JP2015193859A - liquid detergent - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a liquid detergent good in liquid fluidity and liquid stability, having high detergency to various dirt, especially excellent in odor removability and application detergency needed to remove dirt by direct application to product to be cleaned.SOLUTION: The invention relates to a liquid detergent containing specific aliphatic acid alkyl ester sulfonate (A), specific aliphatic acid alkyl ester alkoxylate (B), and at least one kind of organic solvent (C) selected from alcohol having 2 to 4 carbon atoms and a compound represented by general formula (c-1) with the total of the (A) component and the (B) component of 40 mass% or more, (A) component/(B) component (mass ratio) of 5/95 to 60/40, and mass ratio represented by [(A) component+(B) component]/(C) component of 23 or less.

Description

The present invention relates to a liquid cleaning agent.
This application includes Japanese Patent Application No. 2011-092214 filed in Japan on April 18, 2011, Japanese Patent Application No. 2011-092215 filed in Japan on April 18, 2011, and Japan on April 18, 2011. Claimed priority based on Japanese Patent Application No. 2011-092216 filed and Japanese Patent Application No. 2011-092217 filed in Japan on April 18, 2011, the contents of which are incorporated herein.

In recent years, the development of products in consideration of the global environment has been demanded also in the daily necessities field such as laundry detergents. For example, reducing the size of the detergent container is expected to reduce energy consumption and the amount of garbage in logistics.
On the other hand, due to the widespread use of drum-type washing machines, etc., the bath ratio in washing (ratio of washing water to the object to be washed) has been decreasing. It is also desired that the amount of water used is small or the amount of water required for rinsing is small.
On the other hand, in the liquid detergent field, development (concentration) of a composition having a high surfactant concentration is in progress.

The liquid detergent needs to ensure liquid stability (transparency uniformity, stability over time, etc.) as well as high detergency.
However, when the concentration of the surfactant is increased, viscosity increase or gelation occurs in the composition itself, resulting in poor liquid fluidity. Along with this, it becomes difficult to weigh the cap or apply it to the object to be washed. In addition, it becomes difficult to ensure a transparent and uniform appearance such as turbidity and precipitation.
These defects are particularly noticeable under low temperature conditions such as in winter.

As a method for reducing the viscosity of the liquid detergent, a water-miscible organic solvent has been conventionally used.
For example, certain non-ionic surfactants such as polyoxyethylene or polyoxyalkylene ethers, anionic surfactants (linear alkylbenzene sulfonates or polyoxyethylene alkyl ether sulfates) and water-miscible organics A liquid detergent containing a solvent at a specific blending ratio is disclosed (see Patent Document 1). According to this liquid detergent, the composition itself is hardly gelled or increased in viscosity.
In addition, a liquid detergent containing 50 to 70% by mass of a specific alkylene oxide adduct, 1 to 10% by mass of a non-soap anionic surfactant, and a water-miscible organic solvent is disclosed (patent) Reference 2). According to this liquid detergent, it is said that it has a uniform appearance and is less likely to gel with time.

JP 2010-229385 A JP 2009-173858 A

By the way, recently, awareness of health has increased, and the percentage of people who actively incorporate exercise in daily life is increasing. The clothing worn during the exercise is of various designs and colors, or one that is not only excellent in sweat absorption by controlling the surface shape of the fibers but also provided quick drying (easy to dry) Has been released. Many of such garments use hydrophobic chemical fibers such as polyester and polyurethane. However, after wearing the clothes, even if washing is performed using a conventional liquid cleaning agent, dirt such as sweat and sebum adhering to the chemical fiber cannot be sufficiently removed, and odors caused by these dirt remain. There is a problem that it feels uncomfortable when it is next worn.
As one of the causes of odor generation from clothes after washing, it is known that dirt such as sebum that is not completely removed by washing is decomposed by microorganisms. Such an odor is likely to occur especially on days with high humidity such as during the rainy season. With the recent changes in lifestyle, clothes that have been washed at night are dried indoors (rooms are dried), and odors (dry room odors) generated from clothes after washing are increasing. Is required.

In addition, liquid detergents do not have the detergency (application washing power) necessary to remove protein stains by directly applying the liquid detergent to foods and other items to which protein stains adhere. It is enough.
Furthermore, re-contamination of clothes is likely to occur during washing due to bulk washing in a large-capacity washing machine represented by a drum type washing machine and a decrease in bath ratio accompanying water-saving washing. In particular, re-contamination is likely to occur in hydrophobic chemical fibers such as polyester.

On the other hand, with the recent increase in the size of washing machines or the spread of water-saving washing machines, washing has been performed under conditions of a low bath ratio with less water. In addition, there are many cases where a lot of clothing is packed in a washing machine and washed. When washing is performed under such conditions, re-contamination is likely to occur, in which dirt once removed during washing adheres to clothing and the like again.
In addition, when washing is performed under such a low bath ratio condition, the objects to be washed rub against each other in the washing tub, so that the fibers are damaged, the fiber surface becomes fuzzy, and the portion is whitened by irregular reflection of light. It tends to cause a problem that it can be seen or the texture (comfort) after drying is deteriorated.
For such a problem, a method of imparting flexibility to the object to be washed by blending a cationic component is useful. However, in a liquid detergent containing a linear alkyl benzene sulfonate or polyoxyethylene alkyl ether sulfate as an anionic surfactant, if the cationic component is blended, precipitation or precipitation is likely to occur and the liquid stability is improved. It is difficult to secure.

  This invention is made | formed in view of the said situation, and makes it a subject to provide the liquid cleaning agent which has the liquid fluidity | liquidity and liquid stability favorable, and has high cleaning power with respect to various stain | pollution | contamination. In particular, in addition to liquid flowability and liquid stability, it is an object to provide a liquid cleaning agent that is excellent in odor removal properties and coating detergency necessary for removing dirt by applying directly to an object to be washed And

  Another object of the present invention is to provide a liquid detergent that has good liquid flowability and liquid stability, has high detergency against various stains, and is excellent in recontamination prevention performance. .

  Another object of the present invention is to provide a liquid cleaning agent that has good liquid flowability and liquid stability, has a high detergency against various types of dirt, and has an excellent flexibility imparting effect. .

  The present invention also provides a liquid detergent that has good liquid flowability and liquid stability, has a high detergency against various stains, and is excellent in deodorizing performance and recontamination prevention performance. Is an issue.

  As described above, when a cationic component is added to a liquid detergent containing a linear alkylbenzene sulfonate or polyoxyethylene alkyl ether sulfate as an anionic surfactant, the cationic component and the anionic surfactant Precipitation and precipitation are likely to occur due to electrostatic interaction with the. In particular, in a composition having a high surfactant concentration, it has been difficult to stably mix the cationic component and the anionic surfactant.

For the deodorization of odors generated from clothes after washing as described above, a method is conceivable in which a cationic compound having antibacterial properties is blended and caused to exert a deodorizing effect by acting on microorganisms such as microorganisms.
In order to prevent re-contamination, a method of blending a linear alkylbenzene sulfonate as an anionic surfactant can be considered.
However, even when a cationic compound as an antibacterial or deodorant component and a linear alkylbenzene sulfonate as a component for preventing recontamination are blended in a composition having a high surfactant concentration, the respective performances are not fully exhibited. Also, it has been difficult to ensure liquid stability as a liquid preparation.

  As a result of intensive studies, the present inventors have found that fatty acid alkyl ester sulfonates, which are surfactants that are generally used in granular detergents and are not normally used in liquid detergents, and fatty acid alkyl ester alkoxylates at a specific blending ratio. It has been found that the above-mentioned problems can be solved by using in combination with a water-miscible organic solvent at a specific blending ratio, and the present invention has been completed.

  In addition, as a result of intensive studies, the present inventors have found that a fatty acid alkyl ester sulfonate, a fatty acid alkyl ester alkoxylate, which is a surfactant that is generally used in granular detergents and is not usually used in liquid detergents, and water-miscible. It has been found that the above problem can be solved by blending a specific polymer and a fatty acid or a salt thereof in a mixed system in which an organic solvent is used in combination at a specific blending ratio, and the present invention has been completed.

  In addition, as a result of intensive studies, the present inventors have found that a fatty acid alkyl ester sulfonate, a fatty acid alkyl ester alkoxylate, which is a surfactant that is generally used in granular detergents and is not usually used in liquid detergents, and water-miscible. It has been found that the above problems can be solved by blending a tertiary amine in a mixed system in which an organic solvent is used in a specific blending ratio, and the present invention has been completed.

  In addition, as a result of intensive studies, the present inventors have found that a fatty acid alkyl ester sulfonate, a fatty acid alkyl ester alkoxylate, which is a surfactant that is generally used in granular detergents and is not usually used in liquid detergents, and water-miscible. It has been found that the above problems can be solved by blending a cationic surfactant into a mixed system in which an organic solvent is used in combination at a specific blending ratio, and the present invention has been completed.

  As one aspect of the present invention, an anionic surfactant (A) represented by the following general formula (a-1) and a nonionic surfactant (B) represented by the following general formula (b-1) And at least one organic solvent (C) selected from the group consisting of compounds having 2 to 4 carbon atoms and a compound represented by the following general formula (c-1), and the component (A) The sum total with said (B) component is 40 mass% or more, and mass ratio represented by (A) component / (B) component is (A) component / (B) component = 5 / 95-60 / 40. Further, the present invention relates to a liquid detergent having a mass ratio represented by [(A) component + (B) component] / (C) component of 23 or less.

［式（ａ−１）中、Ｒ^１は炭素数８〜１８の炭化水素基であり、Ｒ^２は炭素数１〜３のアルキル基であり、Ｍは対イオンである。式（ｂ−１）中、Ｒ^３は炭素数９〜１３の炭化水素基であり、Ｒ^４は炭素数２〜４のアルキレン基であり、Ｒ^５は炭素数１〜４のアルキル基である。ｍはＯＲ^４の平均繰返し数を示し、５〜２５の整数である。式（ｃ−１）中、Ｒ^７は炭素数１〜６のアルキル基又はフェニル基であり、Ｒ^８は炭素数２〜４のアルキレン基である。ｎはＯＲ^８の平均繰返し数を示し、１〜５の整数である。］

[In Formula (a-1), R ¹ is a hydrocarbon group having 8 to 18 carbon atoms, R ² is an alkyl group having 1 to 3 carbon atoms, and M is a counter ion. In formula (b-1), R ³ is a hydrocarbon group having 9 to 13 carbon atoms, R ⁴ is an alkylene group having 2 to ⁴ carbon atoms, and R ⁵ is an alkyl group having 1 to 4 carbon atoms. . m represents the average number of repetitions of OR ⁴ and is an integer of 5 to 25. In formula (c-1), R ⁷ is an alkyl group having 1 to 6 carbon atoms or a phenyl group, and R ⁸ is an alkylene group having 2 to 4 carbon atoms. n represents an average repeating number of OR ^8, an integer of 1 to 5. ]

  As another aspect of the present invention, an anionic surfactant (A) represented by the following general formula (a-1), and any one of the following general formula (b-1) and general formula (b-2) At least one nonionic surfactant (B) selected from the group consisting of the compounds represented by formula (1), an alcohol having 2 to 4 carbon atoms, and a compound represented by the following general formula (c-1). A polymer (D) having at least one organic solvent (C), at least one repeating unit (d1) selected from alkylene terephthalate units and alkylene isophthalate units, and an oxyalkylene unit (d2), a fatty acid or a salt thereof (E) is contained, the sum total of the said (A) component and the said (B) component is 40 mass% or more, and the mass ratio represented by (A) component / (B) component is (A) component / (B) component = 5 / 95- It is 0/50, and relates to [(A) component + (B) component] / (C) weight ratio expressed by component liquid detergent is 14 or less.

［式（ｂ−２）中、Ｒ^６は炭素数１０〜２０の炭化水素基である。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る。ｓはＥＯの平均繰返し数を示し、５〜２０の整数であり、ｔはＰＯの平均繰返し数を示し、１〜４の整数である。Ｒ^１、Ｒ^２、Ｍ、Ｒ^３、Ｒ^４、Ｒ^５、ｍ、Ｒ^７、Ｒ^８及びｎは前記と同じ意味を有する。］

[In Formula (b-2), R ⁶ is a hydrocarbon group having 10 to 20 carbon atoms. EO is an oxyethylene group and PO is an oxypropylene group. s represents the average number of repetitions of EO and is an integer of 5 to 20, and t represents the average number of repetitions of PO and is an integer of 1 to 4. R ¹ , R ² , M, R ³ , R ⁴ , R ⁵ , m, R ⁷ , R ⁸ and n have the same meaning as described above. ]

  As another aspect of the present invention, an anionic surfactant (A) represented by the following general formula (a-1), any one of the following general formula (b-1) and general formula (b-2) And at least one nonionic surfactant (B) selected from the group consisting of the compounds represented by formula (1), an alcohol having 2 to 4 carbon atoms, and a compound represented by the following general formula (c-1). At least one organic solvent (C) and a tertiary amine (F), and the total of the component (A) and the component (B) is 40% by mass or more. The mass ratio represented by (B) component is (A) component / (B) component = 5 / 95-40 / 60, and is represented by [(A) component + (B) component] / (C) component. The liquid cleaning agent has a mass ratio of 13 or less and a mass ratio represented by (A) component / (F) component of 1 to 15. .

［Ｒ^１、Ｒ^２、Ｍ、Ｒ^３、Ｒ^４、Ｒ^５、ｍ、Ｒ^６、ＥＯ、ＰＯ、ｓ、ｔ、Ｒ^７、Ｒ^８、及びｎは、前記と同じ意味を有する。］

[R ¹ , R ² , M, R ³ , R ⁴ , R ⁵ , m, R ⁶ , EO, PO, s, t, R ⁷ , R ⁸ , and n have the same meaning as described above. ]

  As another aspect of the present invention, the liquid detergent may contain at least one silicone compound (G) selected from the group consisting of an amino-modified silicone compound, a carboxy-modified silicone compound, and a polyether-modified silicone compound. preferable.

  As another aspect of the present invention, an anionic surfactant (A) represented by the following general formula (a-1), any one of the following general formula (b-1) and general formula (b-2) A group consisting of at least one nonionic surfactant (B) selected from the group consisting of the compounds represented by (2), a C2-4 alcohol and a compound represented by the following general formula (c-1) At least one organic solvent (C) selected from the above and a cationic surfactant (H), and the total of the component (A) and the component (B) is 40% by mass or more, The mass ratio represented by A) component / (B) component is (A) component / (B) component = 5 / 95-40 / 60, and [(A) component + (B) component] / (C) The mass ratio represented by the components is 10 or less, and the mass ratio represented by (A) component / (H) component is 1-15. Body cleaning agent on.

［Ｒ^１、Ｒ^２、Ｍ、Ｒ^３、Ｒ^４、Ｒ^５、ｍ、Ｒ^６、ＥＯ、ＰＯ、ｓ、ｔ、Ｒ^７、Ｒ^８、及びｎは、前記と同じ意味を有する。］

[R ¹ , R ² , M, R ³ , R ⁴ , R ⁵ , m, R ⁶ , EO, PO, s, t, R ⁷ , R ⁸ , and n have the same meaning as described above. ]

［Ｒ^１、Ｒ^２、Ｍ、Ｒ^３、Ｒ^４、Ｒ^５、ｍ、Ｒ^６、ＥＯ、ＰＯ、ｓ、ｔ、Ｒ^７、Ｒ^８、及びｎは、前記と同じ意味を有する。］ That is, the present invention relates to the following.
(1) An anionic surfactant (A) represented by the following general formula (a-1) and any one of the following general formulas (b-1) and (b-2) Selected from the group consisting of at least one nonionic surfactant (B) selected from the group consisting of the following compounds, an alcohol having 2 to 4 carbon atoms and a compound represented by the following general formula (c-1): A liquid detergent comprising at least one organic solvent (C), wherein the total of the component (A) and the component (B) is 40% by mass or more based on the total mass of the liquid detergent.

[R ¹ , R ² , M, R ³ , R ⁴ , R ⁵ , m, R ⁶ , EO, PO, s, t, R ⁷ , R ⁸ , and n have the same meaning as described above. ]

(2) The nonionic surfactant (B) is a compound represented by the general formula (b-1), and the mass ratio represented by (A) component / (B) component is (A) component / (B) component = 5 / 95-60 / 40, and the mass ratio represented by [(A) component + (B) component] / (C) component is 23 or less, as described in (1) Liquid detergent.
(3) A polymer (D) having at least one repeating unit (d1) selected from the group consisting of an alkylene terephthalate unit and an alkylene isophthalate unit and an oxyalkylene unit (d2), and a fatty acid or a salt thereof (E) Further, the mass ratio represented by the (A) component / (B) component is (A) component / (B) component = 5/95 to 50/50, and the [(A) component + (B) Liquid cleaning agent as described in (1) whose mass ratio represented by component] / (C) component is 14 or less.
(4) A tertiary amine (F) is further contained, and the mass ratio represented by the component (A) / component (B) is (A) component / (B) component = 5 / 95-40 / 60. Yes, the mass ratio represented by the [(A) component + (B) component] / (C) component is 13 or less, and the mass ratio represented by the (A) component / (F) component is 1. The liquid cleaning agent according to (1), which is ˜15.
(5) The liquid detergent according to (4), further comprising at least one silicone compound (G) selected from the group consisting of amino-modified silicone compounds, carboxy-modified silicone compounds, and polyether-modified silicone compounds.
(6) A cationic surfactant (H) is further contained, and the mass ratio represented by the component (A) / component (B) is (A) component / (B) component = 5 / 95-40 / 60. The mass ratio represented by the [(A) component + (B) component] / (C) component is 10 or less, and the mass ratio represented by the (A) component / (H) component is The liquid cleaning agent according to (1), which is 1 to 15.

  According to the present invention, it is possible to provide a liquid detergent having good liquid flowability and liquid stability and having a high detergency against various stains. In particular, according to the present invention, in addition to liquid fluidity and liquid stability, the liquid cleaning agent is excellent in odor removability and coating detergency necessary for directly applying to the object to be washed to remove dirt. Can be provided.

  Further, according to the present invention, it is possible to provide a liquid detergent that has good liquid flowability and liquid stability, has a high detergency against various stains, and is excellent in anti-recontamination performance. .

  Further, according to the present invention, it is possible to provide a liquid detergent that has good liquid flowability and liquid stability, has a high detergency against various stains, and has an excellent flexibility imparting effect. .

  In addition, according to the present invention, there is provided a liquid detergent that has good liquid flowability and liquid stability, has a high detergency against various types of dirt, and is excellent in deodorization performance and recontamination prevention performance. can do.

  The liquid detergent according to the first aspect of the present invention includes the anionic surfactant (A) represented by the general formula (a-1), the general formula (b-1), and the general formula (b-2). ) At least one nonionic surfactant (B) selected from the group consisting of compounds represented by any one of the general formulas, an alcohol having 2 to 4 carbon atoms, and the general formula (c-1). And at least one organic solvent (C) selected from the group consisting of the above compounds.

  The liquid detergent according to the second aspect of the present invention includes an anionic surfactant (A) represented by the general formula (a-1) and a nonionic interface represented by the general formula (b-1). It contains an activator (B), at least one organic solvent (C) selected from the group consisting of a compound represented by an alcohol having 2 to 4 carbon atoms and the general formula (c-1).

  The liquid detergent according to the third aspect of the present invention includes the anionic surfactant (A) represented by the general formula (a-1), the general formula (b-1), and the general formula (b-2). ) At least one nonionic surfactant (B) selected from the group consisting of compounds represented by any one of the general formulas, an alcohol having 2 to 4 carbon atoms, and the general formula (c-1). At least one organic solvent (C) selected from the group consisting of the above compounds, at least one repeating unit (d1) selected from the group consisting of alkylene terephthalate units and alkylene isophthalate units, and oxyalkylene units (d2). And a polymer (D) having a fatty acid or a salt thereof (E).

  The liquid detergent of the 4th aspect of this invention is the anionic surfactant (A) represented by the said general formula (a-1), the said general formula (b-1), and general formula (b-2). ) At least one nonionic surfactant (B) selected from the group consisting of compounds represented by any one of the general formulas, an alcohol having 2 to 4 carbon atoms, and the general formula (c-1). And at least one organic solvent (C) selected from the group consisting of the above compounds and a tertiary amine (F).

The liquid detergent according to the fifth aspect of the present invention includes the anionic surfactant (A) represented by the general formula (a-1), the general formula (b-1), and the general formula (b-2). ) At least one nonionic surfactant (B) selected from the group consisting of compounds represented by any one of the general formulas, an alcohol having 2 to 4 carbon atoms, and the general formula (c-1). And at least one organic solvent (C) selected from the group consisting of the above compounds and a cationic surfactant (H).
Hereinafter, these components are also referred to as (A) component, (B) component, (C) component, (D) component, (E) component, (F) component, and (H) component, respectively.

  The liquid detergent of the present invention can be used for household or industrial use, and can be suitably used for household use, and is a liquid of a concentrated type (composition having a high surfactant concentration) for clothing. Particularly suitable as a cleaning agent.

<Anionic surfactant (A)>
In the liquid cleaning agent of the present invention, by containing an anionic surfactant (A) represented by the following general formula (a-1), cleaning performance and recontamination prevention performance are mainly imparted.

［Ｒ^１、Ｒ^２、及びＭは、前記と同じ意味を有する。］

[R ¹ , R ² , and M have the same meaning as described above. ]

In the formula (a-1), the hydrocarbon group for R ¹ may be linear or branched, or may contain a cyclic structure. Among these, the hydrocarbon group for R ¹ is preferably an aliphatic hydrocarbon group, more preferably a linear or branched alkyl group, or a linear or branched alkenyl group. As mentioned.
R ¹ has 8 to 18 carbon atoms, preferably 10 to 16 carbon atoms. When the carbon number of R ¹ is 8 or more, the detergency is improved, and in particular, odor removal is enhanced. On the other hand, when the carbon number of R ¹ is 18 or less, the liquid stability is improved, and in particular, precipitation during gelation or low-temperature storage is suppressed.

In said formula (a-1), R < ² > is a C1-C3 alkyl group, Specifically, a methyl group, an ethyl group, n-propyl group, or an isopropyl group is mentioned, a methyl group, or An ethyl group is preferred. When the carbon number of R ² is 1 or more, precipitation during low-temperature storage is easily suppressed. On the other hand, when the carbon number of R ² is 3 or less, the solubility of the liquid detergent in water under low temperature conditions increases.

In the formula (a-1), M is a counter ion and may be any one that can form a water-soluble salt with R ¹ CH (COOR ² ) SO ₃ ^— , and may be an alkali metal, an alkaline earth metal, a proton. An amine or ammonium that has been converted into an ammonium salt.
Examples of the alkali metal include sodium or potassium.
Examples of the alkaline earth metal include calcium and magnesium.
In the protonated amine, the amine may be any of 1 to 3 grades, and preferably has 1 to 6 carbon atoms in total. The amine may or may not have a hydroxy group, but it has a hydroxy group because the solubility of the liquid detergent in water under low temperature conditions is increased. Is preferred. Examples of such protonated amines include alkanolamines, and the alkanol group preferably has 1 to 3 carbon atoms.
Specific examples of the alkanolamine include monoethanolamine, diethanolamine, or triethanolamine.
Among these, as M, an alkali metal or a protonated amine is preferable, and sodium, potassium, or alkanolamine is more preferable, and sodium, monoethanolamine, or triethanolamine is more preferable.

(A) A component can be manufactured by a well-known method. For example, α-sulfo fatty acid alkyl ester (acid type) is obtained by bringing a raw material fatty acid ester into contact with sulfuric anhydride or the like and sulfonating and esterifying by a conventional method using a tank reactor equipped with a stirrer. Get.
Next, when the obtained α-sulfo fatty acid alkyl ester (acid type) is neutralized with an alkali such as sodium hydroxide, a salt is formed at the sulfonic acid portion, and an α-sulfo fatty acid alkyl ester salt paste is obtained. You may bleach with hydrogen peroxide etc. before and after neutralization.
Taking the case where R ² is a methyl group as an example, the paste of α-sulfo fatty acid alkyl ester salt usually obtained by the above reaction has α-sulfo fatty acid di-salt (also referred to as α-sulfo fatty acid disodium salt). Or a by-product such as methyl sulfate (also referred to as sodium methyl sulfate), methanol, water, or an unreacted raw material fatty acid methyl ester.

(A) A component may be used individually by 1 type and may be used in combination of 2 or more types as appropriate.
Among the components (A), α-sulfo fatty acid methyl ester salt is more preferable. _{Specifically, C 10 H 21 -CH (SO} 3 Na) -COOCH 3, C 12 H 25 -CH (SO 3 Na) -COOCH 3, C 14 H 29 -CH (SO 3 Na) -COOCH 3, or _{C 16 H 33 -CH (SO 3} Na) compound represented by the formula -COOCH ₃ and the like.
Among the components (A), α-sulfolauric acid methyl ester sodium salt, α-sulfomyristic acid methyl ester sodium salt, α-sulfopalmitic acid methyl ester sodium salt, or α-sulfostearic acid methyl ester sodium salt is particularly preferable. preferable.
In the 2nd aspect of this invention, it is preferable that the compounding quantity of (A) component in a liquid detergent is 2-42 mass% with respect to the total mass of the said liquid detergent, More preferably, it is 4.2. It is -33 mass%, Most preferably, it is 7.5-26 mass%.
In the 3rd aspect of this invention, it is preferable that the compounding quantity of (A) component is 2-35 mass% with respect to the total mass of the said liquid cleaning agent in a liquid cleaning agent, More preferably, it is 4.5. It is -29 mass%, Most preferably, it is 7.5-26 mass%.
In the 4th aspect of this invention, it is preferable that the compounding quantity of (A) component in a liquid detergent is 2-26 mass% with respect to the total mass of the said liquid detergent, More preferably, 4.2. It is -22 mass%, Most preferably, it is 6.8-18 mass%.
In the 5th aspect of this invention, it is preferable that the compounding quantity of (A) component in a liquid detergent is 2-28 mass% with respect to the total mass of the said liquid detergent, More preferably, it is 4.5. It is -23 mass%, Most preferably, it is 7.5-20 mass%.
When the blending amount of the component (A) is 2% by mass or more with respect to the total mass of the liquid detergent, the detergency is further improved. On the other hand, when it is the upper limit or less, the liquid stability is further improved.

<Nonionic surfactant (B)>
In the liquid detergent of this invention, it represents with the compound (henceforth this compound is also called "(B1) component") represented by the following general formula (b-1), and general formula (b-2). It contains at least one nonionic surfactant (B) selected from the group consisting of compounds (hereinafter this compound is also referred to as “component (B2)”). This mainly provides cleaning performance.

［Ｒ^３、Ｒ^４、Ｒ^５、及びｍは、前記と同じ意味を有する。］

[R ³ , R ⁴ , R ⁵ , and m have the same meaning as described above. ]

-Compound represented by general formula (b-1): Component (B1) In the formula (b-1), the hydrocarbon group of R ³ may be linear or branched. Or an annular structure. The hydrocarbon group for R ³ is preferably an aliphatic hydrocarbon group, and a linear or branched alkyl group or a linear or branched alkenyl group is more preferable.
R ³ has 9 to 13 carbon atoms, preferably 10 to 13 carbon atoms, and more preferably 11 to 13 carbon atoms. When the carbon number of R ³ is 9 or more, the detergency increases. On the other hand, when the carbon number of R ³ is 13 or less, the liquid stability is improved, and particularly gelation is suppressed.

In the formula (b-1), ^{R 4} is an alkylene group having 2 to 4 carbon atoms, an ethylene group or a propylene group is preferred.
Two or more R ^{4 s} in the formula may be the same as or different from each other. That is, the alkylene group for R ⁴ may be one kind alone, or two or more kinds may be combined. Especially, since foaming at the time of washing is good and inexpensive, m OR ⁴ in the formula is all oxyethylene groups or oxyethylene groups and oxypropylene groups are mixed. preferable.
When two or more alkylene groups of R ⁴ are combined, the addition method of OR ⁴ is not particularly limited. For example, the addition method in the case where oxyethylene group and oxypropylene group are mixed includes random addition. There may be a block addition.
The block addition method includes adding propylene oxide after adding ethylene oxide, adding ethylene oxide after adding propylene oxide, or adding ethylene oxide after adding ethylene oxide, and the like. Is mentioned.

In the formula (b-1), ^{R 5} is an alkyl group having 1 to 4 carbon atoms, preferably an alkyl group having 1 to 3 carbon atoms. Specific examples of R ⁵ include a methyl group, an ethyl group, an n-propyl group, an isopropyl group, and an n-butyl group. A methyl group or an ethyl group is preferable, and a methyl group is more preferable. When the carbon number of R ⁵ is 1 or more, precipitation during low-temperature storage is easily suppressed. On the other hand, when the carbon number of R ⁵ is 4 or less, the solubility of the liquid detergent in water under low temperature conditions increases.

In the formula (b-1), m represents an average repeating number of OR ^4, is an integer of 5-25. When m is 5 or more, the detergency, particularly the detergency against sebum dirt is improved. On the other hand, when m is 25 or less, the solubility of the liquid detergent in water is improved.
When all of OR ⁴ are oxyethylene groups, m is preferably an integer of 5 to 20, more preferably an integer of 12 to 18.
When OR ⁴ is a mixture of an oxyethylene group and an oxypropylene group, m is particularly preferably an integer of 12 to 21. In this case, the average number of repeating oxypropylene groups is preferably an integer of 5 or less, more preferably an integer of 4 or less, and even more preferably an integer of 3 or less. If the average number of repeating oxypropylene groups exceeds 5, the cleaning power and liquid stability (transparency uniformity, stability over time, etc.) as a liquid cleaning agent may be deteriorated.

In the component (B1) represented by the formula (b-1), it is preferable that a narrow ratio indicating a distribution ratio of compounds having different OR ⁴ repeat numbers is 20% by mass or more. It is preferable that the upper limit of the narrow ratio is substantially 80% by mass or less. The range of the narrow ratio is preferably 20 to 80% by mass, more preferably 20 to 50% by mass, and liquid stability and solubility in water are further improved. More preferably. The higher the narrow rate, the easier it is to obtain better cleaning power. Moreover, when the said narrow rate becomes like this. Preferably it is 20 mass% or more, Most preferably, it is 30 mass% or more, and it becomes easy to obtain the liquid detergent composition with few raw material odors derived from (B1) component. This is because, after the production of the component (B1), the fatty acid ester which is the raw material of the component (B1) coexisting with the component (B1) and the alkylene oxide adduct wherein m in the formula (b-1) is 1 or 2 This is because it decreases.

  In this specification, the “narrow ratio” refers to a value represented by the following mathematical formula (S), which indicates a distribution ratio of alkylene oxide adducts having different numbers of added moles of alkylene oxide.

In the formula (S), m _max represents the number of added moles of alkylene oxide of the alkylene oxide adduct present most frequently in the whole component represented by the formula (b-1).
i represents the number of added moles of alkylene oxide.
Yi represents the proportion (mass%) of the alkylene oxide adduct having an added mole number of alkylene oxide present in the whole component represented by the formula (b-1).
The narrow rate can be controlled by, for example, the method for producing the component (B1).

The method for producing the component (B1) is not particularly limited. For example, a method of addition polymerization of an alkylene oxide to a fatty acid alkyl ester using a surface-modified composite metal oxide catalyst (JP 2000-2000A). 144194179)).
As a preferable example of such a surface-modified composite metal oxide catalyst, specifically, metal ions (Al ³⁺ , Ga ³⁺ , In ³⁺ , Tl ³⁺ , Co 1) surface-modified with a metal hydroxide or the like are used. ³⁺ , Sc ³⁺ , La ³⁺ , Mn ^2+, etc.) and a composite metal oxide catalyst such as magnesium oxide, or a hydrotalcite fired product whose surface is modified by a metal hydroxide and / or a metal alkoxide, etc. It is a catalyst.
Further, in the surface modification of the composite metal oxide catalyst, the mixing ratio of the composite metal oxide and the metal hydroxide and / or metal alkoxide is changed to metal hydroxide with respect to 100 parts by mass of the composite metal oxide. The ratio of the product and / or metal alkoxide is preferably 0.5 to 10 parts by mass, and more preferably 1 to 5 parts by mass.

  (B1) A component may be used individually by 1 type and may be used in combination of 2 or more types as appropriate.

［Ｒ^６、ＥＯ、ＰＯ、ｓ及びｔは前記と同じ意味を有する。］

[R ⁶ , EO, PO, s and t have the same meaning as described above. ]

-Compound represented by general formula (b-2): component (B2) In the formula (b-2), the hydrocarbon group of R ⁶ may be linear or branched. Or an annular structure. The hydrocarbon group for R ⁶ is preferably an aliphatic hydrocarbon group, and a linear or branched alkyl group or a linear or branched alkenyl group is more preferable.
The hydrocarbon group of R ⁶ has 10 to 20 carbon atoms, preferably 12 to 18 carbon atoms, and more preferably 12 to 14 carbon atoms. When the carbon number of R ⁶ is 10 or more, the detergency increases. On the other hand, when the carbon number of R ⁶ is 20 or less, the liquid stability is improved, and particularly gelation is suppressed.
The component (B2) may be a single chain length mixture or a mixture of two or more chain lengths. R ⁶ is derived from a raw material alcohol (R ⁶ —OH), and examples of the alcohol include alcohols derived from natural fats and oils such as coconut oil, palm oil, and beef tallow, and synthetic alcohols derived from petroleum.

In said formula (b-2), s shows the average repeating number of EO (oxyethylene group), is an integer of 5-20, and it is preferable that it is an integer of 5-18. When s is within the above range, the cleaning power of the liquid cleaning agent, particularly the cleaning power against sebum dirt is improved.
t represents the average number of repetitions of PO (oxypropylene group), is an integer of 1 to 4, and is preferably an integer of 1 to 3. When t is within the above range, gelation of the liquid detergent is likely to be suppressed, and good foaming properties are easily obtained at the time of rinsing.
In the formula (b-2), EO and PO may be added in a block shape or may be added in a random shape. When EO and PO are added in block form, the addition method includes adding ethylene oxide followed by propylene oxide, adding propylene oxide followed by ethylene oxide, or adding ethylene oxide and propylene. Examples thereof include a method of adding an oxide and further adding ethylene oxide. In particular, since the rinsing property in washing in a fully automatic washing machine is better, a method of adding ethylene oxide after adding ethylene oxide and further adding ethylene oxide (the terminal is -O-CH ₂ CH ₂ O-H and Is preferred).

In the component (B2), the addition mole number distribution of the alkylene oxide is not particularly limited, and the addition mole number distribution can be controlled by the production method of the component (B2).
For example, when an alkylene oxide is added to a hydrophobic raw material using a general alkali catalyst such as sodium hydroxide or potassium hydroxide, a relatively wide addition mole number distribution tends to be obtained. In addition, specific oxides such as magnesium oxide added with metal ions such as Al ³⁺ , Ga ³⁺ , In ³⁺ , Tl ³⁺ , Co ³⁺ , Sc ³⁺ , La ³⁺ , or Mn ²⁺ described in JP-B-615038 When an alkylene oxide is added to a hydrophobic raw material using an alkoxylation catalyst, a relatively narrow addition mole number distribution tends to be obtained.

  (B2) A component may be used individually by 1 type and may be used in combination of 2 or more types as appropriate.

  Among the components (B), it is preferable to use the component (B1) because the combined use with the component (A) increases the cleaning power (especially odor removal).

  In the 2nd aspect of this invention, it is preferable that the compounding quantity of (B) component in a liquid detergent is 16-67 mass% with respect to the total mass of the said liquid detergent, More preferably, it is 23-59. It is mass%, Most preferably, it is 30-55 mass%.

In the 3rd aspect of this invention, the compounding quantity (the sum total of (B1) component and (B2) component) of (B) component in a liquid detergent is 20-67 with respect to the total mass of the said liquid detergent. It is preferable that it is mass%, More preferably, it is 25-59 mass%, Most preferably, it is 30-55 mass%.
In the 4th aspect of this invention, the compounding quantity (total of (B1) component and (B2) component) of (B) component in liquid detergent is 24-62 with respect to the total mass of the said liquid detergent. It is preferable that it is mass%, More preferably, it is 27-57 mass%, Most preferably, it is 32-51 mass%.
In the 5th aspect of this invention, the compounding quantity (the sum total of (B1) component and (B2) component) of (B) component in liquid detergent is 24-67 with respect to the gross mass of the said liquid detergent. It is preferable that it is mass%, More preferably, it is 29-59 mass%, Most preferably, it is 35-55 mass%.
(B) When the compounding quantity of a component is more than a lower limit, detergency improves more and especially odor removal property increases. On the other hand, liquid stability improves more as it is below an upper limit.

Further, the sum of the (B1) component and the (B2) component with respect to the total of the nonionic surfactants blended in the liquid detergent of the present invention is [(B1) component + (B2) component] / nonionic interface. The mass ratio represented by the activator is preferably 0.5 or more and 1.0 or less, more preferably 0.7 or more and 1.0 or less, and 0.85 or more and 1.0 or less. More preferably.
When the mass ratio represented by [(B1) component + (B2) component] / nonionic surfactant is 0.5 or more and 1.0 or less, the detergency (especially odor removal property) is likely to be improved. In addition, usability as a liquid cleaning agent is improved. If the mass ratio is less than 0.5, detergency (particularly odor removal) is reduced.
Here, “[(B1) component + (B2) component] / nonionic surfactant” means that (B1) component, (B2) component and the total content of nonionic surfactant in the liquid detergent are Represents the ratio (mass ratio) of the total content.

In the liquid detergents of the second, third and fifth aspects of the present invention, the total of the component (A) and the component (B) is 40% by mass or more based on the total mass of the liquid detergent. Yes, it is preferably 40 to 70% by mass, more preferably 45 to 65% by mass, and still more preferably 50 to 65% by mass with respect to the total mass of the liquid detergent.
In the liquid detergent according to the fourth aspect of the present invention, the sum of the component (A) and the component (B) is 40% by mass or more based on the total mass of the liquid detergent, and the liquid detergent The total mass is preferably 40 to 65 mass%, more preferably 42 to 63 mass%, still more preferably 45 to 60 mass%.
The effect of this invention is notably exhibited as the sum total of (A) component and (B) component is 40 mass% or more with respect to the total mass of the said liquid cleaning agent. Further, high cleaning performance is imparted to the liquid cleaning agent. On the other hand, when the total of the component (A) and the component (B) exceeds the preferable upper limit value, gelation hardly occurs and the liquid stability of the liquid detergent does not deteriorate.

In the present invention, “component (A) / component (B)” represents the ratio (mass ratio) of the content of component (A) to the content of component (B) in the liquid detergent.
In the liquid detergent of the second aspect of the present invention, the blending ratio of the component (A) and the component (B) is such that the mass ratio represented by the component (A) / component (B) is the component (A) / ( B) Component = 5/95 to 60/40, preferably 10/90 to 50/50, more preferably 15/85 to 40/60, particularly preferably 20/80 to 35/65, more than 20/80 30/70 or less is most preferable.
In the liquid detergent of the third aspect of the present invention, the mixing ratio of the component (A) and the component (B) is such that the mass ratio represented by the component (A) / component (B) is the component (A) / ( B) Component = 5/95 to 50/50, preferably 10/90 to 45/55, more preferably 15/85 to 40/60, particularly preferably 20/80 to 35/65, more than 20/80 30/70 or less is most preferable.
In the liquid detergent of the fourth aspect of the present invention, the mixing ratio of the component (A) and the component (B) is such that the mass ratio represented by the component (A) / component (B) is the component (A) / ( B) Component = 5/95 to 40/60, preferably 10/90 to 35/65, more preferably 15/85 to 30/70, particularly preferably 20/80 to 30/70, more than 20/80 30/70 or less is most preferable.
In the liquid detergent of the fifth aspect of the present invention, the blending ratio of the component (A) and the component (B) is such that the mass ratio represented by the component (A) / component (B) is (A) component / ( B) Component = 5/95 to 40/60, preferably 10/90 to 35/65, more preferably 15/85 to 30/70, particularly preferably 20/80 to 30/70, more than 20/80 30/70 or less is most preferable.

When the mass ratio represented by (A) component / (B) component exceeds (A) component / (B) component = 5/95 (the ratio of (A) component is too high), gelation tends to occur. The liquid flowability and liquid stability of the liquid detergent may be reduced. On the other hand, if the mass ratio is less than 30/70 (the ratio of the component (B) is too high), the viscosity at low temperatures tends to be high, and the coating cleaning power may be inferior.
Since the blending ratio of the component (A) and the component (B) is within the above range, in particular, sweat or sebum adhering to a chemical fiber such as polyester or polyurethane, or a blended garment of these chemical fiber and cotton. The detergency against dirt is enhanced, and the odor removal property due to the sweat and sebum dirt residue is improved.

<Organic solvent (C)>
The liquid cleaning agent of this invention contains the C2-C4 alcohol and at least 1 type of organic solvent (C) selected from the group which consists of a compound represented by the below-mentioned general formula (c-1).

(C2-C4 alcohol)
Among the alcohols having 2 to 4 carbon atoms, examples of the monohydric alcohol include ethanol, 1-propanol, 2-propanol, and 1-butanol.
Examples of the polyhydric alcohol having 2 to 4 carbon atoms include ethylene glycol, propylene glycol, butylene glycol, and glycerin.

［式（ｃ−１）中、Ｒ^７は炭素数１〜６のアルキル基又はフェニル基であり、Ｒ^８は炭素数２〜４のアルキレン基である。ｎはＯＲ^８の平均繰返し数を示し、１〜５の整数である。］

[In Formula (c-1), R ⁷ is an alkyl group having 1 to 6 carbon atoms or a phenyl group, and R ⁸ is an alkylene group having 2 to 4 carbon atoms. n represents an average repeating number of OR ^8, an integer of 1 to 5. ]

  Examples of the compound represented by the formula (c-1) include glycol ethers such as ethylene glycol monobutyl ether, ethylene glycol monohexyl ether, ethylene glycol monophenyl ether, propylene glycol monophenyl ether, diethylene glycol monomethyl ether, and diethylene glycol monobutyl ether. System solvents and the like.

(C) A component may be used individually by 1 type and may be used in combination of 2 or more type as appropriate.
Among the components (C), ethanol, propylene glycol, or diethylene glycol monobutyl ether is preferable from the viewpoint of easy improvement of the liquid flowability of the liquid detergent, mild odor, or easy availability of raw materials. .
In the liquid detergent of the second aspect, the amount of component (C) is preferably 3 to 20% by mass, more preferably 4 to 18% by mass, based on the total mass of the liquid detergent. Especially preferably, it is 5-15 mass%.
In the liquid detergents of the third and fourth aspects, the amount of component (C) is preferably 5 to 30% by mass, more preferably 5 to 25% by mass with respect to the total mass of the liquid detergent. %, More preferably 6 to 23% by mass, and particularly preferably 7 to 21% by mass.
In the liquid detergent of the fifth aspect, the blending amount of the component (C) is preferably 7 to 30% by mass, more preferably 7 to 25% by mass with respect to the total mass of the liquid detergent. More preferably, it is 8-23 mass%, Most preferably, it is 9-21 mass%.
When the blending amount of the component (C) is at least the lower limit value, the liquid flowability of the liquid detergent becomes good, the gel does not gel, and it is easy to use as a liquid detergent. On the other hand, even if blending more than the upper limit, it is difficult to obtain the effect of improving the liquid fluidity corresponding to it, which is economically disadvantageous.

In the present invention, “[(A) component + (B) component] / (C) component” means the sum of the (A) component and the (B) component with respect to the content of the (C) component in the liquid detergent. The ratio (mass ratio) of the content of.
In the liquid detergent of the second aspect of the present invention, the blending ratio of the component (A), the component (B), and the component (C) is [(A) component + (B) component] / (C) component. The expressed mass ratio is 23 or less, preferably 2 to 23, more preferably 2.5 to 16.3, and still more preferably 3.3 to 13.
In the liquid detergent of the third aspect of the present invention, the blending ratio of the component (A), the component (B), and the component (C) is [(A) component + (B) component] / (C) component. The expressed mass ratio is 14 or less, preferably 2 to 14, more preferably 2 to 13, and still more preferably 2.4 to 9.3.
In the liquid detergent of the fourth aspect of the present invention, the blending ratio of the component (A), the component (B), and the component (C) is [(A) component + (B) component] / (C) component. The represented mass ratio is 13 or less, preferably 1.6 to 13, more preferably 1.8 to 10.5, and further preferably 2.1 to 8.6.
In the liquid detergent of the fifth aspect of the present invention, the blending ratio of the component (A), the component (B), and the component (C) is [(A) component + (B) component] / (C) component. The expressed mass ratio is 10 or less, preferably 1.6 to 10, more preferably 2 to 8.1, and even more preferably 2.4 to 7.2.
When the mass ratio represented by [(A) component + (B) component] / (C) component exceeds the upper limit (the ratio of (A) component + (B) component is too high), the viscosity of the liquid detergent Becomes higher (may cause gelation), the liquid fluidity of the liquid detergent tends to be lowered. Moreover, there exists a possibility that the usability as a liquid cleaning agent may worsen. On the other hand, if the mass ratio is less than the lower limit (the ratio of the component (C) is too high), the viscosity of the liquid cleaning agent becomes too low, making it difficult to apply to the object to be cleaned, usability and application cleaning power. Tends to decrease.

<Polymer (D)>
The liquid detergent according to the third aspect of the present invention is a polymer (D) having at least one repeating unit (d1) selected from the group consisting of an alkylene terephthalate unit and an alkylene isophthalate unit and an oxyalkylene unit (d2). Containing.
In the liquid cleaning agent of the present invention, by using a combination of the component (D) and the component (E) described later, mainly the anti-contamination performance of clothing is imparted.

-At least one repeating unit (d1) selected from alkylene terephthalate units and alkylene isophthalate units
Examples of the alkylene terephthalate unit (hereinafter, this repeating unit is also referred to as “repeating unit (d11)”) include repeating units represented by the following general formula (d1-1).

［式（ｄ１−１）中、Ｒ^２１は炭素数１〜４のアルキレン基である。］

[In Formula (d1-1), R ²¹ represents an alkylene group having 1 to 4 carbon atoms. ]

In the formula ^(d1-1), the number of carbon atoms in the alkylene group ^{R 21} is 1 to 4, preferably 2-4.
Specific examples of the repeating unit (d11) include an ethylene terephthalate unit, an n-propylene terephthalate unit, an isopropylene terephthalate unit, an n-butylene terephthalate unit, an isobutylene terephthalate unit, a sec-butylene terephthalate unit, or a tert-butylene terephthalate unit. Can be mentioned. Of these, isopropylene terephthalate units are preferred.

  Examples of the alkylene isophthalate unit (hereinafter, this repeating unit is also referred to as “repeating unit (d12)”) include repeating units represented by the following general formula (d1-2).

［式（ｄ１−２）中、Ｒ^２２は炭素数１〜４のアルキレン基である。］

[In the formula (d1-2), R ²² represents an alkylene group having 1 to 4 carbon atoms. ]

In the formula ^(d1-2), the number of carbon atoms in the alkylene group ^{R 22} is 1 to 4, preferably 2-4.
Specific examples of the repeating unit (d12) include an ethylene isophthalate unit, a propylene isophthalate unit, an n-butylene isophthalate unit, a sec-butylene isophthalate unit, and a tert-butylene isophthalate unit. Of these, propylene isophthalate units are preferred.

A repeating unit (d1) may be used individually by 1 type, and may be used in combination of 2 or more type as appropriate.
That is, the component (D) may have only an alkylene terephthalate unit as a repeating unit (d1) in one molecule, may have only an alkylene isophthalate unit, You may have both an alkylene isophthalate unit.
In the molecule (D), the number of repeating units (d1) in the molecule is preferably an integer of 1 to 10, more preferably an integer of 1 to 6, and an integer of 2 to 4. Is more preferable.
When the number of repeating units (d1) is 1 or more, the recontamination preventing performance is further improved, and when it is 10 or less, the liquid stability is further improved.

・ Oxyalkylene units (d2)
Examples of the oxyalkylene unit (hereinafter, this repeating unit is also referred to as “repeating unit (d2)”) include a repeating unit represented by the following general formula (d2-1).

［式（ｄ２−１）中、Ｒ^２３は炭素数１〜４のアルキレン基である。］

[In formula (d2-1), R ²³ represents an alkylene group having 1 to 4 carbon atoms. ]

In the formula ^(d2-1), the number of carbon atoms in the alkylene group ^{R 23} is 1 to 4, preferably is 2 to 4, particularly preferably 2 or 3 ^(as the ^{R 23} O oxyethylene group or oxypropylene Group).

A repeating unit (d2) may be used individually by 1 type, and may be used in combination of 2 or more types as appropriate.
That is, the component (D) may have, for example, only an oxyethylene unit, only an oxypropylene unit, or only an oxyethylene unit as a repeating unit (d2) in one molecule. And an oxypropylene unit.
In the molecule (D), the number of repeating units (d2) in the molecule is preferably an integer of 1 to 100, more preferably an integer of 1 to 80, and an integer of 1 to 50. Is more preferable.
When the repeating number of the repeating unit (d2) is 1 or more, the liquid stability is further improved. On the other hand, when it is 100 or less, the effect of preventing recontamination is more easily obtained.
The component (D) may have only an oxyalkylene group (when the number of repetitions is 1) as a repeating unit (d2) in one molecule, and a polyoxyalkylene unit (the number of repetitions is 2 or more). In the case of ()), it may have both an oxyalkylene group and a polyoxyalkylene unit.

The component (D) is preferably a polymer in which the repeating unit (d1) and the repeating unit (d2) are polymerized in a block shape or a random shape, and more preferably a polymer polymerized in a block shape. .
The component (D) may have other units other than the repeating unit (d1) and the repeating unit (d2). Examples of the other unit include a unit derived from a polymerization initiator, a polymerization terminator and the like, or a repeating unit derived from a monomer copolymerizable with a monomer that provides the repeating unit (d1) or the repeating unit (d2). .
When the component (D) has other units, the total of the repeating unit (d1) and the repeating unit (d2) is 80 mol% or more and 100 mol% with respect to all the units constituting the component (D). Or less, more preferably 90 mol% or more and 100 mol% or less. When the total of the repeating unit (d1) and the repeating unit (d2) is 80 mol% or more and 100 mol% or less, the anti-contamination performance of the clothes is further enhanced. On the other hand, if the total of the repeating unit (d1) and the repeating unit (d2) is less than 80 mol%, the recontamination preventing performance is lowered.

The component (D) is preferably a water-soluble polymer from the viewpoint of its own solubility and the liquid stability of the liquid detergent.
The term “water-soluble polymer” as used herein means that 10 g of a polymer is added to 1000 g of water at 40 ° C. in a 1 liter beaker and stirred for 12 hours (200 rpm) with a stirrer (thickness 8 mm, length 50 mm). When it is completely dissolved,

The weight average molecular weight of the component (D) is preferably from 500 to 8000, more preferably from 800 to 7000, and particularly preferably from 1000 to 6000, since dissolution and dispersibility in water is enhanced.
The “weight average molecular weight” here refers to a value obtained by converting a value measured by GPC (gel permeation chromatography) using THF (tetrahydrofuran) as a solvent by a calibration curve in PEG (polyethylene glycol).

(D) As a component, that whose pH (measured at 20 degreeC) of the 5 mass% aqueous solution is 3-7 is preferable. This pH indicates a value measured by a pH meter (product name: HM-30G, manufactured by Toa DKK Co., Ltd.) or the like.
The component (D) preferably has a viscosity (measured at 50 ° C.) of 100 to 1000 mPa · s. This viscosity is a value measured using a No. 2 rotor in a Brookfield viscometer.
(D) What can be easily obtained in a market can be used for a component. Also, synthesis methods disclosed in literature and the like, for example, Journal of Polymer Science, Volume 3, pages 609-630 (1948); Journal of Polymer Science, Volume 8, pages 1-22 (1951); It can be produced by the method described in JP-A-61-218699.

  Specific examples of the component (D) include those each containing a polymer represented by the following general formula (d-1) or a polymer represented by the general formula (d-2).

［式中、Ａ及びＢはそれぞれ独立して水素原子又はメチル基であり、Ｒ^２４〜Ｒ^２９はそれぞれ独立して炭素数２〜４のアルキレン基である。ｘ１及びｘ２はそれぞれ独立して１〜１０の整数である。ｙ１、ｙ２、ｚ１及びｚ２はそれぞれ独立して１〜１００の整数である。］

[Wherein, A and B are each independently a hydrogen atom or a methyl group, and R ^{24 to} R ²⁹ are each independently an alkylene group having 2 to 4 carbon atoms. x1 and x2 are each independently an integer of 1 to 10. y1, y2, z1 and z2 are each independently an integer of 1 to 100. ]

In the formula (d-1), A and B are each preferably a methyl group, and more preferably a methyl group.
R ²⁴ , R ²⁵ and R ²⁶ are each preferably an alkylene group having 2 carbon atoms or an alkylene group having 3 carbon atoms.
x1 is an integer of 1 to 10, preferably an integer of 1 to 6, and more preferably an integer of 2 to 4.
y1 and z1 are each an integer of 1 to 100, preferably an integer of 1 to 80, more preferably an integer of 1 to 50, still more preferably an integer of 10 to 50, and particularly preferably. It is an integer of 20-30.

In the formula (d-2), A, B, x2, y2, and z2 are the same as A, B, x1, y1, and z1 in the formula (d-1), respectively.
R ²⁷ , R ²⁸ and R ²⁹ are each preferably an alkylene group having 2 carbon atoms or an alkylene group having 3 carbon atoms.

In the polymer represented by the formula (d-1) and the formula (d-2), the ratio of x and y (x: y) and the ratio of x and z (x: z) are respectively The ratio is preferably 1: 5 to 1:20, more preferably 1: 8 to 1:18. When the ratio (x: y) and the ratio (x: z) are within such ranges, the recontamination prevention performance is sufficiently exhibited and the solubility in water is further improved.
Here, “ratio (x: y)” means x1: y1 in the polymer represented by formula (d-1), and x2: y2 in the polymer represented by formula (d-2). Means.
“Ratio (x: z)” means x1: z1 in the polymer represented by the formula (d-1), and x2: z2 in the polymer represented by the formula (d-2). To do.

(D) As a specific example of a component, brand name TexCare SRN-100 (made by Clariant, weight average molecular weight 2000-3000) or brand name TexCare SRN-300 (made by Clariant, weight average molecular weight 7000) etc. are marketed. Are listed.
Among these, TexCare SRN-100, which has high solubility in water and little deterioration in washing performance after storage, is preferable, and is a 70% by mass aqueous solution of TexCare SRN-100, which is trade name TexCare SRN-170 (Clariant). (Commercially available) is particularly preferred.

(D) A component may be used individually by 1 type and may be used in combination of 2 or more type as appropriate.
In the liquid detergent, the blending amount of the component (D) is preferably 0.1 to 10% by mass, more preferably 0.1 to 5% by mass with respect to the total mass of the liquid detergent. Most preferably, it is 0.5-3 mass%.
When the blending amount of the component (D) is 0.1% by mass or more with respect to the total mass of the liquid detergent, an effect of preventing recontamination is easily obtained. Further, the cleaning power is further improved. On the other hand, when it is 10% by mass or less, the liquid stability of the liquid detergent can be maintained better.

<Fatty acid or salt thereof (E)>
(E) As a fatty acid in a component, C8-C18 chain | strand-shaped monocarboxylic acid is mentioned as a suitable thing. Specifically, the general formula: R ⁹ —COOH [wherein R ⁹ is an aliphatic hydrocarbon group having 7 to 17 carbon atoms. ] The compound represented by this is mentioned.
In the above formula, the aliphatic hydrocarbon group for R ⁹ may be linear or branched, linear or branched alkyl, or linear or branched Alkenyl groups are preferred. The carbon number of the aliphatic hydrocarbon group for R ⁹ is 7 to 17, and preferably 11 to 17 carbon atoms. The aliphatic hydrocarbon group for R ⁹ is preferably derived from coconut oil. When the carbon number of R ⁹ is 7 or more, the effect of preventing recontamination is further improved. On the other hand, when the carbon number of R ⁹ is 17 or less, the solubility of the component (E) in water increases.
(E) As a form of the salt in a component, alkali metal salt, alkaline-earth metal salt, amine salt, or ammonium salt etc. are mentioned. Examples of the alkali metal salt include sodium salt and potassium salt. Examples of alkaline earth metal salts include calcium salts and magnesium salts. Examples of the amine salt include alkanolamine salts (monoethanolamine salt, diethanolamine salt, triethanolamine salt, etc.) and the like.

(E) A component may be used individually by 1 type and may be used in combination of 2 or more type as appropriate.
The component (E) may be a single chain length mixture or a mixture of two or more chain lengths.
In the liquid detergent, the blending amount of the component (E) is preferably 0.05 to 5% by mass, more preferably 0.05 to 4% by mass with respect to the total mass of the liquid detergent, Especially preferably, it is 0.1-3 mass%.
(E) When the compounding quantity of a component is 0.05 mass% or more with respect to the total mass of the said liquid detergent, favorable rinse property is easy to be obtained and the recontamination prevention effect improves more. Further, the cleaning power is further improved. On the other hand, the liquid stability of a liquid cleaning agent improves more that it is 5 mass% or less.

In the liquid detergent of the present invention, the mixing ratio of the (D) component and the (E) component is such that the mass ratio represented by the (D) component / (E) component is (D) component / (E) component = 0. It is preferable that it is 0.1-50, More preferably, it is 0.15-30, More preferably, it is 0.25-20.
Due to the blending ratio of the component (D) and the component (E) being within the above-mentioned range, even in washing conditions under a low bath ratio, excellent re-contamination for clothing made of hydrophobic fibers such as polyester The prevention effect is easily exhibited.
Further, when the mass ratio represented by the component (D) / component (E) is 50 or less, better recontamination prevention ability is exhibited and the cleaning power is further improved. On the other hand, when the mass ratio is 0.1 or more, it is easy to obtain both an excellent anti-contamination effect and rinsing properties.
Here, “(D) component / (E) component” represents the ratio (mass ratio) of the content of (D) component to the content of (E) component in the liquid detergent.

<Tertiary amine (F)>
In the liquid detergent of the 4th aspect of this invention, the effect of providing a softness | flexibility to the clothes etc. after washing is mainly exhibited by containing tertiary amine (F).
In the present invention, “tertiary amine” means a compound in which three hydrogen atoms of ammonia (NH ₃ ) are substituted with a hydrocarbon group (the hydrocarbon group may have a substituent or a linking group). Is included. Examples of the substituent that the hydrocarbon group may have include a hydroxy group and an amino group. Examples of the linking group that the hydrocarbon group may have include an amide group, an ester group, and an ether group.

  As a suitable thing in (F) component, the compound represented by the following general formula (f-1) is mentioned.

［式中、Ｒ^１１及びＲ^１２はそれぞれ独立して炭素数１〜４のアルキル基、炭素数１〜４のヒドロキシアルキル基、又はオキシエチレン基若しくは繰返し数が２〜２５の整数のポリオキシエチレン基である。Ｒ^１３は置換基又は連結基を有していてもよい炭素数７〜２７の炭化水素基である。］

[Wherein, R ¹¹ and R ¹² are each independently an alkyl group having 1 to 4 carbon atoms, a hydroxyalkyl group having 1 to 4 carbon atoms, or an oxyethylene group or an integer of 2 to 25 polyoxyethylene repeats] It is a group. R ¹³ is a hydrocarbon group having 7 to 27 carbon atoms which may have a substituent or a linking group. ]

In the formula (f-1), the alkyl group or hydroxyalkyl group of R ¹¹ and R ¹² may be linear or branched.
In the formula (f-1), R ¹³ may have a substituent or a linking group, a hydrocarbon group of 7 to 27 carbon atoms. The hydrocarbon group for R ¹³ may be linear or branched, may contain a cyclic structure, and may be a saturated hydrocarbon group or an unsaturated hydrocarbon group. May be. The number of carbon atoms of R ¹³ is 7-27, preferably a 7 to 25 carbon atoms. When the carbon number of R ¹³ is 7 or more, the effect of imparting flexibility to the article to be washed is enhanced. On the other hand, when the carbon number of R ¹³ is 27 or less, the solubility of the component (F) in water increases. When the hydrocarbon group of R ¹³ has a substituent or a linking group, “carbon number of R ¹³ ” does not include carbon in the substituent or linking group. The hydrocarbon group for R ¹³ may have a hydroxy group or the like as a substituent, and may have an amide group, an ester group, an ether group or the like as a linking group in the hydrocarbon chain. .

  Among the compounds represented by the formula (f-1), a compound represented by the following general formula (f-1-1) and a compound represented by the general formula (f-1-2) are particularly preferable. .

［式中、Ｒ^１１及びＲ^１２は、前記式（ｆ−１）におけるＲ^１１及びＲ^１２とそれぞれ同じである。式（ｆ−１−１）中、Ｒ^１４は炭素数７〜２３の炭化水素基であり、Ｒ^１５は炭素数１〜４の炭化水素基である。式（ｆ−１−２）中、Ｒ^１６は炭素数１１〜２３の炭化水素基であり、Ｒ^１７は炭素数１〜４の炭化水素基である。］

^{Wherein, R 11} and ^{R 12} are each the same as ^{R 11} and ^{R 12} in the formula (f-1). In the formula (f-1-1), R ¹⁴ is a hydrocarbon group having 7 to 23 carbon atoms, and R ¹⁵ is a hydrocarbon group having 1 to 4 carbon atoms. In the formula (f-1-2), R ¹⁶ is a hydrocarbon group having 11 to 23 carbon atoms, and R ¹⁷ is a hydrocarbon group having 1 to 4 carbon atoms. ]

In the formula (f-1-1), the hydrocarbon group of R ¹⁴ may be linear or branched, or may contain a cyclic structure, and is a saturated hydrocarbon group. Or an unsaturated hydrocarbon group. The hydrocarbon group for R ¹⁴ is preferably a linear or branched alkyl group, or a linear or branched alkenyl group. The number of carbon atoms in R ¹⁴ is 7 to 23, preferably a 7 to 21 carbon atoms.
The hydrocarbon group for R ¹⁵ is preferably a linear alkylene group or a branched alkylene group.

In the formula (f-1-2), the hydrocarbon group of R ¹⁶ may be linear or branched, or may contain a cyclic structure, and is a saturated hydrocarbon group. Or an unsaturated hydrocarbon group. The hydrocarbon group for R ¹⁶ is preferably a linear or branched alkyl group, or a linear or branched alkenyl group. R ¹⁶ has 11 to 23 carbon atoms, and preferably 12 to 20 carbon atoms.
The hydrocarbon group for R ¹⁷ is preferably a linear alkylene group or a branched alkylene group.

  Specific examples of the component (F) include caprylic acid dimethylaminopropylamide, capric acid dimethylaminopropylamide, lauric acid dimethylaminopropylamide, myristic acid dimethylaminopropylamide, palmitic acid dimethylaminopropylamide, stearic acid dimethylaminopropyl. Long-chain aliphatic amide dialkyl tertiary amines such as amide, behenic acid dimethylaminopropylamide, or oleic acid dimethylaminopropylamide (compound represented by the above formula (f-1-1)); palmitic acid diethanolaminopropylamide Or a long-chain aliphatic amide dialkanol tertiary amine such as stearic acid diethanolaminopropylamide (compound represented by the above formula (f-1-1)); palmitate ester propyldimethylamino Or aliphatic ester dialkyl tertiary amines such as stearate ester propyldimethylamine (compound represented by the formula (f-1-2)); or lauryl dimethylamine, myristyl dimethylamine, coconut alkyl dimethylamine, palmityl Examples include dimethylamine, beef tallow alkyl dimethylamine, cured beef tallow alkyl dimethylamine, stearyl dimethylamine, stearyl diethanolamine, or polyoxyethylene cured beef tallow alkylamine (product name: ETHOMEEN HT / 14, manufactured by Lion Akzo Co., Ltd.) .

  As an example of the production of the component (F), the above-mentioned “long chain aliphatic amide dialkyl tertiary amine” will be described. The long chain aliphatic amide dialkyl tertiary amine is a fatty acid or a fatty acid derivative (fatty acid lower alkyl ester, animal or plant). Oily fats and the like) and a dialkyl (or alkanol) aminoalkylamine are subjected to a condensation reaction, and then unreacted dialkyl (or alkanol) aminoalkylamine is distilled off under reduced pressure or nitrogen blowing.

Here, as the fatty acid or fatty acid derivative, caprylic acid, capric acid, lauric acid, myristic acid, palmitic acid, stearic acid, oleic acid, behenic acid, erucic acid, 12-hydroxystearic acid, coconut oil fatty acid, cottonseed oil fatty acid, Examples include corn oil fatty acid, beef tallow fatty acid, palm kernel oil fatty acid, soybean oil fatty acid, linseed oil fatty acid, castor oil fatty acid, vegetable oil or animal oil fatty acid such as olive oil fatty acid, or the like, or methyl ester, ethyl ester or glyceride thereof. Of these, caprylic acid, capric acid, lauric acid, myristic acid, palmitic acid, stearic acid, oleic acid, behenic acid and the like are particularly preferable.
These fatty acids or fatty acid derivatives may be used alone or in combination of two or more.
“Dialkyl (or alkanol) aminoalkylamine” refers to dialkylaminoalkylamine or dialkanolaminoalkylamine.
Specific examples of the “dialkyl (or alkanol) aminoalkylamine” include dimethylaminopropylamine, dimethylaminoethylamine, diethylaminopropylamine, diethylaminoethylamine, etc. Among them, dimethylaminopropylamine is particularly preferable.

The amount of dialkyl (or alkanol) aminoalkylamine used in the production of the long-chain aliphatic amidodialkyl tertiary amine is preferably 0.9 to 2.0 times the moles of the fatty acid or derivative thereof, and is 1.0 to A 1.5-fold mole is particularly preferred. The reaction temperature for producing the long-chain aliphatic amidodialkyl tertiary amine is usually 100 to 220 ° C, preferably 150 to 200 ° C. If the reaction temperature is less than 100 ° C., the reaction is too slow, and if it exceeds 220 ° C., the resulting tertiary amine may be markedly colored.
The production conditions other than those described above for the long-chain aliphatic amidodialkyl tertiary amine can be appropriately changed. The pressure during the reaction may be normal pressure or reduced pressure, and is introduced by blowing an inert gas such as nitrogen during the reaction. It is also possible.
In addition, when using a fatty acid, an acid catalyst such as sulfuric acid or p-toluenesulfonic acid, or when using a fatty acid derivative, an alkali catalyst such as sodium methylate, caustic potash, or caustic soda can be used at a low reaction temperature. The reaction can proceed efficiently in a short time.
In addition, when the resulting tertiary amine is a long chain amine having a high melting point, it is preferably molded into a flake shape or a pellet shape after the reaction in order to improve handling properties, or in an organic solvent such as ethanol. It is preferable to dissolve and make it liquid.

(F) A component may be used individually by 1 type and may be used in combination of 2 or more type as appropriate.
Among the above, as the component (F), a long-chain aliphatic amide dialkyl tertiary amine is particularly preferable because the effect of imparting flexibility to an object to be washed and liquid stability are both better.
Specific examples of commercially available long-chain aliphatic amidodialkyl tertiary amines include Kachinal MPAS-R (trade name) manufactured by Toho Chemical Co., Ltd.

In the liquid detergent, the blending amount of the component (F) is preferably 0.1 to 10% by mass, more preferably 0.5 to 8% by mass with respect to the total mass of the liquid detergent. Especially preferably, it is 1-5 mass%.
When the blending amount of the component (F) is 0.1% by mass or more with respect to the total mass of the liquid cleaning agent, an effect of imparting flexibility to the object to be cleaned is easily obtained. On the other hand, even if blending more than 10% by mass, it is difficult to obtain an effect of imparting flexibility to the object to be washed, which is disadvantageous economically.

In the present invention, “component (A) / component (F)” represents the ratio (mass ratio) of the content of component (A) to the content of component (F) in the liquid detergent.
In the liquid detergent of the present invention, the mixing ratio of the component (A) and the component (F) is 1 to 15 in terms of the mass ratio represented by the component (A) / (F), and 1.5 to 10 It is preferable that it is, and it is more preferable that it is 2-8.
When the mass ratio represented by (A) component / (F) component is less than 1 (the ratio of (F) component is too high), the liquid stability of the liquid detergent may be lowered. On the other hand, when the mass ratio exceeds 15 (the ratio of the component (A) is too high), it is difficult to obtain the blending effect of the component (F) (the effect of imparting flexibility to the wash object).

<Cationic surfactant (H)>
In the liquid detergent of the 5th aspect of this invention, the deodorizing effect with respect to the odor which generate | occur | produces from the clothes etc. after washing is mainly exhibited by containing a cationic surfactant (H).

  Among the components (H), a quaternary ammonium salt type cationic surfactant is preferable. Among these, since the liquid stability and deodorizing effect of the liquid detergent are better, the compound represented by the following general formula (h-1), the compound represented by the general formula (h-2) Or a compound represented by formula (h-3) is more preferable.

［式中、Ｒ^４１１〜Ｒ^４１４のうち、少なくとも１つは、炭素数８〜２２の炭化水素基であり、残りの２つ以上は、それぞれ独立して炭素数１〜３のアルキル基又は炭素数１〜３のヒドロキシアルキル基である。Ｚ⁻は対イオンである。］

[Wherein, at least one of R ^{411 to} R ⁴¹⁴ is a hydrocarbon group having 8 to 22 carbon atoms, and the remaining two or more are each independently an alkyl group or carbon having 1 to 3 carbon atoms. It is a hydroxyalkyl group of formulas 1-3. Z ⁻ is a counter ion. ]

· Formula Formula The compound represented by (h-1) in ^(h-1), the hydrocarbon group of R 411 ^{to R 414,} the number of carbon atoms thereof is from 8 to 22, a linear May be branched or may contain a cyclic structure.
The hydrocarbon group in R ^{411 to} R ⁴¹⁴ is preferably an aliphatic hydrocarbon group, and a linear or branched alkyl group or a linear or branched alkenyl group is more preferable. Can be mentioned.
Z ⁻ is a counter ion, and examples thereof include a halogen ion or an alkyl sulfate ion. When Z < ^- > is a halogen ion, examples of Z constituting the halogen ion include a fluorine atom, a chlorine atom, a bromine atom, or an iodine atom, and a chlorine atom is preferable. When Z < ^- > is an alkyl sulfate ion, as Z which comprises an alkyl sulfate ion, what has a C1-C3 alkyl group is preferable. Among these, Z ⁻ is preferably a halogen ion.

Among the compounds represented by the formula (h-1), preferred are:
R ⁴¹¹ is a linear or branched alkyl group having 8 to 22 carbon atoms, or a linear or branched alkenyl group having 8 to 22 carbon atoms, and R ^{412 to} R ⁴¹⁴ are independent of each other. Compound (H11) (hereinafter referred to as “component (H11)”) which is an alkyl group having 1 to 3 carbon atoms or a hydroxyalkyl group having 1 to 3 carbon atoms;
R ⁴¹¹ and R ⁴¹² are each independently a linear or branched alkyl group having 8 to 22 carbon atoms, or a linear or branched alkenyl group having 8 to 22 carbon atoms, and R ⁴¹³ And R ⁴¹⁴ are each independently an alkyl group having 1 to 3 carbon atoms or a hydroxyalkyl group having 1 to 3 carbon atoms (hereinafter referred to as “component (H12)”).
Etc.

In the component (H11), the alkyl group of R ⁴¹¹ and the alkenyl group have 8 to 22 carbon atoms, preferably 10 to 22 carbon atoms, and more preferably 16 to 18 carbon atoms. R ⁴¹¹ is preferably a linear or branched alkyl group, and more preferably a linear alkyl group.
R ^{412 to} R ⁴¹⁴ are each preferably an alkyl group having 1 to 3 carbon atoms, more preferably a methyl group, and particularly preferably a methyl group.

In the component (H12), R ⁴¹¹ and the alkyl group or alkenyl group of R ⁴¹² each have 8 to 22 carbon atoms, preferably 8 to 12 carbon atoms, and more preferably 8 to 10 carbon atoms. . R ⁴¹¹ and R ⁴¹² are each preferably a linear or branched alkyl group, more preferably a linear alkyl group, and both are linear alkyl groups. It is particularly preferred.
R ⁴¹³ and R ⁴¹⁴ are each preferably an alkyl group having 1 to 3 carbon atoms, more preferably a methyl group, and particularly preferably a methyl group.

［式中、Ｒ^４１５は、炭素数１０〜１８の炭化水素基であり、Ｒ^４１６は、置換基を有していてもよい芳香族炭化水素基又は炭素数１〜３のアルキル基である。ｘ及びｙはいずれも（ＣＨ_２ＣＨ_２Ｏ）の平均繰返し数を示し、それぞれ独立して０以上の整数で、かつ、ｘ＋ｙは１０以上の整数である。Ｚ⁻は対イオンである。］

[Wherein, R ⁴¹⁵ is a hydrocarbon group having 10 to 18 carbon atoms, and R ⁴¹⁶ is an aromatic hydrocarbon group which may have a substituent or an alkyl group having 1 to 3 carbon atoms. x and y both represent the average number of repetitions of (CH ₂ CH ₂ O), each independently an integer of 0 or more, and x + y is an integer of 10 or more. Z ⁻ is a counter ion. ]

· Formula Formula The compound represented by (h-2) in ^(h-2), the hydrocarbon group of ^{R 415,} the number of carbon atoms thereof is 10 to 18, branched-chain be straight Or may include an annular structure. The hydrocarbon group for R ⁴¹⁵ is preferably an aliphatic hydrocarbon group, and a linear or branched alkyl group or a linear or branched alkenyl group is more preferable.
Examples of the aromatic hydrocarbon group for R ⁴¹⁶ include a phenyl group and a naphthyl group.
Examples of the substituent that the aromatic hydrocarbon group may have include an alkyl group having 1 to 5 carbon atoms or an alkoxy group having 1 to 5 carbon atoms. Preferable specific examples of R ⁴¹⁶ include a methyl group, an ethyl group, a phenyl group, or a tolyl group.
x + y is an integer of 10 or more, preferably an integer of 10-50. If x + y is less than 10, the solubility of the compound itself in water tends to decrease, and the liquid stability of the liquid detergent may be deteriorated.
Z ^- is, Z in formula (h-1) ^- is the same as.

［式中、Ｒ^４１７は炭素数８〜２２の炭化水素基であり、Ｒ^４１８及びＲ^４１９は、それぞれ独立して炭素数１〜３のアルキル基又は炭素数１〜３のヒドロキシアルキル基であり、Ｒ^４２０は炭素数１〜３のアルキレン基である。Ｚ⁻は対イオンである。］

[Wherein, R ⁴¹⁷ is a hydrocarbon group having 8 to 22 carbon atoms, and R ⁴¹⁸ and R ⁴¹⁹ are each independently an alkyl group having 1 to 3 carbon atoms or a hydroxyalkyl group having 1 to 3 carbon atoms. , R ⁴²⁰ is an alkylene group having 1 to 3 carbon atoms. Z ⁻ is a counter ion. ]

· Formula Formula The compound represented by (h-3) in (h-3), the hydrocarbon group of R ^417, the number of carbon atoms thereof is from 8 to 22, branched-chain be straight Or may include an annular structure. The hydrocarbon group for R ⁴¹⁷ is preferably an aliphatic hydrocarbon group, and a linear or branched alkyl group or a linear or branched alkenyl group is more preferable. Among these, as R ^417, preferably a linear or branched alkyl group, more preferably a linear alkyl group. The number of carbon atoms of the hydrocarbon group for R ⁴¹⁷ is 8 to 22, preferably from 10 to 18, and more preferably from 12 to 14.
R ⁴¹⁸ and R ⁴¹⁹ are each preferably an alkyl group having 1 to 3 carbon atoms, more preferably a methyl group, and particularly preferably a methyl group.
R ⁴²⁰ is preferably a methylene group.
Z ^- is, Z in formula (h-1) ^- is the same as.

(H) A component may be used individually by 1 type and may be used in combination of 2 or more type as appropriate.
Among these, as the component (H), the compound represented by the general formula (h-1) or the general formula is excellent because of the deodorizing effect and it is easy to ensure the liquid stability of the liquid detergent. The compound represented by (h-3) is preferable, and the compound represented by General Formula (h-1) is particularly preferable.
Specific examples of suitable component (H) include alkyltrimethylammonium chloride (for example, “Arcard T-800”, manufactured by Lion Akzo Corporation; (H11) component), didecyldimethylammonium chloride (for example, , Trade name “Arcade 210”, manufactured by Lion Akzo Co., Ltd .; (H12) component), or coconut alkyldimethylbenzylammonium chloride (eg, trade name “Arcade CB-50” manufactured by Lion Akzo Co., Ltd.), etc. it can.

In the liquid detergent, the blending amount of the component (H) is preferably 0.1 to 10% by mass, more preferably 0.5 to 7% by mass with respect to the total mass of the liquid detergent. Especially preferably, it is 1-5 mass%.
When the blending amount of the component (H) is 0.1% by mass or more with respect to the total mass of the liquid detergent, the deodorizing effect of odors (such as room-dried odors) generated from clothes after washing is further improved. To do. On the other hand, if the content is 10% by mass or less, transfer to the object to be washed, recontamination, and the like are suppressed. In addition, effects such as suppression of coloring in the liquid cleaning agent, prevention of viscosity reduction, and stabilization of aroma are further improved. Furthermore, it becomes economically advantageous.

In the liquid cleaning agent of the present invention, by blending the component (A) and the component (H) at a specific ratio, the deodorant performance (antibacterial property) is improved and the recontamination prevention performance is improved. Can be compatible.
In the present invention, “component (A) / component (H)” represents the ratio (mass ratio) of the content of component (A) to the content of component (H) in the liquid detergent.
In the liquid detergent of the present invention, the mixing ratio of the component (A) and the component (H) is 1 to 15 in mass ratio represented by the component (A) / (H), and is 1.5 to 10 It is preferable that it is, and it is more preferable that it is 2-8.
When the mass ratio represented by the component (A) / component (H) is less than 1 (the ratio of the component (A) is too low), it is difficult to sufficiently obtain the effect of preventing recontamination by blending the component (A). Moreover, there is a possibility that stable blending becomes difficult as a liquid detergent. On the other hand, if the mass ratio exceeds 15 (the ratio of the component (H) is too low), the effect of imparting antibacterial properties due to the blending of the component (H) is low, and sufficient deodorizing performance is difficult to be imparted.

<Solvent: Water>
The liquid detergent of the present invention preferably contains water as a solvent from the viewpoint of ease of preparation of the liquid detergent, solubility in water when used, liquid stability, and the like.
5-55 mass% is preferable with respect to the total mass of a liquid cleaning agent, and, as for the compounding quantity of the water in the liquid cleaning agent of the 2nd-4th aspect of this invention, 5-45 mass% is more preferable, 10- 45 mass% is further more preferable, and 10-40 mass% is especially preferable.
The amount of water in the liquid detergent according to the fifth aspect of the present invention is preferably 5 to 53% by mass, more preferably 5 to 50% by mass, and more preferably 10 to 45% by mass with respect to the total mass of the liquid detergent. Is more preferable.
If the blending amount of water is 5% by mass or more, the liquid stability of the liquid detergent with time will be better, and if it is not more than the upper limit, the liquid viscosity will be moderately low and good from the viewpoint of usability. Become.

<Other ingredients>
In the liquid cleaning agent of the present invention, other components other than the components described above may be blended as desired as long as the effects of the present invention are not impaired.
Other components are not particularly limited, and components usually used in liquid detergent compositions for clothing can be blended, and specific examples include the following.

The liquid detergent of the present invention can contain a surfactant other than the component (A), the component (B), the component (E), and the component (H). Examples of the surfactant include an anionic surfactant other than the components (A) and (E), a nonionic surfactant other than the component (B), a cationic surfactant other than the component (H), or amphoteric. Surfactant etc. are mentioned.
Examples of the anionic surfactant other than the component (A) and the component (E) include linear alkylbenzene sulfonate, α-olefin sulfonate, linear or branched alkyl sulfate ester salt, and alkyl ether. Sulfate ester or alkenyl ether sulfate ester, alkane sulfonate having alkyl group, higher fatty acid salt, alkyl ether carboxylate, polyoxyalkylene ether carboxylate, alkyl amide ether carboxylate, alkenyl amide ether carboxylate Or carboxylic acid type such as acylaminocarboxylate; or alkyl phosphate ester salt, polyoxyalkylene alkyl phosphate ester salt, polyoxyalkylene alkyl phenyl phosphate ester salt, or glycerin fatty acid ester monophosphate Such as ester phosphate ester type, such as salts.
Examples of these salts include alkali metal salts such as sodium or potassium; alkaline earth metal salts such as magnesium; or alkanolamine salts such as monoethanolamine or diethanolamine.

In the liquid detergent of the 3rd-5th aspect of this invention, since a detergency improves more, as a nonionic surfactant other than (B) component, it represents with the following general formula (b'-3). It is preferable to use these compounds together.
The compound represented by the formula (b′-3) is an alcohol ethoxylate (polyoxyethylene alkyl ether) in which an ethylene oxide having an average addition mole number v is added to an alcohol (R ¹⁰ —OH).

［式（ｂ’−３）中、Ｒ^１０は炭素数１０〜２２の炭化水素基である。ｖは（ＣＨ_２ＣＨ_２Ｏ）の平均繰返し数を示し、５〜２０の整数である。］

[In formula (b′-3), R ¹⁰ represents a hydrocarbon group having 10 to 22 carbon atoms. v represents an average repeating number of _(CH 2 CH 2 O), is an integer of 5-20. ]

In the formula (b′-3), the hydrocarbon group for R ¹⁰ may be linear or branched, or may contain a cyclic structure. The hydrocarbon group for R ¹⁰ is preferably an aliphatic hydrocarbon group, and a linear or branched alkyl group or a linear or branched alkenyl group is more preferable.
The hydrocarbon group of R ¹⁰ has 10 to 22 carbon atoms, preferably 10 to 20 carbon atoms, and more preferably 10 to 18 carbon atoms. When the number of carbon atoms of R ¹⁰ is 10 or more, the detergency is improved especially with respect to sebum. On the other hand, when the carbon number of R ¹⁰ is 22 or less, the liquid stability and the solubility in water are further improved.
The compound represented by the formula (b′-3) may be a single chain length mixture or a mixture of two or more chain lengths. R ¹⁰ is derived from a raw material alcohol (R ¹⁰ -OH), and examples of the alcohol include alcohols derived from natural fats and oils such as coconut oil, palm oil and beef tallow, and synthetic alcohols derived from petroleum.

In the formula (b′-3), v represents an average number of repetitions of (CH ₂ CH ₂ O), and is an integer of 5 to 20, preferably an integer of 8 to 18, More preferably, it is an integer.
When v is in the above range, it exhibits excellent cleaning power against sebum dirt. Furthermore, when v is 5 or more, it becomes easy to prevent deterioration of the odor of the liquid cleaning agent. On the other hand, when v exceeds 20, HLB (Hydrophile-Lipophile Balance) becomes too high, and there is a possibility that the detergency against sebum soil may be reduced.
In the compound represented by the formula (b′-3), the addition mole number distribution of ethylene oxide is not particularly limited, and can be controlled by the production method of the compound represented by the formula (b′-3). For example, when ethylene oxide is added to a hydrophobic raw material using a general alkali catalyst such as sodium hydroxide or potassium hydroxide, a relatively wide addition mole number distribution tends to be obtained. In addition, specific oxides such as magnesium oxide added with metal ions such as Al ³⁺ , Ga ³⁺ , In ³⁺ , Tl ³⁺ , Co ³⁺ , Sc ³⁺ , La ³⁺ , or Mn ²⁺ described in JP-B-615038 When ethylene oxide is added to a hydrophobic raw material using an alkoxylation catalyst, a relatively narrow addition mole number distribution tends to be obtained.

Specific examples of the compound represented by the formula (b′-3) include 12 or 15 moles with respect to an alcohol such as trade name Neodol (C12 / C13) manufactured by Shell or Safol 23 (C12 / C13) manufactured by Sasol. A product obtained by adding a considerable amount of ethylene oxide; a product obtained by adding 9, 12, or 15 moles of ethylene oxide to a natural alcohol such as the trade name CO-1214 or CO-1270 manufactured by P &G; or having 12 to 14 carbon atoms Examples include those obtained by adding 9, 12, or 15 moles of ethylene oxide to secondary alcohol (Nippon Shokubai Co., Ltd., Softanol 90, 120 or 150).
“C12 / C13” means a mixture of an alcohol having 12 carbon atoms and an alcohol having 13 carbon atoms.
The compounds represented by the formula (b′-3) may be used singly or in appropriate combination of two or more.

  Examples of nonionic surfactants other than the compounds represented by the formula (b-1) and the formula (b′-3) include alkylene oxide adducts of higher alcohols, alkylene oxide adducts of alkylphenols, and higher fatty acids. Alkylene oxide adducts, higher amine alkylene oxide adducts, polyoxyethylene polyoxypropylene block copolymers, fatty acid alkanolamines, fatty acid alkanolamides, polyhydric alcohol fatty acid esters or their alkylene oxide adducts, polyhydric alcohol fatty acid ethers, alkyls Examples include amine oxide, alkenyl amine oxide, alkylene oxide adduct of hydrogenated castor oil, sugar fatty acid ester, N-alkyl polyhydroxy fatty acid amide, or alkyl glycoside.

  Examples of the cationic surfactant other than the component (H) include alkyltrimethylammonium salts, dialkyldimethylammonium salts, alkylbenzyldimethylammonium salts, and alkylpyridinium salts.

  Examples of amphoteric surfactants include amphoteric interfaces such as alkylbetaines, alkylamidebetaines, imidazolines, alkylaminosulfones, alkylaminocarboxylic acids, alkylamidecarboxylic acids, amide amino acids, or phosphates. An activator is mentioned.

  In the liquid detergent of the fourth aspect of the present invention, at least one silicone compound (G) selected from the group consisting of an amino-modified silicone compound, a carboxy-modified silicone compound and a polyether-modified silicone compound (hereinafter referred to as “(G)”. It is preferable to contain a component ". By containing the component (G), slipperiness is imparted to the washed object after washing, and the comfort of the washed object becomes better. In addition, excellent comfort can be easily obtained even under harsh washing conditions such as when a large amount of clothing is packed at once. Especially, the feeling of comfort at the time of wearing especially the clothing which consists of wool fibers improves more.

  The amino-modified silicone compound is not particularly limited as long as it is a silicone having at least an amino group as a functional group. Examples of commercially available examples include BY16-871 and BY16-853U manufactured by Toray Dow Corning Co., Ltd. , FZ-3705, SF8417, BY16-849, FZ-3785, BY16-890, BY16-208, BY16-893, FZ-3789, BY16-878, or BY16-891 (all are trade names) It is done.

  The carboxy-modified silicone compound is not particularly limited as long as it is a silicone having at least a carboxy group as a functional group. Specific examples of commercially available BY16-880 (trade name) manufactured by Toray Dow Corning Co., Ltd. Etc.

  The polyether-modified silicone compound is not particularly limited as long as it is a silicone having at least a polyether group (such as a polyoxyethylene group or a polyoxypropylene group) as a functional group, and in particular, the following general formula (g-3) The polyether-modified silicone represented is preferred.

［式中、Ｒ^１８は水素原子又は炭素数１〜４のアルキレン基である。Ｒ^１９は炭素数１〜４のアルキル基、炭素数２〜４のアルケニル基、又は水素原子である。Ｙはポリオキシアルキレン基である。ａは１０〜１００００の整数、ｂは１〜１０００の整数である。］

[Wherein, R ¹⁸ represents a hydrogen atom or an alkylene group having 1 to 4 carbon atoms. R ¹⁹ is an alkyl group having 1 to 4 carbon atoms, an alkenyl group having 2 to 4 carbon atoms, or a hydrogen atom. Y is a polyoxyalkylene group. a is an integer of 10 to 10,000, and b is an integer of 1 to 1,000. ]

In formula (g-3), the alkylene group for R ¹⁸ may be linear or branched. If the number of carbon atoms of the alkylene group is within the above range, it is easy to synthesize industrially.
The alkyl group or alkenyl group for R ¹⁹ may be linear or branched. When the carbon number of the alkyl group or alkenyl group is within the above range, the fluidity of the component (G) itself is good and its handling is easy.
Y is a polyoxyalkylene group, and the oxyalkylene group is preferably an oxyethylene group, an oxypropylene group, or an oxybutylene group, and two or more oxyalkylene groups may be mixed. The number of repeating oxyalkylene groups is preferably an integer of 1 to 50, and more preferably an integer of 5 to 20.
a is an integer of 10 to 10000, and preferably an integer of 20 to 1000. b is an integer of 1-1000, and is preferably an integer of 2-100. If a and b are each in the said range, the feeling of comfort at the time of wearing especially the clothing which consists of wool fibers will improve more.
The order of each repeating unit to which a or b is attached may be different. That is, the repeating unit to which a is attached and the repeating unit to which b is attached may be added randomly, or each repeating unit may be added in a block form.

  Specific examples of commercially available polyether-modified silicone compounds include SH3772M, SH3775M, SH3749, SF8410, SH8700, BY22-008, SF8421, manufactured by Toray Dow Corning Co., Ltd., SILWET L-7001, and SILWET L-7002. , SILWET L-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 ZILF 009-09, ABN SILWET FZ-F1-009-54, or ABN SILWET FZ-2222 (all are trade names); Shin-Etsu Chemical Co., Ltd. KF352A, KF6008, KF615A, KF6016, or KF6017 (all are trade names) manufactured by a formula company; or TSF4450, TSF4452 (all are trade names) manufactured by GE Toshiba Silicone Co., Ltd., and the like.

(G) A component may be used individually by 1 type and may be used in combination of 2 or more types as appropriate.
Among these, as the component (G), a polyether-modified silicone compound is particularly preferable because both the comfort of the object to be washed and the liquid stability are better.
In the liquid detergent, the blending amount of the component (G) is preferably 0.1 to 5% by mass, more preferably 0.2 to 3% by mass with respect to the total mass of the liquid detergent.
(G) When the compounding quantity of component is 0.1 mass% or more with respect to the total mass of the said liquid detergent, the feeling of comfort at the time of wearing especially the clothing which consists of wool fibers improves more. On the other hand, even if it is added in an amount of more than 5% by mass, it is difficult to obtain an effect of improving the comfort feeling commensurate with it, which is disadvantageous economically.

In the liquid cleaning agent of the present invention, by blending the component (F) and the component (G) at a specific ratio, even under severe washing conditions such as when a large amount of clothing is packed at once. , Easy to get excellent comfort. In particular, the feeling of comfort when wearing clothing made of wool fibers is further improved.
The blending ratio of the (F) component and the (G) component is preferably 1 to 100, more preferably 1 to 25, as expressed by the (F) component / (G) component. 1 to 20 is more preferable, and 1 to 10 is particularly preferable.
When the mass ratio represented by (F) component / (G) component is less than 1 (the ratio of (F) component is too low), it is difficult to obtain an excellent feeling of comfort for clothing made of wool fibers. . On the other hand, when the mass ratio exceeds 100 (the ratio of the component (G) is too low), when a large amount of clothing is packed and washed at the same time, particularly a good feeling of comfort for clothing made of wool fibers is obtained. It's hard to be done.
In the present invention, “(F) component / (G) component” represents the ratio (mass ratio) of the content of (F) component to the content of (G) component in the liquid detergent.

In addition, a thinning agent and a solubilizer, a metal ion scavenger, an antioxidant, or an antiseptic can be blended in the liquid detergent of the present invention.
Examples of the thinning agent and solubilizer include triethylene glycol, tetraethylene glycol, or glycols such as polyethylene glycol having an average molecular weight of about 200 to 5000; paratoluenesulfonic acid or a salt thereof, cumenesulfonic acid or a salt thereof, xylene Examples thereof include sulfonic acid or a salt thereof, benzoic acid or a salt thereof (also having an effect as a preservative), urea, and the like. The blending amount of the viscosity reducing agent and the solubilizer in the liquid detergent is preferably 0.01 to 15% by mass with respect to the total mass of the liquid detergent.
Examples of the metal ion scavenger include malonic acid, succinic acid, malic acid, diglycolic acid, tartaric acid, citric acid, and lactic acid. In the liquid detergent, the compounding amount of the metal ion scavenger is preferably 0.1 to 20% by mass with respect to the total mass of the liquid detergent.
Examples of the antioxidant include butylhydroxytoluene, distyrenated cresol, sodium sulfite, sodium hydrogensulfite and the like. The blending amount of the antioxidant in the liquid detergent is preferably 0.01 to 2% by mass with respect to the total mass of the liquid detergent.
As a preservative, Rohm and House's Caisson CG (trade name) or the like can be used. In the liquid detergent, the blending amount of the preservative is preferably 0.001 to 1% by mass with respect to the total mass of the liquid detergent.

  In addition, the liquid detergent of the present invention includes a flexibility imparting agent described later or a texture improving agent described later; alkanolamine (for example, monoethanolamine, diethanolamine, triethanolamine, etc.) for the purpose of improving detergency and liquid stability. Alkali builders such as ethanolamine, N-methyl-diethanolamine, or N, N-dimethylmonoethanolamine; pH adjusters, hydrotropes, fluorescent agents, enzymes (for example, protease, amylase, lipase, cellulase, mannanase, etc.) ), Dye transfer inhibitors, anti-staining agents other than component (D) (for example, water-soluble polymers having alkylene terephthalate and / or alkylene isophthalate units, polyvinyl pyrrolidone, carboxymethyl cellulose, etc.), pearl agents, or soil releases Agents It can be included.

  Flexibility agents include caprylic acid dimethylaminopropylamide, capric acid dimethylaminopropylamide, lauric acid dimethylaminopropylamide, myristic acid dimethylaminopropylamide, palmitic acid dimethylaminopropylamide, stearic acid dimethylaminopropylamide, and behenine. Long chain aliphatic amide alkyl tertiary amines such as acid dimethylaminopropylamide or oleic acid dimethylaminopropylamide or salts thereof; palmitic acid diethanolaminopropylamide, stearic acid diethanolaminopropylamide, and the like. In the liquid detergent, the blending amount of the flexibility-imparting agent is preferably 1 to 5% by mass with respect to the total mass of the liquid detergent.

  As the texture improver, FZ-3707, FZ-3504, BY16-205, FZ-3760, FZ-3705, BY16-209, FZ-3710, SF8417, BY16-849, BY16 manufactured by Toray Dow Corning Co., Ltd. -850, BY16-879B, BY16-892, FZ3501, FZ-3785, BY16-872, BY16-213, BY16-203, BY16-898, BY16-890, BY16-878, BY16-891, BY16-893, FZ -3789, BY16-880, SF8428, FZ-3704, BY16-606, CF1188HV, SH3748, SH3794, SH3772M, SH3775M, SF8410, SH8700, BY22-008, BY22-012, SILWET L-7001, SILWET L-7002, SILWET L-7602, SILWET L-7604, SILWET FZ-2104, SILWET FZ-2120, SILWET FZ-2161, SILWET FZ-2162, SILWET FZ-2164, SILWET FZ-217 SILWET FZ-F1-009-01, ABN SILWET FZ-F1-009-02, ABN SILWET FZ-F1-009-03, ABN SILWET FZ-F1-009-05, ABN SILWET FZ-F1-009-09, ABN SILWET FZ-F1-009-11, ABN SILWET FZ-F1-009-13, ABN SILWET FZ-F1-009-54, or ABN SI WET FZ-22-22; X-20-8010B, KF352A, KF6008, KF615A, KF6012, KF6016, or KF6017 manufactured by Shin-Etsu Chemical Co., Ltd .; or TSF4450, TSF4452, or TSF4445 manufactured by GE Toshiba Silicone Co., Ltd. As mentioned above, modified silicones such as trade names) are mentioned. The blending amount of the texture improver in the liquid detergent is preferably 0.1 to 3% by mass with respect to the total mass of the liquid detergent.

Examples of pH adjusters include inorganic acids such as hydrochloric acid, sulfuric acid, nitric acid, or phosphoric acid; organic acids such as polyvalent carboxylic acids or hydroxycarboxylic acids; or sodium hydroxide, potassium hydroxide, alkanolamine, or ammonia. Can be mentioned. Of these, sulfuric acid, sodium hydroxide, potassium hydroxide, or alkanolamine is preferable, and sulfuric acid, sodium hydroxide, or alkanolamine is more preferable from the viewpoint of the temporal stability of the liquid detergent.
A pH adjuster may be used individually by 1 type, and may be used in combination of 2 or more types as appropriate.

As the enzyme, an enzyme conventionally blended in a detergent for clothing can be used, and examples thereof include protease, amylase, lipase, cellulase, and mannanase.
Specific examples of the protease include protease preparations such as Savinase 16L, Savinase Ultra 16L, Savinase Ultra 16XL, Everase 16L Type 2.5, Erase Ultra 2.5L, Esperase Ultra 2.5L, Esperase Ultra 16L, Esperase Ultra L .5L, Liquanase Ultra 2.5L, Liquanase Ultra 2.5XL, or Coronase 48L (all are trade names); or Purefect L, Perfect OX, or Properase L (all are trade names) available from Genencor. Etc.
Specific examples of amylase include, as an amylase preparation, Termamyl 300L, Termamyl Ultra 300L, Duramyl 300L, Stainzyme 12L, or Steinzyme Plus 12L available from Novozymes, Inc. Name), pullulanase Amano (trade name) available from Amano Pharmaceutical, or DB-250 (trade name) available from Seikagaku Corporation.
Specific examples of the lipase include Lipex 100L and Lipolase 100L (all of which are trade names) available from Novozymes as lipase preparations.
Specific examples of the cellulase include Endolase 5000L, Celluzyme 0.4L, or Carzyme 4500L (all are trade names) available from Novozymes as cellulase preparations.
Specific examples of mannanase include Mannavay 4L (trade name) available from Novozymes as a mannanase preparation.
An enzyme may be used individually by 1 type and may be used in combination of 2 or more type as appropriate. In the liquid detergent, the amount of the enzyme is preferably 0.1 to 3% by mass with respect to the total mass of the liquid detergent.

Furthermore, in the liquid cleaning agent of the present invention, a flavoring agent, a coloring agent, an emulsifying agent, or an extract such as a natural product may be blended for the purpose of improving the added value of the product.
As a flavoring agent, the fragrance | flavor composition as described in Unexamined-Japanese-Patent No. 2002-146399 and Unexamined-Japanese-Patent No. 2009-108248 is mentioned as a typical example.
In the liquid detergents of the second and third aspects of the present invention, the blending amount of the flavoring agent is preferably 0.1 to 2% by mass with respect to the total mass of the liquid detergent.
In the liquid detergents according to the fourth and fifth aspects of the present invention, the blending amount of the flavoring agent is preferably 0.1 to 3% by mass with respect to the total mass of the liquid detergent.
As the colorant, Acid Red 138, Polar Red RLS, Acid Yellow 203, Acid Blue 9, Blue No. 1, Blue No. 205, Green No. 3, or Turquoise P-GR (all of which are trade names) are used. Examples include pigments and pigments. The blending amount of the colorant in the liquid detergent is preferably 0.00005 to 0.005% by mass with respect to the total mass of the liquid detergent.
Examples of the emulsion include polystyrene emulsion and polyvinyl acetate emulsion, and usually an emulsion having a solid content of 30 to 50% by mass is suitably used. Specific examples include polystyrene emulsion (trade name Cybinol RPX-196 PE-3, solid content 40% by mass, manufactured by Seiden Chemical Co., Ltd.) and the like. The blending amount of the emulsion in the liquid detergent is preferably 0.01 to 0.5% by mass with respect to the total mass of the liquid detergent.
Examples of extracts such as natural products include Inuenju, Uwaurushi, Echinacea, Koganebana, Yellowfin, Ouren, Allspice, Oregano, Enju, Chamomile, Honeysuckle, Clara, Keigai, Kay, Bay bay, Honoki, Burdock, Comfrey, Jasho, Waremokou, Peonies, Ginger, Solidago, Elderberry, Sage, Mistletoe, Prunus, Thyme, Prunus, Clove, Satsuma Mandarin, Tea Tree, Barberry, Dokudami, Nanten, Nyuko, Yorigusa, Shirogaya, Bow Fu, Dutch Hyu, Mountain, Gray , Murasakitagayasan, yamahakka, cypress, yamajiso, eucalyptus, lavender, rose, rosemary, balun, cedar, gilead balsamno , Ringworm, kochia, Polygonum aviculare, Jingyou, Liquidambar formosana, Adenophortriphylla, Yamabishi, cayratia japonica, licorice, or oilseed extract, and the like of plants such as Hypericum may be mentioned.
In the liquid detergent of the present invention, the amount of extract such as a natural product is preferably 0 to 0.5% by mass, more preferably 0.0001 to 0.00%, based on the total mass of the liquid detergent. 5% by mass.

The pH of the liquid detergent of the present invention is preferably 4 to 9 at 25 ° C, more preferably 4 to 8. When the pH is 4 to 9, the stability over time is easily maintained even when the liquid detergent is stored for a long period of time.
Adjustment of the pH of the liquid detergent is controlled by adding a certain amount of sulfuric acid, sodium hydroxide, alkanolamine or the like, and then an inorganic acid (preferably hydrochloric acid or sulfuric acid) or water is used for fine adjustment of pH. It is preferable to carry out by further adding potassium oxide or the like.
In the present invention, the pH of the liquid detergent (controlled at 25 ° C.) indicates a value measured by a pH meter (product name: HM-30G, manufactured by Toa DKK Co., Ltd.) or the like.

The liquid detergent of the present invention can be produced by a conventional method, for example, by mixing the above-described components.
The liquid detergent of this invention can be used by the method similar to the normal usage method of the general liquid detergent for clothes. That is, a method in which the liquid detergent is poured into the water together with the object to be washed at the time of washing, a method in which the liquid detergent is directly applied to the mud soil part or sebum soil part of the object to be washed, Examples include a method of dissolving and immersing clothes. Also preferred is a method in which the liquid detergent is applied to the article to be washed and then allowed to stand as appropriate, followed by ordinary washing using ordinary washing liquid.
In that case, the usage-amount of the liquid cleaning agent of this invention can be made smaller than the usage-amount of the conventional liquid cleaning agent.

A first aspect of the present _{invention, C 10 H 21 -CH (SO} 3 Na) -COOCH 3 (α- Suruhoraurin acid methyl ester sodium _{salt), C 12 H 25 -CH (} SO 3 Na) -COOCH 3 ( α-sulfomyristic acid methyl ester sodium salt), C ₁₄ H ₂₉ —CH (SO ₃ Na) —COOCH ₃ (α-sulfopalmitic acid methyl ester sodium salt), and C ₁₆ H ₃₃ —CH (SO ₃ Na) — At least one anionic surfactant (A) selected from the group consisting of COOCH ₃ (α-sulfostearic acid methyl ester sodium salt), the compound represented by the general formula (b-1), and the general formula At least one nonionic surfactant (B) selected from the group consisting of compounds represented by (b-2), and having 2 to 4 carbon atoms A liquid detergent containing alcohol and at least one organic solvent (C) selected from the group consisting of the compounds represented by formula (c-1) is preferred.

A second aspect of the present _{invention, C 10 H 21 -CH (SO} 3 Na) -COOCH 3, C 12 H 25 -CH (SO 3 Na) -COOCH 3, C 14 H 29 -CH (SO 3 Na) -COOCH _3, and _{C 16 H 33 -CH (SO 3} Na) -COOCH least one anionic surfactant ₃ is selected from the group consisting of _{(a), C 11 H 23} -CO- (OCH 2 CH _{2) m} -OCH _3, and _{C 13 H 27 -CO- (OCH 2} CH 2) m of at least one nonionic surfactant is selected from the group consisting of -OCH ₃ (B), and diethylene glycol monobutyl ether, propylene A liquid detergent containing at least one organic solvent (C) selected from the group consisting of glycol and ethanol is preferred. The number after the C represents the number of carbon atoms (the same applies hereinafter). The above m is 15 on average.

A third aspect of the present _{invention, C 10 H 21 -CH (SO} 3 Na) -COOCH 3, C 12 H 25 -CH (SO 3 Na) -COOCH 3, C 14 H 29 -CH (SO 3 Na) -COOCH _3, and _{C 16 H 33 -CH (SO 3} Na) -COOCH least one anionic surfactant ₃ is selected from the group consisting of _{(a), C 11 H 23} -CO- (OCH 2 CH _{2) m -OCH 3, C 13} H 27 -CO- (OCH 2 CH 2) m -OCH 3, and natural alcohol [a mixture of alcohols having 12 carbon atoms (C12OH) and carbon 14 alcohol (C14OH), C12OH / C14OH (mass ratio) = 7/3] is obtained by random addition of 16 moles of ethylene oxide and 2 moles of propylene oxide. At least one nonionic surfactant (B) selected from the group consisting of a surfactant, and at least one organic solvent (C) selected from the group consisting of diethylene glycol monobutyl ether, propylene glycol, and ethanol; A polymer represented by the general formula (d-1) or a polymer (D) each containing a polymer represented by the general formula (d-2), and a general formula: R ⁹ -COOH (R ⁹ is (E) component which is a compound represented by the above or a salt thereof is preferable. M is 15 on average.

A fourth aspect of the present _{invention, C 10 H 21 -CH (SO} 3 Na) -COOCH 3, C 12 H 25 -CH (SO 3 Na) -COOCH 3, C 14 H 29 -CH (SO 3 Na) -COOCH _3, and _{C 16 H 33 -CH (SO 3} Na) -COOCH least one anionic surfactant ₃ is selected from the group consisting of _{(a), C 11 H 23} -CO- (OCH 2 CH _{2) m -OCH 3, C 13} H 27 -CO- (OCH 2 CH 2) m -OCH 3, and natural alcohol [a mixture of alcohols having 12 carbon atoms (C12OH) and carbon 14 alcohol (C14OH), C12OH / C14OH (mass ratio) = 7/3] is obtained by random addition of 16 moles of ethylene oxide and 2 moles of propylene oxide. At least one nonionic surfactant (B) selected from the group consisting of a surfactant, and at least one organic solvent (C) selected from the group consisting of diethylene glycol monobutyl ether, propylene glycol, and ethanol; A liquid detergent containing at least one tertiary amine (F) selected from the group consisting of stearic acid dimethylaminopropylamide and palmitic acid dimethylaminopropylamide is preferred, an amino-modified silicone compound, a carboxy-modified silicone compound And a liquid detergent further containing at least one silicone compound (G) selected from the group consisting of a polyether-modified silicone compound. M is 15 on average.
Examples of the polyether-modified silicone compound include a silicone compound represented by the general formula (g-3) (a = 210, b = 9, R ¹⁸ = C ₃ H ₆ , Y = (OC ₂ H ₄ ) ₁₀ , R ¹⁹ = CH ₃ ) and the like.

A fifth aspect of the _{invention, C 10 H 21 -CH (SO} 3 Na) -COOCH 3, C 12 H 25 -CH (SO 3 Na) -COOCH 3, C 14 H 29 -CH (SO 3 Na) -COOCH _3, and _{C 16 H 33 -CH (SO 3} Na) -COOCH least one anionic surfactant ₃ is selected from the group consisting of _{(a), C 11 H 23} -CO- (OCH 2 CH _{2) m -OCH 3, C 13} H 27 -CO- (OCH 2 CH 2) m -OCH 3, and natural alcohol [a mixture of alcohols having 12 carbon atoms (C12OH) and carbon 14 alcohol (C14OH), C12OH / C14OH (mass ratio) = 7/3] is obtained by random addition of 16 moles of ethylene oxide and 2 moles of propylene oxide. At least one nonionic surfactant (B) selected from the group consisting of a surfactant, and at least one organic solvent (C) selected from the group consisting of diethylene glycol monobutyl ether, propylene glycol, and ethanol; A liquid detergent containing at least one cationic surfactant (H) selected from the group consisting of alkyltrimethylammonium chloride, didecyldimethylammonium chloride, and coconut alkyldimethylbenzylammonium chloride is preferred. M is 15 on average.

The anionic surfactant _{(A), C 12 H 25 -CH (SO} 3 Na) -COOCH 3 (; C 14 H 29 -CH (SO 3 Na) -COOCH 3; C 10 H 21 -CH (SO ₃ Na) -COOCH ₃ and _{C 12 H 25 -CH (SO 3} Na) mixture of _{-COOCH 3; C 12 H 25 -CH} (SO 3 Na) -COOCH 3 and _{C 14 H 29 -CH (SO 3} Na ) —COOCH ₃ mixture (; C ₁₄ H ₂₉ —CH (SO ₃ Na) —COOCH ₃ and C ₁₆ H ₃₃ —CH (SO ₃ Na) —COOCH ₃ ; or C ₁₀ H ₂₁ —CH ( the SO ₃ Na) -COOCH _3, and _{C 12 H 25 -CH (SO 3} Na) -COOCH 3, and _{C 14 H 29 -CH (SO 3} Na) -COOCH 3, C 16 H ₃₃ mixture of -CH _{(SO 3} Na) -COOCH 3 are more preferable.

The nonionic surfactant (B) of the second aspect of the present invention is C ₁₁ H ₂₃ —CO— (OCH ₂ CH ₂ ) _m —OCH ₃ ; or C ₁₁ H ₂₃ —CO— (OCH ₂ CH ₂ ). mixture of _m -OCH ₃ and _{C 13 H 27 -CO- (OCH 2} CH 2) m -OCH 3 are more preferred.
Nonionic surfactant of the 3-5 embodiment of the present invention (B) _{is, C 11 H 23 -CO- (OCH} 2 CH 2) m -OCH 3; C 11 H 23 -CO- (OCH 2 CH 2 ) _m -OCH ₃ and _{C 13 H 27 -CO- (OCH 2} CH 2) a mixture of m -OCH _3; or a natural alcohol [12 carbon atoms alcohol (C12OH) and an alcohol having a carbon number of 14 (C14OH) A nonionic surfactant obtained by randomly adding 16 mol of ethylene oxide and 2 mol of propylene oxide to a mixture, C12OH / C14OH (mass ratio) = 7/3], is more preferable.
M is 15 on average.

  The component (E) is more preferably coconut fatty acid or palmitic acid.

The tertiary amine (F) is a fatty acid (C16 / C18) dimethylaminopropylamide, that is, a mixture of stearic acid dimethylaminopropylamide and palmitic acid dimethylaminopropylamide; or C ₁₇ H ₃₅ CONH (CH ₂ ) ₃ N (CH ₃ ) ₂ is more preferable.

  The cationic surfactant (H) is more preferably alkyl chloride (C16-C18) trimethylammonium, didecylmethylammonium chloride, or benzalkonium chloride.

The liquid detergent of the present invention described above has good liquid flowability and liquid stability, and has a high detergency against various stains. The liquid detergent of the present invention has good liquid flowability and liquid stability, has a high detergency against various stains, and is excellent in recontamination prevention performance. The liquid detergent of the present invention has good liquid flowability and liquid stability, has a high detergency against various stains, and is excellent in flexibility imparting effect. Further, the liquid detergent of the present invention has good liquid flowability and liquid stability, has a high detergency against various stains, and is excellent in deodorization performance and recontamination prevention performance. .
In particular, the liquid cleaning agent of the present invention removes dirt by applying it directly to the item to be washed, in addition to liquid flowability and liquid stability, and removing odor caused by sweat and sebum dirt residue after washing. It is excellent in the application cleaning power required. The reason why such an effect is obtained is presumed as follows.
In general, when the concentration of a surfactant as a cleaning component increases, the liquid cleaning agent increases the detergency, but the composition itself increases in viscosity, gels, and the like, resulting in poor liquid flowability. On the other hand, in a composition having a high surfactant concentration, conventionally, a water-miscible organic solvent is used in combination to reduce the viscosity. However, the combined use of water-miscible organic solvents can easily reduce the cleaning power. Depending on the type of dirt, the cleaning power required to remove dirt by applying a liquid cleaning agent directly on the object to be cleaned (particularly The coating cleaning power is not sufficient. In addition, since removal of sweat and sebum stains adhering to chemical fibers such as polyester and polyurethane is not sufficient, an odor due to the remaining sweat or sebum stains may occur after washing.

  In the liquid detergent of this invention, the group which consists of an anionic surfactant (A) represented by general formula (a-1), and the compound of general formula (b-1) and general formula (b-2). When combined with at least one nonionic surfactant (B) that is more selected, even if a water-miscible organic solvent (C) is used in combination, the detergency is not reduced. This is presumed to be due to the interaction between the ester bond portion present in the component (A) and the ester bond portion present in the component (B). Such interaction is considered to increase the cleaning power, thus increasing the cleaning power against various types of dirt, and is considered to be excellent in odor removal and coating cleaning power. Moreover, even if the sum total of (A) component and (B) component is as high as 40 mass or more with respect to the total mass of a liquid detergent, (A) component and (B) component are a specific mixture ratio. By using together, since the increase in a remarkable viscosity is suppressed, it is excellent in liquid fluidity | liquidity and liquid stability. Thereby, meterability or applicability is improved and the usability is excellent. In addition, (A) component, (B) component, and (C) component are used in combination at a specific blending ratio, and further exhibit good liquid fluidity and liquid stability and high cleaning effect. Is considered to be demonstrated.

In addition, in the liquid detergent of the third aspect of the present invention, a specific polymer (D) and a fatty acid or a salt thereof (E) are blended in the mixed system of the components (A) to (C). Therefore, the anti-recontamination performance is also excellent. The reason is presumed as follows.
The calcium ions contained in the tap water and the fatty acid anion derived from the component (E) are combined with each other to produce water-insoluble fatty acid calcium.
The component (A) (fatty acid alkyl ester sulfonate) has a very excellent soap dispersibility (scum dispersibility) compared to an anionic surfactant such as alkylbenzene sulfonate. In the present invention, the combination of the component (A) and the component (E) increases the dispersibility of the water-insoluble fatty acid calcium during the cleaning treatment. Thereby, foaming is suppressed at the time of washing, cleaning components are quickly drained at the time of rinsing, and good rinsing properties are exhibited. This good rinsing property increases the adsorption efficiency of the component (D) on clothes made of hydrophobic chemical fibers such as polyester even under washing conditions at a low bath ratio. For this reason, it is speculated that the liquid detergent of the present invention exhibits excellent anti-recontamination performance.

In addition, the liquid detergent according to the fourth aspect of the present invention has a softening effect by adding the tertiary amine (F) to the mixed system of the components (A) to (C). Excellent. The reason is presumed as follows.
The component (A) (fatty acid alkyl ester sulfonate) is more likely to form a complex with the component (F) in water at the time of washing than an anionic surfactant such as an alkylbenzene sulfonate. This composite has moderate hydrophobicity and exhibits higher adsorptivity than the component (F) alone, especially on the surface of clothing made of hydrophobic chemical fibers such as polyester or polyurethane.
For this reason, in the liquid cleaning agent of this invention, it is estimated that the outstanding softness | flexibility provision effect expresses.

  Moreover, in the liquid cleaning agent of the 4th aspect of this invention, the comfort of the to-be-washed | cleaned material becomes better by mix | blending a specific silicone compound (G). This is because a complex of (F) component and (G) component or a complex of (A) component, (F) component, and (G) component is formed in water during washing, and the complex is not covered. By adsorbing to the wash, the component (G) is efficiently adsorbed to the wash and high slipperiness is imparted to the wash. Thereby, during washing, rinsing or dehydration, the friction between the fibers is reduced, and the object to be washed is given flexibility without impairing the elasticity of the fibers, so that a good feeling of comfort is obtained. Guessed. Such an effect is remarkably exhibited especially for clothing made of wool fibers.

  The liquid cleaning agent of the present invention removes the odor of clothes (for example, those using hydrophobic chemical fibers such as polyester and polyurethane) that are worn during exercise, and feels finished (flexibility or comfort). Excellent grant.

In addition, the liquid cleaning agent according to the fifth aspect of the present invention has a deodorizing performance and re-treatment by mixing the cationic surfactant (H) in the mixed system of the components (A) to (C). Excellent anti-contamination performance. The reason is presumed as follows.
In the fifth aspect of the present invention, the components (A) to (C) and (H) are blended at a predetermined blending ratio, so that the anionic (A) component and the cationic (H) component. Both can be dissolved stably. For this reason, the compounding effect of each component shown below is exhibited.
The component (A) (fatty acid alkyl ester sulfonate) is more likely to form a complex with the component (H) in water at the time of washing than an anionic surfactant such as an alkylbenzene sulfonate. This composite has moderate hydrophobicity and exhibits higher adsorptivity than the component (H) alone, particularly on the clothing surface made of hydrophobic chemical fibers such as polyester and polyurethane.
The antibacterial property is enhanced by adsorption of the complex to the clothing surface. For this reason, it is estimated that the liquid cleaning agent of this invention is excellent in the deodorization of the odor (room-dried odor etc.) generated from the clothes after washing.
Furthermore, the component (A) has very excellent soap dispersibility (scum dispersibility) as compared with anionic surfactants such as alkylbenzene sulfonates. Thereby, foaming is suppressed at the time of washing, cleaning components are quickly drained at the time of rinsing, and good rinsing properties are exhibited. This good rinsing property is presumed to exhibit excellent anti-recontamination performance even under washing conditions at a low bath ratio.

  In the liquid cleaning agent of the fifth aspect of the present invention, even if the amount of the cationic surfactant (H) is small, the effect of deodorizing odors that are likely to occur due to room drying is exhibited.

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

The composition of the liquid cleaning agent in each example is shown in Tables 1-13.
The raw materials used in this example are as follows.

[Anionic surfactant (A)]
_{a-1: C 10 H 21} -CH (SO 3 Na) -COOCH 3 and _{C 12 H 25 -CH (SO 3} Na) in the mass ratio of the -COOCH ₃ mixture of 7/3.
_{a-2: C 12 H 25} -CH (SO 3 Na) -COOCH 3.
_a-3: C ₁₀ H and 21 -CH (SO 3 Na) -COOCH 3, and _{C 12 H 25 -CH (SO 3} Na) -COOCH 3, C 14 H 29 -CH (SO 3 Na) -COOCH 3 And C ₁₆ H ₃₃ —CH (SO ₃ Na) —COOCH ₃ in a mass ratio of 6/2/1/1.
a-4: A mixture of C ₁₂ H ₂₅ —CH (SO ₃ Na) —COOCH ₃ and C ₁₄ H ₂₉ —CH (SO ₃ Na) —COOCH ₃ in a mass ratio of 2/8.
_{a-5: C 14 H 29} -CH (SO 3 Na) -COOCH 3.
a-6: Mixture of C ₁₄ H ₂₉ —CH (SO ₃ Na) —COOCH ₃ and C ₁₆ H ₃₃ —CH (SO ₃ Na) —COOCH ₃ in a mass ratio of 8/2.

(A) Synthesis Method _{C 10 H 21 -CH (SO 3} Na) components -COOCH ₃ (alpha-Suruhoraurin acid methyl ester sodium salt) Synthesis of, stirrer, a dropping funnel and a drying calcium chloride tube attached In addition, 54 g of lauric acid methyl ester (product name: Pastel M-12, manufactured by Lion Corporation) and 540 g of carbon tetrachloride were charged into a 1 L four-necked flask, and the reaction temperature was maintained at 10 to 15 ° C. 24 g of sulfuric anhydride (manufactured by Nisso Metal Chemical Co., Ltd., trade name Nisso Sulfan) was added dropwise.
After completion of the dropwise addition, the mixture was stirred at reflux for 3 hours.
Next, after distilling off the reaction solvent (carbon tetrachloride) at a water bath of 50 ° C. using an evaporator, 500 mL of methanol (manufactured by Kanto Chemical Co., Inc.) was added and stirred at reflux for 20 minutes. Then, the reaction liquid was adjusted to pH 7 using 20 mass% sodium hydroxide aqueous solution. Subsequently, the reaction solvent (methanol) was distilled off under reduced pressure. At that time, since it foamed, isopropanol was added, and water was also distilled off azeotropically.
Next, the residue (crude product) was heated to 50 to 60 ° C. and dissolved in a mixed solution of ethanol and water (volume ratio: ethanol / water = 9/1) to remove insoluble matters. Next, the filtrate was cooled to 5 ° C. and recrystallized, and then the precipitate was collected by filtration and vacuum dried to obtain α-sulfolauric acid methyl ester sodium salt (C12MES).

_{C 12 H 25 -CH (SO 3} Na) -COOCH 3 in place of the synthetic lauric acid methyl ester (alpha-sulfo myristate methyl ester sodium salt), myristic acid methyl ester (Lion Corp., trade name Pastel M- 14) An α-sulfomyristic acid methyl ester sodium salt (C14MES) was obtained by the same synthesis method as that for the α-sulfolauric acid methyl ester sodium salt except that 60 g was used.

C ₁₄ H ₂₉ instead of the synthetic methyl laurate of _{-CH (SO 3 Na) -COOCH 3} (α- Suruhoparumichin acid methyl ester sodium salt), methyl palmitate ester (manufactured by Lion Corporation, trade name Pastel M- 16) α-sulfopalmitic acid methyl ester sodium salt (C16MES) was obtained by the same synthesis method as in the above α-sulfolauric acid methyl ester sodium salt except that 68 g was used.

Synthesis of C ₁₆ H ₃₃ —CH (SO ₃ Na) —COOCH ₃ (α-sulfostearic acid methyl ester sodium salt) Instead of lauric acid methyl ester, stearic acid methyl ester (product name: Pastel M-, manufactured by Lion Corporation) 18) α-Sulfostearic acid methyl ester sodium salt (C18MES) was obtained by the same synthesis method as that of α-sulfolauric acid methyl ester sodium salt except that 75 g was used.

  C12 to C18 MES obtained by the synthesis method described above were mixed at a predetermined mass ratio or used alone to obtain a-1 to a-6.

・ Comparative component (A ′) of component (A)
a′-1: linear alkylbenzenesulfonic acid (LAS) having a linear alkyl group having 10 to 14 carbon atoms, trade name “Lypon LH-200”, manufactured by Lion Corporation, average molecular weight 322.

[Nonionic surfactant (B)]
· (B1) component _b-1-1: weight ratio of _{C 11 H 23 -CO- (OCH 2} CH 2) m -OCH 3 and _{C 13 H 27 -CO- (OCH 2} CH 2) m -OCH 3 8/2 mixtures, both m = 15 (average value), all with a narrow ratio of 33% by mass; each synthetic product.
_{b-1-2: C 11 H 23} -CO- (OCH 2 CH 2) m -OCH 3, m = 15 ( average value), narrow ratio 33 wt%; synthetic.
_b-1-3: the _{C 11 H 23 -CO- (OCH 2} CH 2) m -OCH 3 and _{C 13 H 27 -CO- (OCH 2} CH 2) in a weight ratio of m -OCH ₃ 8/2 Mixtures, all m = 15 (average value), all narrow ratio 45% by mass; each synthetic product.
b-1-4: The mass ratio of C ₁₁ H ₂₃ —CO— (OCH ₂ CH ₂ ) _m —OCH ₃ and C ₁₃ H ₂₇ —CO— (OCH ₂ CH ₂ ) _m —OCH ₃ is 8/2. Mixtures, all m = 15 (average value), all narrow ratio 60 mass%; each synthetic product.

-(B2) component b-2-1: natural alcohol [mixture of 12-carbon alcohol (C12OH) and 14-carbon alcohol (C14OH), C12OH / C14OH (mass ratio) = 7/3], 16 A nonionic surfactant obtained by random addition of 2 mol of ethylene oxide and 2 mol of propylene oxide. The number after the C represents the number of carbon atoms.

(B) Component Synthesis Method b-1-1 Synthesis A synthetic product produced according to Production Example 1 in the examples described in JP-A No. 2000-144179 was used.
That is, alumina hydroxide / magnesium having a chemical composition of 2.5 MgO.Al ₂ O ₃ .nH ₂ O (manufactured by Kyowa Chemical Industry Co., Ltd., trade name: 300) under a nitrogen atmosphere at 600 ° C. for 1 hour. Calcined alumina hydroxide / magnesium (unmodified) catalyst (2.2 g) obtained by firing with 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 Were charged into a 4 liter autoclave and the catalyst was reformed in the autoclave. Next, after the inside of the autoclave was replaced with nitrogen, the temperature was raised, and while maintaining the temperature at 180 ° C. and the pressure at 3 atm, 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 b-1-1.
By controlling the amount of alkali added to the catalyst, b-1-1 having a narrow rate of 33% by mass was obtained.

Synthesis of b-1-2 In the same manner as in the synthesis method of b-1-1 above, except that lauric acid methyl ester 350 g was used instead of lauric acid methyl ester 280 g and myristic acid methyl ester 70 g, b-1- 2 was obtained.
By controlling the amount of alkali added to the catalyst, b-1-2 having a narrow rate of 33% by mass was obtained.

Synthesis of b-1-3 The synthesis was carried out in the same manner as the synthesis method of b-1-1 (the amount of lauric acid methyl ester and myristic acid methyl ester charged was the same), and the amount of alkali added to the catalyst was controlled. B-1-3 having a narrow rate of 45% by mass was obtained.

Synthesis of b-1-4 The synthesis was carried out in the same manner as the synthesis method of b-1-1 (the amounts of lauric acid methyl ester and myristic acid methyl ester were the same), and the amount of alkali added to the catalyst was controlled. B-1-4 having a narrow rate of 65% by mass was obtained.

Synthesis of b-2-1 224.4 g of “CO-1270” manufactured by P & G and 2.0 g of 30 mass% NaOH aqueous solution were collected in a pressure-resistant reaction vessel, and the inside of the vessel was purged with nitrogen. Next, after dehydrating for 30 minutes at a temperature of 100 ° C. and a pressure of 2.0 kPa or less, the temperature was raised to 160 ° C. While stirring the alcohol, 704 g of ethylene oxide (gaseous) and 116 g of propylene oxide were gradually added to the alcohol liquid while controlling the addition rate so that the reaction temperature did not exceed 180 ° C. using a blowing tube. I let you. After completion of the addition of ethylene oxide and propylene oxide, aging was performed at a temperature of 180 ° C. and a pressure of 0.3 MPa or less for 30 minutes. Thereafter, unreacted ethylene oxide and propylene oxide were 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 the reaction product so that the pH of the 1% by mass aqueous solution was about 7, whereby b-2- 1 was obtained.

・ Nonionic surfactant other than component (B) (B ′)
b′-1-1: C ₁₇ H ₃₃ —CO— (OCH ₂ CH ₂ ) _m —OCH ₃ , m = 9 (average value), narrow ratio 65% by mass; synthetic product.
b′-3-1: polyoxyethylene alkyl ether obtained by adding ethylene oxide to a secondary alcohol having 12 to 14 carbon atoms with an average addition mole number of 9 moles, trade name “Softanol 90” manufactured by Nippon Shokubai Co., Ltd.
b′-3-2: Polyoxyethylene alkyl ether obtained by adding ethylene oxide corresponding to an average addition mole number of 15 moles to natural alcohol CO-1270 manufactured by P & G.

(B ′) Component Synthesis Method b′-1-1 Synthesis Except for using oleic acid methyl ester 350 g instead of lauric acid methyl ester 280 g and myristic acid methyl ester 70 g, and changing the amount of ethylene oxide introduced to 781 g. B′-1-1 was obtained in the same manner as in the synthesis method of b-1-1.
By controlling the amount of alkali added to the catalyst, b'-1-1 having a narrow rate of 65% by mass was obtained.

Synthesis of b′-3-2 224.4 g of natural alcohol CO-1270 manufactured by P & G and 2.0 g of 30% by mass NaOH aqueous solution were collected in a pressure-resistant reaction vessel, and the inside of the vessel was purged with nitrogen. Next, after dehydrating for 30 minutes at a temperature of 100 ° C. and a pressure of 2.0 kPa or less, the temperature was raised to 160 ° C. While stirring the alcohol, 760.4 g of ethylene oxide (gaseous) was gradually added to the alcohol liquid using a blowing tube while controlling 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. Thereafter, 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 weight p-toluenesulfonic acid is added and neutralized so that the pH of the 1% by weight aqueous solution of the reaction is about 7, thereby b′-3. -2 was obtained.

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

[Organic solvent (C)]
c-1: Diethylene glycol monobutyl ether, manufactured by Nippon Emulsifier Co., Ltd., trade name “butyl diglycol”.
c-2: Propylene glycol, manufactured by BASF.
c-3: Ethanol, manufactured by Nippon Alcohol Sales Co., Ltd. Trade name “specific alcohol 95 degree synthesis”.

[Polymer (D)]
d-1: Product name “TexCare SRN-170” manufactured by Clariant. Weight average molecular weight 2000 to 3000, pH 4 (measured at 20 ° C., 5 mass% aqueous solution), viscosity 300 mPa · s (measured at 50 ° C.). TexCare SRN-170 is trade name TexCare SRN-100 [manufactured by Clariant, weight average molecular weight 2000 to 3000, pH 4 (measured at 20 ° C., 5 mass% aqueous solution), viscosity 340 mPa · s (measured at 50 ° C.), the above formula It is a 70 mass% aqueous solution of the aggregate | assembly containing the polymer represented by (d-1).
d-2: Product name “TexCare SRN-300” manufactured by Clariant. A weight average molecular weight of 7000, a pH of 5 (measured at 20 ° C., 5 mass% aqueous solution), a viscosity of 650 mPa · s (measured at 50 ° C.), and an aggregate containing the polymer represented by the formula (d-1).
d-1 and d-2 were both added to 1000 g of water under the conditions of the above-mentioned “water-soluble polymer” (in a 1 liter beaker, at 40 ° C., and stirred with a stirrer (thickness 8 mm, long 50 mm), which completely dissolves when stirred (200 rpm) for 12 hours.

[Fatty acid or salt thereof (E)]
e-1: Palm fatty acid, trade name “coconut fatty acid” manufactured by NOF Corporation.
e-2: Palmitic acid, trade name “NAA-160”, manufactured by NOF Corporation.

[Tertiary amine (F)]
f-1: Fatty acid (C16 / C18) dimethylaminopropylamide, manufactured by Toho Chemical Co., Ltd., trade name “Catinal MPAS-R”; mass ratio of stearic acid dimethylaminopropylamide to palmitic acid dimethylaminopropylamide 7 / A mixture of 3.
_{f-2: C 17 H 35} CONH (CH 2) 3 N (CH 3) 2, dimethylaminopropyl amide stearic acid; synthetic.

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

・ Comparison component (F ') of component (F)
f′-1: Laurylamine, manufactured by Lion Akzo Co., Ltd., trade name “Armin 12D”.

[Silicone compound (G)]
g-1: Amino-modified silicone, manufactured by Toray Dow Corning Co., Ltd., trade name “SZ8417”.
g-2: Polyether-modified silicone, manufactured by Toray Dow Corning Co., Ltd., trade name “SH3775M”.
g-3: polyether-modified silicone, a silicone compound represented by the above general formula (e-3) (a = 210, b = 9, R ¹⁸ = C ₃ H ₆ , Y = (OC ₂ H ₄ ) ₁₀ , R ¹⁹ = CH ₃ ); synthetic product.

Synthesis of g-3 An organohydrogenpolysiloxane (α) represented by the following general formula (g-3-01) was added to a 1 L four-necked flask equipped with a stirrer, a condenser, a thermometer, and a nitrogen insertion port. = 210, β = 9) 100 g, isopropyl alcohol 50 g, polyoxyalkylene compound (γ = 10, Z = CH ₃ ) 29 g represented by the following general formula (g-3-02), and platinum for addition reaction 0.2 g of a system catalyst and 0.3 g of an isopropyl alcohol solution of 2% by mass sodium acetate were added, and these were reacted at 90 ° C. for 3 hours in a nitrogen atmosphere. After completion of the reaction, the solvent was distilled off under reduced pressure to obtain g-3.

[Cationic surfactant (H)]
h-1: Alkyl chloride (C16-C18) trimethylammonium, manufactured by Lion Akzo Co., Ltd., trade name “ARCARD T-800”.
h-2: Didecylmethylammonium chloride, manufactured by Lion Akzo Co., Ltd., trade name “Arcade 210”.
h-3: Benzalkonium chloride, manufactured by Lion Akzo Co., Ltd., trade name “ARCARD CB-50”.

[Other ingredients]
Sodium benzoate: manufactured by Toagosei Co., Ltd., trade name “Sodium benzoate”.
Citric acid: trade name “Liquid Citric Acid” manufactured by Otsuka Kogyo Co., Ltd.
Trisodium citrate: trade name “soda citrate” manufactured by Miles (USA).
Paratoluenesulfonic acid: Kyowa Hakko Kogyo Co., Ltd., trade name “PTS acid”.
Coconut fatty acid: NOF Corporation, trade name “Zushi fatty acid”.
Polyethylene glycol: Product name PEG # 1000, manufactured by Lion Corporation.
Dibutylhydroxytoluene: Sumitomo Chemical Co., Ltd., trade name “SUMILZER BHT-R”.
Monoethanolamine: manufactured by Nippon Shokubai Co., Ltd.
Fragrance: Fragrance a described in JP2009-108248A.
Dye: Product name “Green No. 3”, manufactured by Sakai Kasei Co., Ltd.
pH adjuster: sodium hydroxide (manufactured by Tsurumi Soda Co., Ltd.), sulfuric acid (manufactured by Toho Zinc Co., Ltd.) or monoethanolamine (manufactured by Nippon Shokubai Co., Ltd.)
purified water.

<Preparation of liquid detergent>
According to the compounding components of the compositions shown in Tables 1 to 13 and the compounding amount (% by mass), liquid detergents of respective examples were prepared by the following production methods. The blending amount shown in the table indicates the blending amount (pure equivalent amount) of the blending component. In the table, a blank means that the blending component is not blended.
In the table, “(A) + (B) [mass%]” indicates the total content of the component (A) and the component (B) in the liquid detergent.
“(A) / (B)” means the mass ratio of the content of the component (A) to the content of the component (B) in the liquid detergent.
“[(A) + (B)] / (C)” is the mass ratio of the total content of the component (A) and the component (B) to the content of the component (C) in the liquid detergent. means.
In Tables 4 to 13, the content of the component (B) means the total content of the component (B1) and the component (B2).
“(D) / (E)” means the mass ratio of the content of the component (D) to the content of the component (E) in the liquid detergent.
“(A) / (F)” means the mass ratio of the content of the component (A) to the content of the component (F) in the liquid detergent.
“(F) / (G)” means the mass ratio of the content of the component (F) to the content of the component (G) in the liquid detergent.
“(A) / (H)” means the mass ratio of the content of the component (A) to the content of the component (H) in the liquid detergent.

The composition of the common component (X) or common component (Y) contained in the liquid cleaning agent of each example is shown below.
The “appropriate amount” indicating the blending amount of the pH adjuster refers to an amount blended for adjusting the pH (25 ° C.) of the liquid detergent to 7.0.
“Balance” indicating the blending amount of purified water means the balance added so that the total blending amount (% by mass) of all the blending components contained in the liquid detergent is 100% by mass.
Common component (X) in Examples 1 to 16, Comparative Examples 1 to 4, and Reference Examples 1 to 2: sodium benzoate 1.5% by mass, citric acid 0.1% by mass, p-toluenesulfonic acid 3.0% by mass %, Polyethylene glycol 1.0% by mass, dibutylhydroxytoluene 0.05% by mass, monoethanolamine 1.0% by mass, perfume 0.4% by mass, dye 0.0003% by mass, pH adjusting agent appropriate amount, and purified water balance.

  Common component (X) in Examples 17 to 39, Comparative Examples 5 to 9, and Reference Examples 3 to 5: sodium benzoate 0.5 mass%, citric acid 0.1 mass%, paratoluenesulfonic acid 2.0 mass %, Dibutylhydroxytoluene 0.05% by mass, monoethanolamine 1.0% by mass, perfume 0.4% by mass, pigment 0.0003% by mass, pH adjuster appropriate amount, and purified water balance.

Common component (X) in Examples 40 to 67, Comparative Examples 10 to 15 and Reference Examples 6 to 9: sodium benzoate 0.5 mass%, citric acid 0.1 mass%, paratoluenesulfonic acid 2.0 mass %, Palm fatty acid 0.5% by mass, dibutylhydroxytoluene 0.05% by mass, monoethanolamine 1.0% by mass, pigment 0.0001% by mass, pH adjusting agent appropriate amount, and purified water balance.
Common component (Y) in Examples 40 to 67, Comparative Examples 10 to 15 and Reference Examples 6 to 9: sodium benzoate 0.5 mass%, citric acid 0.1 mass%, paratoluenesulfonic acid 1.0 mass %, Palm fatty acid 1.0% by mass, polyethylene glycol 4.0% by mass, pigment 0.0001% by mass, fragrance 1.8% by mass, and purified water balance.

  Common component (X) in Examples 68 to 92, Comparative Examples 16 to 20, and Reference Examples 10 to 13: citric acid 0.1% by mass, dibutylhydroxytoluene 0.05% by mass, perfume 0.4% by mass, dye 0.0002 mass%, pH adjusting agent appropriate amount, and purified water balance.

(Examples 1-16, Comparative Examples 1-4, and Reference Examples 1-2)
According to the compounding components of the compositions shown in Tables 1 to 3 and the compounding amount (mass%), liquid detergents of each example were prepared by the following procedure.
(A) component or (A ') component, (B) component or (B') component, and (C) component were put into a 500 mL beaker, and it fully stirred with the magnetic stirrer (MITAMURA KOGYO INC.). Subsequently, while adding and stirring the common component (X) excluding the pH adjuster and purified water, purified water was added so that the total amount became 98 parts by mass, and the mixture was further stirred. After adding an appropriate amount of pH adjuster (sodium hydroxide or sulfuric acid) so that the pH at 25 ° C. becomes 7.0, purified water is added so that the total amount becomes 100 parts by mass to obtain a liquid detergent. It was.

(Examples 17 to 39, Comparative Examples 5 to 9, and Reference Examples 3 to 5)
According to the compounding components of the compositions shown in Tables 4 to 6 and the compounding amount (% by mass), the liquid detergents of each example were prepared by the following procedure.
In a 500 mL beaker, put (A) component or (A ′) component, (B1) component, (B2) component or (B ′) component, (E) component, and (C) component, and add a magnetic stirrer ( The mixture was sufficiently stirred with MITAMURA KOGYO INC.). Subsequently, while adding the component (D) and the common component (X) excluding the pH adjuster and purified water and stirring, purified water was added so that the total amount became 98 parts by mass, and further stirred. After adding an appropriate amount of pH adjuster (sodium hydroxide or sulfuric acid) so that the pH at 25 ° C. becomes 7.0, purified water is added so that the total amount becomes 100 parts by mass to obtain a liquid detergent. It was.

(Examples 40-67, Comparative Examples 10-15, and Reference Examples 6-9)
According to the compounding components of the compositions shown in Tables 7 to 10 and the compounding amount (mass%), liquid detergents of each example were prepared by the following procedure.
In a 500 mL beaker, put (A) component or (A ′) component; (B1) component, (B2) component or (B ′) component; in Examples 55-59 and Reference Example 15, add (G) component The mixture was sufficiently stirred with a magnetic stirrer (MITAMURA KOGYO INC.). Subsequently, while adding the component (C), the component (F), and the common component (X) excluding the pH adjuster and purified water and stirring, the purified water is added so that the total amount becomes 98 parts by mass. Stir well. After adding an appropriate amount of pH adjuster (sodium hydroxide or sulfuric acid) so that the pH at 25 ° C. becomes 7.0, purified water is added so that the total amount becomes 100 parts by mass to obtain a liquid detergent. It was.

(Examples 68-92, Comparative Examples 16-20, and Reference Examples 10-13)
According to the blending components of the compositions shown in Tables 11 to 13 and the blending amount (mass%), the liquid detergents of each example were prepared by the following procedure.
In a 500 mL beaker, put (A) component or (A ′) component; (B1) component, (B2) component or (B ′) component; and (C) component, and use a magnetic stirrer (MITAMURA KOGYO INC.). Stir well. Subsequently, while adding the component (H) and the common component (X) excluding the pH adjuster and purified water and stirring, purified water was added so that the total amount became 98 parts by mass, and further stirred. After adding an appropriate amount of pH adjuster (monoethanolamine or sulfuric acid) so that the pH at 25 ° C. becomes 7.0, purified water is added so that the total amount becomes 100 parts by mass to obtain a liquid detergent. It was.

  The pH of the liquid cleaning agent (25 ° C.) was adjusted by adding the pH meter electrode to a solution adjusted to 25 ° C. using a pH meter (product name: HM-30G, manufactured by Toa DKK Corporation) for 2 minutes. It was measured by reading the later value.

<Evaluation of liquid detergent>
About the liquid detergent of Examples 1-16, Comparative Examples 1-4, and Reference Examples 1-2, "liquid fluidity | liquidity", "liquid stability", "detergency", and "usability" by the evaluation method shown below. Was evaluated. The results are also shown in Tables 1-3.

  For the liquid detergents of Examples 17 to 39, Comparative Examples 5 to 9, and Reference Examples 3 to 5, “liquid fluidity”, “liquid stability”, “detergency”, “recontamination” were performed according to the evaluation methods shown below. The prevention performance and the usability were evaluated. The results are also shown in Tables 4-6.

  For the liquid detergents of Examples 40 to 67, Comparative Examples 10 to 15, and Reference Examples 6 to 9, “liquid fluidity”, “liquid stability”, “detergency”, “flexibility” were evaluated by the following evaluation methods. “Effects”, “feeling comfort” and “usability” were evaluated. The results are shown in Tables 7-10.

  About the liquid cleaning agent of Examples 68-92, Comparative Examples 16-20, and Reference Examples 10-13, "liquid fluidity | liquidity", "liquid stability", "detergency", "deodorant" by the evaluation method shown below. "Performance", "Recontamination prevention performance" and "Usability" were evaluated. The results are shown in Tables 11-13.

[Evaluation of fluidity]
The beaker (capacity 500 mL) containing the liquid cleaning agent 500g prepared by the said procedure was left still in a 25 degreeC thermostat. After 3 hours, the beaker was taken out of the thermostatic chamber, and the beaker was tilted to remove about 100 mL of the contents (liquid cleaning agent) into a transparent glass bottle (wide-mouth standard bottle PS-NO.11). .
At this time, the time required to take about 100 mL of the contents from the beaker into the glass bottle was measured. The operation of taking out each sample was performed twice, the time required was measured, and the average value was used to evaluate the liquid flowability of each liquid detergent according to the following evaluation criteria.
Evaluation criteria B: The required time was less than 10 seconds.
D: The time required was 10 seconds or more.
The liquid cleaning agent determined as “D” in the liquid fluidity evaluation was not evaluated as described below.

[Evaluation of liquid stability]
As the liquid stability evaluation, the initial appearance and the temporal stability were evaluated by the following methods.
-Initial appearance In the above liquid fluidity evaluation, the external appearance of the liquid detergent taken out into the glass bottle was visually observed, and the initial appearance of each liquid detergent was evaluated according to the following evaluation criteria.
Evaluation criteria B: Transparent and uniform.
D: Turbidity or presence of floating / precipitate was observed.
The liquid cleaning agent determined as “D” in the liquid stability evaluation was not evaluated as described below.

・ Stability over time 100 mL of liquid cleaning agent was taken in a transparent glass bottle (wide-mouth bottle, PS-NO.11), sealed with the lid closed, and stored in a constant temperature bath at 5 ° C. for 1 month in this state. .
Thereafter, the glass bottle containing the liquid detergent was taken out of the thermostatic bath, and within 1 minute, the appearance of the contents was visually observed at room temperature (25 ° C.), and the temporal stability was evaluated according to the following evaluation criteria. .
Evaluation criteria B: The appearance was transparent and uniform.
D: Although turbidity, precipitation, or gelation was observed, the appearance became transparent and uniform when immersed in a hot water bath at 40 ° C. for 1 hour.
E: Turbidity, precipitation or gelation was observed, and even when immersed in a 40 ° C. hot water bath for 1 hour, the appearance did not become transparent and uniform.

[Evaluation of cleaning power]
As an evaluation of the cleaning power of the liquid cleaning agent, the odor removing property of the liquid cleaning agent and the coating cleaning power required for removing dirt by applying to the object to be cleaned were confirmed by the following methods.

-Odor removal The odor removal of Examples 1-16, Comparative Examples 1-4, and Reference Examples 1-2 was confirmed by the following method.
0.83% by mass of Terg-O-Tometer (manufactured by UNITED STATES TESTING), wet artificial dirt cloth (5 cm × 5 cm), clean knitted cloth, and liquid detergent in tap water (15 ° C.) 900 mL of an aqueous solution was added and washed for 10 minutes (bath ratio 20, 120 rpm). After this washing, it was rinsed with 900 mL of tap water (15 ° C.) for 3 minutes.
A wet artificial soil cloth made by the Laundry Science Association was used.
After rinsing, the wet artificial soil cloth was taken out and allowed to dry naturally, and sensory evaluation of odor was performed by 10 subjects. The sensory evaluation of odor was performed according to the following evaluation criteria (1), the average score was calculated, and the odor removal property was evaluated according to the following evaluation criteria (2).
Evaluation criteria (1)
5 points: odorless, 4 points: finally a strong smell that can be sensed, 3 points: a smell that is strong enough to sense what kind of odor, 2 points: a smell that is easy to sense, 1 point: a strong smell, 0 points: Strong smell Evaluation criteria (2)
A: 4 points or more, B: 3 points or more, less than 4 points, C: 2 points or more, less than 3 points, D: less than 2 points

The odor removing properties of Examples 17 to 39, Examples 68 to 92, Comparative Examples 5 to 9, Comparative Examples 16 to 20, Reference Examples 3 to 5, and Reference Examples 10 to 13 were confirmed by the following method.
Fully automatic electric washing machine (manufactured by Haier, JW-Z23A) was charged with 2 pieces of wet artificially contaminated cloth (10cm × 10cm) and commercially available cotton towel (100% cotton). The total was adjusted to about 800 g together with the cloth).
A wet artificial soil cloth made by the Laundry Science Association was used.
Thereto, 5 mL of a liquid detergent was added, and a washing operation was performed in which washing, rinsing, and dehydration were sequentially performed using a standard course. With regard to washing time, rinsing, dehydration, and water volume (set to low water level, water volume of about 12 L), no adjustment was made and the standard course setting of the washing machine was used.
After completion of the cleaning operation, the wet artificial soiled cloth subjected to the cleaning operation was left to dry in a constant temperature and humidity chamber at 25 ° C. and a relative humidity of 65% RH.
After leaving for 1 day, the odor remaining on the contaminated cloth was compared with a control cloth (wet artificial contaminated cloth not subjected to washing operation) by sensory evaluation, and scored according to the following evaluation criteria (3).
Evaluation criteria (3)
1 point: It smells almost the same as that of the control cloth (the odor is hardly dropped).
2 points: Slightly weak odor (slight odor slightly decreased) compared to the control fabric.
3 points: Smell is slightly weaker than the control cloth (smell is slightly reduced).
4 points: The odor is considerably reduced compared to the control cloth.
5 points: There is almost no odor remaining compared to the control cloth.
And the average score of 5 panelists' scoring was computed, and the odor removal property was evaluated by the following evaluation criteria (4).
Evaluation criteria (4)
A: 4 points or more, B: 3.5 points or more, less than 4 points, C: 3 points or more, less than 3.5 points, D: less than 3 points

The odor removal property of Examples 40-67, Comparative Examples 10-15, and Reference Examples 6-9 was confirmed by the following method.
a) Preparation of test cloth In a polyester jersey cloth (100% polyester) cut to 5 cm × 5 cm, oleic acid (Kanto Chemical Grade 1 reagent) becomes 1 mass% (1% owf) relative to the mass of the polyester jersey cloth. As described above, a test cloth was prepared by applying a mixed solution of oleic acid / ethanol, drying overnight and evaporating ethanol.

b) Cleaning of the test cloth In a fully automatic electric washing machine (manufactured by Haier, JW-Z23A), the above-mentioned five test cloths and the same polyester jersey cloth (100% polyester) used for the test cloth are 20 cm × 20 cm. 2 pieces of the cloth for flexibility evaluation cut into 2 and a commercially available cotton towel (100% cotton) were added (the amount of the cotton towel was adjusted so that the total weight of the cloth was about 800 g).
Thereto, 5 mL of a liquid detergent was added, and a washing operation was performed in which washing, rinsing, and dehydration were sequentially performed with a soft course. With regard to washing time, rinsing, dehydration, and water volume (low water level set, water volume about 12 L), no adjustment was made and the soft course setting of the washing machine was used.
After the washing, the test cloth subjected to the above washing treatment was left in a constant temperature and humidity room at 25 ° C. and a relative humidity of 65% RH for one day and dried.

c) Washing of control cloth Odor removal property obtained by cutting a polyester jersey cloth (100% polyester) same as that used in the above test cloth into a fully automatic electric washing machine (manufactured by Haier, JW-Z23A) to 5 cm × 5 cm. Two control cloths for evaluation, two control cloths for flexibility evaluation cut into 20 cm × 20 cm, and a commercially available cotton towel (100% cotton) were put in (the amount of cotton towels to be charged is the total amount of cloth) The mass was adjusted to about 800 g).
Thereto was added 10 mL of a liquid cleaning agent for cleaning the control cloth, and a cleaning operation was performed in which washing, rinsing, and dehydration were sequentially performed with a soft course. With regard to washing time, rinsing, dehydration, and water volume (low water level set, water volume about 12 L), no adjustment was made and the soft course setting of the washing machine was used.
After the washing was completed, the control cloth subjected to the washing treatment was left in a constant temperature and humidity room at 25 ° C. and a relative humidity of 65% RH and dried.
As a liquid cleaning agent for cleaning the control cloth, a 20% by mass aqueous solution of alcohol ethoxylate (trade name: EMALEX 715, Japan Emulsion) was used.

d) Evaluation of odor removability The test cloth washed in b) above was allowed to stand for 1 day, and the odor remaining on the test cloth was compared with the control cloth and scored according to the following evaluation criteria (5).
Evaluation criteria (5)
1 point: It smells intensely compared to the control cloth (dirt (oleic acid) is hardly removed).
2 points: It smells considerably compared to the control cloth (stain (oleic acid) is slightly removed).
3 points: Slightly weak smell compared to the control cloth (dirt (oleic acid) is slightly removed).
4 points: The smell is considerably lower than that of the control cloth.
5 points: Almost no odor remains compared to the control cloth.
And the average score of five panelists' scoring was computed, and the odor removal property was evaluated by the following evaluation criteria (6).
Evaluation criteria (6)
A: 4 points or more, B: 3.5 points or more, less than 4 points, C: 3 points or more, less than 3.5 points, D: less than 3 points.

・ Coating cleaning power for removing dirt by applying to the object to be washed Put stainless steel bat with mamma meat sauce (trade name, manufactured by Nisshin Foods) with gauze, and 100th cotton A plain weave cloth (raw cloth) was immersed for about 1 hour. Thereafter, the meat sauce stains which were excessively adhered by brushing were removed and air-dried overnight, and the six cloths cut into 10 cm × 10 cm were used as meat sauce stain cloths (contaminated cloth).
Next, 0.1 g of the liquid detergent after being stored at 15 ° C. for 24 hours was applied to each of the six contaminated cloths (0.1 g of liquid detergent / one contaminated cloth), left for 5 minutes, and then Terg-O-Tometer. The contaminated cloth, a clean knitted cloth, and 900 mL of tap water (25 ° C., hardness 3 ° DH) were put into (UNITED STATES TESTING) and stirred for 10 minutes (bath ratio 20, 120 rpm). Then, it moved to the 2 tank type washing machine (the Mitsubishi Electric company make, CW-C30A1 type), and spin-dry | dehydrated for 1 minute. Next, it was rinsed with running water for 1 minute, dehydrated for 1 minute, and then air-dried.
Then, using a colorimetric colorimeter (Nippon Denshoku Co., Ltd., product name SE2000), the raw cloth before adhering meat sauce dirt and the Z value (reflectance) of the meat sauce dirt cloth (contaminated cloth) before and after cleaning are used. Each was measured, and the washing rate (%) was calculated by the following formula.
Washing rate (%) = (Z value of contaminated cloth after washing−Z value of contaminated cloth before washing) / (Z value of raw cloth−Z value of contaminated cloth before washing) × 100
For the evaluation of the coating cleaning power against the meat sauce stain, it was determined that the coating cleaning power was good if it was C, B or A in the following evaluation criteria using the cleaning rate (%) calculated by the above formula.
For the cleaning rate (%), the average point of 6 contaminated cloths was used.
Evaluation criteria A: The cleaning rate is 20% or more.
B: The cleaning rate is 15% or more and less than 20%.
C: The cleaning rate is 10% or more and less than 15%.
D: The cleaning rate is less than 10%.

[Evaluation of recontamination prevention performance]
The recontamination prevention performance of Examples 17 to 39, Comparative Examples 5 to 9, and Reference Examples 3 to 5 was confirmed by the following method.
900 mL of tap water (25 ° C., hardness 3 ° DH) and 0.3 mL of a liquid detergent were placed in a Terg-O-Tometer (UNITED STATES TESTING CO. INC. Model 243S) and stirred at 60 rpm for 3 minutes.
Next, 5 sheets of red soil cloth (3 cm x 4 cm), 8 sheets of oil dirt cloth (5 cm x 5 cm), 2 sheets of white polyester jersey test cloth (5 cm x 5 cm), and cotton cloth for adjusting the bath ratio to 20. A piece (a total of 45 g of a red soil dirt cloth, an oil dirt cloth, a test cloth, and a cotton cloth piece) was added and washed for 10 minutes (120 rpm, 15 ° C.).
After the washing, the washing solution was removed and the test cloth was taken out. The test cloth was dehydrated for 1 minute in a dehydration tank of a two-tank washing machine (manufactured by Mitsubishi Electric, CW-C30A1). Further, the test cloth was rinsed in a Terg-O-Tometer bath containing 900 mL of tap water for 3 minutes and dehydrated in a dewatering tank of a two-tank washing machine for 1 minute. Thereafter, this operation was repeated twice (a total of three rinses).
Next, the reflectances of two test cloths subjected to the above operation and the untreated one (white cloth) of the white polyester jersey test cloth were measured.
Then, the difference (average value) in reflectance between the two test cloths subjected to the above operation and the white cloth was calculated as the “recontamination degree (ΔZ)”.
The reflectance was measured using a color difference meter SE2000 (NIPPON DENSHOKU), and the ΔZ value was less than 9 (C, B, or A) as the acceptable range.
Evaluation criteria A: ΔZ value is less than 3.
B: The ΔZ value is 3 or more and less than 6.
C: The ΔZ value is 6 or more and less than 9.
D: The ΔZ value is 9 or more.

The recontamination prevention performance of Examples 68 to 92, Comparative Examples 16 to 20, and Reference Examples 10 to 13 was confirmed by the following method.
900 mL of tap water (25 ° C., hardness 3 ° DH) and 0.3 mL of a liquid detergent were placed in a Terg-O-Tometer (UNITED STATES TESTING CO. INC. Model 243S) and stirred at 60 rpm for 3 minutes.
Next, 2 pieces of red soil cloth (3 cm x 4 cm), 2 pieces of oil dirt cloth (5 cm x 5 cm), 2 pieces of white polyester tropical test cloth (5 cm x 5 cm), and cotton cloth for adjusting the bath ratio to 30 A piece (a total of 30 g of the red soil dirt cloth, the oil dirt cloth, the test cloth, and the cotton cloth piece) was added and washed for 10 minutes (120 rpm, 25 ° C.).
After the washing, the washing solution was removed and the test cloth was taken out. The test cloth was dehydrated for 1 minute in a dehydration tank of a two-tank washing machine (manufactured by Mitsubishi Electric, CW-C30A1). Further, the test cloth was rinsed in a Terg-O-Tometer bath containing 900 mL of tap water for 3 minutes and dehydrated in a dewatering tank of a two-tank washing machine for 1 minute. Thereafter, this operation was repeated twice (a total of three rinses).
Next, the reflectances of the two test cloths subjected to the above operation and the untreated (before washing) test cloth (white cloth) of the white polyester tropical were measured.
Then, the difference (average value) in reflectance between the two test cloths subjected to the above operation and the white cloth was calculated as the “recontamination degree (ΔZ)”.
The reflectance was measured using a color difference meter SE2000 (NIPPON DENSHOKU), and the ΔZ value was less than 9 (C, B, or A) as the acceptable range.
Evaluation criteria A: ΔZ value is less than 3.
B: The ΔZ value is 3 or more and less than 6.
C: The ΔZ value is 6 or more and less than 9.
D: The ΔZ value is 9 or more.

[Evaluation of the effect of imparting flexibility]
For the softness of the test cloth that was subjected to the washing treatment b) in the evaluation of odor removal and left for 1 day, a pair comparison with the control cloth by sensory function was made according to the following evaluation criteria (7). went.
Evaluation criteria (7)
1 point: Harder than the control cloth.
2 points: Equivalent to the control cloth.
3 points: Slightly softer than the control cloth.
4 points: considerably softer than the control cloth.
5 points: Very softer than the control fabric.
And the average score of five panelists' scoring was computed, and the softness | flexibility provision effect was evaluated by the following evaluation criteria (8). If it was C, B, or A in the following evaluation criteria (8), it was determined that the flexibility-imparting effect was good.
Evaluation criteria (8)
A: 4 points or more, B: 3.5 points or more, less than 4 points, C: 3 points or more, less than 3.5 points, D: less than 3 points.

[Evaluation of comfort]
A light pink cardigan blouse (100% wool), a T-shirt (100% cotton) and a cotton towel (100% cotton) to adjust the mass so that the total amount of fabric is 6 kg, a drum-type washing machine ( (Made by Matsushita Electric Industrial Co., Ltd., National NA-VR1100 type), 25 g of liquid detergent was put into the detergent inlet, and washing (packed washing) was performed on the Omakase Course.
The cardigan blouse washed by repeating this washing operation 5 times was left in a constant temperature and humidity room at 25 ° C. and a relative humidity of 65% RH. After leaving for one day, the panelists (5 persons) were scored for the comfort of a cardigan blouse (wool clothing) according to the following evaluation criteria (9) in comparison with a new article (control article) not subjected to the washing operation.
Evaluation criteria (9)
1 point: The comfort is considerably worse than the control product.
2 points: Slightly less comfortable than the control.
3 points: Comfort is equivalent to the control product.
4 points: Slightly more comfortable than the control.
5 points: Comfort is much better than the control product.
And the average score of 5 panelists' scoring was computed, and the feeling of comfort was evaluated by the following evaluation criteria (10).
Evaluation criteria (10)
A: 4 points or more, B: 3.5 points or more, less than 4 points, C: 3 points or more, less than 3.5 points, D: less than 3 points.

[Evaluation of deodorization performance]
Apparel with severe sebum stains and the like tends to generate off-flavors and malodors derived from bacteria when dried in a humid room after washing. In this evaluation, an evaluation method was used that models (reproduces at the laboratory level) a phenomenon in which off-flavors and malodors derived from the bacteria are likely to occur.
A fully automatic electric washing machine (Haier Co., Ltd., JW-Z23A) was worn for 1 day in an actual home so that about 100 g of cotton towel with dirt used for one week was attached and the total cloth mass was about 800 g. A cotton skin shirt and 10 mL of a liquid cleaning agent were added, and a cleaning operation was performed in which cleaning, rinsing, and dehydration were sequentially performed in a standard course. With regard to washing, rinsing, dehydration, and water volume (set to low water level, water volume of about 12 L), no adjustment was made and the standard course setting of the washing machine was used.
After the washing, the film was dried all day and night in a constant temperature and humidity room at 25 ° C. and a relative humidity of 85% or more. Each “unpleasant odor” of the dried clothes was evaluated according to the following six evaluation criteria (11) by sensory sense. The evaluation was conducted by five expert panelists.
Evaluation criteria (11)
0 point: odorless.
1 point: The smell that can finally be detected.
2 points: Smell that shows what kind of smell it is.
3 points: A smell that can be easily detected.
4 points: Strong odor.
5 points: Strong smell.
Based on the evaluation results based on the six-stage evaluation criteria (11), the average score of five professional panelists was calculated, and the deodorization performance was evaluated according to the following evaluation criteria (12). If the average score of the evaluation was less than 3.0 (C, B, or A), it was determined that the deodorizing performance was good.
Evaluation criteria (12)
A: Less than 1.5 points.
B: 1.5 points or more and less than 2.5 points.
C: 2.5 points or more and less than 3.0 points.
D: 3.0 points or more.

[Evaluation of usability]
About 300 g of the liquid cleaning agent in each example was put in a container of a commercially available liquid detergent top NANOX (manufactured by Lion Corporation) (all the detergent contained in the container was drained, washed with water and dried), and then capped. It put in the 5 degreeC thermostat in the state. After 3 hours, the container containing the liquid cleaning agent was taken out of the thermostatic bath.
After that, the cap is opened, and the liquid cleaning agent is poured up to the “−45” line printed on the cap. At that time, the ease of measurement (measuring property) and a commercially available T-shirt (100% cotton, B Evaluation of the ease with which the liquid detergent can be applied (applicability) to the portion around the neck of V.D. The evaluation of meterability and applicability was performed according to the following evaluation criteria (13), the average score was calculated, and the usability was evaluated according to the following evaluation criteria (14).
Evaluation criteria (13)
5 points: Both meterability and applicability are very good.
4 points: Both meterability and applicability are slightly good.
3 points: Neither can be said.
Two points: Both meterability and applicability are not good.
1 point: Both meterability and applicability are not very good.
Evaluation criteria (14)
A: The average score is 4 or more.
B: The average score is 3.5 points or more and less than 4 points.
C: The average score is 3 or more and less than 3.5.
D: The average score is less than 3.

  From the results shown in Tables 1 to 3, the liquid detergents of Examples 1 to 16 to which the present invention is applied have good liquid flowability and liquid stability, and a high detergency (odor removal property, In addition, it can be seen that it has a coating cleaning power necessary for directly applying to an object to be cleaned and removing dirt.

  From the results shown in Tables 4 to 6, the liquid detergents of Examples 17 to 39 to which the present invention is applied have good liquid flowability and liquid stability, and have high detergency (odor removal property) against various stains. In addition, it can be seen that it has a coating cleaning power necessary for removing stains by directly applying to an object to be cleaned, and is excellent in re-contamination prevention performance.

  From the results shown in Tables 7 to 10, the liquid detergents of Examples 40 to 67 to which the present invention is applied have good liquid flowability and liquid stability, and have high detergency (odor removal property) against various stains. And a coating and detergency necessary to remove stains by directly applying to an object to be washed, and also excellent in flexibility imparting effect and good comfort.

  From the results shown in Tables 11 to 13, the liquid detergents of Examples 68 to 92 to which the present invention is applied have good liquid flowability and liquid stability, and have high detergency (odor removal property) against various stains. In addition, it can be seen that it has a coating detergency necessary for removing dirt by applying it directly to the object to be cleaned, and is excellent in deodorizing performance and anti-recontamination performance.

  The liquid detergent of the present invention has good liquid flowability and liquid stability, has a high detergency against various stains, and removes stains by directly applying to odor removal and washing objects. Therefore, it has excellent application cleaning power, recontamination prevention performance, flexibility imparting effect, deodorization performance and recontamination prevention performance, so that it can be used as a detergent for clothing.

Claims (1)

An anionic surfactant (A) represented by the following general formula (a-1);
At least one nonionic surfactant (B) selected from the group consisting of compounds represented by any one of the following general formulas (b-1) and (b-2);
Containing at least one organic solvent (C) selected from the group consisting of a compound represented by an alcohol having 2 to 4 carbon atoms and the following general formula (c-1);
The liquid cleaning agent whose sum total of the said (A) component and the said (B) component is 40 mass% or more with respect to the total mass of a liquid cleaning agent.

[In Formula (a-1), R ¹ is a hydrocarbon group having 8 to 18 carbon atoms, R ² is an alkyl group having 1 to 3 carbon atoms, and M is a counter ion. In formula (b-1), R ³ is a hydrocarbon group having 9 to 13 carbon atoms, R ⁴ is an alkylene group having 2 to ⁴ carbon atoms, and R ⁵ is an alkyl group having 1 to 4 carbon atoms. . m represents the average number of repetitions of OR ⁴ and is an integer of 5 to 25. In formula (b-2), R ⁶ is a hydrocarbon group having 10 to 20 carbon atoms. EO is an oxyethylene group and PO is an oxypropylene group. s represents the average number of repetitions of EO and is an integer of 5 to 20, and t represents the average number of repetitions of PO and is an integer of 1 to 4. In formula (c-1), R ⁷ is an alkyl group having 1 to 6 carbon atoms or a phenyl group, and R ⁸ is an alkylene group having 2 to 4 carbon atoms. n represents an average repeating number of OR ^8, an integer of 1 to 5. ]