} ) CH—CH ₂ O— (PO) p— (EO) ) q-SO ₃ ^- with as long as it can form a water-soluble salt.
Examples of the alkali metal include sodium and potassium. Examples of the alkaline earth metal include calcium and magnesium. Examples of the alkanolamine include monoethanolamine, diethanolamine, and triethanolamine.

(A) A component may be used individually by 1 type and may be used in combination of 2 or more type as appropriate.
Among these, the component (a) is preferably a sulfate of an alkylene oxide adduct of an alcohol having a branched structure at the β-position, which is obtained by bimolecular condensation by a gerbet reaction.
As the component (a), an alkylene oxide adduct of gerbet alcohol is mixed with, for example, liquid sulfuric anhydride or SO ₃ using a tank type reaction method, a film type reaction method, a tube type gas-liquid mixed phase reaction method, or the like. It can be produced by sulfating by contact with a gas or the like and then neutralizing with an alkali metal compound, an alkaline earth metal compound, ammonium or alkanolamine or the like.
Specific examples of gerbet alcohol alkylene oxide adducts include BASF's Rutensol XP30 (average number of moles of ethylene oxide added 3), Rutensol XP40 (average number of moles of ethylene oxide added 4), Rutensol XL40 (average of propylene oxide added) The number of moles is 1, and the average number of moles of ethylene oxide added is 3) (above, trade name).
Specifically, as component (a), a compound obtained by sulfating an alkylene oxide adduct having an average addition mole number of ethylene oxide of 3 and neutralizing with sodium hydroxide, an sulfation of an alkylene oxide adduct having an average addition mole number of ethylene oxide of 4 Preferred examples include compounds neutralized with sodium hydroxide, and compounds obtained by sulfating an alkylene oxide adduct having an average addition mole number of 4 of propylene oxide and neutralizing with sodium hydroxide.

In the liquid detergent, the blending amount of the component (a) is preferably 5% by mass or more, and more preferably 15% by mass or more, as a lower limit with respect to the total mass of the liquid detergent. Preferably, it is 20 mass% or more. As an upper limit, it is preferable that it is 40 mass% or less, and it is more preferable that it is 35 mass% or less. The upper limit value and the lower limit value can be arbitrarily combined. More specifically, the blending amount of the component (a) in the liquid detergent is preferably 5 to 40% by mass, and more preferably 15 to 35% by mass with respect to the total mass of the liquid detergent. Is more preferable, and it is further more preferable that it is 20-35 mass%.
When the blending amount of the component (a) is less than the lower limit, it is difficult to obtain a washed feeling. In addition, it is difficult for bubbles to form, and the rinsing properties are likely to decrease. On the other hand, if the upper limit value is exceeded, the rinsing properties tend to decrease.
(A) When the compounding quantity of a component is more than a lower limit, the foaming property and rinse property at the time of washing | cleaning the tableware etc. which the soil with much oil amount adhered will become more favorable. In addition, it is easy to obtain a feeling of being washed (a feeling of friction and a feeling of gulp). On the other hand, if the upper limit is exceeded, the rinsing properties may be reduced.

<Amphoteric surfactant and semipolar surfactant (b)>
In the present invention, at least one of the amphoteric surfactant and the semipolar surfactant (b) and the component (a) are used in combination at a predetermined blending ratio, so that mainly stains from dishes and the like during washing. When falling, friction starts to occur between the sponge and tableware and the like, and a feeling of being washed is given. In addition, high detergency against oil stains, good foaming and rinsing properties can be obtained.

(Amphoteric surfactant)
Amphoteric surfactants include betaine types such as aminoacetic acid betaines (such as alkylbetaines and alkylamidobetaines) and sulfobetaines (such as alkylhydroxysulfobetaines); glycine-based (such as imidazolinium betaines), and aminopropion. Amino acid type ones such as acid type ones can be mentioned.
Specific examples of amphoteric surfactants include betaine aminoacetates such as lauryldimethylaminoacetic acid betaine and amidopropyldimethylaminoacetic acid betaine; N-lauryl-N, N-dimethylammonium-N-propylsulfobetaine, N-lauryl Sulfobetaines such as -N, N-dimethylammonium-N- (2-hydroxypropyl) sulfobetaine, N-lauryl-N, N-dimethyl-N- (2-hydroxy-1-sulfopropyl) ammonium sulfobetaine; 2 -Glycines such as lauryl-N-carboxymethyl-N-hydroxyethylimidazolinium betaine and sodium lauryldiaminoethylglycine; aminopropionic acids such as sodium laurylaminopropionate and sodium laurylaminodipropionate Include those of.

(Semipolar surfactant)
In the present invention, the “semipolar surfactant” is a surfactant having a semipolar bond (a bond having an intermediate property between a nonpolar bond and a polar bond), and the semipolar surfactant is dissolved therein. Depending on the pH of the solution or dispersion system to be dispersed, it means that it becomes cationic, anionic, or bipolar.
Suitable examples of the semipolar surfactant include amine alkylene oxide surfactants and amine oxide surfactants. Of these, amine oxide type surfactants are preferred because they have good detergency against oil stains, foaming, and good foaming properties.
Examples of the amine oxide surfactant include alkylamine oxide, alkylamidopropyldimethylamine oxide, and the like. Among them, a compound represented by the following general formula (b1) is preferable.

［式中、Ｒ^２は炭素数８〜１８の直鎖状若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^３、Ｒ^４はそれぞれ独立して炭素数１〜３のアルキル基又はヒドロキシアルキル基であり、Ｒ^５は炭素数１〜４のアルキレン基である。Ｂは−ＣＯＮＨ−、−ＮＨＣＯ−、−ＣＯＯ−、−ＯＣＯ−又は−Ｏ−である。ｒは０又は１である。］

[Wherein, R ² is a linear or branched alkyl group or alkenyl group having 8 to 18 carbon atoms, and R ³ and R ⁴ are each independently an alkyl group or hydroxyalkyl having 1 to 3 carbon atoms. R ⁵ is an alkylene group having 1 to 4 carbon atoms. B is —CONH—, —NHCO—, —COO—, —OCO— or —O—. r is 0 or 1; ]

In the formula (b1), R ² is a linear or branched alkyl group having 8 to 18 carbon atoms, or a linear or branched alkenyl group having 8 to 18 carbon atoms, 8-18 linear or branched alkyl groups are preferred.
In the alkyl group and alkenyl group of R ^2, the number of carbon atoms is 8 to 18, and foaming properties when washing dishes with a large amount of oil attached, detergency against oil stains, and imparting a feeling of being washed Since an effect improves more, it is preferable that it is 10-14.
R ³ and R ⁴ are each independently an alkyl group having 1 to 3 carbon atoms or a hydroxyalkyl group having 1 to 3 carbon atoms, preferably an alkyl group having 1 to 3 carbon atoms, and more preferably a methyl group. R ³ and R ⁴ are more preferably methyl groups.
R ⁵ is an alkylene group having 1 to 4 carbon atoms.
B is —CONH—, —NHCO—, —COO—, —OCO— or —O—. r is 0 or 1, and 0 is preferable.

  Specific examples of the amine oxide type surfactant include alkyl dimethyl amine oxides such as lauryl dimethyl amine oxide, coconut alkyl dimethyl amine oxide, and lauryl diethyl amine oxide; And the like. Among them, alkyldimethylamine oxide has particularly good foaming and rinsing properties when washing dishes with a large amount of oil, such as detergency, cleaning power against oil stains, and the effect of providing a washed feeling. The system type is more preferred.

(B) A component may be used individually by 1 type and may be used in combination of 2 or more types as appropriate.
Among the above, as the component (b), in combination with the component (a), or in combination with the component (a) and the component (d) described later, dishes having a large amount of oil attached, etc. Is particularly good in terms of foaming and rinsing properties, washing power against oil stains, and the effect of imparting a washed feeling, so that aminoacetic acid betaines, sulfobetaines, alkyldimethylamine oxides, or alkanoylamides are used. Alkyldimethylamine oxides are preferred, and alkyldimethylamine oxides are particularly preferred.

In the liquid detergent, the blending amount of the component (b) is preferably 2% by mass or more, more preferably 3% by mass or more, and further preferably 5% by mass or more as a lower limit with respect to the total mass of the liquid detergent. . Moreover, it is preferable that it is 20 mass% or less as an upper limit, and it is more preferable that it is 15 mass% or less. The upper limit value and the lower limit value can be arbitrarily combined. More specifically, the blending amount of the component (b) in the liquid detergent is preferably 2 to 20% by mass and more preferably 3 to 15% by mass with respect to the total mass of the liquid detergent. Is more preferable, and it is further more preferable that it is 5-15 mass%.
(B) When the compounding quantity of a component exists in the said range, detergency will increase and a bubble will become easy to stand. Further, when the blending amount of the component (b) is equal to or more than the preferable lower limit value, the detergency against oil stains is increased, and the foamability and rinsing properties when washing dishes with a large amount of oil stains are better. (Foamability is further improved). On the other hand, when the preferable upper limit is exceeded, the viscosity of the liquid cleaning agent increases excessively, bubbles are less likely to be formed (foaming properties are reduced), and rinsing properties may be reduced.

In the present invention, “mass ratio represented by (a) component / (b) component” means the ratio (mass ratio) of the content of (a) component to the content of (b) component in the liquid detergent. Represents.
In the liquid detergent of the present invention, the mixing ratio of the component (a) and the component (b) is such that the mass ratio represented by the component (a) / (b) is 0.5 or more as a lower limit value. It is preferable that it is 1.5 or more. Moreover, it is 6 or less as an upper limit, and it is preferable that it is 5 or less. The upper limit value and the lower limit value can be arbitrarily combined. More specifically, the mass ratio represented by component (a) / component (b) is 0.5 to 6, preferably 1.5 to 5.
When the mass ratio is equal to or more than the lower limit value, a feeling of being cleaned during cleaning can be obtained. In addition, bubbles are easily formed, and the amount of foam and the persistence of the bubbles are further improved. In addition, the foaming property and the rinsing property when washing dishes with a large amount of oil attached are improved. On the other hand, if it is less than or equal to the upper limit value, in addition to the feeling of being cleaned during cleaning, the cleaning power against oil stains is further improved.

<Solvent: Water>
The liquid detergent of the present invention preferably contains water as a solvent from the viewpoint of ease of preparation of the liquid detergent, solubility in water when used, and the like.
The amount of water in the liquid detergent is preferably 40% by mass or more, more preferably 45% by mass or more, and more preferably 50% by mass or more as a lower limit with respect to the total mass of the liquid detergent. More preferably it is. Moreover, as an upper limit, it is preferable that it is 90 mass% or less, It is more preferable that it is 85 mass% or less, It is further more preferable that it is 80 mass% or less. The upper limit value and the lower limit value can be arbitrarily combined. More specifically, the blending amount of water in the liquid detergent is preferably 40 to 90 mass%, more preferably 45 to 85 mass%, and more preferably 50 to 80 mass% with respect to the total mass of the liquid detergent. Further preferred.
When the blending amount of water is at least the lower limit, the liquid stability of the liquid detergent with time will be better, and when it is not more than the upper limit, the liquid viscosity will be moderately low and good from the viewpoint of usability. .

<Other ingredients>
In the liquid cleaning agent of the present invention, other components other than the above-described components may be arbitrarily blended as necessary within the range not impairing the effects of the present invention.
The other components are not particularly limited, and components used in cleaning agents for hard surfaces or clothing can be blended. Specifically, those shown below are preferable.

(Fatty acid monoethanolamide compound (c))
The liquid detergent of the present invention preferably further contains a fatty acid monoethanolamide compound (c) (hereinafter referred to as “component (c)”). By containing the component (c), the persistence of the foam during cleaning and the cleaning power against oil stains are mainly increased.
Preferred examples of the component (c) include compounds represented by the following general formula (c1).

［式中、Ｒ^６は炭素数５〜１９のアルキル基を表す。ｍはオキシエチレン基（−Ｃ_２Ｈ_４Ｏ−）の平均繰返し数を表し、０〜９の数である。］

[Wherein R ⁶ represents an alkyl group having 5 to 19 carbon atoms. m represents the average number of repetitions of the oxyethylene group (—C ₂ H ₄ O—), and is a number from 0 to 9. ]

In the formula (c1), R ⁶ represents an alkyl group having 5 to 19 carbon atoms, and may be linear or branched.
In the alkyl group of R ⁶ , the carbon number is 5 to 19, and the detergency against oil stains and the persistence of foam are improved, and therefore, the number of carbon atoms is preferably 7 to 13.
m represents the average number of repetitions of the oxyethylene group (—C ₂ H ₄ O—), is a number from 0 to 9, is preferably a number from 0 to 4, and is a number from 0 to 2. More preferred.

Specific examples of the component (c) include polyoxyethylene (2) lauric acid monoethanolamide (R ⁶ in formula (c1) = a linear alkyl group having 11 carbon atoms, m = 2), polyoxyethylene (2) Capric acid monoethanolamide (R ⁶ in formula (c1) = a linear alkyl group having 9 carbon atoms, m = 2) and the like. Of these, polyoxyethylene (2) capric acid monoethanolamide is more preferable.

(C) A component may be used individually by 1 type and may be used in combination of 2 or more types as appropriate.
In the liquid detergent, the blending amount of the component (c) is preferably 1% by mass or more, and more preferably 2% by mass or more, as a lower limit with respect to the total mass of the liquid detergent. Moreover, it is preferable that it is 15 mass% or less as an upper limit, and it is more preferable that it is 10 mass% or less. The upper limit value and the lower limit value can be arbitrarily combined. In the liquid detergent, the blending amount of the component (c) is more preferably 1 to 15% by mass, and more preferably 2 to 10% by mass with respect to the total mass of the liquid detergent. It is.
When the blending amount of the component (c) is less than the preferred lower limit value, it may be difficult to obtain the effect of improving the foam persistence. On the other hand, when the preferred upper limit value is exceeded, the foam persistence increases, May be difficult.

In the liquid detergent of the present invention, the mass ratio represented by (c) component / [(a) component + (b) component] is preferably 0.1 or more as a lower limit, and is 0.2 or more. More preferably. Moreover, it is preferable that it is 0.5 or less as an upper limit, and it is more preferable that it is 0.4 or less. The upper limit value and the lower limit value can be arbitrarily combined. More specifically, the mass ratio represented by (c) component / [(a) component + (b) component] is preferably 0.1 to 0.5, more preferably 0.2 to 0.4. It is more preferable that
When the mass ratio is at least the lower limit, the sustainability of the foam is further improved. On the other hand, when the mass ratio is at most the upper limit, the foam is more likely to be formed, and the foamability, the amount of foaming, and the rinsing property are further improved.
In the present invention, “mass ratio represented by (c) component / [(a) component + (b) component]” is the total content of (a) component and (b) component in the liquid detergent. The ratio (mass ratio) of the content of the component (c) with respect to.

<Compound (d)>
The liquid detergent of the present invention preferably contains compound (d) (hereinafter referred to as “component (d)”).
The component (d) is represented by the following general formula (d1), and at least one of an oxyethylene group and an oxypropylene group is introduced into the alcohol, and the hydrophobic portion (hydrocarbon group) is a β-position carbon atom. It is a compound having a structure branched into C _i H _{2i + 1} and C _j H _{2j + 1} .
By containing the component (d), the foaming property is mainly maintained well even when a large amount of oil stains adhere to the sponge, and even when the cleaning liquid directly adheres to tableware, etc. Sex is obtained.
In addition, a unique effect by the blending of the component (d), that is, a feeling of elasticity can be felt when the sponge is gripped with a liquid detergent. By feeling this elasticity, the number of times the liquid detergent is added to the sponge when washing dishes, cooking utensils, etc. can be reduced, and the amount of liquid detergent used can be reduced. This is because when a liquid detergent is included in a sponge and gripped, (a) component, (b) component and (d) component, or (a) to (d) components associate to form a creamy foam. Therefore, it is considered.

［式（ｄ１）中、ｉとｊはそれぞれ１〜６の整数であり、６≦ｉ＋ｊ≦１２である。ＰＯはオキシプロピレン基、ＥＯはオキシエチレン基を表す。ｓはＰＯの平均繰返し数、ｔはＥＯの平均繰返し数を表し、ｓ＋ｔは６〜１２である。］

[In the formula (d1), i and j are each an integer of 1 to 6, and 6 ≦ i + j ≦ 12. PO represents an oxypropylene group, and EO represents an oxyethylene group. s represents the average number of repetitions of PO, t represents the average number of repetitions of EO, and s + t is 6-12. ]

In the formula (d1), i and j are each an integer of 1 to 6, and 6 ≦ i + j ≦ 12. Among them, 6 ≦ i + j ≦ 10 is preferable, 6 ≦ i + j ≦ 8 is more preferable, and i + j = 8 is particularly preferable because the foamability of the liquid cleaning agent and the persistence of the foam amount are further improved.
When i + j is 6 or more, the surface activity is increased, the adsorptivity to the liquid surface is increased, and both the foaming property and the sustainability of the foam amount are good when washing dishes with a large amount of oil attached. Become. In addition, a feeling of elasticity can be felt when the liquid detergent is held in a sponge. When i + j is 12 or less, the foaming property and the sustainability of the foam amount are excellent when washing dishes with a large amount of oil attached.
C _i H _{2i + 1} and C _j H _{2j + 1} each include a linear or branched alkyl group, preferably a linear alkyl group, such as a methyl group, an ethyl group, a propyl group, or a butyl group. Preferred examples include a group, a pentyl group and a hexyl group.
Among these, C _i H _{2i + 1} and C _j H _{2j + 1} are a combination of an ethyl group and a butyl group, a combination of a propyl group and a pentyl group (the above may be any one of the combinations). A combination of a propyl group and a pentyl group (one may be any group) is particularly preferable.

In the formula (d1), PO represents an oxypropylene group, and EO represents an oxyethylene group.
The component (d) has an oxyethylene group in the molecule because the foaming speed and the amount of foam of the liquid cleaning agent are further improved, and a good feeling of elasticity is obtained when it is included in a sponge. More preferable are those having only an oxyethylene group (no oxypropylene group), those having an oxyethylene group and an oxypropylene group and having more oxyethylene groups, and among them, Those having only an ethylene group are particularly preferred.
(D) In the case where the component has an oxyethylene group and an oxypropylene group, the foaming property when washing dishes with a large amount of oil attached, and a liquid cleaning agent are included in the sponge. The average number of repetitions (s) of the oxypropylene group is preferably 3 or less, and more preferably 1 or 2 because of excellent elasticity at the time.
When the component (d) has an oxyethylene group and an oxypropylene group, these oxyethylene group and oxypropylene group may be mixed in a random form or in a block form. .

In the formula (d1), s represents the average number of repetitions of PO, and t represents the average number of repetitions of EO. s + t is 6 to 12, preferably 9 to 10, and more preferably 9 or 10. When s + t is 6 or more, the foaming property and the sustainability of the foam amount are excellent when washing dishes with a large amount of oil attached. When s + t is 12 or less, the detergency against oil stains is good. In addition, a feeling of elasticity can be felt when the liquid detergent is held in a sponge. When s + t is 9 or 10, it is superior in foaming property and durability of the amount of foam when washing dishes with a large amount of oil attached, and when a liquid detergent is included in a sponge and grasped A feeling of elasticity can be felt more.
Here, s and t indicate “average” repetition numbers of PO and EO, respectively. Therefore, the compound represented by the formula (d1) is an assembly of molecules having different numbers of PO and EO repeats.

(D) A component can be used individually by 1 type or in mixture of 2 or more types.
Among these, as the component (d), s = 0, t = 9 or 10 is preferable, and one of i and j is 3 and the other is 5.
Further, as the component (d), an ethylene oxide adduct of alcohol having a branched structure at the β-position obtained by bimolecular condensation by the gerbet reaction is particularly preferable.
Examples of such commercially available products include polyoxyethylene mono (2-propylheptyl) ether manufactured by BASF Corporation. Specifically, i + j = 8, s = 0, t = 6 in the above formula (d1). The product name “Lutensol XP60”, i + j = 8 in the above formula (d1), s = 0, t = 9 and the product name “Lutensol XP90”, i + j = 8 in the above formula (c1), s = 0 , T = 10 compound and trade name “Lutensol XP100”.
Further, polyoxyethylene polyoxypropylene mono (2-propylheptyl) ether manufactured by BASF may be mentioned. Specifically, compounds of i + j = 8 and s + t = 9 in the above formula (d1) (oxyethylene group and Product name “Lutensol XL90”, i + j = 8 in the above formula (d1), and s + t = 10 compound (a mixture of oxyethylene group and oxypropylene group). Lutensol XL100 ".

The content of the component (d) in the liquid detergent composition is preferably 1% by mass or more, and more preferably 3% by mass or more, as a lower limit. The upper limit is preferably 15% by mass or less, and more preferably 10% by mass or less. The upper limit value and the lower limit value can be arbitrarily combined. More specifically, the content is preferably 1 to 15% by mass, and more preferably 3 to 10% by mass.
(D) If content of a component is more than a lower limit, the foaming property and rinse property at the time of washing | cleaning the tableware etc. which the soil with much oil amount adhered will become more favorable. On the other hand, if it is not more than the upper limit value, the detergency against oil stains is further improved.

In the liquid detergent of the present invention, the blending ratio of the component (a), the component (b), and the component (d) is a mass ratio represented by [(a) component + (b) component] / (d) component. However, the lower limit is preferably 1.5 or more, more preferably 2 or more, further preferably 3 or more, and particularly preferably 4 or more. The upper limit is preferably 15 or less, more preferably 10 or less, and even more preferably 7 or less. The upper limit value and the lower limit value can be arbitrarily combined. More specifically, it is preferably 1.5 to 15, more preferably 2 to 15, further preferably 3 to 10, and particularly preferably 4 to 7.
When the mass ratio is equal to or higher than the lower limit value, it is easy to obtain a feeling of being cleaned during cleaning. In addition, bubbles are easier to stand up faster. On the other hand, if it is less than or equal to the upper limit value, the foaming property and the rinsing property when washing dishes with a large amount of oil attached are improved.
In the present invention, the “mass ratio represented by [(a) component + (b) component] / (d) component” refers to (a) component and ( b) The ratio (mass ratio) of the total content with the component is represented.

In the liquid detergent of the present invention, the components (a) to (d) are preferably used in combination, and the mass ratio represented by (c) component / [(a) component + (b) component + (d) component] Is preferably 0.6 or less, more preferably 0.05 to 0.6.
When the mass ratio is less than or equal to the upper limit value, bubbles are more likely to stand up faster even when cleaning dishes or the like having a large amount of oil attached thereto. In addition, the amount of foam and rinsing properties are also improved. On the other hand, if it is at least the lower limit value, the sustainability of the foam is further improved. In the present invention, “mass ratio represented by (c) component / [(a) component + (b) component + (d) component]” refers to (a) component and (b) component in the liquid detergent. The ratio (mass ratio) of the content of (c) component with respect to the total content with (d) component is represented.

(Divalent metal salt (e))
The liquid detergent of the present invention preferably further contains a divalent metal salt (e) (hereinafter referred to as “component (e)”). (E) By containing a component, a detergency improves mainly.
As the component (e), magnesium salts such as magnesium chloride, magnesium sulfate, magnesium iodide, magnesium nitrate and magnesium bromide; calcium salts such as calcium chloride, calcium iodide, calcium bromide and calcium nitrate; zinc nitrate and sulfide Examples thereof include zinc salts such as zinc, zinc sulfate, zinc chloride, zinc acetate, ammonium zinc chloride, zinc gluconate, zinc tartrate, zinc perchlorate and zinc oxide.
Among these, zinc salts are preferable, and zinc sulfate and zinc oxide are particularly preferable because they can provide a sterilizing effect and an antibacterial effect in addition to the effect of improving detergency.

(E) A component may be used individually by 1 type and may be used in combination of 2 or more types as appropriate.
In the liquid detergent, the blending amount of the component (e) is preferably 0.01% by mass or more, and 0.05% by mass or more as a lower limit with respect to the total mass of the liquid detergent. Is more preferable, and it is further more preferable that it is 0.1 mass% or more. Moreover, as an upper limit, it is preferable that it is 2 mass% or less, it is more preferable that it is 1.5 mass% or less, and it is further more preferable that it is 1 mass% or less. The upper limit value and the lower limit value can be arbitrarily combined. More specifically, the blending amount of the component (e) in the liquid detergent is preferably 0.01 to 2% by mass, more preferably 0.05 to the total mass of the liquid detergent. It is -1.5 mass%, More preferably, it is 0.1-1 mass%.
When the blending amount of the component (e) is less than the preferred lower limit, it is difficult to obtain an effect of improving the cleaning power. Moreover, it is difficult to obtain a sterilizing effect and an antibacterial effect. On the other hand, even if the preferable upper limit is exceeded, further improvement in detergency, disinfection effect and antibacterial effect cannot be expected.

In the liquid detergent, the preferred concentration of the divalent metal derived from the component (e) is preferably 0.001% by mass or more as a lower limit with respect to the total mass of the liquid detergent. More preferably, the content is 0.01% by mass or more. As an upper limit, it is preferable that it is 0.5 mass% or less, and it is more preferable that it is 0.4 mass% or less. The upper limit value and the lower limit value can be arbitrarily combined. In the liquid cleaning agent, the preferred concentration of the divalent metal derived from the component (e) is more specifically 0.001 to 0.5% by mass with respect to the total mass of the liquid cleaning agent. Preferably, it is 0.01-0.4 mass%.
When the concentration of the divalent metal is less than the lower limit, it is difficult to obtain an effect of improving the detergency, a sterilizing effect, and an antibacterial effect (particularly in the case of zinc). On the other hand, even if the upper limit is exceeded, further improvement in detergency, disinfection effect and antibacterial effect (especially in the case of zinc) cannot be expected.

The concentration of the divalent metal derived from the component (e) relative to the total mass of the liquid detergent can be determined as follows.
For example, when 1 mass% of zinc sulfate heptahydrate (molecular weight 287.61) is contained in the liquid detergent, the content (mass%) of zinc in the liquid detergent is as follows.
Content of zinc in liquid detergent = blending amount of zinc sulfate heptahydrate in liquid detergent x (molecular weight of zinc / molecular weight of zinc sulfate heptahydrate)
= 1% by mass x (65.39 / 287.61)
= 0.23 mass%

In the liquid detergent of the present invention, the mass ratio represented by (a) component / (divalent metal) is preferably 150 to 3000, and more preferably 200 to 3000.
When the mass ratio is at least the lower limit value, the stability at low temperatures is further improved, and when it is at most the upper limit value, the detergency becomes better.
In the present invention, “mass ratio represented by (a) component / (divalent metal)” means the content of component (a) relative to the content of divalent metal derived from component (e) in the liquid detergent. Represents the ratio (mass ratio).

<Compound (f)>
The liquid detergent of the present invention preferably contains compound (f) (hereinafter referred to as “component (f)”). The component (f) is an alkyl glyceryl ether represented by the following general formula (f1), and the hand skin when washing dishes and the like is used by combining the component (a) and the component (b). The nulling is suppressed.

［式中、Ｒ^１は炭素数６〜１４の直鎖状もしくは分岐鎖状のアルキル基、又は炭素数６〜１４の直鎖状もしくは分岐鎖状のアルケニル基を表す。ｎは平均繰返し数を表し、１〜４の数である。］

[Wherein, R ¹ represents a linear or branched alkyl group having 6 to 14 carbon atoms, or a linear or branched alkenyl group having 6 to 14 carbon atoms. n represents the average number of repetitions and is a number of 1 to 4. ]

In the formula (f1), R ¹ is a linear or branched alkyl group having 6 to 14 carbon atoms, or a linear or branched alkenyl group having 6 to 14 carbon atoms.
In the alkyl group and the alkenyl group of R ^1, the number of carbon atoms is 6 to 14, and it is preferable that the number of carbon atoms is 6 to 12 because nulling of the hand skin when washing dishes and the like is easily suppressed. More preferably, it is C6-C11, More preferably, it is C6-C10, Most preferably, it is C8-C10.
Among them, R ¹ is preferably a linear or branched alkyl group having 6 to 14 carbon atoms because it is more suppressed from being null on the hand skin, specifically, an n-hexyl group, Examples include isohexyl group, n-heptyl group, n-octyl group, 2-ethylhexyl group, n-nonyl group, n-decyl group, isodecyl group, n-lauryl group and the like, and 2-ethylhexyl group and isodecyl group are particularly preferable. .
In the formula (f1), n _represents an average repeating number of _{(CH 2 CH (OH) CH} 2 O), the number of 1-4, a number of preferably 1-2, more preferably 1 It is.

(F) A component may be used individually by 1 type and may be used in combination of 2 or more types as appropriate.
Among the above, as the component (f), 2-ethylhexyl glyceryl ether and isodecyl glyceryl ether are preferable, and 2-ethylhexyl is preferable from the viewpoint that the nullification of the hand skin is more easily suppressed and the foaming property is good. Most preferred is glyceryl ether.
In the liquid detergent, the blending amount of the component (f) is preferably 0.1% by mass or more, and 0.3% by mass or more as a lower limit with respect to the total mass of the liquid detergent. Is more preferable, and it is further more preferable that it is 0.5 mass% or more. The upper limit is preferably 10% by mass or less, more preferably 8% by mass or less, and further preferably 7% by mass or less. The upper limit value and the lower limit value can be arbitrarily combined. More specifically, the content is preferably 0.1 to 10% by mass, more preferably 0.3 to 8% by mass, and still more preferably 0.5 to 7% by mass.
When the blending amount of the component (f) is within the above range, it is possible to more easily prevent the hand skin from being null when washing tableware and the like, and it is easy to obtain a composition having good foamability. Further, when the blending amount of the component (f) is less than the preferred lower limit value, it becomes difficult to obtain an effect of suppressing the nullification of the hand skin. On the other hand, when the preferred upper limit value is exceeded, the detergency against oil stains, foaming property Tends to decrease.

In the present invention, “mass ratio represented by [(a) component + (b) component] / (f) component” means that the (a) component and the (f) component content in the liquid detergent are ( b) The ratio (mass ratio) of the total content with the component is represented.
The mixing ratio of the component (a), the component (b), and the component (f) is such that the mass ratio represented by [(a) component + (b) component] / (f) component is 3 or more as a lower limit. Preferably, it is 6 or more. The upper limit is preferably 160 or less, more preferably 125 or less, and even more preferably 10 or less. The upper limit value and the lower limit value can be arbitrarily combined. More specifically, it is preferably 3 to 160, more preferably 3 to 125, particularly preferably 3 to 10, and most preferably 6 to 10.
When the mass ratio is at least the lower limit value, the detergency against oil stains is further improved. On the other hand, when it is equal to or lower than the upper limit, nulling of the hand skin when washing tableware and the like is further suppressed.

(Hydrotrope (g))
The liquid detergent of the present invention preferably further contains a hydrotrope agent (g) (hereinafter referred to as “component (g)”). By containing the component (g), the storage stability (particularly low-temperature stability) of the liquid detergent is mainly improved, and it becomes easier to ensure a more stable transparent appearance.

(G) As a component, aromatic sulfonic acid or its salt, aromatic carboxylic acid or its salt, C2-C4 alcohol, or other water-soluble solvents are mentioned.
Examples of the aromatic sulfonic acid include toluene sulfonic acid, cumene sulfonic acid, xylene sulfonic acid, substituted or unsubstituted naphthalene sulfonic acid, and the like, among which toluene sulfonic acid and cumene sulfonic acid are preferable.
Toluene sulfonic acid and cumene sulfonic acid may be any of the three isomers, o-form, m-form and p-form, respectively, and since they are easily available, p-form is preferred. Among them, p- Toluenesulfonic acid is more preferred.
Examples of the aromatic carboxylic acid include benzoic acid.
Salt forms of aromatic sulfonates and aromatic carboxylates include alkali metal salts such as sodium and potassium; alkaline earth metal salts such as magnesium and calcium; ammonium salts; monoethanolamine, diethanolamine, Examples include alkanolamine salts such as ethanolamine. Of these, alkali metal salts are preferable, and sodium salts are more preferable.
Among the alcohols having 2 to 4 carbon atoms, examples of the monohydric alcohol include ethanol, 1-propanol, 2-propanol, and 1-butanol. Examples of the polyhydric alcohol having 2 to 4 carbon atoms include ethylene glycol, propylene glycol, butylene glycol, glycerin and the like.
Examples of water-soluble solvents other than the above include polyethylene glycol and phenyl glycol.

(G) A component may be used individually by 1 type and may be used in combination of 2 or more types as appropriate.
As the component (g), since it is excellent in storage stability even under a low temperature condition, from the group consisting of an aromatic sulfonic acid or a salt thereof, an aromatic carboxylic acid or a salt thereof, and an alcohol having 2 to 4 carbon atoms. It is preferable to use at least one selected. Among them, it is preferable to use at least two selected from the group consisting of aromatic sulfonic acid, aromatic sulfonate, aromatic carboxylic acid, aromatic carboxylate, and alcohol having 2 to 4 carbon atoms. It is more preferable to use at least two selected from the group consisting of sulfonic acid, toluenesulfonic acid salt, cumenesulfonic acid, cumenesulfonic acid salt, benzoic acid, benzoic acid salt and ethanol, and among them, toluenesulfonic acid, It is particularly preferable to use ethanol in combination with at least one selected from the group consisting of toluene sulfonate, cumene sulfonate, cumene sulfonate, benzoic acid and benzoate.

In the liquid detergent, the blending amount of the component (g) is preferably 5% by mass or more and more preferably 6% by mass or more as a lower limit with respect to the total mass of the liquid detergent. As an upper limit, it is preferable that it is 30 mass% or less, It is more preferable that it is 20 mass% or less, It is further more preferable that it is 10 mass% or less. The upper limit value and the lower limit value can be arbitrarily combined. More specifically, the blending amount of the component (g) in the liquid detergent is preferably 5 to 30% by mass, more preferably 5 to 20% by mass with respect to the total mass of the liquid detergent. More preferably, it is 6-10 mass%.
When the blending amount of the component (g) is less than the preferred lower limit value, the blending effect of the component (g) may not be sufficiently obtained. On the other hand, when the blending amount exceeds the preferred upper limit value, the detergency may be reduced. .

In the liquid detergent of the present invention, the mass ratio represented by (g) component / [(a) component + (b) component] is preferably 0.15 to 0.5.
When the mass ratio is not less than the lower limit, stability at low temperatures is further improved, and when it is not more than the upper limit, detergency and foaming are improved.
In the liquid detergent composition of the present invention, the mass ratio represented by (g) component / [(a) component + (b) component + (d) component] is 0.15 or more as a lower limit. It is preferable that it is 0.2 or more. The upper limit is preferably 0.5 or less, and more preferably 0.4 or less. The upper limit value and the lower limit value can be arbitrarily combined. More specifically, it is preferably 0.15 to 0.5, and more preferably 0.2 to 0.4.
Within the range of this mass ratio, the low-temperature stability of the liquid detergent becomes better. In addition, when the mass ratio is at least the lower limit value, the sustainability of the foam is further improved, and when the mass ratio is not more than the upper limit value, the foam is likely to rise more quickly and the amount of foam is also improved.
In the present invention, “mass ratio represented by (g) component / [(a) component + (b) component + (d) component]” refers to (a) component and (b) component in the liquid detergent. The ratio (mass ratio) of the content of (g) component with respect to the total content with (d) component is represented.

  In the liquid cleaning agent of the present invention, as other components other than the components described above, a surfactant other than the above components (a) and (b), a pH adjuster such as sodium hydroxide, sulfuric acid, glycolic acid; Chelating agents, antioxidants, colorants, enzymes, fragrances, and the like can also be optionally blended.

The pH of the liquid cleaning agent of the present invention is preferably 5 to 8 at 25 ° C., more preferably 6.5 to 7.5.
When the pH of the liquid cleaning agent is 5 or more, the interaction between the component (a) and the component (b) is not too strong and can be moderately suppressed, so both components dissolve well and the liquid detergent has a transparent appearance. Makes it easier to keep more stable. In addition, gelation or solidification of the liquid detergent is less likely to occur. On the other hand, when the pH is 8 or less, the interaction between the component (a) and the component (b) does not become too weak, and the detergency against oil stains is further improved. Moreover, the persistence of foaming and foaming (foaming property and foam amount) of the liquid cleaning agent is further improved.
The pH of the liquid detergent (controlled at 25 ° C.) is a value measured by a method based on JIS K3362-1998 using a pH meter (product name: Horiba F-22, manufactured by Horiba, Ltd.). .

As described above, one aspect of the liquid cleaning agent of the present invention includes a compound (a) of a sulfate ester salt having a branched structure represented by the general formula (a1), an amphoteric surfactant, and a semipolar surfactant. At least one (b) is contained at a predetermined blending ratio (mass ratio of 0.5 to 6 represented by (a) component / (b) component). According to this liquid cleaning agent, it is possible to realize that the dirt has been removed while maintaining the foaming power, even if the dishes are covered with foam during the cleaning. The reason why such an effect is obtained is not certain but is presumed as follows.
Since a compound having a branched structure is generally difficult to form an associated state, it is often used to suppress foaming (for antifoaming agents, low foaming compositions, etc.).
However, it is considered that the component (a) can form a stable association state by mixing with the component (b) at a predetermined blending ratio. In addition, the component (a) having a specific structure branched at the β-position has a higher dynamic interfacial tension lowering ability than a general linear or branched anionic surfactant. For this reason, the component (a) has a high diffusion speed in the cleaning liquid, and accordingly, the component (a) and the component (b) do not stay for a long time between the sponge and the tableware. As a result, when oil stains are removed while washing dishes with a sponge containing a liquid cleaning agent, a feeling of friction is felt between the sponge and the dishes. . From the above, according to the liquid cleaning agent of the present invention, it is presumed that it is possible to feel that the dirt has been removed even if the dishes and the like are covered with foam while maintaining the foaming power.

In addition, the liquid detergent of the present invention has high detergency, is easy to foam, and has good rinsing properties. The reason is presumed as follows.
As described above, since the component (a) has a high ability to reduce the dynamic surface tension, the component (a) is quickly adsorbed to oil stains and the like, and the component (b) is quickly adsorbed to oil stains. Therefore, the decomposition (dispersion and dissolution) of the oil stain is promoted. Further, since the surfactant molecular film is rapidly formed, it is considered that bubbles are likely to be formed (foaming is quick). Furthermore, in the branched structure only at the β-position, the hydrophobic group tends to be bulky as compared with a general branched anionic surfactant. For this reason, it is presumed that rinsing properties (goodness of bubble breakage, non-nullness) are improved by being difficult to orientate densely at the gas-liquid interface and easily rupturing when the cleaning liquid is diluted.

In addition, according to the liquid cleaning agent of the present invention, foaming properties (foam amount, speed of foaming) and rinsing properties (non-nullness) can be achieved even when cleaning dishes with a large amount of oil attached. , And bubbles are all excellent. The reason why such an effect is obtained is not certain but is presumed as follows.
In one aspect of the liquid detergent of the present invention, an anionic surfactant (a) having a specific branched structure and at least one of an amphoteric surfactant and a semipolar surfactant (b) are mixed at a predetermined ratio. While containing by (mass ratio 0.5-6 represented by (a) component / (b) component), the nonionic surfactant (d) which has a specific branched structure is contained.
The component (a) having a specific structure branched at the β-position has a higher dynamic interfacial tension reducing ability than a general linear or branched anionic surfactant. Thereby, (a) component can be quickly orientated to the interface when a new interface is formed. Similarly, the component (d) having a specific structure branched at the β-position also has a characteristic that it is rapidly oriented at the gas-liquid interface during cleaning. Along with this, the orientation of the component (b) to the gas-liquid interface also becomes faster. The component (b) is blended with the component (a) at a predetermined ratio, and after the components (a) to (d) are oriented at the gas-liquid interface, the static between the component (a) and the component (b) A stable association state is formed by the electrical action and the interaction between the oxyalkylene group having an appropriate number of repetitions in the components (a) and (d) and the hydrophilic portion in the component (b). . By these actions, formation of the surfactant molecular film of the components (a) to (d) is promoted. For this reason, it is considered that bubbles are formed quickly and abundant amounts of bubbles are formed quickly even when washing dishes with a large amount of oil attached thereto.
Furthermore, since both the component (a) and the component (d) have a β-position branched structure, the hydrophobic group tends to be bulky as compared with a general branched anionic surfactant. For this reason, it is difficult to orientate densely at the gas-liquid interface, and when the cleaning liquid is diluted, bubbles are easily broken. For this reason, it is thought that the rinsing property is good.

Moreover, the liquid detergent of this invention has the outstanding washing | cleaning performance, and the nullification of the hand skin at the time of washing | cleaning tableware etc. is suppressed.
One aspect of the liquid detergent of the present invention includes an anionic surfactant (a) having a specific branched structure, at least one of an amphoteric surfactant and a semipolar surfactant (b), and a specific alkyl glyceryl ether. (F).
The component (a) having a specific structure branched at the β-position has a higher dynamic interfacial tension reducing ability than a general linear or branched anionic surfactant. Thereby, (a) component can be quickly orientated to the interface when a new interface is formed. Therefore, at the time of washing, the component (a) is quickly adsorbed to the oil stain and the like, and the adsorption of the component (b) to the oil stain is also accelerated, and the decomposition (dispersion and dissolution) of the oil stain is promoted. In addition, since the component (a) has a β-position branched structure, the hydrophobic group tends to be bulky as compared with a general branched anionic surfactant. For this reason, it is hard to orientate densely at the interface and is easily washed away by rinsing.
In the present invention, due to the synergistic action of the component (a), the component (b), and the component (f) as described above, a large amount of liquid detergent is added to the sponge, and the amount of use increases. Even if it is a case, since these components are washed away from a finger | toe quickly by rinsing, it is thought that the nullification of a hand skin is suppressed.

  The liquid cleaning agent of the present invention has a high concentration of surfactant when it is washed while pouring onto a sponge, so the hand skin may become null due to an excess of the surfactant. Is preferred.

  Hereinafter, the present invention will be described in more detail using examples, but the present invention is not limited to these examples.

<Preparation of liquid detergent>
According to the blending composition shown in the table, each of the liquid detergents of each example was prepared by the following production method (when there is an unblended component, the component is not blended).
The unit of the blending amount in the table is “mass%”, and all the components indicate the equivalent amount of pure component. About (e) component, the compounding quantity as a bivalent metal salt (e-1 and e-2 are hydrated salts) was shown in the upper stage, and the bivalent metal conversion quantity was shown in the parenthesis of the lower stage. The divalent metal equivalent for e-1 and e-2 is the zinc equivalent, and the divalent metal equivalent for e-3 is the magnesium equivalent.
The liquid detergent of each example was prepared by balancing with water so that the total of each component described in the table was 100% by mass. Each component used was kept at 50 ° C.

[Method for producing liquid detergent]
First, in a 200 mL beaker, (a) component or (a ′) component, (c) component or (c ′) component, (d) component or (d ′) component, (e) component, (f ) Component, (g) component and PEG 1000 were added and stirred with a magnetic stirrer. Next, the component (b) was added and stirred.
Next, water was added and stirred so that the total amount (the total amount was 100 parts by mass) was 93 parts by mass. Thereafter, glycolic acid and sodium hydroxide (0.1N sodium hydroxide) are added to adjust the pH, and the remaining water is added and balanced so that the total amount becomes 100 parts by mass. Were manufactured respectively.
“Balance” indicating the blending amount of water means the balance added so that the total blending amount (% by mass) of all the blending components contained in the liquid detergent is 100% by mass.
“Suitable amount” indicating the blending amount of sodium hydroxide indicates the amount of sodium hydroxide blended in order to adjust the pH (25 ° C.) of the liquid detergent to 7.0 after blending a predetermined amount of glycolic acid. .
The pH was measured by adjusting the liquid detergent to 25 ° C. and using a glass electrode type pH meter (product name: Horiba F-22, manufactured by Horiba, Ltd.). The measuring method was performed based on JIS K3362-1998.

In the table, (a) / (b) means the ratio (mass ratio) of the content of component (a) to the content of component (b) in the liquid detergent.
(C) / [(a) + (b)] is the ratio (mass ratio) of the content of component (c) to the total content of component (a) and component (b) in the liquid detergent. Means.
(A) / (Divalent metal) means the ratio (mass ratio) of the content of the component (a) to the content of the divalent metal derived from the component (e) in the liquid detergent.

[(A) + (b)] / (d) is the ratio (mass ratio) of the total content of the component (a) and the component (b) to the content of the component (d) in the liquid detergent. Means.
(C) / [(a) + (b) + (d)] is the component (c) relative to the total content of the components (a), (b), and (d) in the liquid detergent. The ratio (mass ratio) of the content of.
[(A) + (b)] / (f) is the ratio (mass ratio) of the total content of the component (a) and the component (b) to the content of the component (f) in the liquid detergent. Means. (G) / [(a) + (b) + (d)] is the component (g) relative to the total content of component (a), component (b) and component (d) in the liquid detergent. The ratio (mass ratio) of the content of.
Below, the component shown in the table | surface is demonstrated.

(A) Component a-1: Polyoxyethylene mono (2-propylheptyl) ether sulfate Na, C _x H _{2x + 1} = propyl group, C _y H _{2y + 1} = pentyl group, x + y = 8 in the above formula (a1) Corresponds to p = 0, q = 3, M = sodium.
[Preparation example of a-1]
290 g of “Lutensol XP30” manufactured by BASF 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, this was neutralized with an aqueous sodium hydroxide solution to obtain a-1.

a-2: Polyoxyethylene mono (2-propylheptyl) ether sulfate Na, C _x H _{2x + 1} = propyl group, C _y H _{2y + 1} = pentyl group, x + y = 8, p = 0, q in the above formula (a1) = 4, M = corresponding to sodium.
[Preparation example of a-2]
It was prepared in the same manner as a-1 except that 334 g of “Lutensol XP40” manufactured by BASF was used instead of “Lutensol XP30” manufactured by BASF.

a-3: Polyoxyethylene polyoxypropylene mono (2-propylheptyl) ether sulfate Na, C _x H _{2x + 1} = propyl group, C _y H _{2y + 1} = pentyl group, x + y = 8, p in the above general formula (a1) = 1, q = 3, M = corresponding to sodium.
[Preparation example of a-3]
It was prepared in the same manner as a-1 except that 349 g of “Lutensol XL40” manufactured by BASF was used instead of “Lutensol XP30” manufactured by BASF.

a-4: mono (2-propylheptyl) ether sulfate Na, C _x H _{2x + 1} = propyl group, C _y H _{2y + 1} = pentyl group, x + y = 8, p = 0, q = 0 in the above formula (a1) M = corresponds to sodium.
[Preparation Example of a-4] Hexylaldehyde was subjected to Gelbe condensation (dimerization) with an alkali, and 158 g of 2-propylheptanol obtained in this manner was placed in a 500 mL flask equipped with a stirrer. After nitrogen substitution, liquid sulfuric anhydride ( 81 g of sulfone 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 alkyl ether sulfuric acid. Furthermore, a-4 was obtained by neutralizing this with sodium hydroxide aqueous solution.

-Comparison component of component (a) [hereinafter referred to as “component (a ′)”. ]
a′-1: polyoxyethylene mono (2-butyloctyl) ether sulfate Na, C _x H _{2x + 1} = butyl group, C _y H _{2y + 1} = hexyl group, x + y = 10, p = 0 in the above formula (a1) q = 2, M = corresponding to sodium.
[Preparation example of a′-1]
In a 4 L autoclave, 372 g of a trade name “ISOFOL12” (C _x H _{2x + 1} = butyl group, C _y H _{2y + 1} = hexyl group in the above formula (a1)) manufactured by Sasol Co., and 0.8 g of potassium hydroxide catalyst The autoclave was charged with nitrogen and the temperature was raised while stirring. Thereafter, 181 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 addition 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 dropwise addition, stirring was continued for 1 hour to obtain the desired polyoxyethylene alkyl ether sulfuric acid. Furthermore, this was neutralized with an aqueous sodium hydroxide solution to obtain a′-1.

a′-2: mono (2-propylheptyl) ether sulfate Na, C _x H _{2x + 1} = propyl group, C _y H _{2y + 1} = pentyl group, x + y = 8, p = 0, q = 0 in the above formula (a1) , M = corresponding to sodium.
[Preparation example of a′-2]
Hexylaldehyde was subjected to gel condensation (dimerization) with alkali, and 158 g of 2-propylheptanol obtained in this manner was placed in a 500 mL flask equipped with a stirrer, and after nitrogen substitution, 81 g of liquid sulfuric anhydride (sulfane) It was dripped slowly, keeping at 40 degreeC. After completion of the dropwise addition, stirring was continued for 1 hour to obtain the desired alkyl ether sulfuric acid. Furthermore, this was neutralized with an aqueous sodium hydroxide solution to obtain a′-2.

a'-3: Sulfur oxide of an ethylene oxide average 3 mol addition product of a branched alcohol having 13 carbon atoms
[Preparation example of a′-3]
BASF “Lutensol TO3” (332 g) 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, this was neutralized with an aqueous sodium hydroxide solution to obtain a′-3.

a′-4: Sulfur oxide of an ethylene oxide average 3 mol addition product of a synthetic alcohol having 12 to 13 carbon atoms.
[Preparation example of a′-4]
A 4 L autoclave was charged with 400 g of a trade name “Safol23” manufactured by Sasol and 0.8 g of a potassium hydroxide catalyst. The autoclave was purged with nitrogen and heated while stirring. Thereafter, 271 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 3. Next, 334 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, this was neutralized with an aqueous sodium hydroxide solution to obtain a′-4.

a′-5: Sulfur oxide of an addition product of an average of 2 moles of ethylene oxide of a synthetic alcohol having 12 to 13 carbon atoms.
[Preparation example of a′-5]
In a 4 L autoclave, 400 g of a trade name “Neodol 23” manufactured by Shell and 0.8 g of a potassium hydroxide catalyst were charged, and the inside of the autoclave was purged with nitrogen and heated while stirring. Thereafter, 181 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 addition mole number of ethylene oxide of 2. Next, 280 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, this was neutralized with an aqueous sodium hydroxide solution to obtain a′-5.

-(B) component b-1: AX, C12 alkyldimethylamine oxide (the product name "Aromox DM12D-W" by the Lion Akzo company).
b-2: HSB, N-lauryl-N, N-dimethyl-N- (2-hydroxy-1-sulfopropyl) ammonium sulfobetaine, abbreviated as C12 hydroxysulfobetaine (trade name “Amphithol 20HD” manufactured by Kao Corporation) .

-(C) component c-1: C12MEA (2), polyoxyethylene lauric acid monoethanolamide, R < ⁶ > in said formula (c1) = C11 linear alkyl group, m = 2. Abbreviation LME (2).
[Preparation Example of c-1]
214 g of methyl laurate (product name “Pastel M-12”, manufactured by Lion Corporation), 64.1 g of monoethanolamine (manufactured by Tokyo Chemical Industry Co., Ltd.) and sodium methylate (product name, manufactured by Nippon Shokubai Co., Ltd.) “SM-28”, 28 mass% product) 7.7 g (1.0 mass% to fatty acid methyl ester) was added, and methanol by-product was heated and stirred while distilling off under reduced pressure (40 Pa to 1.3 kPa, When the reaction pressure reached 1.3 kPa, the mixture was aged at a reaction temperature of 90 ° C. for 3 hours to prepare 240 g of lauric acid monoethanolamide.
The obtained lauric acid monoethanolamide was charged into a 1 L autoclave, 1.0 mol of ethylene oxide was charged with respect to lauric acid monoethanolamide, and an addition reaction was performed at 90 ° C. for 2 hours to obtain C12MEA (2). It was.

c-2: C10MEA (2), polyoxyethylene capric acid monoethanolamide, R ⁶ in the above formula (c1) = a linear alkyl group having 9 carbon atoms, m = 2. Abbreviation CME (2).
[Preparation example of c-2]
C10MEA (2) was prepared in the same manner as C12MEA (2), except that methyl caprate (manufactured by Lion Corporation, trade name “Pastel M-10”) was used instead of methyl laurate.

(D) Component d-1: Polyoxyethylene mono (2-propylheptyl) ether, manufactured by BASF, trade name “Lutensol XP60”, C _i H _{2i + 1} in the above general formula (d1) = propyl group, C _j H _{2j + 1} = pentyl group, i + j = 8, s = 0, t = 6.
d-2: Polyoxyethylene mono (2-propylheptyl) ether, manufactured by BASF, trade name “Lutensol XP90”, C _i H _{2i + 1} = propyl group, C _j H _{2j + 1} = pentyl group in the above general formula (d1) , I + j = 8, s = 0, t = 9.
d-3: Polyoxyethylene mono (2-propylheptyl) ether, manufactured by BASF, trade name “Lutensol XP100”, C _i H _{2i + 1} = propyl group, C _j H _{2j + 1} = pentyl group in the above general formula (d1) , I + j = 8, s = 0, t = 10.
d-4: Polyoxyethylene polyoxypropylene mono (2-propylheptyl) ether, manufactured by BASF, trade name “Lutensol XL90”, C _i H _{2i + 1} in the above general formula (d1) = propyl group, C _j H _{2j + 1} = Corresponds to pentyl group, i + j = 8, s + t = 9 (a mixture of oxyethylene group and oxypropylene group).
d-5: polyoxyethylene polyoxypropylene mono (2-propylheptyl) ether, manufactured by BASF, trade name “Lutensol XL100”, C _i H _{2i + 1} in the above general formula (d1) = propyl group, C _j H _{2j + 1} = Corresponding to pentyl group, i + j = 8, s + t = 10 (a mixture of oxyethylene group and oxypropylene group).

-Comparison component of component (d) [hereinafter referred to as “component (d ′)”. ]
d′-1: polyoxyethylene mono (2-propylheptyl) ether, manufactured by BASF, trade name “Lutensol XP40”, C _i H _{2i + 1} = propyl group, C _j H _{2j + 1} = pentyl in the above general formula (d1) Group, i + j = 8, s = 0, t = 4.
d′-2: polyoxyethylene mono (2-propylheptyl) ether, manufactured by BASF, trade name “Lutensol XP140”, C _i H _{2i + 1} = propyl group, C _j H _{2j + 1} = pentyl in the above general formula (d1) Group, i + j = 8, s = 0, t = 14.

(E) Component e-1: Zinc sulfate heptahydrate, manufactured by Junsei Chemical Co., Ltd., reagent grade (molecular weight of heptahydrate 289).
e-2: Zinc oxide, manufactured by Mitsui Kinzoku Co., Ltd. (molecular weight 81).
e-3: Magnesium sulfate heptahydrate, manufactured by Umai Kasei Kogyo, purified magnesium sulfate (molecular weight 247 of heptahydrate).

-(F) component f-1: 2-ethylhexyl monoglyceryl ether, R < ¹ > = 2-ethylhexyl group in said formula (f1), n = 1 is corresponded.
f-2: Isodecyl monoglyceryl ether, R ¹ = isodecyl group in the above formula (f1), corresponding to n = 1.

(F) Component comparison component [hereinafter referred to as “(f ′) component”. ]
f′-1: equivalent to isodecyl monoglyceryl ether, R ¹ in the above formula (f1) = isodecyl group, n = 6.
-(G) component g-1: p-toluenesulfonic acid, the Kyowa Hakko Chemical Co., Ltd. product, the abbreviation p-TSH of p-toluenesulfonic acid.
g-2: Ethanol, manufactured by Junsei Chemical Co., Ltd., reagent special grade.

Other components PEG1000: Polyethylene glycol 1000, manufactured by Lion Corporation, trade name “PEG # 1000” (average molecular weight 1000).
Glycolic acid: DuPont's trade name “Grip Pure 70”.
Na hydroxide: sodium hydroxide, manufactured by Tsurumi Soda Co., Ltd.
Water: tap water.

<Evaluation of liquid detergent>
Each liquid cleaning agent in each example was evaluated by the following evaluation methods, and the results were also shown in the table.

[Evaluation of ease of foaming]
Take a sponge for dishwashing (product name: Scotch Bright, Sumitomo 3M Co., Ltd., product name: Scotch Bright) measuring 11.5 cm long × 7.5 cm wide × 3 cm high and take 38 g of water and 2 g of the liquid cleaning agent in each case. The state after foaming (the state of foam formation) was evaluated by 10 people according to the following evaluation criteria (a).
(Evaluation criteria (a))
3 points: Foam covered the entire surface of the sponge.
2 points: The ratio of foam covering the sponge surface was 80% or more and less than 100% of the surface area of the sponge.
1 point: The ratio of foam covering the sponge surface was 50% or more and less than 80% of the surface area of the sponge.
0 point: The ratio of the foam covering the sponge surface was less than 50% of the surface area of the sponge.
The average value of the 10 persons was calculated, and the ease of foaming (speed of foaming) was evaluated according to the following evaluation criteria (b).
(Evaluation criteria (b))
S: The average value of 10 people is 2.8 points or more.
A: The average value of 10 people is 2.6 points or more and less than 2.8 points.
B: The average value of 10 people is 2.4 points or more and less than 2.6 points.
C: The average value of 10 people is less than 2.4 points.

[Evaluation of washed feeling]
Into a dishwashing sponge (product name: Scotch Bright, 11.5 cm long × 7.5 cm wide × 3 cm high), 38 g of water and 2 g of the liquid cleaning agent in each example were taken, 1 g of olive oil, A ceramic dish (φ = 23 cm) on which 5 mL of water was placed was washed while being rubbed with the sponge. The cleaning is done by rubbing around the pottery plate once and with a sponge so that a circle is drawn five times on one side of the pottery plate (φ = 23 cm) and then a circle is drawn twice on the other side. By the method. According to the following evaluation criteria (c), an evaluation was made on the washed feeling of the earthenware dish being washed.
(Evaluation criteria (c))
Two points: During the cleaning, the dirt from the ceramic dish was clearly felt by the change in friction between the sponge and the ceramic dish.
1 point: During cleaning, it was felt that dirt was removed from the pottery plate due to a change in friction between the sponge and the pottery plate.
0 point: No change in friction between sponge and earthenware dish was felt during washing.
In addition, in the case of 2 points and 1 point of the evaluation standard (c), the scrubbing is interrupted when friction is felt between the sponge and the ceramic dish, and the ceramic dish in which bubbles remain is treated with tap water (flow rate 100 mL / s). , 25 ° C.) for 5 seconds, and it was confirmed whether or not dirt was removed from the ceramic dish. As a result, in all cases, there was no oil film, no stickiness when touched by hand due to residual oil, and the dirt was removed from the ceramic dish.
Evaluation of the washed feeling was performed by 10 people, and the average score of the 10 people was calculated and shown in the table.

[Rinse evaluation-1]
Take a sponge for dishwashing (product name: Scotch Bright, Sumitomo 3M Co., Ltd., product name: Scotch Bright) measuring 11.5 cm in length, 7.5 cm in width, and 3 cm in height. Frozen and foamed by hand 5 times. With a foamed sponge, 5 pieces of a ceramic dish (φ = 23 cm) were rubbed 5 times so as to draw a circle on the surface of the ceramic dish. Next, while rinsing the pottery plate in which bubbles remained, tap water (flow rate 100 mL / s, 25 ° C.) was used to measure the time from when bubbles disappeared until the fingers no longer felt null. This operation was repeated 5 times, the average value was calculated, and the rinsing property was evaluated according to the following evaluation criteria. A or more was considered as good rinsing property.
(Evaluation criteria)
S: The average value of 5 times was within 30 seconds.
A: The average value of 5 times was within the range of 31 to 35 seconds.
B: The average value of 5 times was in the range of 36 to 40 seconds.
C: The average value of 5 times was 41 seconds or more.

[Evaluation of cleaning power]
1 g of beef tallow was applied uniformly on the entire inner surface of a tapper container having a length of 10 cm, a width of 15 cm, and a height of 5 cm to obtain a dirt model.
Next, 38 g of 25 ° C. tap water and 2 g of liquid detergent are taken into a sponge for dishwashing (product name: Scotch Bright, manufactured by Sumitomo 3M Co., Ltd.) measuring 11.5 cm long × 7.5 cm wide × 3 cm high. After rubbing by hand, the soil model was washed in the same way as is done at home.
Next, after rinsing well with tap water at 25 ° C., the tactile sensation when touching the portion of the inner surface of the tappa container on which the beef tallow was applied was evaluated.
This evaluation was performed according to the following evaluation criteria (S to A are acceptable ranges), and was used as an evaluation of detergency against oil stains.
(Evaluation criteria)
SSS: When any part of the tapper container was touched, there was no oil film, no stickiness due to residual oil was felt, and a strong frictional force was felt when rubbed with a finger.
SS: When touching any part of the tapper container, there was no oil film, no luster due to residual oil was felt, and a frictional force was felt when rubbed with a finger.
S: Even if any part of the tapper container was touched, there was no oil film, and the oily residue was not felt.
A: A slight amount of luster remains on the corner of the inside of the tapper container. However, when the bottom and side surfaces of the inner side of the tapper container are touched, there is no film due to oil, and no luster due to residual oil is felt. There was no level.
B: When the bottom surface inside the tapper container was touched, there was no oil film, and no sliminess due to residual oil was felt, but there was a slimness left on the side surfaces and corners inside the tapper container.
C: It was found that the entire tapper container was slippery and oil remained clearly.

[Evaluation of foam persistence]
Take a sponge for washing dishes (product name: Scotch Bright, 11.5 cm long x 7.5 cm wide x 3 cm high) with 38 g of water and 2 g of the liquid cleaning agent in each case. I got in. Thereafter, the sponge was brought into contact with a ceramic dish (φ = 23 cm) on which 1 g of olive oil and 5 g of water were placed, so that the dirt and the sponge were mixed.
Then, with the sponge pressed against the earthenware dish, it was scrubbed by moving it so as to draw a circle twice on the surface of the earthenware dish. The end point was the time when the foam reached 5% of the entire surface of the pottery plate, and the number of pottery plates that had been washed up to the end point was determined to evaluate the sustainability of the bubble.
Moreover, the sustainability of foam was evaluated according to the following evaluation criteria.
(Evaluation criteria)
S: The number of ceramic plates was 24 or more.
A: The number of ceramic plates was 22-23.
B: The number of ceramic plates was 20-21.
C: The number of pottery plates was 19 or less.

[Evaluation of foaming property]
This test method evaluated the ease of foaming when soil with a large amount of oil coexists.
Take a sponge for dishwashing (product name: Scotch Bright, Sumitomo 3M Co., Ltd., trade name: Scotch Bright) measuring 11.5 cm in length, 7.5 cm in width, and 3 cm in height. The state after squeezing with a hand (the state of foaming) was evaluated based on the following evaluation criteria. When the evaluation results were S and A, the foamability (the amount of foam and the speed of foaming) was considered good.
(Evaluation criteria)
S: Foam covered the entire surface of the sponge.
A: The ratio of the foam covering the sponge surface was 80% or more and less than 100% of the surface area of the sponge.
B: The ratio of the foam covering the sponge surface was 50% or more and less than 80% of the surface area of the sponge.
C: The ratio of the foam covering the sponge surface was less than 50% of the surface area of the sponge.

[Rinseability Evaluation-2]
This test evaluated the ease of rinsing the tableware when the liquid detergent adhered directly to the tableware.
One piece was prepared by placing 1.0 g of a liquid detergent on a pottery dish (φ = 23 cm) and lightly extending the liquid detergent over one surface of the pottery dish with a finger. Then, this one piece of the ceramic dish was rinsed with tap water (25 ° C.) having a flow rate of 5 L / min. At that time, the rinsing time required until the null cleaning derived from the liquid detergent disappeared was measured with a stopwatch.
This measurement was performed by 10 persons, the average value of the rinsing time was determined, and rinsing properties were evaluated based on the following evaluation criteria.
(Evaluation criteria)
S: The rinsing time was 3 seconds or more and less than 6 seconds.
A: The rinsing time was 6 seconds or more and less than 9 seconds.
B: The rinsing time was 9 seconds or more and less than 12 seconds.
C: The rinse time was 12 seconds or more.

[Evaluation of nullability of hand skin]
Into a dishwashing sponge (Sumitomo 3M Co., Ltd., trade name: Scotch Bright) measuring 11.5 cm in length × 7.5 cm in width × 3 cm in height, 38 g of water and 6 g of the liquid cleaning agent in each example were taken. Frozen and foamed by hand 5 times. With a foamed sponge, five ceramic dishes (φ = 23 cm) were scrubbed 5 times so as to draw a circle on the surface of the ceramic dish. Thereafter, the hand was rinsed with tap water (flow rate 100 mL / s, 25 ° C.), and the rinsing time until the finger was not nullified was measured.
The measurement of the rinsing time was performed by five persons, the average value of the five persons was calculated, and the nullability of the hand skin was evaluated according to the following evaluation criteria. A and S were assumed to have good nullness on the hand skin.
(Evaluation criteria)
Rinse time (average value of 5 people) until there is no null fingering
SS: 4 seconds or less.
S: It was in the range of 5 to 7 seconds.
A: It was in the range of 8 to 10 seconds.
B: Within the range of 11-20 seconds.
C: It was 21 seconds or more.

[Evaluation of low-temperature stability]
100 mL of the liquid cleaning agent of each example was filled in a cylindrical glass bottle having a diameter of 50 mm and a height of 100 mm, and the lid was closed and sealed. In this state, the appearance of the liquid detergent after being stored in a thermostatic bath at −5 ° C. (low temperature condition) for one month was visually observed to determine whether or not the “uniformly transparent” state was maintained. When the presence of an object was recognized, the low-temperature stability (appearance) of the liquid detergent was evaluated by determining “the ratio (%) of the amount of precipitates to the total volume of the cylindrical glass bottle”.

From the results shown in the table, it can be confirmed that the liquid detergents of Examples 1 to 29 to which the present invention is applied are easily foamed and have a high feeling of being washed. Therefore, according to the liquid detergents of Examples 1 to 29, it can be seen that the dirt is removed even if the dishes and the like are covered with foam during cleaning while maintaining the foaming power.
In addition, it can be seen that the liquid detergents of Examples 1 to 29 have good rinsing properties and excellent detergency.

From the results shown in Table 3, it can be seen that the liquid detergents of Examples 15 to 22 that further contain the component (c) have good foam persistence.
From the evaluation results of the liquid detergents of Examples 2, 14, 23 to 29, it can be seen that the cleaning power is further increased by further containing the component (e).

  From the results shown in the table, the liquid detergents of Examples 30 to 58 to which the present invention is applied are excellent in washed feeling, excellent in foaming property against dirt with a large amount of oil, and good in rinsing properties. I understand that.

  From the results shown in the table, the liquid detergents of Examples 59 to 76 to which the present invention is applied have excellent cleaning performance, and the skin with a null skin when washing dishes and the like is suppressed. I understand that.

According to the liquid cleaning agent of the present invention, it is possible to realize that the dirt has been removed even if the dishes are covered with foam during cleaning while maintaining the foaming power.

Claims (6)

A compound (a) represented by the following general formula (a1), and at least one of an amphoteric surfactant and a semipolar surfactant (b),
(A) Liquid cleaning agent characterized by the mass ratio represented by component / (b) component being 0.5-6.

[Wherein, x and y are each an integer of 1 to 7, and x + y = 8. PO represents an oxypropylene group, and EO represents an oxyethylene group. p represents the average number of repetitions of PO, q represents the average number of repetitions of EO, and p + q is 1 to 10. M represents an alkali metal, alkaline earth metal, ammonium or alkanolamine. ]   The liquid detergent according to claim 1, further comprising a fatty acid monoethanolamide compound (c). The liquid cleaning agent according to claim 1, further comprising a compound (d) represented by the following general formula (d1).

[In the formula (d1), i and j are each an integer of 1 to 6, and 6 ≦ i + j ≦ 12. PO represents an oxypropylene group, and EO represents an oxyethylene group. s represents the average number of repetitions of PO, t represents the average number of repetitions of EO, and s + t is 6-12. ]   The liquid detergent according to claim 3, wherein the mass ratio represented by [(a) component + (b) component] / (d) component is 2-15. The liquid cleaning agent according to any one of claims 1 to 4, further comprising a compound (f) represented by the following general formula (f1).

[Wherein, R ¹ represents a linear or branched alkyl group having 6 to 14 carbon atoms, or a linear or branched alkenyl group having 6 to 14 carbon atoms. n represents the average number of repetitions and is a number of 1 to 4. ]   6. The liquid detergent according to claim 5, wherein a mass ratio represented by [(a) component + (b) component] / (f) component is 3 to 160.