JP2015203101A - liquid detergent - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a liquid detergent having high detergency for oil stains and excellent antibacterial performance.SOLUTION: There is provided a liquid detergent which comprises (A) component: a cationic surfactant, (B) component: a polymer having at least one repeating unit (b1) selected from the group consisting of an alkylene terephthalate unit and alkylene isophthalate unit and an oxyalkylene unit (b2) and (C) component: at least one selected from the group consisting of an amphoteric surfactant and a semipolar surfactant.

Description

  The present invention relates to a liquid cleaning agent.

In recent years, liquid detergents are often used as household detergents. Detergents for clothing need cleaning power against various stains attached to clothing or the like (objects to be washed). In particular, a high detergency is required for oil stains such as sebum stains that are difficult to remove.
Recently, large-capacity washing machines such as drum type washing machines and water-saving washing machines have become widespread. Along with this, many objects to be washed are washed together, and washing is performed under conditions of a low bath ratio with little water. When washing is performed under such conditions, so-called re-contamination tends to occur, in which dirt once removed during washing adheres to the object to be washed again. In particular, hydrophobic chemical fibers such as polyester have a problem that re-contamination is likely to occur and oil stains cannot be removed sufficiently.
On the other hand, for the purpose of removing hydrophobic soil adhering to hydrophobic fibers such as polyester, a water-soluble polymer having alkylene terephthalate units and / or alkylene isophthalate units, and oxyalkylene units and / or polyoxyalkylene units; A liquid detergent containing a nonionic surfactant composed of a specific ethylene oxide adduct and an organic acid or a salt thereof is disclosed (see Patent Document 1).

In addition, due to the growing awareness of hygiene, products with antibacterial effects in addition to cleaning effects have been put on the market for laundry detergents. Cationic fungicides such as cationic surfactants are widely used as active ingredients that exhibit antibacterial effects.
In the present specification, the “antibacterial effect” means an effect of suppressing the growth of bacteria. The higher the antibacterial effect, the higher the effect of deodorizing the item to be washed.

JP 2009-155606 A

However, when a cationic surfactant is simply added as a cationic disinfectant to the liquid detergent described in Patent Document 1, there is a problem that the cleaning power against oil stains is reduced.
This invention is made | formed in view of the said situation, and makes it a subject to provide the liquid cleaning agent which has high detergency with respect to oil dirt, and was excellent in antibacterial performance.

As a result of intensive studies, the present inventors provide the following means in order to solve the above problems.
That is, the liquid detergent of the present invention comprises (A) component: a cationic surfactant and (B) component: at least one repeating unit (b1) selected from the group consisting of alkylene terephthalate units and alkylene isophthalate units, and It contains a polymer having an oxyalkylene unit (b2) and (C) component: at least one selected from the group consisting of amphoteric surfactants and semipolar surfactants.

  The liquid detergent of the present invention has a high detergency against oil stains and is excellent in antibacterial performance.

The liquid detergent of the present invention comprises (A) component: a cationic surfactant and (B) component: at least one repeating unit (b1) selected from the group consisting of alkylene terephthalate units and alkylene isophthalate units, and oxyalkylene. The polymer which has a unit (b2), and (C) component: At least 1 type selected from the group which consists of an amphoteric surfactant and a semipolar surfactant is contained.
The liquid detergent of the present invention can be used for household and industrial applications, and can be suitably used for household use, and is particularly suitable for clothing.
Examples of the types of objects to be cleaned include those similar to those to be cleaned in laundry at home, and examples thereof include textiles such as clothing, cloths, towels, and sheets.

<(A) component: Cationic surfactant>
In the liquid cleaning agent of this invention, antibacterial performance is provided mainly by containing (A) component.
As the component (A), for example, a quaternary ammonium salt can be used.
Examples of the quaternary ammonium salt include conventionally known quaternary ammonium salts that are generally used in garment detergents. Among them, preferable quaternary ammonium salts include compounds represented by the following general formula (A-1), (A-2) or (A-3) because high antibacterial effects are easily obtained. .

［式（Ａ−１）中、Ｒ^１〜Ｒ^４のうちの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り、それ以外は、炭素数８〜２２の直鎖状もしくは分岐鎖状のアルキル基、又は炭素数８〜２２の直鎖状もしくは分岐鎖状のアルケニル基である。Ｚ⁻は、ハロゲンイオン又はアルキル硫酸イオンである。］

[In Formula (A-1), two or more of R ^{1 to} R ⁴ are each independently an alkyl group having 1 to 3 carbon atoms or a hydroxyalkyl group having 1 to 3 carbon atoms; Other than these, 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. Z ⁻ is a halogen ion or an alkyl sulfate ion. ]

  Preferred examples of the compound represented by the formula (A-1) (hereinafter also referred to as “component (A-1)”) include, for example, the following component (A-1-1), (A-1 -2) A component is mentioned.

(A-1-1) Component: ^Three of R ^{1 to} R ³ are each independently an alkyl group having 1 to 3 carbon atoms or a hydroxyalkyl group having 1 to 3 carbon atoms, and R ⁴ is the number of carbon atoms. A compound which is a linear or branched alkyl group having 8 to 22 or a linear or branched alkenyl group having 8 to 22 carbon atoms.
In the component (A-1-1), R ^{1 to} R ³ are each independently preferably an alkyl group having 1 to 3 carbon atoms, and more preferably a methyl group. Among these, the component (A-1-1) in which R ^{1 to} R ³ are all methyl groups is preferable.
In the alkyl group or alkenyl group of R ⁴ , the carbon number is 8 to 22, preferably 10 to 20, more preferably 12 to 18, and still more preferably 12 to 16. R ⁴ is preferably a linear or branched alkyl group, and more preferably a linear alkyl group.

(A-1-2) Component: R ¹ and R ² are each independently a linear or branched alkyl group having 8 to 22 carbon atoms, or a linear or branched group having 8 to 22 carbon atoms. a chain alkenyl group, and R ³ and R ⁴ are each independently an alkyl group or hydroxyalkyl group having 1 to 3 carbon atoms having 1 to 3 carbon atoms.
In the component (A-1-2), in the alkyl group or alkenyl group of R ¹ and R ² , the carbon number is 8 to 22, preferably 8 to 12, and more preferably 8 to 10. preferable. R ¹ and R ² are each independently preferably a linear or branched alkyl group, and more preferably a linear alkyl group. Among these, the component (A-1-2) in which R ¹ and R ² are both linear alkyl groups is preferable.
R ³ and R ⁴ are each independently preferably an alkyl group having 1 to 3 carbon atoms, and more preferably a methyl group. Among these, the component (A-1-2) in which R ³ and R ⁴ are both methyl groups is preferable.

  In said formula (A-1), as Z which comprises a halogen ion, a fluorine atom, a chlorine atom, a bromine atom, an iodine atom, etc. are mentioned, A chlorine atom is preferable. As Z which comprises an alkyl sulfate ion, what has a C1-C3 alkyl group is preferable, for example, a methyl sulfate etc. are mentioned.

  Specific examples of the component (A-1) include alkyl chloride (having 12 to 16 carbon atoms) trimethylammonium and didecyldimethylammonium chloride.

［式（Ａ−２）中、Ｒ^５は、炭素数８〜２２の直鎖状もしくは分岐鎖状のアルキル基、又は炭素数８〜２２の直鎖状もしくは分岐鎖状のアルケニル基である。Ｒ^６は、炭素数１〜３のアルキル基、炭素数１〜３のヒドロキシアルキル基、又は炭素数５〜２０の芳香族炭化水素基である。ｘ及びｙは、オキシエチレン基の平均繰り返し数を示し、それぞれ独立して０以上の整数であって、ｘ＋ｙが１０以上である。Ｚ⁻は、ハロゲンイオン又はアルキル硫酸イオンである。］

[In Formula (A-2), R ⁵ represents 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. R ⁶ is an alkyl group having 1 to 3 carbon atoms, a hydroxyalkyl group having 1 to 3 carbon atoms, or an aromatic hydrocarbon group having 5 to 20 carbon atoms. x and y represent the average number of repeating oxyethylene groups, each independently an integer of 0 or more, and x + y is 10 or more. Z ⁻ is a halogen ion or an alkyl sulfate ion. ]

In the formula (A-2), in the alkyl group or alkenyl group of R ⁵ , the carbon number is 8 to 22, preferably 10 to 22, and more preferably 10 to 18. R ⁵ is preferably a linear or branched alkyl group, and more preferably a linear alkyl group.
The carbon number of the aromatic hydrocarbon group in R ⁶ is 5 to 20, and preferably 6 to 10. Examples of R ⁶ include a phenyl group, a methylphenyl group (tolyl group), a dimethylphenyl group, a trimethylphenyl group, a tetramethylphenyl group, and a naphthyl group.
x + y is 10 or more, preferably 10-50. If x + y is less than 10, the effect of dispersing dirt attached to the object to be washed is small, and the effect of removing dirt from the object to be washed may be difficult to obtain.
Z ^- is, Z in the formula (A-1) ^- the same as the like.

Among the compounds represented by the formula (A-2) (hereinafter also referred to as “component (A-2)”), R ⁵ is a linear or branched chain having 10 to 18 carbon atoms. An alkyl group, or a linear or branched alkenyl group having 10 to 18 carbon atoms, R ⁶ is a methyl group or a tolyl group, x + y is 10 or more, and Z ⁻ is a halogen ion or an alkyl sulfate ion. The compound etc. which are are mentioned.

［式（Ａ−３）中、Ｒ^７及びＲ^８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^９は、炭素数８〜２２の直鎖状もしくは分岐鎖状のアルキル基又はアルケニル基であり、Ｒ^１０は、炭素数１〜３のアルキレン基である。Ｚ⁻は、ハロゲンイオン又はアルキル硫酸イオンである。］

[In Formula (A-3), R ⁷ and R ⁸ are each independently an alkyl group having 1 to 3 carbon atoms or a hydroxyalkyl group having 1 to 3 carbon atoms, and R ⁹ has 8 to 8 carbon atoms. 22 is a linear or branched alkyl group or alkenyl group, and R ¹⁰ is an alkylene group having 1 to 3 carbon atoms. Z ⁻ is a halogen ion or an alkyl sulfate ion. ]

In the formula (A-3), R ⁷ and R ⁸ are each independently preferably an alkyl group having 1 to 3 carbon atoms, and more preferably a methyl group. Of these, compounds in which R ⁷ and R ⁸ are both methyl groups are preferred.
In the alkyl group or alkenyl group of R ⁹ , the carbon number is 8 to 22, preferably 10 to 18, and more preferably 12 to 14. R ⁹ is preferably a linear or branched alkyl group, and more preferably a linear alkyl group.
R ¹⁰ is an alkylene group having 1 to 3 carbon atoms, and is preferably a methylene group.
Z ^- is, Z in the formula (A-1) ^- the same as the like.

Among the compounds represented by the formula (A-3) (hereinafter also referred to as “component (A-3)”), R ⁷ and R ⁸ are both methyl groups, and R ⁹ is carbon. Examples thereof include compounds having a linear or branched alkyl group of formula 8 to 22, R ¹⁰ is a methylene group, and Z ⁻ is a halogen ion or an alkyl sulfate ion.

(A) A component may be used individually by 1 type and may use 2 or more types together.
Among the components (A), it is preferable to use at least one selected from the group consisting of the components (A-1), (A-2) and (A-3) described above, (A-1) It is more preferable to use at least one selected from the group consisting of the component and the component (A-3), and it is more preferable to use the component (A-1).
In the liquid cleaning agent, the content of the component (A) is preferably 0.2 to 10% by mass, more preferably 0.5 to 6% by mass, and still more preferably 0 with respect to the total mass of the liquid cleaning agent. 0.5 to 4% by mass.
When the content of the component (A) is less than the preferable lower limit value, it is difficult to obtain an antibacterial effect. On the other hand, when the content exceeds the preferable upper limit value, stain transfer or recontamination occurs on the object to be washed. It becomes easy.

<Component (B): a polymer having a specific repeating unit (b1) and an oxyalkylene unit (b2)>
In the present invention, the component (B) is a polymer having at least one repeating unit (b1) and oxyalkylene unit (b2) selected from the group consisting of alkylene terephthalate units and alkylene isophthalate units.
In the present specification, “repeating unit” refers to a monomer unit constituting a polymer.
In the liquid cleaning agent of this invention, the cleaning power with respect to an oil stain becomes high by mainly containing (B) component.

-Specific repeating unit (b1) Among the specific repeating units (b1), the alkylene terephthalate unit (hereinafter, this repeating unit is also referred to as "repeating unit (b11)") is represented by the following general formula (b1-1). The repeating unit represented is mentioned.

In the formula (b1-1), R ²¹ represents a lower alkylene group. The number of carbon atoms of lower alkylene group for R ²¹ is preferably 5 or less, more preferably 4 or less, more preferably from 2 to 4.
Specific examples of the repeating unit (b11) include an ethylene terephthalate unit, a propylene terephthalate unit, an n-butylene terephthalate unit, an isobutylene terephthalate unit, a sec-butylene terephthalate unit, and a tert-butylene terephthalate unit. Of these, propylene terephthalate units are preferred.

  Among the specific repeating units (b1), examples of the alkylene isophthalate unit (hereinafter, this repeating unit is also referred to as “repeating unit (b12)”) include repeating units represented by the following general formula (b1-2). .

In the formula (b1-2), R ²² represents a lower alkylene group. The number of carbon atoms of lower alkylene group for R ²² is preferably 5 or less, more preferably 4 or less, more preferably from 2 to 4.
Specific examples of the repeating unit (b12) 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.

  As the repeating unit (b1), one type may be used alone, or two or more types may be used in combination. That is, the component (B) may have only the repeating unit (b11) as the repeating unit (b1) or may have only the repeating unit (b12) in one molecule. You may have both a unit (b11) and a repeating unit (b12). Moreover, you may have 2 or more types of repeating units (b11) and / or 2 or more types of repeating units (b12).

In one molecule in the component (B), the number of repeating units (b1) is preferably 1 to 10, more preferably 1 to 6, and further preferably 2 to 4.
When the number of repeating units (b1) is not less than the preferable lower limit, the detergency against oil stains is further improved. On the other hand, when it is not more than the preferable upper limit, liquid stability as a liquid detergent Will be improved.

-Oxyalkylene unit (b2) Examples of the oxyalkylene unit (hereinafter, this repeating unit is also referred to as "repeating unit (b2)") include repeating units represented by the following general formula (b2-1).

In the formula (b2-1), R ²³ is a lower alkylene group. The number of carbon atoms of lower alkylene group for R ²³ is preferably 4 or less, more preferably 2 to 4, more preferably 2 or 3, particularly preferably 2.
Specific examples of the repeating unit (b2) include an oxyethylene unit, an oxypropylene unit, and an oxybutylene unit. Of these, oxyethylene units and oxypropylene units are preferable, and oxyethylene units are more preferable.

  As the repeating unit (b2), one type may be used alone, or two or more types may be used in combination. That is, the component (B) may have, for example, only an oxyethylene unit, only an oxypropylene unit, or only an oxyethylene unit as a repeating unit (b2) in one molecule. And an oxypropylene unit. Among these, it is preferable to have only oxyethylene units.

In one molecule of the component (B), the number of repeating units (b2) is 1 or more, preferably 5 to 150, more preferably 10 to 100.
When the repeating number of the repeating unit (b2) is not less than the above preferable lower limit value, the liquid stability as the liquid cleaning agent is further improved. Will be improved.

  In addition, the component (B) may have only an oxyalkylene group (when the number of repetitions is 1) as a repeating unit (b2) in one molecule, and a polyoxyalkylene unit (the number of repetitions is 2). In the above case), it may have both an oxyalkylene group and a polyoxyalkylene unit.

  The component (B) is preferably a polymer in which the repeating unit (b1) and the repeating unit (b2) are polymerized in a block shape or a random shape, and more preferably a polymer polymerized in a block shape. .

The component (B) may have other repeating units in addition to the repeating unit (b1) and the repeating unit (b2). Examples of the other repeating unit include a repeating unit derived from a polymerization initiator, a polymerization terminator and the like, a repeating unit derived from a monomer copolymerizable with a monomer that provides the repeating unit (b1) or the repeating unit (b2), and the like. It is done.
When component (B) has other repeating units, the total of repeating unit (b1) and repeating unit (b2) is 80 mol% based on the total of all repeating units constituting component (B). The above is preferable, and 90 mol% or more is more preferable. When the sum of the repeating unit (b1) and the repeating unit (b2) is not less than the preferable lower limit, the detergency against oil stains is increased. In addition, recontamination of the object to be cleaned is less likely to occur.

The component (B) is preferably a water-soluble polymer from the viewpoints 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 polymer is added to 1000 g of water in a 1 liter beaker at 40 ° C. and stirred for 12 hours (200 rpm) with a stirrer (thickness 8 mm, length 50 mm). The one that has been dissolved after.

The lower limit of the weight average molecular weight of the component (B) is preferably 500 or more, more preferably 800 or more, and still more preferably 1000 or more, because the solubility and dispersibility in water increases. On the other hand, a preferable upper limit is 10,000 or less, more preferably 8000 or less, and still more preferably 7000 or less. If the weight average molecular weight of (B) component is the said preferable range, the water dispersibility will improve more and it will become easy to obtain sufficient detergency with respect to oil stains.
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 based on a calibration curve in PEG (polyethylene glycol).

  Component (B) is a synthesis method disclosed in various documents, textbooks, patents, and the like, for example, Journal of Polymer Science, Vol. 3, pages 609 to 630 (1948); Journal of Polymer Science, Vol. 1 to 22 (1951); can be produced by the method described in JP-A-61-218699.

  As a suitable specific example of (B) component, what contains the polymer represented by the following general formula (Bp1), the polymer represented by the general formula (Bp2), or a mixture thereof. Can be mentioned.

In the formulas (B-p1) and (B-p2), R ²⁰ and R ³⁰ are each independently a hydrogen atom or a methyl group, each preferably a methyl group, and both are methyl groups. Is more preferable.
R ²⁴ and R ²⁷ are each a methyl group or a hydrogen atom, and each is preferably a methyl group.
R ²⁵ , R ²⁶ , R ²⁸ and R ²⁹ are each independently an alkylene group having 2 to 4 carbon atoms.
Each of s1 and s2 is 0 to 10, preferably 0.5 to 5, and more preferably 0.5 to 2.5. t1, t2, u1 and u2 are each independently 1 to 100, preferably 1 to 80, and more preferably 1 to 50. When s1, s2, t1, t2, u1, and u2 are within the above ranges, the solubility in water is further improved, and the detergency against oil stains is further increased.

(B) A component may be used individually by 1 type and may use 2 or more types together.
Specific examples of the component (B) include trade name TexCare SRN-100 (Germany, manufactured by Clariant GmbH, weight average molecular weight 3000), trade name TexCare SRN-300 (Germany, manufactured by Clariant GmbH, weight average molecular weight 7000), and the like. Are commercially available.
Among these, TexCare SRN-100 is preferable because it is highly soluble in water and easily obtains a liquid cleaning agent with high transparency.

In the liquid detergent, the content of the component (B) is preferably 0.05 to 5% by mass, more preferably 0.1 to 2% by mass with respect to the total mass of the liquid detergent.
When the blending amount of the component (B) is equal to or more than the lower limit value, the cleaning power against oil stains is further increased. On the other hand, if it exceeds the preferable upper limit, the effect of improving the detergency against oil stains reaches a peak. Moreover, it becomes difficult to obtain an antibacterial effect.

<(C) component: at least one selected from the group consisting of amphoteric surfactants and semipolar surfactants>
In the liquid cleaning agent of this invention, even if (A) component is combined with (B) component by containing (C) component, the cleaning power with respect to oil stains is maintained.
(C) As a component, the conventionally well-known thing normally used for the detergent for clothes is mentioned.

-Amphoteric surfactant Examples of the amphoteric surfactant include alkylcarbobetaines, alkylsulfobetaines, alkylamidohydroxysulfobetaines, alkylamidoamine-type betaines, and alkylimidazoline-type betaines.
Among these, preferred amphoteric surfactants include compounds represented by the following general formula (C-1) because the compounding effect of the component (C) described above can be more easily obtained.

［式（Ｃ−１）中、Ｒ^３１は、炭素数８〜１８の炭化水素基である。Ｒ^３２は及びＲ^３３は、それぞれ独立して炭素数１〜３のアルキル基又はヒドロキシアルキル基である。Ｒ^３４は、置換基としてヒドロキシ基を有していてもよい炭素数１〜５のアルキレン基である。Ｒ^３４−Ｒ^３５は、Ｒ^３４−ＳＯ_３ ⁻、Ｒ^３４−ＯＳＯ_３ ⁻、又はＲ^３４−ＣＯＯ⁻である。Ｒ^３７は、炭素数１〜６のアルキレン基である。−Ｒ^３６−Ｒ^３７−は、−Ｃ（＝Ｏ）Ｏ−Ｒ^３７−、−Ｃ（＝Ｏ）ＮＨ−Ｒ^３７−、−ＯＣ（＝Ｏ）−Ｒ^３７−、−ＮＨＣ（＝Ｏ）−Ｒ^３７−、又は−Ｏ−Ｒ^３７−である。ｊは、０又は１の数である。］

[In Formula (C-1), R ³¹ is a hydrocarbon group having 8 to 18 carbon atoms. R ³² and R ³³ are each independently an alkyl group having 1 to 3 carbon atoms or a hydroxyalkyl group. R ³⁴ is an alkylene group having 1 to 5 carbon atoms which may have a hydroxy group as a substituent. R ³⁴ —R ³⁵ is R ³⁴ —SO ₃ ^— , R ³⁴ —OSO ₃ ^— , or R ³⁴ —COO ^— . R ³⁷ is an alkylene group having 1 to 6 carbon atoms. —R ³⁶ —R ³⁷ — is —C (═O) O—R ³⁷ —, —C (═O) NH—R ³⁷ —, —OC (═O) —R ³⁷ —, —NHC (═O) -R ³⁷ -, or ^{-O-R 37} - is. j is a number of 0 or 1. ]

In the formula ^{(C-1), R 31} is a hydrocarbon group having 8 to 18 carbon atoms. As the hydrocarbon group for R ³¹ , an alkyl group or an alkenyl group is preferable, and an alkyl group is more preferable. The number of carbon atoms in the hydrocarbon group in R ³¹ is from 8 to 18, preferably 9 to 17 carbon atoms, more preferably 10 to 16 carbon atoms.
R ³² and R ³³ are each independently an alkyl group having 1 to 3 carbon atoms or a hydroxyalkyl group, each preferably an ethyl group or a hydroxyethyl group, and more preferably a methyl group.
R ³⁴ is an alkylene group having 1 to 5 carbon atoms which may have a hydroxy group as a substituent, and among them, an alkylene group having 1 to 3 carbon atoms which may have a hydroxy group as a substituent. preferable.
R ³⁴ —R ³⁵ is R ³⁴ —SO ₃ ^— , R ³⁴ —OSO ₃ ^— , or R ³⁴ —COO ^— , preferably R ³⁴ —COO ^— .
R ³⁷ is an alkylene group having 1 to 6 carbon atoms.
—R ³⁶ —R ³⁷ — is —C (═O) O—R ³⁷ —, —C (═O) NH—R ³⁷ —, —OC (═O) —R ³⁷ —, —NHC (═O) -R ³⁷ -, or ^{-O-R 37} - is.
j is a number of 0 or 1, preferably 0.

-About a semipolar surfactant In this specification, a "semipolar surfactant" is a surfactant having a semipolar bond (a bond having a property intermediate between a nonpolar bond and a polar bond). This refers to those that are cationic, anionic, or bipolar depending on the pH of the solution in which the surfactant is dissolved or the dispersion in which the surfactant is dispersed.
Preferred examples of the semipolar surfactant include amine alkylene oxide surfactants and amine oxide surfactants. Of these, amine oxide surfactants are preferred because of their good detergency against oil stains and foaming.

As the component (C), one type may be used alone, or two or more types may be used in combination.
Among the components (C), the amphoteric surfactant is preferably used, the alkylcarbobetaine is more preferably used, and the alkyl (preferably the number of carbon atoms is preferred) because the compounding effect of the component (C) is more easily obtained. 10-16) Dimethylaminoacetic acid betaine and fatty acid (preferably 9 to 17 carbon atoms) amidopropyl betaine are particularly preferred.
In the liquid cleaning agent, the content of the component (C) is preferably 0.01 to 6% by mass, more preferably 0.03 to 4% by mass, and still more preferably 0 with respect to the total mass of the liquid cleaning agent. 0.04 to 2% by mass, particularly preferably 0.1 to 1% by mass.
When the content of the component (C) is less than the preferable lower limit value, it is difficult to obtain the blending effect of the component (C). On the other hand, when the content exceeds the preferable upper limit value, the liquid stability as a liquid detergent is obtained. It becomes easy to fall. Moreover, it becomes difficult to obtain an antibacterial effect.

The mixing ratio of the component (A) and the component (C) in the liquid detergent is such that the molar ratio represented by the component (C) / the component (A) is preferably 0.01 to 2, more preferably It is 0.02-1, More preferably, it is 0.03-0.6, Especially preferably, it is 0.05-0.6, Most preferably, it is 0.1-0.5.
When the molar ratio represented by the component (C) / component (A) is within the above range, it is possible to achieve both the detergency against oil stains and the antibacterial performance. Moreover, if the molar ratio represented by (C) component / (A) component is more than the said preferable lower limit, the detergency with respect to oil dirt will increase more, On the other hand, if it is below the said preferable upper limit, An antibacterial effect is more easily obtained.
In this specification, “molar ratio represented by component (C) / component (A)” means the content of component (C) relative to the content (number of moles) of component (A) contained in the liquid detergent. It means the ratio of the quantity (number of moles).

The mixing ratio of the component (B) and the component (C) in the liquid detergent is such that the mass ratio represented by the component (C) / component (B) is preferably 0.01 to 4, more preferably. It is 0.04-2, More preferably, it is 0.07-1.5, Especially preferably, it is 0.15-1, Most preferably, it is 0.2-0.5.
When the mass ratio represented by the component (C) / component (B) is within the above range, it is possible to achieve both the detergency against oil stains and the antibacterial performance. Moreover, if the mass ratio represented by (C) component / (B) component is more than the said preferable lower limit, the detergency with respect to oil dirt will be maintained more easily, On the other hand, at the said preferable upper limit or less. If it exists, the detergency with respect to oil dirt will increase more. In addition, the antibacterial performance is further increased.
In this specification, “mass ratio represented by component (C) / component (B)” means the content of component (C) relative to the content (% by mass) of component (B) contained in the liquid detergent. It means the ratio of amount (mass%).

<Solvent>
The liquid detergent of the present invention preferably contains water as a solvent from the viewpoint of ease of preparation of the liquid detergent, solubility in water when used, and the like. The content of water in the liquid detergent is preferably 90% by mass or less with respect to the total mass of the liquid detergent.
If water content is below the said preferable upper limit, liquid viscosity will become low moderately and it becomes favorable from a viewpoint of usability.

<Optional component>
The liquid cleaning agent of the present invention may contain other components other than the above-described components as necessary as long as the effects of the present invention are not impaired.
The other components are not particularly limited, and include components that are usually blended in liquid detergents for clothing, such as nonionic surfactants, anionic surfactants, solvents, bleaching components, metal scavenging components, radical traps. Agents, fragrances, pH adjusters, and the like can be used.

-About nonionic surfactant In the liquid cleaning agent of this invention, a nonionic surfactant can be used as a washing | cleaning component with respect to oil stains, such as sebum stain. Examples of nonionic surfactants include conventionally known nonionic surfactants that are generally used in laundry detergents. Among these, preferred nonionic surfactants include compounds represented by the following general formula (ns-1).

In the formula (ns-1), R ⁴⁰ is a hydrocarbon group having 10 to 18 carbon atoms.
Examples of the hydrocarbon group for R ⁴⁰ include an alkyl group and an alkenyl group. These alkyl groups, alkenyl groups and the like may have a hydroxy group or the like as a substituent. Further, the hydrocarbon group for R ⁴⁰ may be linear or branched.
The number of carbon atoms of the hydrocarbon group for R ⁴⁰ is, from the viewpoint of detergency improvement, 12 to 18 is preferred.
In said formula (ns-1), k shows the average repeating number of an oxyethylene group, and is a number of 2-20. When k is less than 2, the function as a nonionic surfactant is hardly exhibited. Therefore, in order to fully exhibit the function as a nonionic surfactant, it is preferable that the value of k is large. On the other hand, if k exceeds 20, the HLB tends to be too high and the cleaning power tends to decrease.
A nonionic surfactant may be used individually by 1 type, and may use 2 or more types together.
In the liquid detergent, the content of the nonionic surfactant is preferably 1 to 18% by mass, more preferably 3 to 10% by mass with respect to the total mass of the liquid detergent. When the content of the nonionic surfactant is equal to or higher than the preferable lower limit value, the detergency against oil stains is further increased. On the other hand, when the content is equal to or lower than the preferable upper limit value, the transparent appearance of the liquid cleaning agent is easily maintained. Also, it is easy to weigh when doing laundry.

-About anionic surfactant In the liquid detergent of this invention, an anionic surfactant can be used from the point of the stability improvement at the time of low temperature as a washing | cleaning component with respect to protein dirt.
Examples of the anionic surfactants include conventionally known anionic surfactants that are generally used in laundry detergents, such as linear alkylbenzene sulfonates, α-olefin sulfonates, linear or branched alkyls. Examples thereof include sulfate ester salts, alkyl ether sulfate ester salts or alkenyl ether sulfate ester salts, alkane sulfonates having an alkyl group, and α-sulfo fatty acid ester salts. Among these, linear alkylbenzene sulfonate and alkane sulfonate having an alkyl group are preferable.
As the linear alkylbenzene sulfonate, one having 8 to 16 carbon atoms in the linear alkyl group is preferable, and one having 10 to 14 carbon atoms is more preferable.
As the alkane sulfonate having an alkyl group, those having 10 to 20 carbon atoms are preferable, and secondary alkane sulfonate having an alkyl group having 14 to 17 carbon atoms is more preferable.
An anionic surfactant may be used individually by 1 type, and may use 2 or more types together.
In addition, in the liquid cleaning agent of this invention, the complex of (A) component or (C) component, and an anionic surfactant is formed by containing an anionic surfactant, Thereby, antibacterial performance is provided. There is a risk that it may be difficult to develop. For this reason, when using an anionic surfactant together, it is preferable that content of an anionic surfactant shall be 9 mass% or less with respect to the total mass of a liquid detergent. If content of an anionic surfactant is below the said preferable upper limit, the detergency with respect to protein dirt can be improved, maintaining the detergency and antibacterial performance with respect to oil dirt.

-About a solvent You may use solvents other than water for the liquid cleaning agent of this invention from the point of the stability improvement of a liquid external appearance.
Examples of solvents other than water include water-miscible organic solvents. “Water-miscible organic solvent” refers to an organic solvent that dissolves 50 g or more in 1 liter of ion-exchanged water at 25 ° C.
Examples of water-miscible organic solvents include alcohols such as ethanol, 1-propanol, 2-propanol, and 1-butanol; glycols such as propylene glycol, butylene glycol, and hexylene glycol; diethylene glycol, triethylene glycol, and tetraethylene glycol. And polyethylene glycol having a weight average molecular weight of about 200, polyglycols such as polyethylene glycol having a weight average molecular weight of about 400, and dipropylene glycol; alkyl ethers such as diethylene glycol monomethyl ether and diethylene glycol dimethyl ether.
Solvents other than water may be used alone or in combination of two or more.
In the liquid cleaning agent, the content of the solvent other than water is preferably 0.1 to 15% by mass with respect to the total mass of the liquid cleaning agent.

-About a bleaching component In the liquid cleaning agent of this invention, hydrogen peroxide can be used as a bleaching component from the point of provision of a bleaching function or a deodorizing function, or the improvement of a coating detergency.
In the liquid detergent, the content of the bleaching component is preferably 0.1 to 5% by mass, and more preferably 1 to 4% by mass with respect to the total mass of the liquid detergent. When the content of hydrogen peroxide is not less than the preferable lower limit, a high bleaching effect is easily obtained. On the other hand, liquid stability can be maintained favorable as it is below the said preferable upper limit. For example, when a container is filled with a liquid cleaning agent and stored, the container hardly expands.

-About metal capture | acquisition component In the liquid detergent of this invention, when using hydrogen peroxide as a bleaching component, it is preferable to use a metal capture | acquisition component together. Thereby, decomposition | disassembly of hydrogen peroxide is suppressed.
As such a metal-trapping component, a phosphonic acid-based metal-trapping component is preferable, and ethane-1,1-diphosphonic acid, ethane-1,1,2-triphosphonate, 1-hydroxyethane-1,1-diphosphonic acid, ethane Examples include hydroxy-1,1,2-triphosphonic acid, ethane-1,2-dicarboxy-1,2-diphosphonic acid, methanehydroxyphosphonic acid, nitrilotrimethylenephosphonic acid, and ethylenediaminetetrakismethylenephosphonic acid.
Among these, 1-hydroxyethane-1,1-diphosphonic acid and ethylenediaminetetrakismethylenephosphonic acid are preferable.
A metal capture component may be used individually by 1 type, and may use 2 or more types together.
In the liquid cleaning agent, the content of the metal-trapping component is preferably 0.05 to 3% by mass, more preferably 0.1 to 3% by mass, and still more preferably 0.1 to 3% by mass with respect to the total mass of the liquid cleaning agent. It is 3 to 3% by mass. When the content of the metal-trapping component is within the above preferred range, the liquid appearance becomes better, and both the stability of the liquid detergent and the stability of the bleaching component are improved.

-About radical trap agent In the liquid cleaning agent of this invention, when using hydrogen peroxide as a bleaching component, it is preferable to use a radical trap agent together. Thereby, decomposition | disassembly of hydrogen peroxide is suppressed.
As a radical trap agent, the conventionally well-known thing used for the detergent for clothes is mentioned. Among these, a phenol radical trapping agent is preferably used as a preferable radical trapping agent because it has a higher effect of trapping radicals than other radical trapping agents.
Examples of the phenol radical trapping agent include dimethoxyphenol, catechol, hydroquinone, p-methoxyphenol, and dibutylhydroxytoluene (BHT).
A phenol type radical trap agent may be used individually by 1 type, and may use 2 or more types together.
In the liquid detergent, the content of the phenol radical trapping agent is preferably 0.01 to 6% by mass, more preferably 0.05 to 5% by mass with respect to the total mass of the liquid detergent, and 0.1 to 3 Mass% is particularly preferred. When the content of the phenol-based radical trapping agent is not less than the preferable lower limit value, decomposition of hydrogen peroxide is sufficiently suppressed. On the other hand, when it is not more than the above-mentioned preferable upper limit value, the stability of the preparation is further improved, for example, precipitation of crystals and separation of the liquid are difficult to occur.

-About fragrance | flavor In the liquid cleaning agent of this invention, you may mix | blend fragrance | flavor amount for a fragrance for the purpose of the added value improvement of goods, etc.
Examples of the fragrance include a fragrance composition containing a fragrance component, a fragrance solvent, and a fragrance stabilizer. As the fragrance component, the fragrance solvent, and the fragrance stabilizer, conventionally known compounds used in garment detergents can be used in appropriate combination.
In the liquid detergent, the content of the fragrance (fragrance composition) is preferably 0.0001 to 15% by mass, and more preferably 0.001 to 10% by mass with respect to the total mass of the liquid detergent.

-About pH adjuster In the liquid detergent of this invention, inorganic acids, such as hydrochloric acid, a sulfuric acid, and phosphoric acid; Organic acids, such as p-toluenesulfonic acid, a citric acid, and a phosphonic acid derivative; Sodium borate; Sodium hydroxide, potassium hydroxide, sodium carbonate, sodium hydrogen carbonate, monoethanolamine, diethanolamine, triethanolamine, ammonia and the like can be used. A pH adjuster may be used individually by 1 type, and may use 2 or more types together.

The liquid detergent of the present invention preferably has a pH of 2 to 7 at 25 ° C, more preferably 4 to 7, and even more preferably 5 to 7. When the pH is in the above preferred range, the storage stability of the liquid detergent is better maintained.
In this specification, the pH of the liquid detergent indicates a value measured by adjusting the liquid detergent to 25 ° C. and using a pH meter (product name: HM-30G, manufactured by Toa DKK Co., Ltd.).

The liquid detergent of the present invention preferably has a viscosity at 25 ° C. of about 10 to 1000 mPa · s, more preferably about 80 to 500 mPa · s, from the viewpoint of dischargeability from the container.
In this specification, the viscosity of the liquid detergent indicates a value measured by adjusting the liquid detergent to 25 ° C. and using a B-type viscometer.

  The liquid detergent of this invention is manufactured by mixing a solvent, (A) component, (B) component, (C) component, and another component as needed by a conventional method.

The liquid detergent of the present invention described above has a high detergency against oil stains and is excellent in antibacterial performance.
By blending the component (B) with the cleaning agent, the effect of removing oil stains attached to the object to be cleaned is enhanced. Moreover, an antibacterial effect is provided by the blending of the component (A). However, when the component (A) is simply added to the component (B), there is a problem that the effect of removing the oil stain is reduced as compared with the case where the component (A) is not used. This is presumably because the addition of the component (A) to the component (B) makes it difficult to obtain the effect of removing oil stains adhering to the object to be washed (the effect of the component (B)).
In the present invention, the component (C) is combined with the component (A) and the component (B). By the synergistic action of these components (A) to (C), the antibacterial effect of the (A) component is exhibited, and the action and effect of the (B) component can be stably obtained. In addition, the liquid detergent of the present invention containing the components (A) to (C) is antibacterial that is higher than the antibacterial effect of the component (A) alone and the oil stain removing effect of the component (B) alone. There are an effect and an oil stain removal effect.
In addition, according to the liquid cleaning agent of the present invention, a sufficient effect of removing oil stains can be obtained even for hydrophobic chemical fibers such as polyester, which have conventionally been difficult to remove oil stains.

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

The composition of the liquid cleaning agent in each example is shown in Tables 1-3.
The raw materials used in this example are as follows.

-(A) component: Cationic surfactant A-1: C12 cation (dodecyl trimethyl ammonium methosulfate), molecular weight 345.1.
A-2: C14 cation (tetradecyltrimethylammonium methosulfate), molecular weight 373.1.
A-3: Didecyldimethylammonium chloride, manufactured by Lion Akzo Co., Ltd., trade name “Arcade 210”, molecular weight 401.1.
A-4: Benzalkonium chloride, manufactured by Lion Akzo Co., Ltd., trade name “Arcade CB-50”, molecular weight 361.5.

-Component (B): Polymer having specific repeating unit (b1) and oxyalkylene unit (b2) B-1: Soil release polymer, manufactured by Clariant GmbH, Germany, trade name "TexCare SRN-100", weight average An assembly comprising a polymer having a molecular weight of 3000, a pH of 4 (measured at 20 ° C., 5 mass% aqueous solution), a viscosity of 340 mPa · s (measured at 50 ° C.), and a polymer represented by the above formula (Bp1).
B-2: Soil release polymer, manufactured by Clariant GmbH, Germany, trade name “TexCare SRN-300”. A weight average molecular weight of 7000, pH 5 (measured at 20 ° C., 5 mass% aqueous solution), viscosity of 650 mPa · s (measured at 50 ° C.), and an aggregate containing the polymer represented by the above formula (Bp1).
Both B-1 and B-2 were prepared by adding 10 g of polymer to 1000 g of water at 40 ° C. in a 1 liter beaker under the above-mentioned conditions of “water-soluble polymer”. 8 mm, length 50 mm) and after 12 hours of agitation (200 rpm), it was dissolved.

-Component (B '): Comparative component of component (B) B'-1: Carboxyvinyl polymer, manufactured by Sumitomo Seika Co., Ltd., trade name "AQUPEC HV-505ED".

-(C) component: amphoteric surfactant C-1: lauryl dimethylamino acetic acid betaine, molecular weight 272.
C-2: Amidopropyl betaine laurate, molecular weight 342.52.

Optional component Nonionic surfactant: R ⁴⁰ in the above general formula (I) = an alkyl group having 12 carbon atoms, polyoxyethylene alkyl ether having k = 6, R ⁴⁰ = an alkyl group having 14 carbon atoms, k = A mixture with 6 polyoxyethylene alkyl ethers.
Anionic surfactant: sodium alkylbenzene sulfonate.
Solvent: diethylene glycol monophenyl ether.
hydrogen peroxide.
Metal capture component: 1-hydroxyethane-1,1-diphosphonic acid.
Radical trapping agent: p-methoxyphenol.
Fragrance: Fragrance composition A described in Tables 7 to 14 of JP-A No. 2003-268398.
pH adjuster: sodium hydroxide.
Water: Purified water.

<Preparation of liquid detergent>
According to the blending components and blending amounts (mass%) of the compositions shown in Tables 1 to 3, 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.
Further, in the table, “(C) / (A) molar ratio” is synonymous with the molar ratio represented by (C) component / (A) component, and the inclusion of component (A) contained in the liquid detergent. It means the ratio of the content (number of moles) of component (C) to the amount (number of moles).
In the table, “(C) / (B) mass ratio” is synonymous with the mass ratio represented by (C) component / (B) component, and the content of component (B) contained in the liquid detergent ( It means the ratio of the content (mass%) of component (C) to (mass%).

The composition of the common component (X) contained in the liquid detergent 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 6.0.
“Balance” indicating the blending amount of water means the balance added so that the total blending amount (% by mass) of all the blending components contained in the liquid detergent is 100% by mass.
Common component (X): Solvent 0.7% by mass, hydrogen peroxide 3% by mass, metal-trapping component 0.75% by mass, radical trapping agent 0.1% by mass, perfume 0.1% by mass, pH adjuster appropriate amount, Water balance.

(Examples 1-21, Comparative Examples 1-8)
According to the blending components and blending amounts (mass%) of the compositions shown in Tables 1 to 3, liquid detergents for each example were prepared by the following procedure.
In a 500 mL beaker, a nonionic surfactant, an anionic surfactant, a component (C), a solvent, a metal-trapping component, a radical trapping agent, and a fragrance are placed, and a magnetic stirrer (MITAMURA KOGYO INC.) Is used. While stirring sufficiently, water was added so that the total amount was 90 parts by mass, and further sufficiently stirred. Subsequently, while adding the component (A) and stirring, an appropriate amount of a pH adjuster was added so that the pH at 25 ° C. was 6.0. Subsequently, while adding the component (B) and hydrogen peroxide and stirring, water was added so that the total amount became 100 parts by mass to obtain a liquid detergent.
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 cleaning agent of each example, "detergency with respect to oil dirt" and "antibacterial performance" were each evaluated by the evaluation method shown below. The results are also shown in Tables 1-3.

[Evaluation of detergency against oil stains]
1) Preparation of oil-stained dirt cloth 0.015 mL of Ra oil (manufactured by Kadoya Oil Co., Ltd.) was dropped on a polyester tropical cloth cut to 3 cm x 3 cm and air-dried at room temperature for 2 to 3 hours. Cloth.
2) Cleaning test 0.12 mL of the same liquid cleaning agent was applied to each of the five oil-stained and soiled cloths and allowed to stand for 5 minutes.
After that, 5 pieces of oily soil dirt cloth were put into a Terg-O-Tometer (manufactured by UNITED STATES TESTING) containing 900 mL of ion exchange water adjusted to a hardness of 3 ° DH and a water temperature of 15 ° C., and washed at 120 rpm for 10 minutes. (Bath ratio 20 times).
Thereafter, 5 sheets of oil-stained dirt cloth after washing are taken out, the cleaning liquid is removed to some extent, and the oil-stained dirt cloth is removed in a dewatering tank of a two-tank washing machine (CW-C30A1 type, manufactured by Mitsubishi Electric Corporation). Dehydrated for a minute.
Further, the dewatered oily soil dirt cloth is rinsed for 3 minutes in a Terg-O-Tometer bath containing 900 mL of ion-exchanged water adjusted to a hardness of 3 ° DH and a water temperature of 15 ° C., and the two-tub washing machine is removed. Dehydrated in a water bath for 1 minute.
The oil-stained and dirty cloth after dehydration is again rinsed for 3 minutes in a Terg-O-Tometer bath containing 900 mL of ion-exchanged water adjusted to a hardness of 3 ° DH and a water temperature of 15 ° C. Was dehydrated in a dehydration tank for 1 minute and then air-dried.
3) Evaluation of detergency Detergency was measured using a colorimetric color difference meter (Nippon Denshoku Co., Ltd., trade name SE2000), before the soil was adhered (polyester tropical cloth before dripping the oil), and before and after the washing test. The Z value of each oil-stained and dirty cloth was measured and evaluated by calculating the washing rate from the following equation. For this evaluation, the average value of the cleaning rate calculated for five oil-stained and dirty cloths was used. The average value of this washing rate is shown in Tables 1-3.
Washing rate (%) = (Z value of the oily soiled cloth after washing−Z value of the oily soiled cloth before washing) / (Z value of the raw soiled dirt cloth−Z value of the oily soiled dirt cloth before washing) ) × 100

[Evaluation of antibacterial performance]
The liquid cleaning agent 0.6g of each example and 1.2g of detergents (JAFET standard detergent, textile product new function evaluation meeting designation | designated detergent) were added to 900 mL of tap water, and it was set as the washing | cleaning liquid.
U.S. previously sterilized with alcohol. S. Using a Terg-O-Tometer of Testing (USA), 0.4 g of a sterilized 3 cm square polyester cloth and a sterilized knitted cloth are put together, the bath ratio is 20 times, 120 rpm, 25 ° C. It was washed under the conditions of This washing was performed for 10 minutes, then dehydrated for 1 minute, and then rinsed with 900 mL of tap water for 2 minutes and dehydrated for 1 minute. The dehydrated 3 cm square polyester cloth was dried on a clean bench at room temperature for 24 hours to obtain a test cloth.

About this test cloth, the bacteriostatic activity value was calculated | required by the following (i) formula according to the quantitative test method (bacterial liquid absorption method) of JISL1902 (the antibacterial test method and antibacterial effect of a textile product). And antibacterial performance was evaluated according to the following evaluation criteria.
Bacteriostatic activity value = (Mb−Ma) − (Md−Mc) (i)
Ma: Average value of common logarithmic values of the number of viable bacteria of three specimens of the standard cloth immediately after inoculation with the test bacteria.
Mb: Average value of common logarithmic values of the number of viable bacteria of three specimens after culturing at 35 ° C. for 18 hours of the standard cloth after inoculation with the test bacteria.
Mc: Average value of the common logarithm of the number of viable bacteria of three specimens of the test cloth immediately after inoculation with the test bacteria.
Md: Average value of common logarithm values of the number of viable bacteria of three specimens after 18 hours of culturing the test cloth after inoculation of the test bacteria.
Standard cloth: Uncleaned and sterilized 3 cm gold cloth.
Test bacteria: Staphylococcus aureus.
Evaluation criteria for antibacterial performance (◎, ○, and △ were accepted)
A: Bacteriostatic activity value is 3 or more.
○: Bacteriostatic activity value is 2.5 or more and less than 3.
(Triangle | delta): Bacteriostatic activity value is 2 or more and less than 2.5.
X: Bacteriostatic activity value is less than 2.

  From the results shown in Tables 1 to 3, the liquid detergents of Examples 1 to 21 to which the present invention was applied have a higher cleaning power against oil stains than the liquid detergents of Comparative Examples 1 to 8, And it can confirm that it is excellent in antibacterial performance.

Claims (1)

(A) component: a cationic surfactant;
(B) component: a polymer having at least one repeating unit (b1) selected from the group consisting of an alkylene terephthalate unit and an alkylene isophthalate unit and an oxyalkylene unit (b2);
(C) component: at least one selected from the group consisting of amphoteric surfactants and semipolar surfactants;
A liquid cleaning agent.