WO2016158724A1 - Cleaning agent for fiber product - Google Patents

Abstract

A cleaning agent for a fiber product, said agent characterized by containing an (A) component: an anionic surfactant; a (B) component: a cationic surfactant; and a (C) component: a polymer having oxyalkylene units (c2) and at least one type of repeating unit (c1) selected from the group consisting of alkylene terephthalate units and alkylene isophthalate units, said polymer having a weight-average molecular weight of 1000-10000, wherein the mass ratio represented by (A) component/(B) component is 1-25.

Description

Cleaning agent for textile products

The present invention relates to a cleaning agent for textile products.
This application claims priority based on Japanese Patent Application No. 2015-070314 filed in Japan on March 30, 2015, the contents of which are incorporated herein by reference.

It is known that oily cosmetics containing polymer compounds such as waxes and silicones typified by lipsticks and foundations are very difficult to remove when attached to textiles. In particular, cosmetics in recent years are prescriptions that are difficult to remove from the skin, and once they adhere to fibers, they become increasingly difficult to remove.
For oily stains (cosmetic stains) derived from such cosmetics, it may not be possible to sufficiently remove the stains even if normal washing is performed by washing, rinsing and dehydrating using an automatic washing machine. Therefore, in addition to performing normal laundry, hand-washed laundry or a stain remover (bleaching agent) that is different from the cleaning agent used for normal laundry, etc. is applied to the part where cosmetic stains are adhered. It is necessary to pre-process. However, there are not a few people who feel that such hand-washing and pretreatment are bothersome, and there is a demand for a cleaning agent that can sufficiently clean cosmetic stains by ordinary washing.
Patent Document 1 discloses a liquid detergent composition containing a nonionic surfactant, xanthan gum, and a specific polyester resin. Patent Document 2 discloses a detergent composition containing a specific ester compound having a branched hydrophilic blocking group and an oligomer or polymer main chain.

Japanese Patent Laid-Open No. 10-298596 Japanese Unexamined Patent Publication No. 63-2954

The present invention has been made in view of the above circumstances, and an object of the present invention is to provide a cleaning agent for textiles that has an excellent cleaning effect against oily dirt.

As a result of intensive studies, the present inventors have found that the following cleaning agents for textile products can solve the above problems.
The present invention has the following aspects.
[1] Component (A): an anionic surfactant;
(B) component: a cationic surfactant;
Component (C): a polymer having at least one repeating unit (c1) selected from the group consisting of an alkylene terephthalate unit and an alkylene isophthalate unit and an oxyalkylene unit (c2) and having a weight average molecular weight of 1,000 to 10,000 Containing,
A cleaning agent for textiles, wherein the mass ratio represented by component (A) / component (B) is 1 to 25.
[2] The detergent for textiles according to [1], further comprising (D) component: a nonionic surfactant.
[3] The cleaning agent for textiles according to claim 1 or 2, wherein the mass ratio represented by (A) component / (C) component is 1 to 30.
[4] The component (A) is selected from the group consisting of linear alkyl benzene sulfonate, polyoxyalkylene alkyl ether sulfate, α-sulfo fatty acid methyl ester, α-olefin sulfonate, and coconut fatty acid salt. The cleaning agent for textiles according to any one of [1] to [3], which is at least one anionic surfactant.
[5] The detergent for textiles according to any one of [1] to [4], wherein the component (B) is a cationic surfactant represented by the following general formula (25).

In the formula (25), R ²⁰ to R ²³ are each independently two or three alkyl groups having 1 to 4 carbon atoms, hydroxyalkyl groups having 1 to 4 carbon atoms, or — (CH ₂ CH ₂ O) _m —. H [m is the average number of repeating oxyethylene groups and is a number from 1 to 25], the other is a straight chain or branched hydrocarbon group having 6 to 28 carbon atoms, and Z ^a− is a pair Is an ion, and a represents the valence of the counter ion.
[6] The fiber product according to any one of [1] to [5], wherein the component (C) includes a polymer compound represented by the following general formula (C1) or the following general formula (C2). Cleaning agent.

In formulas (C1) and (C2), R ³⁰ and R ⁴⁰ are each independently a hydrogen atom or a methyl group, R ³⁴ and R ³⁷ are each a methyl group or a hydrogen atom, R ³⁵ , R ³⁶ , R ³⁸ and R ³⁹ are each independently an alkylene group having 2 to 4 carbon atoms, s1 and s2 are each 0 to 10, and t1, t2, u1 and u2 are each independently 1 to 100.
[7] The detergent for textiles according to any one of [1] to [6], wherein the content of the component (A) is 1 to 40% by mass with respect to the total mass of the detergent. .
[8] The fiber product according to any one of [1] to [7], wherein the content of the component (B) is 0.01 to 15% by mass with respect to the total mass of the cleaning agent. Washing soap.
[9] The fiber product according to any one of [1] to [8], wherein the content of the component (C) is 0.1 to 5% by mass with respect to the total mass of the cleaning agent. Washing soap.

The cleaning agent for textile products of the present invention is superior in the cleaning effect against oily dirt.

(Cleaning agent for textile products)
The detergent for textiles of the present invention (hereinafter also simply referred to as “cleaner”) is a composition containing the components (A) to (C).

<(A) component>
The component (A) is an anionic surfactant. The cleaning agent of the present invention contains the component (A) together with the components (B) and (C), which will be described later, so that the detergency against oily dirt is enhanced.
(A) As a component, the well-known anionic surfactant currently used for cleaning agents for textiles etc. is mentioned.
Examples of the component (A) include linear alkylbenzene sulfonic acid or a salt thereof; α-olefin sulfonate; linear or branched alkyl sulfate ester salt; alkyl ether sulfate ester salt or alkenyl ether sulfate ester salt; Α-sulfo fatty acid ester salt; fatty acid, alkyl ether carboxylic acid, polyoxyalkylene ether carboxylic acid, alkyl (or alkenyl) amide ether carboxylic acid, acylaminocarboxylic acid or anion interface of carboxylic acid type such as salts thereof Activating agent: Phosphate type anionic surface activity such as alkyl phosphate ester salt, polyoxyalkylene alkyl phosphate ester salt, polyoxyalkylene alkylphenyl phosphate ester salt, glycerin fatty acid ester monophosphate ester salt Sex agents and the like.
Examples of these salts include alkali metal salts such as sodium and potassium, alkaline earth metal salts such as magnesium, alkanolamine salts such as monoethanolamine salts and diethanolamine salts.

Of the above, the linear alkyl benzene sulfonic acid or a salt thereof preferably has 8 to 16 carbon atoms in the linear alkyl group, and particularly preferably has 10 to 14 carbon atoms.
As the α-olefin sulfonate, those having 10 to 20 carbon atoms are preferable.
The alkyl sulfate ester salt preferably has 10 to 20 carbon atoms.
The alkyl ether sulfate ester salt or alkenyl ether sulfate ester salt is preferably a polyoxyalkylene alkyl ether sulfate ester salt or a polyoxyalkylene alkenyl ether sulfate ester salt, and is a linear or branched alkyl group or alkenyl having 10 to 20 carbon atoms. A polyoxyalkylene alkyl ether sulfate ester or polyoxyalkylene alkenyl having a group and having an average of 1 to 5 moles of alkylene oxide (for example, at least one alkylene oxide selected from the group consisting of ethylene oxide and propylene oxide) added thereto Ether sulfate ester salts are more preferred.
As the alkane sulfonate, a secondary alkane sulfonate having an alkyl group having 10 to 20 carbon atoms, preferably 14 to 17 carbon atoms is preferable.
The α-sulfo fatty acid ester salt is preferably an α-sulfo fatty acid ester salt having a fatty acid residue having 10 to 20 carbon atoms.
The fatty acid or salt thereof is preferably a fatty acid having 10 to 20 carbon atoms or a salt thereof.

As the component (A), one type may be used alone, or two or more types may be used in combination.
Of these, linear alkylbenzene sulfonic acid or a salt thereof, α-olefin sulfonate, alkyl sulfate ester, alkyl ether sulfate, alkenyl ether sulfate, One or more anionic surfactants selected from alkane sulfonates and α-sulfo fatty acid ester salts are preferred, and one or more selected from linear alkylbenzene sulfonic acids or salts thereof, and polyoxyalkylene alkyl ether sulfate esters. The anionic surfactant is more preferable.
As the component (A), one type may be used alone, or two or more types may be used in combination.

Further, the content of the component (A) in the cleaning agent is preferably 1 to 40% by mass with respect to the total mass of the cleaning agent. Among these ranges, 2 to 30% by mass is preferable, 3 to 25% by mass is more preferable, 5 to 25% by mass is further preferable, 7 to 25% by mass is particularly preferable, and 10 to 20% by mass is most preferable. When the content of the component (A) is in the above preferable range, the reattachment preventing effect is easily enhanced. Furthermore, it is easy to obtain a cleaning agent that suppresses denaturation of enzymes and the like and has excellent blending stability.

In view of further enhancing the cleaning effect on oily soil, the above linear alkylbenzene sulfonic acid or its salt, α-olefin sulfonate, alkyl sulfate ester salt, alkyl ether sulfate ester salt, alkenyl ether sulfate ester salt, alkane sulfonate salt And the content of one or more anionic surfactants selected from α-sulfo fatty acid ester salts is preferably 70% by mass or more, and 75% by mass or more with respect to the total mass of component (A). More preferably, it is more preferably 80% by mass or more, and may be 100% by mass.
In addition, the content of the fatty acid or a salt thereof is preferably 0 to 30% by mass, and preferably 0 to 20% by mass with respect to the total mass of the component (A), in order to further improve the cleaning effect on oily soil. More preferably.

As component (A), at least one anionic surfactant selected from the group consisting of linear alkylbenzene sulfonic acids and salts thereof (hereinafter also referred to as component (a1)), and polyoxyalkylene alkyl ether sulfates It is preferable to use in combination with at least one anionic surfactant selected from the group consisting of a salt and a polyoxyalkylene alkenyl ether sulfate salt (hereinafter also referred to as component (a2)). In this case, the mass ratio of the component (a1) to the component (a2) (the mass ratio represented by the component (a1) / the component (a2)) is preferably 0.05 to 5, and preferably 0.1 to 1. More preferred is 0.2 to 0.5.

<(B) component>
Component (B) is a cationic surfactant. The cleaning agent of the present invention contains the component (B) together with the component (A) and the component (C) described later, thereby increasing the cleaning power against oily dirt.
Examples of the component (B) include quaternary ammonium salt type surfactants (hereinafter sometimes referred to as the component (b1)).

Examples of the component (b1) include a compound represented by the following general formula (25) or a compound represented by the following general formula (26).

(25) In the formula, R ²⁰ to R ²³ are each independently two or three alkyl groups having 1 to 4 carbon atoms, hydroxyalkyl groups having 1 to 4 carbon atoms, or — (CH ₂ CH ₂ O) _m —. H [m is the average number of repeating oxyethylene groups (that is, the average number of moles of ethylene oxide added) and is a number from 1 to 25], and the others are straight-chain or branched carbonization having 6 to 28 carbon atoms. It is a hydrogen group. Z ^a− is a counter ion. a represents the valence of the counter ion.

The hydrocarbon group may be saturated or unsaturated, and may have at least one group selected from the group consisting of a substituent and a linking group. The substituent is preferably a hydroxy group or an amino group, and the linking group is preferably an amide group, an ester group or an ether group. The hydrocarbon group preferably has 7 to 27 carbon atoms, more preferably 7 to 25 carbon atoms. The carbon number of the hydrocarbon group does not include the carbon number of the substituent or the linking group.

Z ^a- The, fluorine ion, chlorine ion, bromine ion, a halogen ion such as iodide ion, alkyl sulfate ion or the like having an alkyl group having 1 to 3 carbon atoms.

In the compound represented by the formula (25), R ²⁰ 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 ²¹ to A compound in which R ²³ is each independently an alkyl group having 1 to 4 carbon atoms or a hydroxyalkyl group having 1 to 4 carbon atoms (hereinafter referred to as component (b25-1)); R ²⁰ and R ²¹ 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, wherein R ²² and R ²³ are each independently an alkyl group having 1 to 4 carbon atoms. Alternatively, a compound having a hydroxyalkyl group having 1 to 4 carbon atoms (hereinafter referred to as component (b25-2)) is preferable.

As the component (b25-1), R ²⁰ is preferably an alkyl group or alkenyl group having 8 to 22 carbon atoms, more preferably an alkyl group or alkenyl group having 10 to 18 carbon atoms, and an alkyl group having 10 to 14 carbon atoms. Or an alkenyl group is more preferable. R ²¹ to R ²³ are each independently preferably an alkyl group having 1 to 3 carbon atoms, any one is more preferably a methyl group, and all are more preferably a methyl group.

As the component (b25-2), R ²⁰ and R ²¹ are each independently preferably an alkyl group or alkenyl group having 8 to 12 carbon atoms, and more preferably an alkyl group or alkenyl group having 8 to 10 carbon atoms. R ²² and R ²³ are each independently preferably an alkyl group having 1 to 3 carbon atoms, and any one is more preferably a methyl group, and both are more preferably a methyl group.

As the compound represented by the formula (25), a compound represented by the following general formula (25-a) can also be used.

In the formula (25-a), R ²⁴ and R ²⁵ 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.
EO represents an oxyethylene group, and x and y are numbers greater than 0 representing the average number of repeating oxyethylene groups. x + y = 10 or more, preferably 10-50. Z ^b- is a counter ion and has the same meaning as Z ^a- in the formula (25).

(25-a) In the formula, any one of R ²⁴ and R ²⁵ is a linear or branched alkyl group having 10 to 18 carbon atoms or a linear or branched alkenyl group having 10 to 18 carbon atoms, The other is preferably a methyl group or a tolyl group.

(26) In the formula, R ²⁶ 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 ²⁷ and R ²⁸ are each independently Or an alkyl group having 1 to 3 carbon atoms or a hydroxyalkyl group having 1 to 3 carbon atoms, and R ²⁹ is an alkylene group having 1 to 4 carbon atoms. Z ^c- is a counter ion and has the same meaning as Z ^a- in the formula (25).

In the formula (26), R ²⁶ preferably has 10 to 18 carbon atoms, more preferably 12 to 14 carbon atoms. R ²⁷ and R ²⁸ are each independently preferably an alkyl group having 1 to 3 carbon atoms, one of which is more preferably a methyl group, and more preferably a methyl group. R ²⁹ is preferably a methylene group.

Examples of the component (b1) include alkyl chloride (C10-18) trimethylammonium, didecyldimethylammonium chloride, benzalkonium chloride, and the like.

As the component (B), any one type may be used alone, or two or more types may be used in combination.
(B) As a component, the compound represented by General formula (25) is preferable. Among the compounds represented by the general formula (25), the component (b25-1) is preferable. Among the components (b25-1), a compound in which R ²⁰ in the general formula (25) is an alkyl group or alkenyl group having 10 to 18 carbon atoms, and R ²¹ to R ²³ are all methyl groups is preferable. More preferred is a compound in which ²⁰ is an alkyl group or alkenyl group having 10 to 14 carbon atoms, and R ²¹ to R ²³ are all methyl groups.
When the compound is used together with the component (A) and the component (C) described later, the cleaning effect on oily soil is more likely to be enhanced.

The content of the component (B) in the cleaning agent is preferably 0.01 to 15% by mass and more preferably 0.1 to 10% by mass with respect to the total mass of the cleaning agent. When the content of the component (B) is in the above-described preferable range, the mass ratio of the component (A) to the component (B) can be easily adjusted to a specific range of the present application, and the cleaning effect on oily dirt is easily enhanced. .

<(C) component>
The component (C) is a polymer having at least one repeating unit (c1) and oxyalkylene unit (c2) selected from the group consisting of alkylene terephthalate units and alkylene isophthalate units.
Since the cleaning agent of the present invention contains the component (C) together with the components (A) and (B), the cleaning effect on oily dirt is enhanced.
In the present specification, “repeating unit” means a monomer unit constituting a polymer.

-Specific repeating unit (c1) Among the specific repeating unit (c1), the alkylene terephthalate unit (hereinafter, this repeating unit is also referred to as "repeating unit (c11)") is represented by the following general formula (c1-1) The repeating unit represented by these is mentioned.

In formula (c1-1), R ³¹ represents a lower alkylene group. The number of carbon atoms of the lower alkylene group for R ³¹ is preferably 1 to 5, more preferably 1 to 4, and still more preferably 2 to 4.
Specific examples of the repeating unit (c11) 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, and a tert-butylene terephthalate unit. It is done. Of these, isopropylene terephthalate units are preferred.
As the repeating unit (c11), one type may be used alone, or two or more types may be used in combination.

Among the specific repeating units (c1), the alkylene isophthalate unit (hereinafter, this repeating unit is also referred to as “repeating unit (c12)”) includes a repeating unit represented by the following general formula (c1-2). It is done.

In the formula (c1-2), R ³² represents a lower alkylene group. The number of carbon atoms of the lower alkylene group for R ³² is preferably 1 to 5, more preferably 1 to 4, and still more preferably 2 to 4.
Specific examples of the repeating unit (c12) include ethylene isophthalate units, n-propylene isophthalate units, isopropylene isophthalate units, n-butylene isophthalate units, sec-butylene isophthalate units, tert-butylene isophthalate units, and the like. Is mentioned. Of these, isopropylene isophthalate units are preferred.
As the repeating unit (c12), one type may be used alone, or two or more types may be used in combination.

(C) A component may have only 1 type of repeating units (c1), and may have 2 or more types. That is, the component (C) may have only the repeating unit (c11) as the repeating unit (c1) or may have only the repeating unit (c12) in one molecule. You may have both a unit (c11) and a repeating unit (c12). Moreover, you may have 2 or more types of repeating units (c11), and may have 2 or more types of repeating units (c12).
The repeating unit (c1) may be introduced as one unit in one molecule, or may be introduced as two or more units (that is, in a block form).

The number of repeating units (c1) contained in one molecule in the component (C) is preferably 1 to 10, more preferably 1 to 6, and further preferably 1 to 4.
When the number of the repeating units (c1) is within the above preferred range, the cleaning effect on oily dirt is likely to be enhanced.

-Oxyalkylene unit (c2) Examples of the oxyalkylene unit (hereinafter, this repeating unit is also referred to as "repeating unit (c2)") include repeating units represented by the following general formula (c2-1).

In formula (c2-1), R ³³ represents a lower alkylene group. The number of carbon atoms of the lower alkylene group for R ³³ is preferably 1 to 4, more preferably 2 to 4, and still more preferably 2 or 3.
Examples of the repeating unit (c2) include an oxyethylene unit, an oxypropylene unit, and an oxybutylene unit. Of these, oxyethylene units and oxypropylene units are preferred.

(C) A component may have 1 type of repeating units (c2), and may have 2 or more types. That is, the component (C) may have, for example, only the oxyethylene unit, only the oxypropylene unit, or only the oxyethylene unit as the repeating unit (c2) in one molecule. And an oxypropylene unit.
In addition, the component (C) may have an oxyalkylene group (one having a repeating unit (c2) of 1) as a repeating unit (c2) in one molecule, and a polyoxyalkylene group (The number of repeating units (c2) is 2 or more) and may have both an oxyalkylene group and a polyoxyalkylene group.

The number of repeating units (c2) contained in one molecule in component (C) is 1 or more, preferably 1 to 100, more preferably 1 to 80, and still more preferably 1 to 50.
When the number of repeating units (c2) is in the above preferred range, the cleaning effect on oily soil is likely to be enhanced.

The component (C) may be a polymer in which the repeating unit (c1) and the repeating unit (c2) are polymerized in a block shape or a polymer in which the repeating unit (c2) is polymerized in a random shape. Among these, as the component (C), a polymer polymerized in a block shape is preferable.

The component (C) may have other repeating units in addition to the repeating unit (c1) and the repeating unit (c2). 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 (c1) or the repeating unit (c2), and the like. It is done.
When component (C) has other repeating units, the total of repeating unit (c1) and repeating unit (c2) is 80 with respect to the total number of moles of all repeating units constituting component (C). It is preferably at least mol%, more preferably at least 90 mol%, and may be 100 mol%. When the total number of moles of the repeating unit (c1) and the repeating unit (c2) is equal to or more than the preferable lower limit value, the cleaning effect on oily dirt is easily enhanced.

The component (C) is preferably a water-soluble polymer from the viewpoint of its own solubility and liquid stability when used as a 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 weight average molecular weight of the component (C) is 1000 to 10000, preferably 1000 to 8000, more preferably 1000 to 7000, and particularly preferably 1500 to 7000. When the weight average molecular weight of the component (C) is in the above preferred range, the cleaning effect on oily soil is likely to be enhanced.
In addition, the weight average molecular weight in this invention shows the value which converted the value measured by GPC (gel permeation chromatography) using THF (tetrahydrofuran) as a solvent based on the calibration curve in PEG (polyethylene glycol).

Component (C) is a synthesis method disclosed in various documents, textbooks, patent documents, etc., for example, Journal of Polymer Science, Volume 3, pages 609-630 (1948); Journal of Polymer Science, 8th. Volume 1 pages 22 (1951); can be produced by the method described in JP-A-61-218699.

Specific examples of suitable component (C) include a polymer compound represented by the following general formula (C1), a polymer compound represented by the general formula (C2), or a mixture thereof. .

In the formulas (C1) and (C2), R ³⁰ and R ⁴⁰ are each independently a hydrogen atom or a methyl group, each preferably a methyl group, and more preferably a methyl group. .
R ³⁴ and R ³⁷ are each a methyl group or a hydrogen atom, and each is preferably a methyl group.
R ³⁵ , R ³⁶ , R ³⁸ and R ³⁹ are each independently an alkylene group having 2 to 4 carbon atoms.
s1 and s2 are each 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, more preferably 1 to 50, still more preferably 10 to 50, and particularly preferably 20 ~ 30. When s1, s2, t1, t2, u1, and u2 are within the above preferred ranges, the blending effect of the component (C) is sufficiently exhibited. Moreover, the solubility with respect to water improves more and when it mix | blends with a liquid cleaning agent, it becomes easy to obtain the cleaning agent which is excellent in a transparent feeling.

In (C1), the ratio [s1: (t1 + u1)] of s1 to (t1 + u1) is preferably 1: 5 to 1:20, and more preferably 1: 8 to 1:18. When the ratio of s1 to (t1 + u1) is in the above preferred range, the cleaning effect on oily soil is enhanced and the solubility in water is enhanced.
The ratio [s2: (t2 + u2)] between s2 and (t2 + u2) in (C2) is preferably in the same range as the ratio [s1: (t1 + u1)].

As the component (C), one type may be used alone, or two or more types may be used in combination.
Moreover, as (C) component, a synthetic product may be used and a commercial item may be used.
Commercially available products of component (C) include trade name TexCare SRN-100 (Clariant, weight average molecular weight 2000-3000), trade name TexCare SRN-300 (Clariant, weight average molecular weight 7000), trade name Repel- Examples thereof include O-Tex Crystal (manufactured by Rhodia) and trade name Repel-O-Tex QC (manufactured by Rhodia).
Among these, TexCare SRN-100 is preferable because it is highly soluble in water and excellent in storage stability. Further, from the viewpoint of excellent handleability, it is preferable to use a trade name TexCare SRN-170 (manufactured by Clariant) commercially available as a 70% aqueous solution of the TexCare SRN-100.

The content of the component (C) is preferably 0.1 to 5% by mass, more preferably 0.5 to 3% by mass, and further preferably 0.5 to 1% by mass with respect to the total mass of the cleaning agent.
When the content of the component (C) is equal to or more than the above preferable lower limit value, the cleaning effect on oily dirt is likely to be enhanced. When the amount is not more than the above preferable upper limit value, it becomes easy to obtain a cleaning agent having excellent blending stability.

Mass ratio represented by (A) component / (B) component [mass ratio of content of (A) component to content of (B) component, hereinafter also referred to as “A / B ratio”. ] Is 1 to 25, preferably 1 to 22, more preferably 4 to 22, and still more preferably 10 to 20. When the A / B ratio is less than 1 or the A / B ratio is more than 25, a sufficient cleaning effect for oily dirt cannot be obtained. On the other hand, if the A / B ratio is less than 1, it is difficult to sufficiently obtain the effect of preventing reattachment to oily dirt.

Mass ratio represented by (A) component / (C) component [mass ratio of content of (A) component to content of (C) component, hereinafter also referred to as “A / C ratio”. ] Is preferably 1 to 30, more preferably 1 to 25, still more preferably 2 to 20, and particularly preferably 5 to 20. If the A / C ratio is less than 1 or more than 30, a sufficient cleaning effect on oily dirt cannot be obtained. On the other hand, if the A / C ratio is less than 1, it is difficult to sufficiently obtain the effect of preventing re-adhesion against oily dirt.

Mass ratio represented by (B) component / (C) component [mass ratio of content of (B) component to content of (C) component, hereinafter also referred to as “B / C ratio”. ] Is preferably from 0.1 to 5, more preferably from 0.2 to 4, still more preferably from 0.5 to 3, particularly preferably from 1 to 2. When the B / C ratio is in the above-described preferable range, the cleaning power against oily dirt is easily increased.

((A) component + (B) component) / mass ratio represented by (C) component [the mass ratio of the total content of (A) component and (B) component to the content of (C) component, below Also referred to as “(A + B) / C ratio”. ] Is preferably 1 to 30, more preferably 1 to 25, still more preferably 1 to 20, and particularly preferably 4 to 20. When the (A + B) / C ratio is in the above-described preferable range, the detergency against oily dirt is easily increased.

<Other ingredients>
In addition to the above components (A) to (C), the cleaning agent of the present invention may contain other components usually used for cleaning agents.
Examples of other components include surfactants other than the components (A) and (B), water-miscible organic solvents, solvents, metal ion scavengers (chelating agents), inorganic salts, antioxidants, proteases, and lipases. Enzymes such as cellulases, alkali builders, hydrotropes, preservatives, enzyme stabilizers, texture improvers, storage stability improvers, fluorescent agents, dye transfer inhibitors, recontamination inhibitors (however, component (C) is Not included), pearl agent, soil release agent (however, component (C) is not included), flavoring agent, coloring agent, emulsifying agent, natural product extract, pH adjusting agent and the like.

Examples of the surfactant other than the component (A) and the component (B) include nonionic surfactants (component (D)) and amphoteric surfactants.
<(D) component>
Nonionic surfactants include, for example, higher alcohols having 10 to 20 carbon atoms, alkylphenols, higher fatty acids having 10 to 20 carbon atoms, alkyl esters of higher fatty acids having 10 to 20 carbon atoms, or higher amines having 10 to 20 carbon atoms. Polyoxyalkylene type nonionic surfactant added with alkylene oxide, polyoxyethylene polyoxypropylene block copolymer, fatty acid alkanolamine, fatty acid alkanolamide, polyhydric alcohol fatty acid ester or alkylene oxide adduct thereof, addition of alkylene oxide of hydrogenated castor oil Body, sugar fatty acid ester, N-alkyl polyhydroxy fatty acid amide, alkyl glycoside and the like.

Among the nonionic surfactants, polyoxyalkylene type nonionic surfactants (hereinafter sometimes referred to as “component (d1)”) represented by the following general formula (d1) are preferable.
R ⁴¹ —X ² — [(EO) _p / (PO) _q ] —R ⁴² (d1)
(In the formula (d1), R ⁴¹ is a hydrocarbon group having 8 to 22 carbon atoms, X ² is O or COO, EO represents an oxyethylene group, and PO represents an oxypropylene group. In [(EO) _p / (PO) _q ], EO and PO may be random polymerization or block polymerization, and when X ² is O, R ⁴² is a hydrogen atom, and p is a number from 3 to 20. And q is a number from 0 to 6. When X ² is COO, R ⁴² is an alkyl group having 1 to 2 carbon atoms, p is a number from 6 to 20, and q is 0 It is a number of ~ 6.)

In the formula (d1), R ⁴¹ is a hydrocarbon group having 8 to 22 carbon atoms. The carbon number of R ⁴¹ is preferably 10 to 18 from the viewpoint of improving detergency. R ⁴¹ is preferably an alkyl group or an alkenyl group, and may be linear or branched. Examples of R ⁴¹ include alkyl groups or alkenyl groups derived from raw materials such as primary or secondary higher alcohols, higher fatty acids, and higher fatty acid amides.

X ² is O or COO.
When X ² is O, R ⁴² is a hydrogen atom. That is, when X ² is O, the component (d1) is an alcohol alkoxylate.
When X ² is O, R ⁴¹ is preferably a linear or branched alkyl group or a linear or branched alkenyl group from the viewpoint of further improving detergency.
When X ² is O, R ⁴¹ preferably has 10 to 22 carbon atoms, more preferably 10 to 20 carbon atoms, and still more preferably 10 to 18 carbon atoms.

When X ² is COO, R ⁴² is an alkyl group having 1 to 2 carbon atoms. That is, when ^{X 2} is COO, (d1) component is a fatty acid alkyl ester alkoxylates.
When X ² is COO, R ⁴¹ is preferably a linear or branched alkyl group or a linear or branched alkenyl group from the viewpoint of further improving the detergency.
When X ² is COO, R ⁴¹ preferably has 9 to 21 carbon atoms, more preferably 11 to 21 carbon atoms.

In formula (d1), p is a number representing the average number of repetitions of EO.
When X ² is O, p is a number of 3 to 20, preferably 5 to 18, more preferably 6 to 18, still more preferably 11 to 18, and particularly preferably 14 to 18. If it is less than the above lower limit, the hydrophilicity becomes low, and the stability of the enzyme tends to deteriorate due to an increase in free water in the system, and if it exceeds the above upper limit, the hydrophilicity becomes too high and the detergency is increased. May decrease.
When X ² is COO, p is a number of 6 to 20, preferably 6 to 18, and more preferably 11 to 18. If it is less than the above lower limit, the hydrophilicity becomes low, and the stability of the enzyme tends to deteriorate due to an increase in free water in the system, and if it exceeds the above upper limit, the hydrophilicity becomes too high and the detergency is increased. May decrease.

In the formula (d1), q is a number representing the average number of repetitions of PO.
When X ² is O, q is a number from 0 to 6, preferably 0 to 3. It becomes easy to improve the liquid stability at the time of mix | blending with a liquid detergent as it is below the said upper limit.
When X ² is COO, q is a number from 0 to 6, preferably 0 to 3. It becomes easy to improve the liquid stability at the time of mix | blending with a liquid detergent as it is below the said upper limit.
When q is 1 or more, the oxyethylene group and the oxypropylene group may be random polymerization or block polymerization.

The distribution of p or q in the formula (d1) varies depending on the reaction method in producing the component (d1). For example, when ethylene oxide or propylene oxide is added to a raw material using sodium hydroxide, potassium hydroxide or the like, which is a general alkali catalyst, the distribution of p or q becomes relatively wide. A specific alkoxylation catalyst such as magnesium oxide to which metal ions such as Al ³⁺ , Ga ³⁺ , In ³⁺ , Tl ³⁺ , Co ³⁺ , Sc ³⁺ , La ³⁺ , Mn ^{2+ and the} like described in JP-B-6-15038 is added. When ethylene oxide or propylene oxide is added to the raw material, the distribution of p or q becomes relatively narrow.

These (d1) components may be used singly or in combination of two or more.

When the cleaning agent of the present invention contains a nonionic surfactant, the content of the nonionic surfactant is preferably more than 0% by mass and 70% by mass or less, and 0.5 to 70% by mass with respect to the total mass of the cleaning agent. % Is more preferable, 5 to 50% by mass is further preferable, and 20 to 40% by mass is particularly preferable.
If it is more than the said lower limit, the further improvement of the cleaning power of a cleaning agent will become easy, and if it is below the said upper limit, the mixing | blending stability of a cleaning agent will become easy to be improved.
The mass ratio represented by (A) component / (D) component [mass ratio of (A) component to the content of (D) component, hereinafter also referred to as “A / D ratio”. ] Is preferably from 0.1 to 5, more preferably from 0.15 to 1. When the A / D ratio is within this range, the cleaning effect for oily dirt can be sufficiently exhibited while the viscosity of the liquid is suitably maintained.

Amphoteric surfactants include alkylbetaine type, alkylamide betaine type, imidazoline type, alkylaminosulfonic acid type, alkylaminocarboxylic acid type, alkylamidecarboxylic acid type, amide amino acid type, and phosphoric acid type. Is mentioned.

In the cleaning agent of the present invention, the total content of the surfactant is preferably 1 to 80% by weight, more preferably 10 to 70% by weight, still more preferably 20 to 65% by weight, based on the total weight of the cleaning agent. 30 to 60% by mass is particularly preferable, and 40 to 55% by mass is most preferable.

When the cleaning agent of the present invention is a liquid cleaning agent, the water-miscible organic solvent is improved in terms of improved coating cleaning performance, improved formulation stability, reduced viscosity and improved usability. It is preferable to contain.
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, tetraethylene glycol, Examples include polyglycols such as polyethylene glycol and dipropylene glycol having a weight average molecular weight of about 200 to 1,000; alkyl ethers such as diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, diethylene glycol monobutyl ether (butyl carbitol), and diethylene glycol dimethyl ether.
Among these, ethanol, propylene glycol, polyethylene glycol, and diethylene glycol monobutyl ether (butyl carbitol) are preferable from the viewpoints of low odor, availability, liquid stability when used as a liquid detergent, fluidity, and the like.
One type of water-miscible organic solvent may be used alone, or two or more types may be used in combination.
The content of the water-miscible organic solvent is preferably 3 to 20% by mass with respect to the total mass of the cleaning agent.
In the present invention, the water-miscible organic solvent means an organic solvent that dissolves 50 g or more in 1 L of ion-exchanged water at 25 ° C.

When the cleaning agent of the present invention is a liquid cleaning agent, it is preferable to contain water as a solvent from the viewpoint of ease of preparation, solubility in water when used, and the like.
The content of water in the case of a liquid detergent can be appropriately set according to the contents of the components (A) to (C) and other optional components, but is usually based on the total mass of the liquid detergent. It is 10 to 90% by mass, preferably 20 to 80% by mass.

Examples of the metal ion scavenger include malonic acid, succinic acid, malic acid, diglycolic acid, tartaric acid, citric acid and the like.
One kind of metal ion scavenger may be used alone, or two or more kinds may be used in combination.
The content of the metal ion scavenger is preferably 0.1 to 20% by mass with respect to the total mass of the cleaning agent.

Although it does not specifically limit as antioxidant, It is preferable to use a phenolic antioxidant from the point which is easy to obtain favorable detergency and compounding stability. Examples of phenolic antioxidants include monophenolic antioxidants such as dibutylhydroxytoluene and butylhydroxyanisole, bisphenolic antioxidants such as 2,2′-methylenebis (4-methyl-6-t-butylphenol), dl And high molecular phenolic antioxidants such as -α-tocopherol. Among these, monophenolic antioxidants and polymer phenolic antioxidants are preferable. As the monophenol antioxidant, dibutylhydroxytoluene is preferable, and as the polymer phenol antioxidant, dl-α-tocopherol is preferable.
One type of antioxidant may be used alone, or two or more types may be used in combination.
The content of the antioxidant is preferably 0.01 to 2% by mass with respect to the total mass of the cleaning agent.

As the enzyme, a protease is preferable. By blending protease, it is possible to further improve the detergency against protein stains and further enhance the bactericidal effect.
As the protease, commercially available protease preparations can be used, for example, Savinase 16L, Savinase Ultra 16L, Savinase Ultra 16XL, Everase 16L Type EX, Everase Ultra 16L, Esperase 8L, Esperase 8L, 2.5 .5L, Liquanase Ultra 2.5L, Liquanase Ultra 2.5XL, Coronase 48L (all are trade names, manufactured by Novozymes), Purefect L, Purefect OX, Properase L (all are trade names, manufactured by Genencor) .
One type of enzyme may be used alone, or two or more types may be used in combination.
When the enzyme is contained in the cleaning agent of the present invention, the total content thereof is preferably 0.01 to 4% by mass, more preferably 0.1 to 2% by mass, more preferably 0. More preferably 4 to 1% by mass.

Examples of the alkali builder include alkanolamines such as monoethanolamine, diethanolamine, and triethanolamine.
One type of alkali builder may be used alone, or two or more types may be used in combination.
The content of the alkali builder is preferably 0.5 to 5% by mass with respect to the total mass of the cleaning agent.

When the cleaning agent of the present invention is a liquid cleaning agent, it preferably contains a hydrotrope agent. As a hydrotrope agent, aromatic sulfonic acid or its salt is mentioned. Examples of the aromatic sulfonic acid or a salt thereof include toluene sulfonic acid, xylene sulfonic acid, cumene sulfonic acid, substituted or unsubstituted naphthalene sulfonic acid, or a salt thereof.
Examples of the salt include sodium salt, potassium salt, calcium salt, magnesium salt, ammonium salt, alkanolamine salt and the like.
One hydrotrope agent may be used alone, or two or more hydrotrope agents may be used in combination.
The content of the hydrotrope is preferably 0.01 to 15% by mass with respect to the total mass of the cleaning agent.

Examples of the preservative include trade name caisson CG manufactured by Rohm and Haas. The content of the preservative is preferably 0.001 to 1% by mass with respect to the total mass of the cleaning agent.
Moreover, you may contain a benzoic acid or its salt (it also has an effect as a preservative) for the purpose of a storage stability improvement. Examples of the salt include sodium salt, potassium salt, calcium salt, magnesium salt, ammonium salt, alkanolamine salt and the like.
The content of benzoic acid or a salt thereof is preferably 0.1 to 5% by mass and more preferably 0.15 to 2% by mass with respect to the total mass of the cleaning agent.

For the purpose of stabilizing the enzyme, boric acid, borax, formic acid, lactic acid or salts thereof; calcium salts such as calcium lactate, calcium chloride, calcium sulfate, etc. are preferably 0 to 2% by mass with respect to the total mass of the cleaning agent. You may contain.
For the purpose of improving the texture, silicone such as dimethyl silicone, polyether-modified silicone, amino-modified silicone and the like may be contained preferably in an amount of 0 to 5% by mass with respect to the total mass of the cleaning agent.
For the purpose of improving the whiteness of white clothing, a fluorescent whitening agent such as a distyrylbiphenyl type may be preferably contained in an amount of 0 to 1% by mass based on the total mass of the cleaning agent.
For the purpose of preventing migration or recontamination, a recontamination inhibitor other than component (C) such as polyvinylpyrrolidone and carboxymethylcellulose may preferably be contained in an amount of 0 to 2% by mass or less based on the total mass of the cleaning agent. Good.
Moreover, you may contain soil release agents other than a pearl agent and (C) component.

For the purpose of improving the added value of products, flavoring agents, coloring agents, emulsifying agents, natural product extracts and other extracts may be blended in the cleaning agent.
Examples of the flavoring agent include fragrance compositions A, B, C, and D described in Tables 11 to 18 of JP-A No. 2002-146399. The blending amount of the flavoring agent is preferably 0.1 to 1% by mass with respect to the total mass of the cleaning agent.
General-purpose dyes and pigments such as Acid Red 138, Polar Red RLS, Acid Yellow 203, Acid Blue 9, Blue No. 1, Blue No. 205, Green No. 3, Turquoise P-GR (all trade names) Is mentioned. The blending amount of the colorant is preferably 0.00005 to 0.005% by mass with respect to the total mass of the cleaning agent.
Examples of the emulsifying agent include polystyrene emulsion and polyvinyl acetate emulsion, and usually an emulsion having a solid content of 30 to 50% by mass is preferably used. Examples of the emulsifying agent include polystyrene emulsion (manufactured by Seiden Chemical Co., Ltd .: trade name: Cybinol RPX-196 PE-3, solid content: 40% by mass).
Extracts include Inuenju, waurusushi, echinacea, koganebana, yellowfin, yellow spider, allspice, oregano, enju, chamomile, honeysuckle, clara, keigai, kei, bay geese, honoki, burdock, comfrey, ginger, walrus, ginger, ginger , Sequoia spp. , Pokeweed, cedar, yamajiso, eucalyptus, lavender, rose, rosemary, balun, cedar, gilead balsam, hakse , Kochia, Polygonum aviculare, Jingyou, sealed and Adenophortriphylla, Yamabishi, cayratia japonica, licorice, include plant extracts such as St. John's Wort. The blending amount of the extracts is preferably 0 to 0.5% by mass with respect to the total mass of the detergent.

Examples of the pH adjuster include sulfuric acid, hydrochloric acid, phosphoric acid, sodium hydroxide, potassium hydroxide, monoethanolamine, diethanolamine, alkanolamines such as triethanolamine, ammonia, and the like. Among these, sulfuric acid, sodium hydroxide, potassium hydroxide, and alkanolamine are preferable, and sulfuric acid, sodium hydroxide, and alkanolamine are more preferable from the viewpoint that stability of the cleaning agent with time is easily increased.
One type of pH adjuster may be used alone, or two or more types may be used in combination.
The total content of components (A) to (C), water, and optional components contained in the cleaning agent of the present invention does not exceed 100% by mass.

When the cleaning agent of the present invention is a liquid cleaning agent, the pH at 25 ° C. is preferably 4 to 9, and more preferably 6 to 9. When the pH is in the above preferred range, the storage stability of the liquid detergent is easily maintained favorably.
The pH at 25 ° C. of the cleaning agent in the present invention is a value measured by adjusting the sample to 25 ° C. and using a pH meter (for example, using a product name “HM-30G” manufactured by Toa DKK Corporation). Show.

When the cleaning agent of the present invention is a liquid cleaning agent, the viscosity at 25 ° C. is preferably 10 to 300 mPa · s, more preferably 25 to 300 mPa · s. If the viscosity is within the above preferred range, the liquid detergent can be easily measured with a measuring cap or the like. Further, when used for application cleaning, it becomes easy to apply a liquid cleaning agent to a textile product or the like.
The viscosity at 25 ° C. of the liquid cleaning agent in the present invention is a value measured using a B-type viscometer (manufactured by TOKIMEC) after adjusting the sample to 25 ° C. (an example of measurement conditions: rotor No. 2. Measure the viscosity after 1 minute from the start of rotation at 60 rpm.

The cleaning agent of the present invention is manufactured by a conventionally known method for manufacturing a liquid cleaning agent or a powder cleaning agent.

Examples of the method for producing the liquid detergent include a method of adding the components (A) to (C) and optional components as necessary to water as a solvent and mixing them.

As a method for producing the powder cleaning agent, dry blending method in which each raw material is mixed with powder, dry granulation method in which the raw material is granulated while flowing, and granulating by spraying a liquid binder while flowing the powdered raw material Stirring granulation method, extruding granulation method in which raw materials are kneaded and extruded with an extruder, pulverizing granulation method in which raw materials are kneaded and pulverized, spray drying method in which slurry containing raw materials is spray dried Etc.

The cleaning agent of the present invention can be stored in a commonly used container. For example, when the cleaning agent of the present invention is a liquid cleaning agent, the container may be a nozzle-type container or a middle plug-type container provided with a measuring cap, a squeeze container or a pump container provided with an automatic measuring mechanism or a simple measuring mechanism, a liquid Examples thereof include a trigger container or a squeeze container that is sprayed or applied in a foam state, an application container having an application surface for applying a liquid, a refill container (pouch, thin bottle, replacement bottle, etc.), and the like.

(How to use detergent)
Examples of the method of using the cleaning agent of the present invention include a method in which the cleaning agent is poured into water together with the laundry at the time of washing, a method in which the laundry is preliminarily dissolved in water, and the laundry is immersed therein. Further, when the cleaning agent of the present invention is a liquid cleaning agent, the liquid cleaning agent may be applied to the laundry and left for a certain period of time, after which normal washing may be performed. When cleaning by such application is performed, the cleaning effect against oily dirt is more likely to be enhanced.
Although it does not specifically limit as washing | cleaning object of the cleaning agent of this invention, For example, textiles, such as clothing, a fabric, a curtain, and a sheet, are mentioned. Especially, since the cleaning agent of this invention is excellent in the cleaning effect with respect to oily stain | pollution | contamination, it can be used suitably as a washing | cleaning agent for textiles with which oily stain | pollution | contamination, such as cosmetics adhere | attached, such as clothes etc., for example.

As described above, the cleaning agent of the present invention contains the components (A) to (C), and the component (A) and the component (B) have a specific mass ratio, so lipstick, foundation, etc. Excellent cleaning effect for oily soils of cosmetics represented by
In the cleaning agent of the present invention, the details of the reason why the cleaning effect on oily dirt is enhanced by using the components (A) to (C) in combination are not clear, but are estimated as follows. The complex formed by the component (A) and the component (B) acts on the oily dirt, and the oily dirt is caught in the complex. (C) component has the effect | action which peels off the complex in which this oil-based dirt was involved from a fiber (to-be-washed | cleaned material) effectively. Further, the component (C) has a re-adhesion preventing effect and suppresses the re-adhesion of the complex peeled off from the fiber to the fiber.

The cleaning agent of the present invention contains (A) component, (B) component, and (C) component,
The component (A) is at least one selected from the group consisting of linear alkylbenzene sulfonates, polyoxyalkylene alkyl ether sulfate esters, α-sulfo fatty acid methyl ester salts, α-olefin sulfonates, and coconut fatty acid salts. Seeds,
The component (B) is a compound represented by the general formula (25),
The component (C) includes a polymer compound represented by the general formula (C1) or the general formula (C2),
The mass ratio represented by component (A) / component (B) is preferably 1 to 25.

The cleaning agent of the present invention contains (A) component, (B) component, and (C) component,
The component (A) is at least one selected from the group consisting of linear alkylbenzene sulfonates, polyoxyalkylene alkyl ether sulfate esters, α-sulfo fatty acid methyl ester salts, α-olefin sulfonates, and coconut fatty acid salts. Seeds,
The component (B) is alkyltrimethylammonium chloride,
The component (C) includes a polymer compound represented by the general formula (C1),
The mass ratio represented by component (A) / component (B) is preferably 1 to 25.

The cleaning agent of the present invention contains (A) component, (B) component, (C) component, and (D) component,
The component (A) is at least one selected from the group consisting of linear alkylbenzene sulfonates, polyoxyalkylene alkyl ether sulfate esters, α-sulfo fatty acid methyl ester salts, α-olefin sulfonates, and coconut fatty acid salts. Seeds,
The component (B) is alkyltrimethylammonium chloride,
The component (C) includes a polymer compound represented by the general formula (C1),
The component (D) is a nonionic surfactant represented by the general formula (d1),
The mass ratio represented by component (A) / component (B) is preferably 1 to 25.

The cleaning agent of the present invention contains (A) component, (B) component, (C) component, and (D) component,
The component (A) is at least one selected from the group consisting of linear alkylbenzene sulfonates, polyoxyalkylene alkyl ether sulfate esters, α-sulfo fatty acid methyl ester salts, α-olefin sulfonates, and coconut fatty acid salts. Seeds,
The component (B) is alkyltrimethylammonium chloride,
The component (C) includes a polymer compound represented by the general formula (C1),
The component (D) is a nonionic surfactant represented by the general formula (d1),
The content of the component (A) is 1 to 40% by mass with respect to the total mass of the cleaning agent,
The content of the component (B) is 0.01 to 15% by mass with respect to the total mass of the cleaning agent,
The content of the component (C) is 0.1 to 5% by mass with respect to the total mass of the cleaning agent,
The content of the component (D) is 1 to 80% by mass with respect to the total mass of the cleaning agent,
The total content of component (A), component (B), component (C), and component (D) does not exceed 100% by mass,
The mass ratio represented by component (A) / component (B) is preferably 1 to 25.

Hereinafter, the present invention will be described in more detail using examples, but the present invention is not limited to these examples. In this example, “%” indicates “% by mass” unless otherwise specified.
The raw materials used in this example are as follows.

<A component>
A-1: Sodium linear alkylbenzene sulfonate (LAS), manufactured by Lion Corporation, trade name “Lypon LH-200”.
A-2: Sodium polyoxyethylene alkyl ether sulfate (AES), manufactured by Shin Nippon Chemical Co., Ltd., trade name “Sinoline SPE-1150”.
A-3: Monoethanolamine salt (AEPS) of polyoxyalkylene alkyl ether sulfate ester, 1-dodecanol and propylene oxide having an average addition mole number of 1.0 mol and an average addition mole number of 2.0 mol by a conventional method A product produced by adding ethylene oxide in this order and then sulfating it and neutralizing with monoethanolamine.
A-4: α-sulfo fatty acid methyl ester salt (MES) produced by the method described in JP-A-8-81694.
A-5: Sodium α-olefin sulfonate (AOS), manufactured by Lion Corporation, trade name “Lipolane LB-840”.
A-6: Sodium coconut fatty acid, manufactured by NOF Corporation.

<B component>
B-1: Alkyltrimethylammonium chloride (manufactured by Lion Akzo, alkyl group carbon chain length of 12 to 14 “Arcade 12-37w”.
B-2: Alkyltrimethylammonium chloride (manufactured by Lion Akzo, alkyl group carbon chain length 16 to 18 “Arcade T-800”.

<C component>
C-1: a polymer having a specific repeating unit (c1) and an oxyalkylene unit (c2). Made by Clariant, trade name “TexCare SRN-170”, weight average molecular weight 2000 to 3000, and a polymer compound represented by the above general formula (C1).
C-2: a polymer having a specific repeating unit (c1) and an oxyalkylene unit (c2). Made by Clariant, trade name “TexCare SRN-300”, weight average molecular weight 7000, high molecular compound represented by the above general formula (C1).
C-3: a polymer having a specific repeating unit (c1) and an oxyalkylene unit (c2). The product name “Plus Coat FR-627” manufactured by Kyodo Chemical Industry Co., Ltd., a weight average molecular weight of 15,000 to 24,000, and a polymer compound represented by the above general formula (C1).
C-1 to C-3 are the conditions of the above-mentioned “water-soluble polymer” (that is, 10 g of polymer in a 1 liter beaker and 1000 g of water at 40 ° C., and a stirrer (thickness 8 mm, long 50 mm), the solution was dissolved after stirring (200 rpm) for 12 hours.

<D component>
D-1: Fatty acid methyl ester ethoxylate (16 to 18 carbon atoms of fatty acid, average number of moles of EO added 15), manufactured by Lion Chemical Co., Ltd., trade name “CEAO-90”.
D-2: Polyoxyethylene alkyl (carbon number 12 to 14) ether (average addition mole number of EO: 15), product name “LMAO-90” manufactured by Lion Chemical Co., Ltd.
D-3: Polyoxyethylene alkyl (carbon number 12-14) ether (average added mole number of EO 7), manufactured by Lion Chemical Co., Ltd., trade name “Leox CL-70”.
D-4: A nonionic surfactant obtained by blocking addition of ethylene oxide having an average addition mole number of 5 and propylene oxide having an average addition mole number of 2 moles to a primary alcohol having 10 to 14 carbon atoms.
D-5: Nonionic surfactant obtained by adding ethylene oxide having an average addition mole number of 9 moles to a secondary alcohol having 12 to 14 carbon atoms, manufactured by Nippon Shokubai Co., Ltd., trade name “Softanol 90”.

<Optional component>
PG: Propylene glycol, manufactured by BASF.
BC: Butyl carbitol, trade name “butyl carbitol”, manufactured by Sankyo Chemical Co., Ltd.
[Common component X]
The numerical value described at the end of each component is the content in the cleaning agent.
-Metal ion scavenger (chelating agent): citric acid (manufactured by Yushi Kogyo Co., Ltd.) ... 0.1% by mass.
-Storage stability improver: Sodium benzoate (manufactured by Toa Gosei Co., Ltd.) ... 0.5% by mass.
Enzyme: Trade name “Coronase 48L” (manufactured by Novozymes) ... 0.5% by mass.
-Antioxidant: Dibutylhydroxytoluene (trade name "K-NOX BHT", manufactured by Degussa) ... 0.01% by mass.
-Water miscible organic solvent: Ethanol (trade name "specific alcohol 95 degree synthesis", manufactured by Nippon Alcohol Sales Co., Ltd.) ... 5% by mass.
Fragrance: Fragrance composition A described in Tables 7 to 14 of JP-A No. 2003-268398, 0.7 mass%.
-Dye: Colorant, trade name "Green No. 3", manufactured by Sakai Kasei Co., Ltd .... 0.0002 mass%.
-PH adjuster: Sodium hydroxide (manufactured by Tsurumi Soda Co., Ltd.) ... appropriate amount, monoethanolamine (manufactured by Nippon Shokubai Co., Ltd.) ... appropriate amount.
・ Solvent: Water (purified water) ... balance.
The content “appropriate amount” of the pH adjusting agent is an amount required to bring the cleaning agent to the pH shown in the table.
The water content “balance” is an amount necessary to make the entire cleaning agent 100 mass%.
[Common component Y]
The numerical value described at the end of each component is the content in the cleaning agent.
-Inorganic salt: Sodium sulfate ... 1 mass%, Magnesium sulfate ... 2 mass%.
Fluorescent agent: distyryl biphenyl derivative, trade name “Tinopearl CBS-X” (manufactured by BASF)... 0.01%.
Preservative: Trade name “Actyside MBS” (manufactured by So Japan).
-PH adjuster: Sodium hydroxide (manufactured by Tsurumi Soda Co., Ltd.) ... appropriate amount, monoethanolamine (manufactured by Nippon Shokubai Co., Ltd.) ... appropriate amount.
・ Solvent: Water (purified water) ... balance.
The content “appropriate amount” of the pH adjusting agent is an amount required to bring the cleaning agent to the pH shown in the table.
The water content “balance” is an amount necessary to make the entire cleaning agent 100 mass%.

(Examples 1 to 24, Comparative Examples 1 to 7)
<Manufacture of detergent for textile products>
According to the compositions shown in Tables 1 to 4, the components (A) to (C) and optional components (excluding water and a pH adjuster) were added to water and mixed. This was adjusted to a pH value in the table with a pH adjusting agent to obtain cleaning agents of Examples 1 to 24 and Comparative Examples 5 to 7.
Further, cleaning agents of Comparative Examples 1 to 3 were obtained in the same manner as in Example 1 except that any of the components (A) to (C) was not added to water. A cleaning agent of Comparative Example 4 was obtained in the same manner as in Example 1 except that the component (C ′) was used instead of the component (C).
Tables 1 to 4 show the compositions (blending components, content (% by mass)) of the cleaning agents obtained in the respective examples.
In the table, when there is a blank blending component, the blending component is not blended.
In the table, the content of the compounding component indicates a pure equivalent amount.
In the table, “A / C ratio”, “B / C ratio”, and “(A + B) / C ratio” of Comparative Example 4 are respectively (A ′) and (C ′) component used instead of (C) component. ) Component, (B) component, and [(A) component + (B) component] mass ratio.

The cleaning effect (1) and the cleaning effect (2) against oily soil were evaluated as follows for the cleaning agents of each example. The evaluation results are shown in Tables 1 to 4.

[Production of evaluation cloth]
As a representative example of oily composite stains that are difficult to remove, an evaluation cloth to which lipstick and liquid foundation were attached was prepared as follows.
・ Lipstick stain cloth Lipstick (trade name “Makiage Moisture Rouge Color On Type Red”, manufactured by Shiseido Co., Ltd.) is transferred to a finger and applied to a circular surface of polyester tropical white cloth in a circle of about 3cm in diameter. Was used as a lipstick dirt cloth.
・ Foundation dirt cloth Liquid foundation (trade name “Makiage Moisture Cream Foundation UV Ocher 10”, manufactured by Shiseido Co., Ltd.) is applied to the back of the hand and transferred to a cotton knitted fabric surface in a circular shape with a diameter of about 5 cm. The foundation was used as a foundation dirt cloth.

<Evaluation of cleaning effect (1)>
[Cleaning test for lipstick dirt cloth]
A Terg-O-meter (manufactured by UNITED STATES TESTING) was used as a cleaning tester. Ten lipstick stain cloths, a cleaning knitted cloth, and 10 mL of the cleaning agent in each example were placed in the cleaning tester and washed at 120 rpm and 15 ° C. for 20 minutes according to the bath ratio of 30 times.
Thereafter, it was transferred to a two-tank washing machine (product number: CW-C30A1-H1 manufactured by Mitsubishi Electric Corporation), dehydrated for 1 minute, rinsed in 30 L of tap water (15 ° C., 4 ° DH) for 3 minutes, and air-dried.
For the lipstick stain cloth before washing and the lipstick stain cloth after washing, the reflectance is measured with a color difference meter (product name: SE200 type) manufactured by Nippon Denshoku Co., Ltd. and washed using the a value (redness). The rate (%) was calculated by the following formula.
Washing rate (%) = 100 × [(a value of lipstick dirt cloth before washing) − (a value of lipstick dirt cloth after washing)] / (a value of lipstick dirt cloth before washing).
The wash rate (%) was calculated for 10 lipstick stain cloths, and the average value was used to make the determination based on the following criteria, and ○ and ◎ were accepted.
A: 60% or more.
○: 50% or more and less than 60%.
Δ: 40% or more and less than 50%.
X: Less than 40%.

[Cleaning test for foundation dirt cloth]
The foundation dirt cloth was the same as the washing test for the lipstick dirt cloth except that the foundation dirt cloth was used instead of the lipstick dirt cloth and the reflectance (%) was calculated by the following formula. The cleaning effect was evaluated.
Washing rate (%) = 100 × (K / S of foundation soiled cloth before washing−K / S of foundation soiled cloth after washing) / (K / S of foundation soiled cloth before washing−unsoiled cloth) K / S).
However, K / S is a value obtained by the formula: (1-R / 100) ² / (2R / 100), and R is an unstained cloth, a foundation dirt cloth before washing, or a foundation dirt after washing. This is the reflectance (%) of the cloth.
The washing rate (%) was calculated for 10 pieces of foundation soiled cloth, and the average value was used to make a judgment based on the following criteria, and ○ and ◎ were accepted.
A: 80% or more.
○: 70% or more and less than 80%.
Δ: 60% or more and less than 70%.
X: Less than 60%.

<Evaluation of cleaning effect (2)>
[Coating cleaning test for lipstick dirt cloth]
0.5 mL of the cleaning agent of each example was applied to each lipstick stain cloth. At that time, the cleaning agent was applied so that lipstick stains attached to the soiled cloth became the center. After allowing to stand for 10 minutes, it was placed in a Terg-O-meter together with a washing knitted cloth, and washed at 120 rpm and 15 ° C. for 10 minutes in accordance with a bath ratio of 30 times. Thereafter, it was transferred to a two-tank washing machine (product number: CW-C30A1-H1 manufactured by Mitsubishi Electric Corporation), dehydrated for 1 minute, rinsed in 30 L of tap water (15 ° C., 4 ° DH) for 3 minutes, and air-dried.
10 panelists visually compared the condition of the lipstick stain after washing with the lipstick stain before washing and an unstained polyester tropical white cloth (polyester tropical white cloth without lipstick stain). The scoring was based on the following criteria. The average value of the 10 scoring results was classified into the following evaluation criteria, and the cleaning effect (2) was evaluated. ○, ◎, ◎◎ were accepted.
(Judgment criteria)
5 points: No dirt remains (equivalent to unstained polyester tropical white cloth).
4 points: Little dirt remains.
3 points: Some dirt remains.
2 points: A lot of dirt remains.
1 point: No dirt is removed (same as lipstick dirt cloth before washing).
(Evaluation criteria)
A: 4.5 or more points.
A: 4 or more and less than 4.5.
○: 3.5 points or more and less than 4 points.
○: 3 points or more and less than 3.5 points.
X: Less than 3 points.

From the results shown in Tables 1 to 4, it was confirmed that the cleaning agents of Examples 1 to 24 to which the present invention was applied provided a good cleaning effect on lipstick stains and foundation stains regardless of whether or not they were applied and washed. did it.
On the other hand, the cleaning agents of Comparative Examples 1, 3 to 4 and 6 did not provide sufficient cleaning power against lipstick stains and foundation stains. When the cleaning agents of Comparative Examples 2 and 7 were coated and washed, a good cleaning effect was obtained against lipstick stains, but when the coating was not washed, washing against lipstick stains and foundation stains was performed. The effect was not sufficiently obtained. The cleaning agent of Comparative Example 5 did not provide a sufficient cleaning effect on lipstick stains.
From the above results, it was confirmed that the cleaning agent to which the present invention was applied was superior in the cleaning effect against oily dirt.

The cleaning agent for textile products of the present invention is superior in the cleaning effect against oily dirt.

Claims (9)

1. (A) component: an anionic surfactant;
   (B) component: a cationic surfactant;
   Component (C): a polymer having at least one repeating unit (c1) selected from the group consisting of an alkylene terephthalate unit and an alkylene isophthalate unit and an oxyalkylene unit (c2) and having a weight average molecular weight of 1,000 to 10,000 Containing,
   A cleaning agent for textiles, wherein the mass ratio represented by component (A) / component (B) is 1 to 25.
2. Furthermore, (D) component: Nonionic surfactant is contained, The cleaning agent for textiles of Claim 1 characterized by the above-mentioned.
3. The cleaning agent for textiles according to claim 1 or 2, wherein the mass ratio represented by component (A) / component (C) is 1 to 30.
4. The component (A) is at least selected from the group consisting of linear alkylbenzene sulfonates, polyoxyalkylene alkyl ether sulfate esters, α-sulfo fatty acid methyl ester salts, α-olefin sulfonates, and coconut fatty acid salts. The detergent for textiles according to any one of claims 1 to 3, which is one kind of anionic surfactant.
5. The detergent for textiles according to any one of claims 1 to 4, wherein the component (B) is a cationic surfactant represented by the following general formula (25).
   

   

   In the formula (25), R ²⁰ to R ²³ are each independently two or three alkyl groups having 1 to 4 carbon atoms, hydroxyalkyl groups having 1 to 4 carbon atoms, or — (CH ₂ CH ₂ O) _m —. H [m is the average number of repeating oxyethylene groups and is a number from 1 to 25], the other is a straight chain or branched hydrocarbon group having 6 to 28 carbon atoms, and Z ^a− is a pair Is an ion, and a represents the valence of the counter ion.
6. The detergent for textiles according to any one of claims 1 to 5, wherein the component (C) comprises a polymer compound represented by the following general formula (C1) or the following general formula (C2).
   

   

   In formulas (C1) and (C2), R ³⁰ and R ⁴⁰ are each independently a hydrogen atom or a methyl group, R ³⁴ and R ³⁷ are each a methyl group or a hydrogen atom, R ³⁵ , R ³⁶ , R ³⁸ and R ³⁹ are each independently an alkylene group having 2 to 4 carbon atoms, s1 and s2 are each 0 to 10, and t1, t2, u1 and u2 are each independently 1 to 100.
7. The cleaning agent for textiles according to any one of claims 1 to 6, wherein the content of the component (A) is 1 to 40% by mass with respect to the total mass of the cleaning agent.
8. The cleaning agent for textiles according to any one of claims 1 to 7, wherein the content of the component (B) is 0.01 to 15% by mass with respect to the total mass of the cleaning agent.
9. The cleaning agent for textiles according to any one of claims 1 to 8, wherein the content of the component (C) is 0.1 to 5% by mass with respect to the total mass of the cleaning agent.