JP6275122B2 - Liquid cleaning agent - Google Patents

Description

The present invention relates to a liquid cleaning agent.
This application claims priority based on Japanese Patent Application No. 2013-085808 for which it applied to Japan on April 16, 2013, and uses the content here.

Cleaning agents used for washing clothes and the like include powder types and liquid types. In recent years, the use ratio of liquid detergents has been increasing in that there are few concerns about undissolved residues and direct application to clothing and the like (see Patent Document 1).
The cleaning agent is required to have a high cleaning power against dirt adhering to clothes and the like. Among dirt adhering to clothing and the like, dirt with a high load (for example, sebum dirt) containing a large amount of solids and oil is difficult to remove, and a high detergency is required for such a heavy dirt.

For dirt with a high load, it is considered effective to apply a liquid cleaning agent directly to the dirt.
In order to improve the coating cleaning power when the liquid cleaning agent is applied directly to the dirt for cleaning, there is a method in which the liquid cleaning agent has a high surfactant concentration (concentrated composition).
As a liquid detergent of concentrated composition, for example, specific alkylene oxide adduct (nonionic surfactant) 50-70 mass% and non-soap anionic surfactant 1-10 with respect to the total mass of the liquid detergent A liquid detergent containing mass% and a water-miscible organic solvent has been proposed (see Patent Document 2).

Special table 2007-500288 JP 2009-173858 A

However, since the liquid detergent having a concentrated composition as described in Patent Document 2 easily penetrates into clothing, there is a problem that the liquid detergent is difficult to stay on the cloth and a sufficient coating cleaning power cannot be exhibited.
For example, if the viscosity of the liquid cleaning agent is increased, the liquid cleaning agent tends to stay on the cloth. However, liquid detergents with high viscosity have poor usability, such as poor fluidity, difficult to pour into caps, poor drainage from caps to the inlet of washing machines, and poor drainage from inlets.

  This invention is made | formed in view of the said situation, and it aims at providing the liquid cleaning agent which is excellent in application | coating cleaning power, and is excellent also in usability.

  As a result of intensive studies, the present inventors have determined that a specific nonionic surfactant, at least one component selected from the group consisting of a specific triglyceride component and a higher alcohol (for example, an alcohol having 6 to 18 carbon atoms), an anion It has been found that the above-mentioned problems can be solved by a liquid detergent that is used in combination with a surfactant and contains a surfactant at a high concentration.

That is, this invention has the following aspects.
[1] The following (A) component, (B) component, and (C) component are contained, and the total content of all the surfactants is 45% by mass or more based on the total mass of the liquid detergent, The liquid detergent, which is 80% by mass or less:
Component (A): a group consisting of a compound represented by the following general formula (a-1), a compound represented by the following general formula (a-2), and a compound represented by the following general formula (a-4) A nonionic surfactant comprising at least one compound selected from:
(B) component: at least one compound selected from the group consisting of a compound represented by the following general formula (b-1) and an alcohol having 6 to 18 carbon atoms; and (C) component: an anionic surfactant;

In formula (a-1), R ¹ is a hydrocarbon group having 9 to 13 carbon atoms, R ² is an alkylene group having 2 to 4 carbon atoms, and R ³ is an alkyl group having 1 to 4 carbon atoms. , M is a number from 5 to 25 indicating the average number of repetitions of OR ² ;

In the formula (a-2), R ⁴ is a hydrocarbon group having 10 to 20 carbon atoms, EO is an oxyethylene group, PO is an oxypropylene group, and s represents an average number of repetitions of EO 5 And t is a number from 1 to 4 indicating the average number of repetitions of PO; [-(EO) _s- (PO) _t- ] is EO and PO,-(EO) _s- (PO) It means that they may be mixed and arranged regardless of the order of _t −. ;

In formula (a-4), R 1 is a hydrocarbon group having 10 to 20 carbon atoms; A ¹ O and A ² O are each independently an oxyalkylene group having 2 to 4 carbon atoms; p is A ¹ O Q represents the average number of repetitions of A ² O, p> 0, q> 0, and p + q is a number of 10 or more and less than 60;

In formula (b-1), Z ^{1 to} Z ³ each independently represent a hydrogen atom, a hydroxy group, or a carboxy group, and a + b = 7 to 19, c + d = 7 to 19, and e + f = 7 to 19.

[2] The liquid cleaning agent according to [1], wherein the (C) component / (A) component, which is a mass ratio of the (C) component and the (A) component, is 0.02 to 0.7.

  The liquid cleaning agent of the present invention is excellent in coating cleaning power and is also excellent in usability.

Hereinafter, the present invention will be described in detail.
The liquid detergent of the present invention contains the following component (A), component (B), and component (C).

<(A) component>
The component (A) is a nonionic surfactant containing at least one compound selected from the group consisting of the following compound (A1), the following compound (A2) and the following compound (A4). The component (A) is a component that imparts cleaning performance to the liquid cleaning agent of the present invention. In addition to at least one compound selected from the group consisting of the compound (A1), the compound (A2) and the compound (A4), the component (A) is a nonionic surfactant (hereinafter referred to as “other nonion”). It may also be referred to as a “surfactant”.

(Compound (A1))
The compound (A1) is a compound represented by the following general formula (a-1).

（式（ａ−１）中、Ｒ^１は炭素数９〜１３の炭化水素基であり、Ｒ^２は炭素数２〜４のアルキレン基であり、Ｒ^３は炭素数１〜４のアルキル基であり、ｍはＯＲ^２の平均繰り返し数を示す５〜２５の数である。）

(In Formula (a-1), R ¹ is a hydrocarbon group having 9 to 13 carbon atoms, R ² is an alkylene group having 2 to 4 carbon atoms, and R ³ is an alkyl group having 1 to 4 carbon atoms. There, m is a number from 5 to 25 showing an average number of repetitions of OR ^2.)

In said formula (a-1), R < ¹ > is a C9-C13 hydrocarbon group. The hydrocarbon group may be linear or branched and may contain a cyclic structure.
R ¹ is preferably an aliphatic hydrocarbon group, more preferably a linear or branched alkyl group, or a linear or branched alkenyl group. Carbon number of a hydrocarbon group is 9-13, 10-13 are preferable and 11-13 are more preferable. If carbon number is 9 or more, detergency will increase. On the other hand, if the number of carbon atoms is 13 or less, the liquid stability is improved, and particularly gelation is suppressed.

R ² is an alkylene group having 2 to 4 carbon atoms, preferably an ethylene group or a propylene group. Incidentally, ethylene group herein is _-CH 2 CH ₂ - means a structure represented by the structure of the propylene group _means a structure represented by -CH _{2 CH} 2 _CH 2.
the m OR ² is, all may be the same or may be different. That is, the alkylene group in one molecule may be one type or a combination of two or more types. In particular, good foaming during cleaning, because it is inexpensive, it is preferable that the m OR ² are all oxyethylene groups, or oxyethylene groups and oxypropylene groups are mixed.
When the alkylene group is a combination of two or more, the method for adding OR ² is not particularly limited. For example, the addition method in the case where an oxyethylene group and an oxypropylene group are mixed may be random addition or block addition. Examples of the block addition method include a method of adding propylene oxide after adding ethylene oxide, a method of adding ethylene oxide after adding propylene oxide, a method of adding propylene oxide after adding ethylene oxide, and further adding ethylene oxide. Can be mentioned.

R ³ is an alkyl group having 1 to 4 carbon atoms, preferably an alkyl group having 1 to 3 carbon atoms.
Specific examples of R ³ include a methyl group, an ethyl group, an n-propyl group, an isopropyl group, and an n-butyl group. Of these, a methyl group and an ethyl group are preferable, and a methyl group is more preferable.
If the carbon number is 1 or more, precipitation during low-temperature storage is likely to be suppressed. On the other hand, if the carbon number is 4 or less, the solubility of the liquid cleaning agent in water under low temperature conditions is improved.

m is a number of 5 to 25 indicating the average number of repeats (average number of added moles) of the OR ² group (oxyalkylene group). If m is 5 or more, the detergency, particularly the detergency against sebum stains is improved. On the other hand, if m is 25 or less, the solubility of the liquid detergent in water is improved. When all m pieces of OR ² are oxyethylene groups, m is preferably 5 to 20, and more preferably 12 to 18. Note that m may be an integer or may include a decimal.
In m OR < ² >, when oxyethylene group and oxypropylene group are mixed, 12-21 are preferable for m. At this time, the average number of repeating oxypropylene groups is preferably 1 or more and 5 or less, more preferably 1 or more and 4 or less, and even more preferably 1 or more and 3 or less. When the average number of repeating oxypropylene groups exceeds 5, the cleaning power and liquid stability (transparency uniformity, stability over time, etc.) as a liquid detergent may be reduced.
Here, the “average number of repeating OR ² groups (average number of added moles)” means the average number of moles of alkylene oxide added to 1 mole of the fatty acid ester used.
The “average number of added moles” in the present specification can be determined by, for example, NMR.

In the compound (A1), the narrow ratio indicating the distribution ratio of compounds (alkylene oxide adducts) having different OR ² repeat numbers is preferably 20% by mass or more based on the total mass of the compound (A1). It is preferable that the upper limit of the narrow ratio is substantially 80% by mass or less. The narrow ratio is 20 to 80% by mass, more preferably 20 to 50% by mass, and the liquid stability and the solubility in water are further improved. preferable.
The higher the narrow rate, the easier it is to obtain good detergency. Further, when the narrow ratio is 20% by mass or more, particularly 30% by mass or more, a liquid cleaning agent with less raw material odor derived from the compound (A1) is easily obtained. This is because, after the production of the compound (A1), a fatty acid ester which is present in the product of the compound (A1) and is a raw material of the compound (A1) coexisting with the compound (A1), and the general formula (a-1) This is because the number of alkylene oxide adducts in which m is 1 or 2 is reduced.

In the present specification, the “narrow ratio” refers to a value represented by the following mathematical formula (S), which indicates a distribution ratio of compounds having different OR ² repetition numbers.

In the formula (S), m _max represents the number of repetitions of OR ² of the compound (alkylene oxide adduct) which is most abundant in the entire compound (A1).
i represents the number of repetitions of OR ² .
Yi represents the ratio (% by mass) of the compound (alkylene oxide adduct) in which the number of repetitions of OR ² present in the entire compound (A1) is i with respect to the total mass of the compound (A1).

The narrow rate can be controlled by, for example, the production method of the compound (A1).
The production method of the compound (A1) is not particularly limited. For example, a method in which an alkylene oxide is addition-polymerized to a fatty acid alkyl ester using a surface-modified composite metal oxide catalyst (JP 2000-144179 A). Can be easily manufactured.
As such a surface-modified suitable composite metal oxide catalyst, specifically, metal ions (Al ³⁺ , Ga ³⁺ , In ³⁺ , Tl ³⁺ , Co ³⁺ , which are surface-modified with a metal hydroxide or the like are used. , Sc ³⁺ , La ³⁺ , Mn ^2+, etc.) and a composite metal oxide catalyst such as magnesium oxide; surface-modified with at least one component selected from the group consisting of metal hydroxides and metal alkoxides Examples thereof include a calcined product of hydrotalcite.
Further, in the surface modification of the composite metal oxide catalyst, the composite metal oxide is mixed with at least one component selected from the group consisting of metal hydroxide and metal alkoxide, and the composite metal oxide is used. When it is 100 parts by mass, the proportion of at least one component selected from the group consisting of metal hydroxides and metal alkoxides relative to 100 parts by mass of the composite metal oxide is 0.5 to 10 parts by mass. Is preferable, and it is more preferable to set it as 1-5 mass parts.

A compound (A1) may be used individually by 1 type, and may be used in combination of 2 or more type as appropriate.
The content of the compound (A1) is preferably 1 to 70% by mass, more preferably 10 to 50% by mass, and further preferably 15 to 45% by mass, when the total mass of the liquid detergent is 100% by mass. When the content of the compound (A1) is 1% by mass or more, good detergency can be obtained. On the other hand, if the content of the compound (A1) is 70% by mass or less, gelation with time will hardly occur.

(Compound (A2))
The compound (A2) is a compound represented by the following general formula (a-2).

（式（ａ−２）中、Ｒ^４は炭素数１０〜２０の炭化水素基であり、ＥＯはオキシエチレン基であり、ＰＯはオキシプロピレン基であり、ｓはＥＯの平均繰り返し数を示す５〜２０の数であり、ｔはＰＯの平均繰り返し数を示す１〜４の数であり；［−（ＥＯ）_ｓ−（ＰＯ）_ｔ−］とは、ＥＯとＰＯとが式−（ＥＯ）_ｓ−（ＰＯ）_ｔ−の順序によらず混在して配列してもよいことを表す。）

(In the formula (a-2), R ⁴ is a hydrocarbon group having 10 to 20 carbon atoms, EO is an oxyethylene group, PO is an oxypropylene group, and s indicates the average number of repetitions of EO 5 T is a number of 1 to 4 indicating the average number of repetitions of PO; [-(EO) _s- (PO) _t- ] means that EO and PO are represented by the formula-(EO) (Indicates that they may be mixed and arranged regardless of the order of _s- (PO) _t- ).)

In said formula (a-2), R < ⁴ > is a C10-C20 hydrocarbon group. The hydrocarbon group may be linear or branched and may contain a cyclic structure.
R ⁴ is preferably an aliphatic hydrocarbon group, more preferably a linear or branched alkyl group and a linear or branched alkenyl group. Carbon number of the said hydrocarbon group is 10-20, 12-18 are preferable and 12-14 are more preferable. If carbon number is 10 or more, detergency will increase. On the other hand, if the number of carbon atoms is 20 or less, the liquid stability is improved, and particularly gelation is suppressed.
Compound (A2) may be a mixture of a single chain length or a mixture of a plurality of chain lengths. R ⁴ is derived from a raw material alcohol (R ⁴ —OH), and examples of the alcohol include alcohols derived from natural fats and oils such as coconut oil, palm oil, and beef tallow; synthetic alcohols derived from petroleum.

s is the number of 5-20 which shows the average repeating number (average addition mole number) of EO group (oxyethylene group). s may be an integer or may include a decimal number. When s is within the above range, the cleaning power, particularly the cleaning power against sebum dirt is improved. As for s, 5-18 are preferable.
t is the number of 1-4 which shows the average repeating number (average addition mole number) of PO group (oxypropylene group). t may be an integer or may include a decimal. If t is in the above range, gelation of the liquid detergent is likely to be suppressed, and good foamability is easily obtained at the time of rinsing. t is preferably 1 to 3.
Here, “average number of repeating EO groups (average number of added moles)” means the average number of moles of ethylene oxide to be added to 1 mole of alcohol used.
Here, “the average number of repeating PO groups (average number of added moles)” means the average number of moles of propylene oxide added to 1 mole of alcohol used.

In the compound (A2), [— (EO) _s — (PO) _t —] means that EO and PO may be mixed and arranged in the order of the left formula. That is, EO and PO may be added in a block shape or may be added in a random shape. Examples of the addition method when EO and PO are added in a block form include the addition methods exemplified above in the description of the compound (A1). In particular, a method of adding ethylene oxide after adding ethylene oxide and further adding ethylene oxide is preferable because rinsing properties in washing in a fully automatic washing machine become better.

In the compound (A2), the addition mole number distribution of EO and PO is not particularly limited, and the addition mole number distribution can be controlled by the production method of the compound (A2) and the like.
For example, when EO and PO are added to a hydrophobic raw material using a general alkali catalyst such as sodium hydroxide or potassium hydroxide, the distribution tends to be relatively wide. Further, specific alkoxyl such as magnesium oxide to which metal ions such as Al ³⁺ , Ga ³⁺ , In ³⁺ , Tl ³⁺ , Co ³⁺ , Sc ³⁺ , La ³⁺ , Mn ^{2+ and the} like described in JP-B-615038 are added. When EO and PO are added to a hydrophobic raw material using an oxidization catalyst, there is a tendency that a relatively narrow addition mole number distribution is obtained.

A compound (A2) may be used individually by 1 type, and may be used in combination of 2 or more type as appropriate.
The content of the compound (A2) is preferably 1 to 70% by mass, more preferably 10 to 50% by mass, and still more preferably 15 to 45% by mass, when the total mass of the liquid detergent is 100% by mass. If the content of the compound (A2) is 1% by mass or more, good detergency can be obtained. On the other hand, if the content of the compound (A2) is 70% by mass or less, gelation with time will hardly occur.

(Compound (A4))
The compound (A4) is a compound represented by the following general formula (a-4).

（式中、Ｒ^１は炭素数１０〜２０の炭化水素基であり；Ａ^１Ｏ及びＡ^２Ｏはそれぞれ独立に炭素数２〜４のオキシアルキレン基であり；ｐはＡ^１Ｏの平均繰返し数を表し、ｑはＡ^２Ｏの平均繰返し数を表し、ｐ＞０、ｑ＞０であり、ｐ＋ｑは１０以上６０未満の数である。）

(Wherein R ¹ is a hydrocarbon group having 10 to 20 carbon atoms; A ¹ O and A ² O are each independently an oxyalkylene group having 2 to 4 carbon atoms; p is an average repeat of A ¹ O) Q represents the average number of repetitions of A ² O, p> 0, q> 0, and p + q is a number of 10 or more and less than 60.)

In said formula (a-4), R < ¹ > is a C10-C20 hydrocarbon group. From the viewpoint of detergency, an alkyl group having 10 to 18 carbon atoms or an alkenyl group having 10 to 18 carbon atoms is preferable, and may be linear or branched.
When the carbon number of R ¹ is 10 or more, the effect of preventing recontamination is enhanced, and the cleaning power is improved. On the other hand, when the carbon number of R ¹ is 20 or less, solubility in water is improved.

In the formula (a-4), A ¹ O and A ² O are each independently an oxyalkylene group having 2 to 4 carbon atoms, preferably an oxyethylene group or an oxypropylene group. A ¹ O and A ² O may be the same as or different from each other.
In the formula (a-4), p represents the average number of repetitions of A ¹ O, q represents the average number of repetitions of A ² O, and p and q each independently exceed 0. p + q is a number of 10 or more and less than 60. When p + q is less than 10, it is difficult to obtain a cleaning effect. On the other hand, when p + q is 60 or more, as the molecular weight of the compound (A4) itself increases, the number of moles of the compound (A4) in the composition decreases at the same blending amount, so that the cleaning effect tends to decrease. Among these, p + q is preferably 15 or more and 40 or less, more preferably 15 or more and 35 or less, because the cleaning power and the effect of preventing recontamination are further enhanced.

(A ¹ O) _p may be a repeating structure of only an oxyethylene group, a repeating structure of only an oxypropylene group, a repeating structure of only an oxybutylene group, or an oxyethylene group, an oxypropylene group and an oxybutylene group. A mixed structure may be used. Among these, a repeating structure having only an oxyethylene group and a structure in which an oxyethylene group and an oxypropylene group are mixed are preferable, and a repeating structure having only an oxyethylene group is more preferable.
In the case of a structure in which an oxyethylene group and an oxypropylene group are mixed, the oxyethylene group and the oxypropylene group may be repeated in a random manner or may be repeated in a block shape. In this case, the total amount of oxyethylene groups in the compound (A4) is 60% by mass or more based on the total mass of all oxyalkylene groups in the compound (A4) from the viewpoint of solubility in water. preferable.
(A ² O) _q has the same meaning as (A ¹ O) _p, and preferred examples thereof are also the same.

As the compound (A4), polyoxyethylene (20) hexadecylamine (R ¹ = alkyl group having 16 carbon atoms, average number of repeating oxyethylene groups of 20, p + q = 20, polyoxyethylene (15) beef tallow alkylamine ( R ¹ = alkyl group having 14 to 18 carbon atoms, average repeating number 15 of oxyethylene group, p + q = 15, polyoxyethylene (50) octadecylamine (R ¹ = average repeating of alkyl group having 18 carbon atoms and oxyethylene group) 50, p + q = 50, polyoxyethylene (42) polyoxypropylene (12) hexadecylamine (R ¹ = alkyl group having 16 carbon atoms, average number of repeating oxyethylene groups 42, average number of repeating oxypropylene groups 12 , P + q = 54), polyoxyethylene (28) polyoxypropylene (8) Rukiruamin ^{(R 1} = alkyl group having 12 to 14 carbon atoms, the average repeating number 28 of oxyethylene groups, corresponding to an average number of repetitions 8, p + q = 36 oxypropylene groups) and the like.

A compound (A4) may be used individually by 1 type, and may use 2 or more types together.
The content of the compound (A4) is preferably 1 to 70% by mass, more preferably 10 to 50% by mass, and further preferably 15 to 45% by mass, when the total mass of the liquid detergent is 100% by mass. If content of a compound (A4) is 1 mass% or more, the recontamination prevention effect will increase and favorable detergency will be obtained. On the other hand, when the content of the compound (A4) is 70% by mass or less, it is preferable from the viewpoint that the fluidity of the liquid detergent is good, and the handling property during production is excellent.

(Other nonionic surfactants)
(Compound (A3))
The compound (A3) is a compound represented by the following general formula (a-3).

（式（ａ−３）中、Ｒ^５は炭素数１０〜２２の炭化水素基であり、ＥＯはオキシエチレン基であり、ｎはＥＯの平均繰り返し数を示す５〜２０の数である。）

(In Formula (a-3), R ⁵ is a hydrocarbon group having 10 to 22 carbon atoms, EO is an oxyethylene group, and n is a number of 5 to 20 indicating the average number of repetitions of EO.)

In the formula (a-3), ^{R 5} is a hydrocarbon group having 10 to 22 carbon atoms. The hydrocarbon group may be linear or branched and may contain a cyclic structure. Furthermore, the hydrocarbon group may have an unsaturated bond, and may be a mixture of a single chain length and a plurality of chain lengths.
R ⁵ is preferably an aliphatic hydrocarbon group, more preferably a linear or branched alkyl group, or a linear or branched alkenyl group. Carbon number of a hydrocarbon group is 10-22, 10-20 are preferable and 10-18 are more preferable. If the carbon number is 10 or more, the detergency is further improved. On the other hand, when the number of carbon atoms is 22 or less, the liquid stability is further improved, and particularly gelation is further suppressed.
R ⁵ is derived from a raw material alcohol (R ⁵ —OH). Examples of the alcohol include alcohols derived from natural fats and oils such as coconut oil, palm oil, and beef tallow, and petroleum-derived synthetic alcohols.

  n is the number of 12-20 which shows the average repeating number (average addition mole number) of EO (oxyethylene group), 12-18 are preferable and 12-16 are more preferable. n may be an integer or may include a decimal. If n is 12 or more, a liquid detergent with little raw material odor derived from the compound (A3) is easily obtained. On the other hand, if n is 20 or less, it can suppress that HLB becomes high too much and can maintain the detergency with respect to sebum dirt favorably. In particular, when n is 12 to 16, it exhibits a high detergency against sebum dirt.

In the compound (A3), the addition mole number distribution of EO is not particularly limited, and the addition mole number distribution can be controlled by the production method of the compound (A3) and the like.
For example, when EO is added to a hydrophobic raw material using a general alkali catalyst such as sodium hydroxide or potassium hydroxide, the distribution tends to be relatively wide. In addition, specific alkoxyl such as magnesium oxide to which metal ions such as Al ³⁺ , Ga ³⁺ , In ³⁺ , Tl ³⁺ , Co ³⁺ , Sc ³⁺ , La ³⁺ , Mn ^{2+ and the} like described in Japanese Patent Publication No. 6-15038 are added. When EO is added to a hydrophobic raw material using a catalyst, it tends to have a relatively narrow addition mole number distribution.

Specific examples of the compound (A3) include a compound obtained by adding 12 and 15 moles of EO to an alcohol such as a product manufactured by Shell: trade name Neodol (C12 / C13) and a product manufactured by Sasol: Safol23 (C12 / C13). Manufactured by P & G: a compound obtained by adding 9, 12 and 15 moles of EO to natural alcohols such as trade names CO-1214 and CO-1270; 9, 12 and 12 to secondary alcohols having 12 to 14 carbon atoms; , Compounds having 15 moles of EO added (Nippon Shokubai Co., Ltd., Softanol 90, 120 and 150), and the like.
A compound (A3) may be used individually by 1 type, and may be used in combination of 2 or more type as appropriate.

Examples of other nonionic surfactants that may be included in addition to the compound (A3) include alkylpolyglucoside (APG), fatty acid diester (manufactured by Lion Corporation: trade name Lionon DT-600S), alkylamine oxide (Lion). Manufactured by Alomox DMC-W).

  The content of the other nonionic surfactant is preferably 1 to 70% by mass, more preferably 10 to 50% by mass, and further preferably 15 to 45% by mass, when the total mass of the liquid detergent is 100% by mass. . If the content of other nonionic surfactant is 1% by mass or more, better detergency can be obtained. On the other hand, if the content of other nonionic surfactants is 70% by mass or less, gelation with time is less likely to occur.

  As the component (A), the compound (A1) is preferable. The compound (A1) is easier to mix with other components than the compound (A2) and the compound (A4) and is easy to concentrate. If it is a compound (A1), since a solvent is not required in the case of concentration, an aroma is hard to be impaired.

Moreover, in order to reduce the viscosity of a liquid detergent and to improve usability, it is preferable to use a compound (A3) together. Compared with the case where only at least one compound selected from the group consisting of compound (A1), compound (A2) and compound (A4) is used, when compound (A3) is used in combination with said compound, compound (A1), compound ( In a molecular assembly composed of at least one compound selected from the group consisting of A2) and compound (A4) and compound (A3), the packing property between molecules is weakened, and the viscosity of the liquid detergent is reduced. Conceivable. In particular, it is preferable to use the compound (A1) and the compound (A3) in combination.
Here, the “molecular assembly” means that at least one compound selected from the group consisting of the compound (A1), the compound (A2) and the compound (A4) and the compound (A3) are the temperature of the solution. It means an aggregate assembled by conditions such as pressure.
The mass ratio of the total of the compound (A1) and the compound (A2) and the compound (A3) (the total of the compound (A1) and the compound (A2) / the compound (A3)) is preferably 0.02 to 4.5, 1.25-4 are more preferable, and 2-4 are more preferable. If the mass ratio is 0.02 or more, gelation with time is less likely to occur. On the other hand, if the mass ratio is 4.5 or less, the viscosity tends to be low, and the usability is likely to be improved.

<(B) component>
The component (B) is at least one compound selected from the group consisting of the following compound (B1) and higher alcohol (B2).

(Compound (B1))
Compound (B1) is a compound (triglyceride component) represented by the following general formula (b-1).

（式（ｂ−１）中、Ｚ^１〜Ｚ^３はそれぞれ独立して水素原子、ヒドロキシ基、またはカルボキシ基であり、ａ＋ｂ＝７〜１９、ｃ＋ｄ＝７〜１９、およびｅ＋ｆ＝７〜１９である。）

(In formula (b-1), Z ^{1 to} Z ³ each independently represent a hydrogen atom, a hydroxy group, or a carboxy group, and a + b = 7 to 19, c + d = 7 to 19, and e + f = 7 to 19 is there.)

In the formula (b-1), Z ^{1 to} Z ³ each independently represent a hydrogen atom, a hydroxy group, or a carboxy group. Z ^{1 to} Z ³ may be the same or different.
Further, a + b = 7 to 19, c + d = 7 to 19, and e + f = 7 to 19, preferably a + b = 11 to 15, c + d = 11 to 15, and e + f = 11 to 15, more preferably a + b. = 13-15, c + d = 13-15, and be + f = 13-15. If each of a + b, c + d, and e + f is 7 or more, the volume of the hydrophobic group becomes sufficiently bulky and the coating cleaning power is increased. On the other hand, if a + b, c + d, and e + f are each 19 or less, the risk of solidification due to an increase in the volume of the hydrophobic group portion is reduced.

Examples of the compound (B1) include a compound (B1-1) in which Z ^{1 to} Z ³ are hydroxy groups, a compound (B1-2) in which Z ^{1 to} Z ³ are hydrogen atoms, and the like. As the compound (B1-1), castor oil is particularly preferable, and as the compound (B1-2), palm oil is particularly preferable.
Moreover, as a compound (B1), you may manufacture by a well-known method and can also use a commercial item. Examples of the compound (B1-1) include “Caster Wax A Flakes” manufactured by NOF Corporation, and examples of the compound (B1-2) include “Palm Extremely Cured Oil A” manufactured by Shin Nippon Chemical Co., Ltd.

A compound (B1) may be used individually by 1 type, and may be used in combination of 2 or more type as appropriate.
The content of the compound (B1-1) is preferably 0.1 to 5% by mass, more preferably 0.1 to 2% by mass, when the total mass of the liquid detergent is 100% by mass, and 0.3 to 1% by mass is more preferable. If content of a compound (B1-1) is 0.1 mass% or more, favorable detergency can be expressed. On the other hand, if content of a compound (B1-1) is 5 mass% or less, the risk of causing solidification will be reduced.
The content of the compound (B1-2) is preferably 0.5 to 10% by mass, more preferably 1 to 5% by mass, and 2 to 4% by mass when the total mass of the liquid detergent is 100% by mass. Further preferred. If content of a compound (B1-2) is 0.5 mass% or more, favorable detergency can be expressed. On the other hand, if content of a compound (B1-2) is 10 mass% or less, the risk of causing solidification will be reduced.

(Higher alcohol (B2))
The higher alcohol (B2) is a monohydric alcohol having 6 to 18 carbon atoms.
The higher the volume of the hydrophobic group portion, the easier it is to form a structural liquid. Therefore, the higher alcohol (B2) is preferably an alcohol having 12 or more carbon atoms, and among them, a branched alcohol is particularly preferable. The number of carbon atoms is preferably 18 or less. If the higher alcohol (B2) has 18 or less carbon atoms, the liquid detergent containing the higher alcohol (B2) can form a structural liquid without causing solidification.
Here, the “structural liquid” means a liquid having thixotropic properties. The “thixotropic property” is a property exhibited by an intermediate material between a plastic solid such as a gel and a non-Newtonian liquid such as a sol. Specifically, when the shear stress is continued, the viscosity gradually decreases. It becomes a liquid, and when it is stationary, its viscosity gradually increases and finally becomes a solid.
In the present invention, when the component (A) is included and the component (B) is not included, the liquid detergent is in a state of spherical micelles. The critical packing parameter (CPP) relating the molecular structure of the surfactant and the self-assembled structure approaches 1, and the liquid changes to a thixotropic liquid.

  Examples of the higher alcohol (B2) include “ISOFOL12” manufactured by SASOL.

A higher alcohol (B2) may be used individually by 1 type, and may be used in combination of 2 or more type as appropriate.
The content of the higher alcohol (B2) is preferably 1 to 7% by mass, more preferably 2 to 6% by mass, and further preferably 3 to 5% by mass, when the total mass of the liquid detergent is 100% by mass. . If the content of the higher alcohol (B2) is 1% by mass or more, good detergency can be expressed. On the other hand, when the content of the higher alcohol (B2) is 7% by mass or less, it becomes easier to form a structural liquid without causing solidification.

<(C) component>
Component (C) is an anionic surfactant.
It does not specifically limit as an anionic surfactant, A well-known anionic surfactant can be used. Specifically, linear alkylbenzene sulfonic acid or a salt thereof; α-olefin sulfonate; linear or branched alkyl sulfate ester salt; alkyl ether sulfate ester salt or alkenyl ether sulfate ester salt; Examples include alkane sulfonates; α-sulfo fatty acid ester salts and the like.
Examples of these salts include alkali metal salts such as sodium and potassium; alkaline earth metal salts such as magnesium; alkanolamine salts such as monoethanolamine and diethanolamine.

Further, as the component (C), in addition to the above, for example, a higher fatty acid salt having 10 to 20 carbon atoms, alkyl ether carboxylate, polyoxyalkylene ether carboxylate, alkyl (or alkenyl) amide ether carboxylate Carboxylic acid type anionic surfactants such as acylaminocarboxylates; alkyl phosphate ester salts, polyoxyalkylene alkyl phosphate ester salts, polyoxyalkylene alkyl phenyl phosphate ester salts, glycerin fatty acid ester monophosphate ester salts, etc. Examples include phosphate ester type anionic surfactants.
Examples of these salts include alkali metal salts such as sodium and potassium; alkaline earth metal salts such as magnesium; alkanolamine salts such as monoethanolamine and diethanolamine.

Of the above, the linear alkylbenzene sulfonic acid or salt thereof is preferably a linear alkylbenzene sulfonic acid having 8 to 16 carbon atoms in the linear alkyl group or a salt thereof, and a linear alkylbenzene sulfonic acid having 10 to 14 carbon atoms or a salt thereof. The salt is particularly preferred.
As the α-olefin sulfonate, an α-olefin sulfonate having 10 to 20 carbon atoms is preferable.
The alkyl sulfate ester salt is preferably an alkyl sulfate ester salt having 10 to 20 carbon atoms.
The alkyl ether sulfate ester salt or alkenyl ether sulfate ester salt has a linear or branched alkyl group having 10 to 20 carbon atoms, or a linear or branched alkenyl group having 10 to 20 carbon atoms. And an alkyl ether sulfate ester salt or alkenyl ether sulfate ester salt (that is, polyoxyethylene alkyl ether sulfate ester salt or polyoxyethylene alkenyl ether sulfate ester salt) added with ethylene oxide having an average repeating number of 1 to 10 moles is preferable. . Further, any one of alkylene oxides having 2 to 4 carbon atoms, or ethylene oxide (EO) and propylene oxide (PO) (molar ratio EO / PO = 0.1 / 9.9 to 9.9 / 0.1), Alkyl (or alkenyl) ether sulfate ester salt (hereinafter referred to as AES, AEPS) having a linear or branched alkyl group (or alkenyl group) having 10 to 20 carbon atoms added with an average of 0.5 to 10 moles Is preferred).
Examples of the alkane sulfonate include alkane sulfonates having 10 to 20 carbon atoms. Alkane sulfonates having 14 to 17 carbon atoms are preferable, and secondary alkane sulfonates are particularly preferable.
As the α-sulfo fatty acid ester salt, an α-sulfo fatty acid ester salt having 10 to 20 carbon atoms is preferable.
These anionic surfactants are easily available on the market. Moreover, you may synthesize | combine by a well-known method.

As the component (C), among the above, linear alkyl benzene sulfonic acid or a salt thereof; alkane sulfonate; polyoxyethylene alkyl ether sulfate ester salt; alkylene oxide having 2 to 4 carbon atoms; or ethylene oxide ( EO) and propylene oxide (PO) (molar ratio EO / PO = 0.1 / 9.9 to 9.9 / 0.1) are added in an average of 0.5 to 10 mol on a straight chain having 10 to 20 carbon atoms. (Or alkenyl) ether sulfate ester salt having a linear or branched alkyl group (or alkenyl group); α-olefin sulfonate salt, and higher fatty acid salt; and at least one anionic surface activity selected from the group consisting of Agents are preferred.

<Optional component>
In addition to the components (A), (B), and (C) described above, the liquid detergent of the present invention contains components that are usually used in liquid detergents within the range that does not impair the effects of the present invention. Can be blended. For example, the following components can be mentioned.

(Optional surfactant)
The liquid detergent of the present invention can contain a surfactant excluding the components (A) and (C) (hereinafter sometimes referred to as optional surfactant).
Optional surfactants include cationic surfactants.

Examples of cationic surfactants include caprylic acid dimethylaminopropylamide, capric acid dimethylaminopropylamide, lauric acid dimethylaminopropylamide, myristic acid dimethylaminopropylamide, palmitic acid dimethylaminopropylamide, stearic acid dimethylaminopropylamide, Long chain aliphatic amide alkyl tertiary amines such as behenic acid dimethylaminopropylamide and oleic acid dimethylaminopropylamide or salts thereof; aliphatic ester alkyl tertiary amines such as palmitate ester propyldimethylamine and stearate ester propyldimethylamine Or salts thereof; palmitic acid diethanolaminopropylamide, stearic acid diethanolaminopropylamide, and the like. These cationic surfactants may be used individually by 1 type, and may be used in combination of 2 or more types as appropriate.
Among them, caprylic acid dimethylaminopropylamide, capric acid dimethylaminopropylamide, lauric acid dimethylaminopropylamide, myristic acid dimethylaminopropylamide, palmitic acid dimethylaminopropylamide, stearic acid dimethylaminopropylamide, behenic acid dimethylaminopropylamide Particularly preferred is dimethylaminopropylamide oleate or a salt thereof. Mixtures of these are also preferred.

  The cationic surfactant can be appropriately selected from known cationic surfactants. For example, cationic surfactants such as alkyltrimethylammonium salts, dialkyldimethylammonium salts, alkylbenzyldimethylammonium salts, alkylpyridinium salts, and the like can be used.

(water)
The liquid cleaning agent of the present invention preferably contains water.
The content of water is preferably 5 to 35% by mass and more preferably 20 to 35% by mass when the total mass of the liquid detergent is 100% by mass. When the water content is 5% by mass or more, the liquid detergent is hardly gelled, and the fluidity and stability can be maintained well. On the other hand, when the content of water is 35% by mass or less, the component (A) and the component (B) can be contained in the liquid detergent within the optimum range, and a structural liquid can be easily formed.

(solvent)
The liquid cleaning agent of the present invention may contain a solvent. As a solvent, the solvent conventionally mix | blended with the washing | cleaning agent for clothes etc. can be used.
Examples of the solvent include alcohols such as ethanol, 1-propanol, 2-propanol, and 1-butanol; glycols such as propylene glycol, butylene glycol, and hexylene glycol; diethylene glycol, triethylene glycol, tetraethylene glycol, and average molecular weight. Polyglycols such as polyethylene glycol having an average molecular weight of about 400, polyethylene glycol having an average molecular weight of about 400, polyethylene glycol having an average molecular weight of about 1000, and dipropylene glycol; alkyl ethers such as diethylene glycol monomethyl ether, diethylene glycol monobutyl ether, and diethylene glycol dimethyl ether. .
The total content of water and solvent is preferably 15 to 45 mass%, more preferably 25 to 45 mass%, when the total mass of the liquid detergent is 100 mass%. When the total content of water and solvent is 15% by mass or more, the liquid detergent is hardly gelled, and fluidity and stability can be maintained well. On the other hand, if the total content of water and solvent is 45% by mass or less, the component (A) and the component (B) can be contained in the liquid detergent within the optimum range, and a structural liquid can be easily formed. .

(Inorganic salt)
The liquid detergent of the present invention may contain an inorganic salt, and is particularly preferably used in combination with the component (C). Since the inorganic salt can cancel the charge of the hydrophilic group of the component (C), it becomes easier to form a structural liquid.
Examples of the inorganic salt include sodium chloride, potassium chloride, sodium citrate, potassium nitrate, potassium sulfate and the like.

An inorganic salt may be used individually by 1 type, and may be used in combination of 2 or more types as appropriate.
The content of the inorganic salt is preferably 0.2 to 1% by mass when the total mass of the liquid detergent is 100% by mass. If content of inorganic salt is 0.2 mass% or more, detergency will improve. On the other hand, if the content of the inorganic salt is 1% by mass or less, it is possible to suppress a reduction in detergency due to excess salt.

(Water-soluble particles, water-insoluble particles)
The liquid detergent of the present invention may contain particles that are hardly soluble in the components constituting the liquid detergent (that is, water-soluble particles and water-insoluble particles).
Specific examples of such particles include a capsule containing a capsule fragrance and an active ingredient instead thereof, beads and a pearlescent agent for imparting specific product aesthetics, bentonite, carboxymethylcellulose (CMC), Laponite. S482, cluster dextrin, etc. are mentioned.
Examples of the capsule flavor include BLUEFLOWERPOP “FFMHN2814” manufactured by Firmenig; AURORACAPS and COSMICCAPS manufactured by Givaudan; UNICAP101 and UNICAP503 manufactured by IFF.
The liquid detergent of the invention may contain a cluster dextrin, and the residual fragrance can be further enhanced by containing the cluster dextrin. Specific examples of cluster dextrin (highly branched cyclic dextrin) include “Cluster Dextrin” (registered trademark) manufactured by Glico Nutrition Foods, Inc. These particles may be used alone or in combination of two or more.
The content of at least one component selected from the group consisting of water-soluble particles and water-insoluble particles is preferably 0.05 to 5% by mass when the total mass of the liquid detergent is 100% by mass.

(Urea or its derivatives)
The liquid detergent of the present invention may contain urea or a derivative thereof, and is particularly preferably used in combination with the compound (A1). Examples of urea or derivatives thereof include urea [CO (NH ₂ ) ₂ ], urea double salts, and other urea derivatives.
Examples of the urea double salt include HNO ₃ · CO (NH ₂ ) ₂ , H ₃ PO ₄ · CO (NH ₂ ) ₂ , H ₂ C ₂ O ₄ · 2CO (NH ₂ ) ₂ , Ca (NO ₃ ) ₂ · 4CO. (NH ₂ ) ₂ , CaSO ₄ · 4CO (NH ₂ ) ₂ , Mg (NO ₃ ) ₂ · CO (NH ₂ ) ₂ · 2H ₂ O, CaSO ₄ · (5-6) 4CO (NH ₂ ) ₂ · 2H ₂ O or the like can be used.
In the present invention, the “urea derivative” includes a compound having a partial structure represented by the following general formula (d-1). Among the urea derivatives, the compound represented by the general formula (d-2) is a suitable compound.

（前記式（ｄ−２）中、Ｒ^ａは、メチル基、エチル基、または炭素数１〜２のヒドロキシアルキル基であり；Ｒ^ｂ、Ｒ^ｃおよびＲ^ｄは、それぞれ独立に、水素原子、メチル基、又はエチル基である。）

(In the formula (d-2), R ^a is a methyl group, an ethyl group, or a hydroxyalkyl group having 1 to 2 carbon atoms; R ^b , R ^c and R ^d are each independently a hydrogen atom, It is a methyl group or an ethyl group.)

Examples of the compound represented by the formula (d-2) include 1,3-dimethylurea and N- (2-hydroxyethyl) urea.
Urea may be used alone or in combination of two or more.
The content of urea in the liquid detergent is preferably 0.1 to 20% by mass, more preferably 0.5 to 15% by mass, and still more preferably 1 to 10% with respect to the total mass of the liquid detergent. % By mass. If the content exceeds the upper limit, ammonia tends to be generated as a decomposition product after storage, and odor may be a problem as a liquid detergent product.

(silicone)
The liquid detergent of the present invention may contain silicone. By containing silicone, it is possible to further improve rinsing properties and foam suppression during production.
Examples of silicone include polyether-modified silicone, amino-modified silicone, and the like. Among these, polyether-modified silicone is preferable.
The polyether-modified silicone is not particularly limited as long as it has a polyether group such as polyethylene oxide or polypropylene oxide as a functional group. In addition, other functional groups may be introduced as long as polyether groups such as polyethylene oxide and polypropylene oxide are introduced.

Commercially available polyether modified silicones include SH3772M, SH3775M, SH3749, SF8410, SH8700, BY22-008, SF8421, SILWET L-7001, SILWET L-7002, SILWET L- manufactured by Toray Dow Corning Co., Ltd. 7602, SILWET L-7604, SILWET FZ-2104, SILWET FZ-2164, SILWET FZ-2171, ABN SILWET FZ-F1-009, ABN SILWET FZ-F1-009-05, ABN SILWET FZ-F1-00 ABN SILWET FZ-F1-009-54, ABN SILWET FZ-2222 (above, trade name); KF352A, KF6008, K manufactured by Shin-Etsu Chemical Co., Ltd. 615A, KF6016, KF6017 (trade names); GE Toshiba made Silicone Co., Ltd. TSF4450, TSF4452 (trade names), and the like.
Examples of the silicone antifoaming agent include KM-7750, KM-90, KM-98, KS-538, KS-66, and KS-69 (above, trade names) manufactured by Shin-Etsu Chemical Co., Ltd.
These may be used individually by 1 type and may be used in combination of 2 or more type.

(Other optional ingredients)
The liquid cleaning agent of the present invention may contain other optional components that are acceptable as a liquid cleaning agent.
Other optional ingredients acceptable as liquid detergents include dispersion media, hydrotropes, detergency builders, stabilizers (eg, sodium benzoate, citric acid, citric acid, known in the liquid detergent art) Sodium, polyhydric alcohol, polyethylene glycol alkyl ether, polypropylene glycol alkyl ether, etc.), alkali agent (eg, alkanolamine such as monoethanolamine, diethanolamine, triethanolamine, etc.), metal ion scavenger (eg, malonic acid, succinate) Acid, malic acid, diglycolic acid, tartaric acid, citric acid, or salts thereof), texture improver such as silicone, preservative, fluorescent agent, dye transfer inhibitor, pearl agent, antioxidant (for example, dibutylhydroxy) Toluene, distyrenated crezo , Sodium sulfite, sodium hydrogen sulfite), an enzyme, a general-purpose dyes and pigments as coloring agents, additives such as flavoring and an emulsifying agent, pH adjusting agents, and the like.

Moreover, the liquid detergent of this invention can contain the enzyme currently mix | blended with the detergent for clothes etc. conventionally. By containing an enzyme, the coating cleaning power is further improved.
In the present invention, “enzyme” refers to an enzyme preparation.
Examples of the enzyme include protease, amylase, lipase, cellulase, mannanase, cellulase and the like.

The protease is preferably a protease having serine, histidine, and aspartic acid in the molecule, such as serine protease.
Specific examples of protease include trade names Savinase 16L, Savinase Ultra 16L, Savinase Ultra 16XL, Everlase 16L Type 2.5, Eraase Ultra 16L, Esperase Ultra 16L, Esperase Ultra 16L, Esperase Ultra L 2.5L, Liquanase Ultra 2.5L, Liquanase Ultra 2.5XL, Coronase 48L; trade names Purefect L, Perfect OX, Properase L, etc. available from Genencor.
Specific examples of amylase include trade names such as Termamyl 300L, Termamyl Ultra 300L, Duramyl 300L, Stainzyme 12L, and Stainzyme Plus 12L available from Genencore; Trade name pullulanase Amano; trade name DB-250 etc. which can be obtained from Seikagaku Corporation are mentioned.

Specific examples of the lipase include trade names Lipex 100L and Lipolase 100L available from Novozymes as lipase preparations.
Specific examples of cellulase include Carezyme 4500L (trade name, manufactured by Novozymes, reducing sugar production amount: 253.2 μM), Carezyme Premium 4500L (trade name, manufactured by Novozymes, reducing sugar production: 307.0 μM), Endolase Examples include endoglucanase preparations such as 5000L (trade name, manufactured by Novozymes, reducing sugar production: 187.0 μM), Cellclean 4500T (trade name, Novozymes, reducing sugar production: 120.6 μM), and the like.
Among these, carezyme 4500L and care enzyme premium 4500L are preferable, and carezyme premium 4500L is more preferable.
Specific examples of mannanase include Mannaway 4L, a trade name available from Novozymes as a mannanase preparation.
These enzymes may be used individually by 1 type, and may be used in combination of 2 or more types as appropriate.
The content of the enzyme is preferably 0.1 to 3% by mass with respect to 100% by mass of the liquid detergent.

Another aspect of other optional ingredients that can be tolerated as liquid detergents includes stabilizers, cationic surfactants, pH adjusters, silicones, fragrances, water, alkaline agents, enzymes, urea, cluster dextrins, and dispersions It is preferably at least one component selected from the group consisting of media.
Another aspect of other optional ingredients that are acceptable as liquid detergents is:
Sodium benzoate, citric acid, dimethylaminopropylamide stearate, alkyltrimethylammonium salt, sodium hydroxide, silicone, fragrance, water, ethanolamine, coronase, urea, cluster dextrin, paratoluenesulfonic acid, polyethylene glycol, ethanol, butyl It is preferably at least one component selected from the group consisting of carbitol (butyl diglycol), propylene glycol, and sodium cumene sulfonate.

<Content of each component>
(Total surfactant content)
The content of all the surfactants (hereinafter, also referred to as “total surfactant”) contained in the liquid detergent is 45% by mass or more when the total mass of the liquid detergent is 100% by mass. . If the total surfactant content is 45% by mass or more, high cleaning performance can be imparted to the liquid cleaning agent, and a structural liquid can be maintained. The total surfactant content is preferably 51% by mass or more, more preferably more than 51% by mass, and particularly preferably 54% by mass or more. Moreover, 80 mass% or less is preferable, 70 mass% or less is more preferable, and 60 mass% or less is further more preferable. If the total surfactant content exceeds 80% by mass, the liquid detergent tends to gel, and the stability may be lowered.
That is, the total surfactant content is 45% by mass or more and 80% by mass or less, preferably 51% by mass or more and 80% by mass or less, and more than 51% by mass with respect to 100% by mass of the liquid detergent. 70 mass% or less is more preferable, and 54 mass% or more and 60 mass% or less are still more preferable.
The term “total surfactant” as used herein means the total content of the component (A), the component (C) and the surfactants included as optional components.

(Content of component (A))
The content of the component (A) is preferably 1 to 70% by mass, more preferably 10 to 50% by mass, and further preferably 15 to 45% by mass, when the total mass of the liquid detergent is 100% by mass. When the content of the component (A) is 1% by mass or more, good detergency can be obtained. On the other hand, if the content of the component (A) is 70% by mass or less, gelation with time is unlikely to occur.

(Content of component (B))
The content of the component (B) is preferably 0.1 to 10% by mass, more preferably 0.1 to 5% by mass, and 0.3 to 4% by mass when the total mass of the liquid detergent is 100% by mass. % Is more preferable. When the content of the component (B) is 0.1% by mass or more, good detergency can be expressed. On the other hand, if content of (B) component is 10 mass% or less, the risk of causing solidification will be reduced.

(Content of component (C))
(C) As for content of a component, when the total mass of a liquid detergent is 100 mass%, 1-20 mass% is preferable, 3-18 mass% is more preferable, 5-16 mass% is further more preferable. If content of (C) component is 1 mass% or more, cleaning performance, especially coating cleaning power will improve. On the other hand, if content of (C) component is 20 mass% or less, liquid stability will improve.

((A) component / (B) component)
15-150 are preferable, as for mass ratio ((A) component / (B) component) of (A) component and (B) component, 37.5-110 are more preferable, and 60-100 are more preferable. If the ratio of the component (B) is too high, gelation occurs, and the fluidity and stability of the liquid detergent may be reduced. On the other hand, when the ratio of the component (B) is too low, the coating cleaning power is hardly improved.

((C) component / (A) component)
The mass ratio of the component (C) to the component (A) (component (C) / component (A)) is preferably 0.02 to 0.7, more preferably 0.06 to 0.5, 0.3 is more preferable. If the ratio of the component (C) is too high, the detergency may be reduced. On the other hand, when the ratio of the component (C) is too low, protein cleaning power and recontamination are deteriorated.

<Physical properties>
(viscosity)
The liquid cleaning agent of the present invention preferably has a viscosity at 60 rpm by a B-type viscometer at 25 ° C. (manufactured by TOKIMEC, rotor No. 2 or 3) of 50 to 1000 mPa · s, and 75 to 800 mPa · s. More preferably, it is more preferably 100 to 500 mPa · s.
Further, the viscosity at 6 rpm by a B-type viscometer at 25 ° C. (manufactured by TOKIMEC, rotor No. 2 or 3) is preferably 500 to 5000 mPa · s, more preferably 500 to 3000 mPa · s. More preferably, it is 500-2000 mPa * s.
Furthermore, the TI value (viscosity at 6 rpm / viscosity at 60 rpm) represented by the ratio of the viscosity at 6 rpm to the viscosity at 60 rpm is preferably 2 or more. The TI value is an index representing thixotropy, and the larger the TI value, the higher the thixotropy and the greater the difference in viscosity due to the change in shear rate. That is, the larger the TI value, the higher the viscosity is at low shear force and the lower the viscosity at high shear force.
In this specification, the viscosity is defined as a value at 25 ° C. unless otherwise specified. That is, even if the value is outside the range specified in the present specification, it is included in the scope of the present invention as long as it is a viscosity value within the range specified in the present specification when corrected to a value at 25 ° C.

(PH)
The liquid detergent of the present invention preferably has a pH at 25 ° C. of 6 to 9, and more preferably 7 to 8. When pH is 6-9, even if a liquid detergent is preserve | saved for a long period of time, temporal stability can be kept favorable.
The pH of the liquid detergent (controlled at 25 ° C.) indicates a value measured by a pH meter (“HM-30G” manufactured by Toa DKK Corporation).
In the present specification, pH is defined as a value at 25 ° C. unless otherwise specified. That is, even if the pH value is outside the range specified in the present specification, it is included in the scope of the present invention as long as the pH value is within the range specified in the present specification when corrected to the pH value at 25 ° C. .

The pH of the liquid detergent of the present invention can be adjusted with a pH adjuster. Examples of the pH adjuster include inorganic acids such as hydrochloric acid, sulfuric acid and phosphoric acid; organic acids such as polyvalent carboxylic acids and hydroxycarboxylic acids; sodium hydroxide, potassium hydroxide, alkanolamine and ammonia. Among these, sulfuric acid, sodium hydroxide, potassium hydroxide, and alkanolamine are preferable, and sulfuric acid and sodium hydroxide are preferable from the viewpoint of the temporal stability of the liquid detergent.
A pH adjuster may be used individually by 1 type, and may use 2 or more types together. For example, when controlled by adding a certain amount of sulfuric acid, sodium hydroxide or the like, an inorganic acid (preferably hydrochloric acid or sulfuric acid) or potassium hydroxide can be further added for fine adjustment of pH.

<Manufacturing method>
The manufacturing method of the liquid detergent of this invention can be manufactured based on a conventional method. For example, after the component (A), the component (C), and an optional component as required are dispersed in a part of water, the solution in which the component is dispersed is heated to the melting point of the component (B). Then, the component (B) heated to the melting point is added to the warmed solution. Then, it adjusts to arbitrary pH and adds the remainder of water, and obtains a liquid cleaning agent. At this time, it is preferable to start from blending the (A) component, the (C) component, and an optional component as necessary, in that gelation can be suppressed.
That is, as a manufacturing method of the liquid detergent of the present invention,
Dispersing the component (A), the component (C), and optionally other components in a part of water;
Heating the solution in which the components are dispersed to the melting point of the component (B);
Adding the component (B) heated to the melting point to the warmed solution;
Adjusting the pH of the solution obtained by adding the component (B); and adding the remainder of the water to the pH adjusted solution;
The manufacturing method of the liquid washing | cleaning liquid containing this is mentioned.

<How to use>
The liquid detergent of this invention can be used by the method similar to the normal usage method of the liquid detergent for clothes. For example, a method in which a liquid cleaning agent is poured into water together with the laundry during washing (normal cleaning), a method in which the liquid cleaning agent is applied directly to dirt sites such as mud and sebum soil (application cleaning), and a liquid cleaning agent. For example, a method of pre-dissolving in water and immersing clothes (pickling washing) may be used. In addition, a method of applying a liquid detergent to the laundry or immersing clothes in a diluted liquid of the liquid detergent and leaving it as it is, and then washing with a washing machine may be used.

<Effect>
Since the liquid cleaning agent of the present invention described above contains the component (A), the component (B), and the component (C), it has a high detergency against hydrophobic dirt and further forms a structural liquid. Therefore, the liquid detergent of the present invention has a thixotropic property due to the structural liquid, and has a viscosity characteristic such that the viscosity is high when no shear force is applied and low when the shear force is applied. That is, the liquid cleaning agent of the present invention has a high viscosity in a state where no shearing force is applied, that is, in a state close to rest, so that it does not easily penetrate into clothing even when directly applied to dirt adhered to clothing, etc. Easy to stay on top. Therefore, if it is the liquid cleaning agent of this invention, the outstanding coating cleaning power can be exhibited.
Moreover, the liquid detergent of the present invention has a low viscosity in a state where shearing force is applied, that is, in a state where the container in which the liquid detergent is stored is tilted, the liquid detergent is stirred, or pressure is applied to the liquid detergent. It is. Therefore, with the liquid cleaning agent of the present invention, it is easy to pour the liquid cleaning agent in the container into the cap, the discharge property from the cap to the input port of the washing machine and the discharge property from the input port are good, and the usability Excellent.

The compound (A4) exhibits a high cleaning effect even with a small use amount (low concentration). In addition, compared with other nonionic surfactants (general-purpose alcohol ethoxylates, etc.), it has a characteristic that it is difficult to adsorb on the object to be washed. In the present invention, the combination of the compound (A4) and the component (B) makes it difficult for the compound (A4) to be adsorbed on the article to be washed, so that the component (B) is preferentially adsorbed. For this reason, it is speculated that the adsorption of the component (B) makes it easier to reduce the moisture content after washing and dewatering, and also expresses a unique effect of imparting quick-drying properties that make it easier to dry. Such an effect is particularly remarkable for an object to be cleaned containing chemical fibers such as acrylic fibers and polyester fibers.

  In addition, since the liquid detergent of the present invention contains a surfactant at a high concentration, it is easy to maintain a structural liquid, and is excellent in detergency in normal washing as well as in washing ability in application washing. In addition, since the liquid detergent of the present invention has good foam breakage during rinsing, the number of times of rinsing can be reduced.

By the way, a product having a higher added value than conventional is required for the cleaning agent.
For example, to give a sufficient scent to clothes after washing, or to add fragrance to capsules and other active ingredients to give a fragrance while wearing clothes, etc. For example, cleaning agents containing water-soluble particles such as beads and water-insoluble particles have been developed. If it is a powder detergent, water-soluble particles and water-insoluble particles can be dispersed uniformly and stably. However, in the case of liquid detergents, water-soluble particles and water-insoluble particles tend to float or settle, and are uniformly dispersed. It was difficult to make.
However, since the liquid cleaning agent of the present invention forms a structural liquid, water-soluble particles and water-insoluble particles can be uniformly and stably dispersed.

Other aspects of the invention include:
Contains the following component (A), the following component (B), the following component (C), water, and optionally an acceptable component as a liquid detergent,
The liquid detergent in which the total content of all the surfactants is 45% by mass or more and 80% by mass or less with respect to the total mass of the liquid detergent:
Component (A): a group consisting of a compound represented by the following general formula (a-1), a compound represented by the following general formula (a-2), and a compound represented by the following general formula (a-4) A nonionic surfactant comprising at least one compound selected from:
(B) component: at least one compound selected from the group consisting of a compound represented by the following general formula (b-1) and an alcohol having 6 to 18 carbon atoms; and
(C) component: anionic surfactant;

（式（ａ−１）中、Ｒ^１は炭素数９〜１３の炭化水素基であり、Ｒ^２は炭素数２〜４のアルキレン基であり、Ｒ^３は炭素数１〜４のアルキル基であり、ｍはＯＲ^２の平均繰り返し数を示す５〜２５の数である。）

(In Formula (a-1), R ¹ is a hydrocarbon group having 9 to 13 carbon atoms, R ² is an alkylene group having 2 to 4 carbon atoms, and R ³ is an alkyl group having 1 to 4 carbon atoms. There, m is a number from 5 to 25 showing an average number of repetitions of OR ^2.)

（式（ａ−２）中、Ｒ^４は炭素数１０〜２０の炭化水素基であり、ＥＯはオキシエチレン基であり、ＰＯはオキシプロピレン基であり、ｓはＥＯの平均繰り返し数を示す５〜２０の数であり、ｔはＰＯの平均繰り返し数を示す１〜４の数であり；［−（ＥＯ）_ｓ−（ＰＯ）_ｔ−］とは、ＥＯとＰＯは、式−（ＥＯ）_ｓ−（ＰＯ）_ｔ−の順序によらず、混在して配列してもよいことを表す。）

(In the formula (a-2), R ⁴ is a hydrocarbon group having 10 to 20 carbon atoms, EO is an oxyethylene group, PO is an oxypropylene group, and s indicates the average number of repetitions of EO 5 Is a number of ˜20, and t is a number of 1 to 4 indicating the average number of repetitions of PO; [— (EO) _s − (PO) _t −] is EO and PO are the formula — (EO) (Indicates that they may be mixed and arranged regardless of the order of _s- (PO) _t- ).)

（式（ａ−４）中、Ｒ^１は炭素数１０〜２０の炭化水素基であり；Ａ^１ＯおよびＡ^２Ｏはそれぞれ独立に炭素数２〜４のオキシアルキレン基であり；ｐはＡ^１Ｏの平均繰返し数を表し、ｑはＡ^２Ｏの平均繰返し数を表し、ｐ＞０、ｑ＞０であり、ｐ＋ｑは１０以上、６０未満の数である。）

(In Formula (a-4), R ¹ is a hydrocarbon group having 10 to 20 carbon atoms; A ¹ O and A ² O are each independently an oxyalkylene group having 2 to 4 carbon atoms; ¹ represents the average number of repetitions of O, q represents the average number of repetitions of A ² O, p> 0, q> 0, and p + q is a number of 10 or more and less than 60.)

（式（ｂ−１）中、Ｚ^１〜Ｚ^３はそれぞれ独立して水素原子、ヒドロキシ基、またはカルボキシ基であり、ａ＋ｂ＝７〜１９であり、ｃ＋ｄ＝７〜１９であり、ｅ＋ｆ＝７〜１９である。）；
が挙げられる。

(In formula (b-1), Z ^{1 to} Z ³ are each independently a hydrogen atom, a hydroxy group, or a carboxy group, a + b = 7 to 19, c + d = 7 to 19, and e + f = 7. ~ 19));
Is mentioned.

Other aspects of the invention include:
Contains the following component (A), the following component (B), the following component (C), water, and optionally an acceptable component as a liquid detergent,
The liquid detergent in which the total content of all the surfactants is 45% by mass or more and 80% by mass or less with respect to the total mass of the liquid detergent:
Component (A): selected from the group consisting of the compound represented by formula (a-1), the compound represented by formula (a-2) and the compound represented by formula (a-4) A nonionic surfactant comprising at least one compound and a compound represented by the following general formula (a-3);
(B) component: at least one compound selected from the group consisting of the compound represented by the formula (b-1) and an alcohol having 6 to 18 carbon atoms; and (C) component: an anionic surfactant ;

（式（ａ−３）中、Ｒ^５は炭素数１０〜２２の炭化水素基であり、ＥＯはオキシエチレン基であり、ｎはＥＯの平均繰り返し数を示す５〜２０の数である。）；
が挙げられる。

(In formula (a-3), R ⁵ is a hydrocarbon group having 10 to 22 carbon atoms, EO is an oxyethylene group, and n is a number of 5 to 20 indicating the average number of repetitions of EO.) ;
Is mentioned.

Other aspects of the invention include:
Contains the following component (A), the following component (B), the following component (C), water, and optionally an acceptable component as a liquid detergent,
The liquid detergent in which the total content of all the surfactants is 45% by mass or more and 80% by mass or less with respect to the total mass of the liquid detergent:
Component (A): selected from the group consisting of the compound represented by the formula (a-1), the compound represented by the formula (a-2) below, and the compound represented by the formula (a-4) A nonionic surfactant comprising at least one compound
(B) component: The compound (B1-1) represented by the following general formula (b1-1), the compound (B1-2) represented by the following general formula (b1-2), and 6 or more carbon atoms, 18 At least one compound selected from the group consisting of the following alcohols; and (C) component: an anionic surfactant;

（式（ｂ１−１）中、Ｚ^１〜Ｚ^３はヒドロキシ基であり、ａ＋ｂ＝７〜１９であり、ｃ＋ｄ＝７〜１９であり、ｅ＋ｆ＝７〜１９である。）；

(In formula (b1-1), Z ^{1 to} Z ³ are hydroxy groups, a + b = 7 to 19, c + d = 7 to 19, and e + f = 7 to 19);

（式（ｂ１−２）中、Ｚ^１〜Ｚ^３は水素原子であり、ａ＋ｂ＝７〜１９であり、ｃ＋ｄ＝７〜１９であり、ｅ＋ｆ＝７〜１９である。）；
が挙げられる。

(In formula (b1-2), Z ^{1 to} Z ³ are hydrogen atoms, a + b = 7 to 19, c + d = 7 to 19, and e + f = 7 to 19);
Is mentioned.

Other aspects of the invention include:
Contains the following (A) component, the following (B) component, the following (C) component, water and optionally an acceptable component as a liquid detergent,
The liquid detergent in which the total content of all the surfactants is 45% by mass or more and 80% by mass or less with respect to the total mass of the liquid detergent:
(A) component: selected from the group consisting of the compound represented by the formula (a-1), the compound represented by the formula (a-2), and the compound represented by the formula (a-4) A nonionic surfactant comprising at least one compound;
(B) component: at least one compound selected from the group consisting of the compound represented by the formula (b-1) and an alcohol having 6 to 18 carbon atoms; and (C) component: linear alkylbenzenesulfone An acid or a salt thereof; an alkane sulfonate; a polyoxyethylene alkyl ether sulfate salt; an alkylene oxide having 2 to 4 carbon atoms, or ethylene oxide (EO) and propylene oxide (PO) (molar ratio EO / PO = 0) Alkyl having a linear or branched alkyl group (or alkenyl group) having 10 to 20 carbon atoms to which an average of 0.5 to 10 mol is added. (Or alkenyl) ether sulfate ester salt; α-olefin sulfonate salt; and at least one selected from the group consisting of higher fatty acid salts Anion surfactants;
Is mentioned.

Other aspects of the invention include:
The following (A) component, the following (B) component, the following (C) component, water, and a component acceptable as a liquid detergent,
The liquid detergent in which the total content of all the surfactants is 45% by mass or more and 80% by mass or less with respect to the total mass of the liquid detergent:
(A) component: selected from the group consisting of the compound represented by the formula (a-1), the compound represented by the formula (a-2), and the compound represented by the formula (a-4) A nonionic surfactant comprising at least one compound and a compound represented by the formula (a-3);
Component (B): Compound (B1-1) represented by Formula (b1-1), Compound (B1-2) represented by Formula (b1-2), and a carbon number of 6 or more and 18 or less. At least one compound selected from the group consisting of alcohols; and component (C): linear alkylbenzene sulfonic acid or a salt thereof; alkane sulfonate; polyoxyethylene alkyl ether sulfate ester salt; alkylene oxide having 2 to 4 carbon atoms Or carbon obtained by adding an average of 0.5 to 10 mol of ethylene oxide (EO) and propylene oxide (PO) (molar ratio EO / PO = 0.1 / 9.9 to 9.9 / 0.1) Alkyl (or alkenyl) ether sulfate ester salt having a linear or branched alkyl group (or alkenyl group) of several tens to 20; α-olefin sulfone At least one anionic surfactant selected from the group consisting of and higher fatty acid salts; salts;
Is mentioned.

Other aspects of the invention include:
Contains the following (A) component, the following (B) component, the following (C) component, at least one component selected from the group consisting of water, urea and cluster dextrin, and optionally a component acceptable as a liquid detergent. ,
The liquid detergent in which the total content of all the surfactants is 45% by mass or more and 80% by mass or less with respect to the total mass of the liquid detergent:
(A) component: selected from the group consisting of the compound represented by the formula (a-1), the compound represented by the formula (a-2), and the compound represented by the formula (a-4) A nonionic surfactant comprising at least one compound and a compound represented by the formula (a-3);
Component (B): Compound (B1-1) represented by Formula (b1-1), Compound (B1-2) represented by Formula (b1-2), and a carbon number of 6 or more and 18 or less. At least one compound selected from the group consisting of alcohols; and component (C): linear alkylbenzene sulfonic acid or a salt thereof; alkane sulfonate; polyoxyethylene alkyl ether sulfate ester; alkylene oxide having 2 to 4 carbon atoms Or carbon obtained by adding an average of 0.5 to 10 mol of ethylene oxide (EO) and propylene oxide (PO) (molar ratio EO / PO = 0.1 / 9.9 to 9.9 / 0.1) Alkyl (or alkenyl) ether sulfate ester salt having a linear or branched alkyl group (or alkenyl group) of several tens to 20; α-olefin sulfone At least one anionic surfactant selected from the group consisting of and higher fatty acid salts; salts;
Is mentioned.

Other aspects of the invention include:
The following (A) component, the following (B) component, the following (C) component, water, and optionally a liquid detergent containing components that can be acceptable as a liquid detergent,
For the total mass of the liquid detergent,
The total content of all the surfactants is 45% by mass or more and 80% by mass or less,
The component (A) is 1 to 70% by mass,
The component (B) is 0.1 to 10% by mass,
The component (C) is 1 to 20% by mass,
Liquid detergent, wherein the water is 5 to 35% by mass and the total amount of each component does not exceed 100% by mass:
(A) component: selected from the group consisting of the compound represented by the formula (a-1), the compound represented by the formula (a-2), and the compound represented by the formula (a-4) A nonionic surfactant comprising at least one compound;
(B) component: at least one compound selected from the group consisting of the compound represented by the formula (b-1) and an alcohol having 6 to 18 carbon atoms; and (C) component: an anionic surfactant ;
Is mentioned.

Other aspects of the invention include:
The following (A) component, the following (B) component, the following (C) component, water, and optionally a liquid detergent containing components that can be acceptable as a liquid detergent,
For the total mass of the liquid detergent,
The total content of all the surfactants is 45% by mass or more and 80% by mass or less,
The component (A) is 1 to 70% by mass,
The component (B) is 0.1 to 10% by mass,
The component (C) is 1 to 20% by mass, the water is 5 to 35% by mass, and the total amount of each component does not exceed 100% by mass;
(C) component / (A) component which is mass ratio of said (C) component and said (A) component is 0.02-0.7;
(A) component / (B) component which is a mass ratio of the said (A) component and the said (B) component is 15-150,
Liquid detergent:
(A) component: selected from the group consisting of the compound represented by the formula (a-1), the compound represented by the formula (a-2), and the compound represented by the formula (a-4) A nonionic surfactant comprising at least one compound;
(B) component: at least one compound selected from the group consisting of the compound represented by the formula (b-1) and an alcohol having 6 to 18 carbon atoms; and (C) component: an anionic surfactant ;
Is mentioned.

Other aspects of the invention include:
The following (A) component, the following (B) component, the following (C) component, water, and optionally a liquid detergent containing components that can be acceptable as a liquid detergent,
For the total mass of the liquid detergent,
The total content of all the surfactants is 45% by mass or more and 80% by mass or less,
The component (A) is 1 to 70% by mass,
The component (B) is 0.1 to 10% by mass,
The component (C) is 1 to 20% by mass, the water is 5 to 35% by mass, and the total amount of each component does not exceed 100% by mass;
(C) component / (A) component which is mass ratio of said (C) component and said (A) component is 0.02-0.7;
The sum of the following compound (A1) and the following compound (A2) and the following compound (A3) and the total ratio of the compound (A1) and the compound (A2) / compound (A3) is 0.02 to 4.5. Liquid detergent that is:
(A) Component: Compound (A1) represented by Formula (a-1), Compound (A2) represented by Formula (a-2), and Compound (A-4) ( A nonionic surfactant comprising at least one compound selected from the group consisting of A4) and the compound (A3) represented by the formula (a-3);
(B) component: at least one compound selected from the group consisting of the compound represented by the formula (b-1) and an alcohol having 6 to 18 carbon atoms; and (C) component: an anionic surfactant ;
Is mentioned.

Other aspects of the invention include:
The following (A) component, the following (B) component, the following (C) component, water, and optionally a liquid detergent containing components that can be acceptable as a liquid detergent,
For the total mass of the liquid detergent,
The total content of all the surfactants is 45% by mass or more and 80% by mass or less,
The component (A) is 1 to 70% by mass,
The component (B) is 0.1 to 10% by mass,
The component (C) is 1 to 20% by mass, the water is 5 to 35% by mass, and the total amount of each component does not exceed 100% by mass;
The (C) component / (A) component, which is a mass ratio of the (C) component and the (A) component, is 0.02 to 0.7.
Liquid detergent:
(A) Component: Compound (A1) represented by Formula (a-1), Compound (A2) represented by Formula (a-2), and Compound (A-4) ( A nonionic surfactant comprising at least one compound selected from the group consisting of A4) and the compound (A3) represented by the formula (a-3);
Component (B): Compound (B1-1) represented by Formula (b1-1), Compound (B1-2) represented by Formula (b1-2), and a carbon number of 6 or more and 18 or less. At least one compound selected from the group consisting of alcohols; and component (C): linear alkylbenzene sulfonic acid or a salt thereof; alkane sulfonate; polyoxyethylene alkyl ether sulfate ester salt; alkylene oxide having 2 to 4 carbon atoms Or carbon obtained by adding an average of 0.5 to 10 mol of ethylene oxide (EO) and propylene oxide (PO) (molar ratio EO / PO = 0.1 / 9.9 to 9.9 / 0.1) Alkyl (or alkenyl) ether sulfate ester salt having a linear or branched alkyl group (or alkenyl group) of several tens to 20; α-olefin sulfone At least one anionic surfactant selected from the group consisting of and higher fatty acid salts; salts.

  Hereinafter, the present invention will be specifically described by way of examples, but the present invention is not limited thereto.

[Raw materials]
As the component (A), the following compounds were used.
A1-1: MEE (nonionic interface synthesized by adding 15 mol equivalent of ethylene oxide to methyl coconut fatty acid (mixture of methyl laurate / methyl myristate = 8/2 by mass ratio) using an alkoxylation catalyst Activators, synthetic products). A compound in which R ¹ in the general formula (a-1) is an alkyl group having 12 or 14 carbon atoms, R ² is an ethylene group, R ³ is a methyl group, and m is 15. The synthesis was performed as follows.
The synthesis was carried out according to the synthesis method described in JP 2000-144179 A (corresponding to sample D). That is, alumina hydroxide / magnesium hydroxide (Kyowa Chemical Industry Co., Ltd., “KYOWARD 330”) having a chemical composition of 2.5 MgO.Al ₂ O ₃ .nH ₂ O was calcined at 600 ° C. for 1 hour in a nitrogen atmosphere. 4 L of calcined alumina / magnesium hydroxide (unmodified) catalyst obtained in this manner, 2.9 mL of 0.5N potassium hydroxide ethanol solution, 280 g of lauric acid methyl ester, and 70 g of myristic acid methyl ester The autoclave was charged and the catalyst was reformed in the autoclave. Next, after replacing the inside of the autoclave with nitrogen, the temperature was raised, and while maintaining the temperature at 180 ° C. and the pressure of 3 × 10 5 Pa, 1052 g of ethylene oxide was introduced and reacted while stirring. Further, the reaction solution was cooled to 80 ° C., 159 g of water and 5 g of activated clay and diatomaceous earth as filter aids were added, and then the catalyst was filtered off to obtain MEE.

A2-1: EOPO (nonionic surfactant in which an average of 9 moles of ethylene oxide, an average of 2 moles of propylene oxide, and an average of 9 moles of ethylene oxide were added in block order to a primary alcohol having 10 to 14 carbon atoms). A compound in which R ⁴ in the general formula (a-2) is an alkyl group having 12 or 14 carbon atoms, s is 18 and t is 2.

A3-1: LMAO-1 (nonionic surfactant having an average of 15 moles of ethylene oxide added to natural alcohol CO-1214 (manufactured by P & G)). The synthesis was performed as follows.
861.2 g of natural alcohol CO-1214 and 2.0 g of 30% NaOH aqueous solution were charged into a pressure-resistant reaction vessel, and the inside of the vessel was purged with nitrogen. Next, after dehydrating for 30 minutes at a temperature of 100 ° C. and a pressure of 2.0 kPa or less, the temperature in the container was raised to 160 ° C. to obtain a reaction solution. Next, 760.6 g of ethylene oxide (gaseous) was gradually added to the reaction solution while stirring the reaction solution. At this time, ethylene oxide was added through the blowing tube while adjusting the addition rate so that the reaction temperature did not exceed 180 ° C. After completion of the addition of ethylene oxide, aging was performed at a temperature of 180 ° C. and a pressure of 0.3 MPa or less for 30 minutes, and then unreacted ethylene oxide was distilled off at a temperature of 180 ° C. and a pressure of 6.0 kPa or less for 10 minutes. Next, after cooling the temperature to 100 ° C. or lower, 70% by mass p-toluenesulfonic acid was added to neutralize so that the pH of the 1% by mass aqueous solution of the reaction product was about 7, thereby obtaining LMAO-1. It was.

A3-2: LMAO-2 (nonionic surfactant having an average of 8 moles of ethylene oxide added to natural alcohol CO-1214 (manufactured by P & G)). The synthesis was performed as follows.
LMAO-2 was obtained in the same manner as the LMAO-1 synthesis method except that the amount of ethylene oxide introduced was changed to 507.4 g.

A4-1: Polyoxyethylene (20) hexadecylamine (R ¹ in the above general formula (a-4) = corresponding to an alkyl group having 16 carbon atoms, an average number of repeating oxyethylene groups of 20, p + q = 20) Synthetic product. A4-1 was synthesized as follows.
Fatty acid amine (manufactured by Tokyo Chemical Industry Co., Ltd., n-hexadecylamine) is charged into an autoclave (manufactured by Pressure Glass Industrial Co., Ltd.), the inside of the system is replaced with nitrogen, and then heated to 150 ° C. until ethylene oxide reaches a predetermined amount. A tertiary amine having an average addition mole number of ethylene oxide (EO) of 2 mol was synthesized (first stage). Next, the obtained tertiary amine and an alkali catalyst (NaOH; 0.8 parts by mass with respect to 100 parts by mass of the tertiary amine, 40% by weight NaOH aqueous solution) are charged into an autoclave, and the system is filled with nitrogen. After dehydration by heating and depressurization, the mixture was heated to 150 ° C., and ethylene oxide was added little by little until reaching a predetermined amount to obtain A4-1 having an average added mole number of EO of 20 mol ( Second stage). After the reaction, the product was neutralized with acetic acid. Moreover, it was 1121 when the molecular weight was computed by amine value measurement.

A4-2: ethylene oxide (13 mol) propylene oxide (2 mol) adduct of stearylamine (in the following general formula (A4-2), R = C18 alkyl group, x + y = 2, a + b = 13 Equivalent) synthetic product. A4-2 was synthesized as follows.

脂肪酸アミン（ライオンアクゾ株式会社、アーミン１８Ｄ）をオートクレーブ（耐圧硝子工業社製）に仕込み、系内を窒素で置換した後、１５０℃に加熱し、プロピレンオキシドを所定量に達するまで少量ずつ添加して、プロピレンオキシド（ＰＯ）の平均付加モル数が２モルの３級アミンを合成した（一段階目）。次に、得られた３級アミンと、アルカリ触媒（４０質量％ＮａＯＨ水溶液を用いて０．８質量％分）とをオートクレーブに仕込み、系内を窒素で置換し、加温減圧による脱水を行った後、１５０℃に加熱し、エチレンオキシドを所定量に達するまで少量ずつ添加して、ＰＯの平均付加モル数が２モル、ＥＯの平均付加モル数が１３モルのポリオキシアルキレンステアリルアミン）を得た（二段階目）。反応後は、生成物を酢酸により中和処理した。また、アミン価測定により、分子量を算出したところ、９３９であった。

A fatty acid amine (Lion Akzo Co., Ltd., Armin 18D) is charged into an autoclave (made by pressure-resistant glass industry), the inside of the system is replaced with nitrogen, heated to 150 ° C., and propylene oxide is added little by little until a predetermined amount is reached. Thus, a tertiary amine having an average addition mole number of propylene oxide (PO) of 2 mol was synthesized (first stage). Next, the obtained tertiary amine and an alkali catalyst (0.8% by mass using a 40% by mass NaOH aqueous solution) are charged into an autoclave, the inside of the system is replaced with nitrogen, and dehydration is performed by heating under reduced pressure. After that, the mixture is heated to 150 ° C., and ethylene oxide is added little by little until a predetermined amount is reached to obtain a polyoxyalkylene stearylamine having an average addition mole number of PO of 2 moles and an average addition mole number of EO of 13 moles). (Second stage). After the reaction, the product was neutralized with acetic acid. Moreover, it was 939 when molecular weight was computed by amine value measurement.

As the component (B), the following compounds were used.
B1-1: castor hydrogenated oil (manufactured by NOF Corporation, “Caster Wax A Flakes”).
B1-2: Hardened palm oil (manufactured by Shin Nippon Rika Co., Ltd., “Palm extremely hardened oil A”).

As the component (C), the following compounds were used.
C-1: LAS-H (linear alkyl (carbon number 10 to 14) benzenesulfonic acid (manufactured by Lion Corporation, “Lypon LH-200”, pure content 96% by mass)).
C-2: Palm fatty acid (manufactured by NOF Corporation).
C-3: polyoxyalkylene alkyl ether sulfate monoethanolamine salt (linear alkyl having 10 to 14 carbon atoms, PO average addition mole number 1, EO average addition mole number 3)

The following compounds were used as optional components.
Common component a: as shown in Table 1 below.
Common component b: as shown in Table 2 below.
Common component c: as shown in Table 3 below.
Common component d: as shown in Table 4 below.
Common component e: shown in Table 5 below.
Common component f: as shown in Table 6 below.

Each compound contained in the common components a to f is as follows.
Amidoamine: dimethylaminopropylamide stearate (manufactured by Toho Chemical Co., Ltd.), cationic surfactant.
PTS-H: p-toluenesulfonic acid (manufactured by Teika Co., Ltd., “Taikatox 300”).
-Benzoic acid Na: Sodium benzoate (made by Toagosei Co., Ltd.).
-Citric acid: Citric acid (manufactured by Yushi Kogyo Co., Ltd.).
PEG: polyethylene glycol.
NaOH: Sodium hydroxide EtOH: Ethanol (specific alcohol 95 degree synthesis, manufactured by Nippon Alcohol Sales Co., Ltd.)
・ Ethanolamine: Monoethanolamine (Mitsui Chemicals)
Alkyltrimethylammonium salt: Dodecyltrimethyl chloride (manufactured by Lion Akzo Co., Ltd.), a cationic surfactant.
Butyl carbitol: butyl diglycol.
Propylene glycol: 1,2-propanediol (manufactured by Dow Chemical Company).
Cumenesulfonic acid Na: cumenesulfonic acid sodium (manufactured by Teikatox Co., Ltd., “Taikatox N5040”).
Coronase: Coronase 48L (manufactured by Novozymes).
Silicone: Silicone emulsion (manufactured by Shin-Etsu Chemical Co., Ltd., “KM-98”).
Fragrance A-1: Fragrance composition a-1-1 described in Examples of JP 2008-7872.
Fragrance A-2: Fragrance composition A described in Tables 11 to 18 of JP-A-2002-146399.
-Fragrance B-1: BLUEFLOWERPOP “FFMHN2814” (manufactured by Firmenich).
Fragrance B-2: COSMICCAPS (manufactured by Givaudan).
Fragrance B-3: UNICAP503 (manufactured by IFF).
・ Urea :: Reagent, Junsei Chemical Co., Ltd. ・ Cluster dextrin: Glico Nutrition Foods Co., Ltd. ・ Water: Purified water

[Examples 1 to 26, Comparative Examples 1 to 6]
By the manufacturing method shown below, the composition which contains each component with content (mass%) of Tables 7-9 was adjusted. In addition, water (purified water) was used as a solvent, and it was made to become 100 mass% combining water and components other than the water of Tables 7-9. The water content was “balance”.

<Manufacturing method>
The component (A) and ethanol were placed in a 500 mL beaker, and the mixture was sufficiently stirred with a magnetic stirrer (manufactured by MITAMURA KOGYO INC.). Add optional components (excluding water and ethanol) and component (C) to this, add water so that the total amount of this solution is 90% by mass with respect to the total mass of the liquid detergent, and further stir Then, the mixture was heated to the melting point of the component (B). To this, the component (B) heated to the melting point was added and stirred until the whole became uniform (that is, each component was uniformly dispersed). Next, an appropriate amount of a pH adjusting agent (sodium hydroxide or sulfuric acid) is added so that the pH at 25 ° C. becomes 7.0, and then the total amount of this solution becomes 100% by mass with respect to the total mass of the liquid detergent. Water was added to obtain a liquid detergent.
About each obtained liquid detergent, application | coating cleaning power, usability, dispersibility, and quick-drying were evaluated by the evaluation method shown below. The results are shown in Tables 7-9.

<Evaluation method>
(Evaluation of cleaning power)
500 g of spinach was washed and the root part was removed. 250 mL of 3DH hard water was placed in a mixer (National Soup & Fruit MX-V350), spinach was added in small portions and pulverized. After all the spinach was put into the mixer, it was rotated for 5 minutes to make it completely juice-like.
A beaker was placed in an ice bath, a colander was placed thereon, six more layers of gauze were placed, and the spinach juice obtained earlier was filtered. At this time, when the gauze was clogged, the gauze was replaced. The filtrate was transferred to a vat (29 × 22 × 4 cm), and 10 pieces of cotton cloth (# 100 26 × 21 cm) were added and immersed for 3 minutes while turning over.
The cotton cloth was taken out from the vat and left overnight with the cloth upside down every 20-30 minutes. Thereafter, it was rinsed with a washing machine (manufactured by Mitsubishi Electric Corporation, “CW-C30A1-H”) for 2 minutes, dehydrated for 30 seconds, air-dried and stored in a dark place to obtain a spinach grass cloth (contaminated cloth).
Next, 0.1 g of the liquid detergent after being stored at 15 ° C. for 24 hours was applied to each of 10 contaminated cloths (0.1 g of liquid detergent / one contaminated cloth) and left for 5 minutes. Thereafter, the contaminated cloth and a commercially available T-shirt (100% cotton, manufactured by BVD) were put into a cleaning tester (Terg-O-Tometer, manufactured by UNITED STATES TESTING). The input amount of the T-shirt was adjusted so that the total fabric mass was about 45 g.
According to the standard course of the cleaning tester, a cleaning operation was performed in which washing was performed for 10 minutes, rinsed twice, and dehydrated for 3 minutes sequentially.
The contaminated cloth after the washing operation was left in a constant temperature and humidity chamber at 25 ° C. and a humidity of 65% RH for 24 hours to dry the contaminated cloth.
Colorimetric colorimeter (manufactured by Nippon Denshoku Co., Ltd.) for b value (reflectance) of raw cloth before spinach dirt adhesion, spinach dirt cloth (contaminated cloth) before washing, and contaminated cloth after washing and drying Name: SE2000), and the coating detergency (%) against spinach stains was calculated by the following formula (1).
Application cleaning power (%) = (b value of contaminated cloth after washing / drying−b value of contaminated cloth before washing) / (b value of raw cloth−b value of contaminated cloth before washing) × 100 (1)

Evaluation of the coating detergency against spinach stains was determined by using the coating detergency (%) calculated by the above formula, that the detergency was good if C, B, and A in the following evaluation criteria.
In addition, the average score of 10 contaminated cloths was used for the coating cleaning power (%).
A: The cleaning rate is 90% or more.
B: The cleaning rate is 85% or more and less than 90%.
C: The cleaning rate is 80% or more and less than 85%.
D: The cleaning rate is less than 80%.

(Evaluation of usability)
A bottle (capacity 200 mL) containing 400 g of the liquid cleaning agent was left in a constant temperature bath at 25 ° C. After 3 hours, the bottle was taken out from the thermostatic bath, and the bottle was tilted, and the contents (liquid cleaning agent) were poured into a transparent cap.
Evaluation of the ease of pouring when the liquid detergent was poured into the cap was carried out by 10 panelists and scored according to the following criteria. The average score of 10 people was classified into the following evaluation criteria, and the usability was evaluated. If C, B, and A, the usability was determined to be good.

Judgment criteria:
1 point: Ease of pouring is very poor compared to Comparative Example 2.
2 points: Ease of pouring is slightly worse than Comparative Example 2.
3 points: equivalent to Comparative Example 2 or Comparative Example 2.
4 points: Easier to pour than in Comparative Example 2.
5 points: Ease of pouring is very good compared to Comparative Example 2.

Evaluation criteria:
A: The average score is 4.5 or more.
B: The average score is 4.0 points or more and less than 4.5 points.
C: The average score is 3.5 points or more and less than 4.0 points.
D: The average score is less than 3.5 points.

(Evaluation of dispersibility)
A 100 mL glass bottle (Hiroguchi standard bottle: PS-No. 6) was filled with 30 g of a liquid detergent, and 0.5 g of beads (“PFL-RED 7155T Lot. . After storing in a thermostatic bath at 25 ° C. for 1 day, the glass bottle was taken out from the thermostatic bath, the dispersion state of the beads in the liquid detergent was visually confirmed, and evaluated according to the following evaluation criteria.
A: The beads are uniformly dispersed in the liquid detergent.
B: The beads are floating or settling.

<Evaluation of quick drying performance>
Commercially available shirts (Heattech manufactured by Uniqlo Corporation. Clothing display composition: acrylic 40%, polyester 33%, rayon 21%, polyurethane 6%) were used as the evaluation fabric.
(1) Pretreatment of evaluation cloth 34 L tap water at 60 ° C. was put into a fully automatic washing machine (product name AW-80VC manufactured by Toshiba Corporation). Thereto, 30 g of detergent for clothing (trade name Blue Diamond manufactured by Lion Co., Ltd.) was added, and then the above-mentioned commercially available shirt was put. Next, a washing operation was sequentially repeated twice for 15 minutes of washing, 3 times of rinsing and 7 minutes of dehydration according to the standard course of the fully automatic washing machine. Next, the washing operation similar to the above was repeated three times without adding a detergent for clothing. Thereafter, it was naturally dried and used as an evaluation cloth.
(2) Quick-drying test 34 L of tap water of 15 ° C. was put into a fully automatic washing machine (product name AW-80VC manufactured by Toshiba Corporation). Three sheets of the evaluation cloth, T-shirt (100% cotton) and cotton towel (100% cotton) were put therein (the amount of T-shirt and cotton towel to be charged is three sheets of evaluation cloth, T-shirt and cotton towel) The total mass was adjusted to 1.7 kg).
Thereto, 10 g of the liquid cleaning agent of each example was added, and cleaning operation was performed once in order of washing for 10 minutes, rinsing once and dehydration for 3 minutes in accordance with the standard course of the fully automatic washing machine.
Next, the evaluation fabric was dried in a thermostatic chamber (MODEL: TBR-2HAOPX manufactured by ESPEC CORP) having a temperature of 25 ° C. and a relative humidity of 60%.
At this time, the mass after drying over time was measured, and this was taken as the weight after drying. The moisture content of the evaluation fabric was followed over time, and the moisture content after 1 hour of drying was measured.
(3) Evaluation of quick-drying performance The moisture content (%) was calculated based on the following formula.
Moisture content (%) = (weight after drying over time (g) −initial weight (g)) / weight after drying over time (g) × 100
The quick drying performance was evaluated using the moisture content (%) calculated by the above formula, and when the moisture content of Comparative Example 3 after 1 hour after drying was 1, the relative moisture content in each example was obtained.
Evaluation was performed according to the following criteria, and it was determined that B and A had good quick-drying performance.

A: Relative moisture content is 0.3 or less with respect to Comparative Example 3 B: Relative moisture content is 0.4 or more and 0.6 or less with respect to Comparative Example 3 C: Relative moisture content is 0. 0 with respect to Comparative Example 3. 7 or more and 0.9 or less D: The relative water content is 1.0 or more with respect to Comparative Example 3.

As is clear from Tables 7 and 8, the liquid detergent obtained in each example was excellent in coating cleaning power and in usability.
Moreover, the liquid cleaning agent obtained in each Example was able to uniformly disperse the beads. From this result, it is considered that the liquid cleaning agent obtained in each example forms a structural liquid.

On the other hand, as is clear from Table 9, the liquid detergent of Comparative Example 1 containing no component (A) and having a total surfactant content of 9% by mass is inferior in coating detergency and usability. It was.
The liquid detergent of Comparative Example 2 containing no component (A) was inferior in usability.
The liquid detergent of Comparative Example 3 containing no component (B) was inferior in coating cleaning power and usability.
The liquid cleaning agent of Comparative Example 4 having a total surfactant content of 39% by mass was inferior in coating cleaning power and usability.
The liquid detergent of Comparative Example 5 containing no component (C) was inferior in usability.
In Comparative Examples 2 to 5, the beads could not be uniformly dispersed. Therefore, it is considered that the liquid detergents of Comparative Examples 2 to 5 do not form a structural liquid and form spherical micelles.

Since the present invention can provide a liquid cleaning agent having excellent coating cleaning power and excellent usability, it is extremely effective industrially.

Claims (3)

The following (A) component, (B) component, and (C) component are contained, and the total content of all the surfactants is 45% by mass or more and 80% by mass or less with respect to the total mass of the liquid detergent. Is a liquid cleaning agent:
Component (A): a group consisting of a compound represented by the following general formula (a-1), a compound represented by the following general formula (a-2), and a compound represented by the following general formula (a-4) A nonionic surfactant comprising at least one compound selected from:
(B) component: a compound represented by the following general formula (b-1) ; and (C) component: an anionic surfactant;

(In Formula (a-1), R ¹ is a hydrocarbon group having 9 to 13 carbon atoms, R ² is an alkylene group having 2 to 4 carbon atoms, and R ³ is an alkyl group having 1 to 4 carbon atoms. There, m is a number from 5 to 25 showing an average number of repetitions of OR ^2.)

(In the formula (a-2), R ⁴ is a hydrocarbon group having 10 to 20 carbon atoms, EO is an oxyethylene group, PO is an oxypropylene group, and s indicates the average number of repetitions of EO 5 Is a number of ˜20, and t is a number of 1 to 4 indicating the average number of repetitions of PO; [— (EO) _s − (PO) _t −] is EO and PO are the formula — (EO) (Indicates that they may be mixed and arranged regardless of the order of _s- (PO) _t- ).)

(In Formula (a-4), R ¹ is a hydrocarbon group having 10 to 20 carbon atoms; A ¹ O and A ² O are each independently an oxyalkylene group having 2 to 4 carbon atoms; ¹ represents the average number of repetitions of ¹ O, q represents the average number of repetitions of A ² O, p> 0, q> 0, and p + q is a number of 10 or more and less than 60.)

(In Formula (b-1), Z ^{1 to} Z ³ are each independently a hydrogen atom, a hydroxy group, or a carboxy group, a + b = 7 to 19, c + d = 7 to 19, and e + f = 7. ~ 19.)
  The liquid cleaning agent of Claim 1 whose (C) component / (A) component which is mass ratio of the said (C) component and the said (A) component is 0.02-0.7. The content of (A) is 1 to 70% by mass with respect to the total mass of the liquid detergent, the content of component (B) is 0.1 to 10% by mass, and (C The liquid cleaning agent according to claim 1, wherein the content of the component is 1 to 20% by mass.