JP2017008137A - Liquid detergent composition for clothing - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a liquid detergent composition for clothing capable of adding excellent deodorization effect to clothing.SOLUTION: There is provided a liquid detergent composition for clothing containing following (a) component, (b) component of 0.5 mass% to 5 mass%, (c) component of 0.5 mass% to 7 mass% and water with mass ratio between content of the (b) component and content of the (c) component of [content of (c) component]/[content of (b) component] of 0.2 to 5. (a) component: one or more kind of surfactant selected from a specific nonionic surfactant and specific 2 kinds of anionic surfactants. (b) component: one or more kind of compound selected from specific 2 kinds of quaternary ammonium salts. (c) component: a salt represented by the following general formula (c1). (M)SO(c1), where (M) is one or more kind of ion selected from a sodium ion, a potassium ion, a magnesium ion, an ammonium ion and an alkanol ammonium ion having 2 to 6 carbon atoms, X is a valence of the ion and the number of 1 or 2, y is 2 when x is 1 and y is 1 when x is 2.SELECTED DRAWING: None

Description

  The present invention relates to a liquid cleaning composition for clothing.

With increasing awareness of hygiene among consumers, interest in clothing smells and fungi has also increased. It is known that various bacterium existing in the skin and the environment are attached to the clothing and propagate. It is believed that the amount of metabolite excretion increases with the growth of fungi, and odors are more likely to occur.
As a detergent composition having a bactericidal effect, for example, Patent Document 1 discloses a cationic bactericidal agent, a metal chelating agent 0.5 mol or more of the bactericidal agent, and a nonionic surfactant and / or amphoteric. Disinfecting and disinfecting detergent compositions that contain a surfactant and do not reduce the bactericidal effect among compositions containing an anionic surfactant are disclosed. Patent Document 2 contains an anionic surfactant such as alkyl polyethoxy sulfate and a quaternary ammonium surfactant, and the anionic surfactant and quaternary ammonium salt surfactant form liquid crystal particles. A structured heavy duty liquid laundry detergent composition is disclosed.
On the other hand, Patent Document 3 contains polyoxyethylene alkyl ether sulfate, linear alcohol alkoxylate, branched alcohol ethoxylate, water-soluble inorganic salt, enzyme, and water-soluble inorganic salt. Also disclosed is a liquid detergent having excellent storage stability. In Patent Document 3, a water-soluble inorganic salt is used to increase the viscosity of a liquid detergent. Patent Document 4 discloses a multiphase liquid detergent composition containing a nonionic surfactant mixture and a water-soluble inorganic salt.

JP 7-53995 A Japanese National Patent Publication No. 11-512768 JP 2014-62231 A JP 2005-82610 A

Although the technique which suppresses the odor which generate | occur | produces from clothing by wash | cleaning clothing with the detergent composition containing a cationic surfactant is disclosed, the further improvement is calculated | required. In particular, there is a demand for imparting a higher deodorizing effect to thick clothing such as cotton towels that are likely to have odors.
The present invention provides a liquid detergent composition for clothing that can impart an excellent deodorizing effect to clothing.

This invention contains 0.5 mass% or more and 5 mass% or less of the following (a) component, (b) component, 0.5 mass% or more and 7 mass% or less of (c) component, and water, (b ) Component content and (c) component mass ratio is [(c) component content] / [(b) component content] and is 0.2 or more and 5 or less. The present invention relates to a liquid detergent composition.
Component (a): Nonionic surfactant having a polyoxyalkylene group, sulfonate having a hydrocarbon group having 8 to 18 carbon atoms, and sulfate ester salt having a hydrocarbon group having 10 to 18 carbon atoms One or more anionic surfactants selected from the group consisting of one or more surfactants (b) selected from: a quaternary ammonium salt having one hydrocarbon group having 12 to 16 carbon atoms and 8 carbon atoms One or more compounds (c) selected from quaternary ammonium salts having two or more hydrocarbon groups of 10 or less: a salt represented by the following general formula (c1)
(M ^{x +} ) _y SO ₄ ²⁻ (c1)
[Wherein, (M ^{x +} ) is one or more ions selected from sodium ions, potassium ions, magnesium ions, ammonium ions, and alkanol ammonium ions having 2 to 6 carbon atoms. x is the valence of the ion and is a number of 1 or 2. When x is 1, y is a number of 2, and when x is 2, y is a number of 1. ]

  ADVANTAGE OF THE INVENTION According to this invention, the liquid cleaning composition for clothing which can provide the deodorizing effect excellent to clothing is provided.

The present invention discloses a technique for further enhancing the deodorizing effect of clothing by a quaternary ammonium salt having a specific chain length.
As a result of repeated investigations, the inventors of the present invention have a particular smell by washing clothes with a detergent composition that uses a quaternary ammonium salt having a hydrocarbon group having a specific chain length and a specific sulfate. The present inventors have found that the odor generated from thick clothing such as cotton towels that can be easily stored can be further suppressed. Although the action of the present invention is presumed, the yarns that make up thick clothing such as cotton towels are often thick, and it is considered that bacteria are likely to be present together with dirt, and quaternary ammonium salts are added to the bacteria. We think that it may be hard to act. It is considered that the quaternary ammonium salt makes it easier to act on the bacteria by the component (c) of the present invention altering the dirt.

<(A) component>
The component (a) is one or more surfactants selected from a specific nonionic surfactant and a specific anionic surfactant. That is, the component (a) has a nonionic surfactant having a polyoxyalkylene group, a sulfonate having a hydrocarbon group having 8 to 18 carbon atoms, and a hydrocarbon group having 10 to 18 carbon atoms. One or more surfactants selected from one or more anionic surfactants selected from sulfate esters. (A) component has the effect | action which wash | cleans the dirt adhering to clothing.

Preferable examples of the nonionic surfactant having a polyoxyalkylene group include (a1) a nonionic surfactant represented by the following general formula (1).
^{_{R 1 (CO) m O- (}} A 1 O) n -R 2 (a1)
[Wherein, R ¹ is a primary aliphatic hydrocarbon group having 9 to 16 carbon atoms, R ² is a hydrogen atom or a methyl group, CO is a carbonyl group, and m is 0 or 1. The A ¹ O group is one or more groups selected from an ethyleneoxy group and a propyleneoxy group, n is the average number of moles added, and is a number from 2 to 30. ]

In general formula (1), R ¹ is a primary aliphatic hydrocarbon group having 9 to 16 carbon atoms. R ¹ is preferably a primary aliphatic hydrocarbon group having 11 to 14 carbon atoms from the standpoint of further improving the deodorizing effect of the clothing.
In terms of further enhancing the deodorizing effect of the clothing, the proportion of the aliphatic hydrocarbon group having 11 to 14 carbon atoms in the total amount of R ¹ is preferably 60% by mass or more, more preferably 70% by mass or more, and 100 The mass% or less is preferable, and may be 100 mass%. That is, in the component (a), the proportion of the nonionic surfactant in which R ¹ is a hydrocarbon group having 11 to 14 carbon atoms is preferably 60% by mass or more, more preferably 70% by mass or more, and 100% by mass. % Or less is preferable, and may be 100% by mass.
Examples of the primary aliphatic hydrocarbon group for R ¹ include a group selected from a primary alkyl group and a primary alkenyl group, and a primary alkyl group is preferable. R ¹ is preferably a linear group.

In General Formula (1), the A ¹ O group is one or more groups selected from an ethyleneoxy group and a propyleneoxy group. From the viewpoint of improving the deodorizing effect of the clothing, the A ¹ O group is preferably a group containing an ethyleneoxy group.

  In general formula (1), n is an average addition mole number, and is a number of 2-30. In terms of further improving the deodorizing effect of the clothing, n is preferably 3 or more, more preferably 4 or more, and preferably 28 or less, more preferably 26 or less, and still more preferably 24 or less.

  More preferable examples of the anionic surfactant include (a2) a sulfonate having an aliphatic hydrocarbon group having 9 to 18 carbon atoms, and (a3) a sulfuric acid having an aliphatic hydrocarbon group having 10 to 18 carbon atoms. One or more anionic surfactants selected from ester salts are exemplified.

  (A2) Preferable specific examples of the sulfonate having an aliphatic hydrocarbon group having 9 to 18 carbon atoms include alkylbenzene sulfonate having an alkyl group having 9 to 18 carbon atoms. The alkyl group having 9 to 18 carbon atoms means an alkyl group substituted on the benzene ring of the alkylbenzene sulfonate, and does not include a benzene skeleton. In order to further improve the deodorizing effect of the garment, the alkyl group preferably has 10 or more carbon atoms, more preferably 11 or more, and preferably 16 or less.

(A3) Preferable examples of the sulfate ester salt having an aliphatic hydrocarbon group having 10 to 18 carbon atoms include one or more sulfate ester salts selected from the following general formula (2).
^{_{R 2 O- (A 2 O)}} m -SO 3 M (2)
[In the formula, R ² is an aliphatic hydrocarbon group having 10 to 18 carbon atoms, A ² O group is one or more groups selected from ethyleneoxy group and propyleneoxy group, and m is an average addition mole. It is a number, and is a number from 0 to 5. M is a counter ion. ]

In general formula (2), R ² is preferably an aliphatic hydrocarbon group having 12 or more carbon atoms, and is preferably an aliphatic hydrocarbon group having 16 or less carbon atoms, from the viewpoint of improving the deodorizing effect of clothing. In terms of further improving the deodorizing effect of the garment, carbon atoms in R ² 12 or more, 16 content of less than aliphatic hydrocarbon group, preferably at least 60 wt%, more preferably at least 70 wt%, 80 wt % Or more is more preferable. That is, in (a3), the proportion of the anionic surfactant in which R ² is an aliphatic hydrocarbon group having 12 to 16 carbon atoms is preferably 60% by mass or more from the viewpoint of further improving the deodorizing effect of the clothing, 70 mass% or more is more preferable, and 80 mass% or more is more preferable.
Examples of the hydrocarbon group for R ² include an alkyl group and an alkenyl group, and an alkyl group is preferable.

In General Formula (2), the A ² O group is one or more groups selected from an ethyleneoxy group and a propyleneoxy group. All of the A ² O groups may be ethyleneoxy groups or all propyleneoxy groups. Further, it may contain an ethyleneoxy group and a propyleneoxy group. When it contains an ethyleneoxy group and a propyleneoxy group, it may be included randomly or may be a block. In terms of further improving the deodorizing effect of the clothing, the A ² O group preferably contains an ethyleneoxy group.

In general formula (2), m is an average addition mole number, and is a number of 0 or more and 5 or less. The meaning of the sulfate ester salt having an average addition mole number of “0” represents a sulfate ester salt in which the A ² O group is not contained in the general formula (2). M is preferably 0.5 or more, more preferably 1 or more, more preferably 1.3 or more, more preferably 1.5 or more, and more than 2 in that the deodorizing effect of the clothing by the component (b) described later is further enhanced. Is more preferable. 4 or less is preferable and 3 or less is more preferable in terms of further improving the deodorizing effect of the clothing.

  For example, in the general formula (2), a sulfate ester salt in which m is greater than 0 and less than or equal to 5 may include a sulfate ester salt in which m is 0. Further, there are cases where two kinds of sulfate ester salts, that is, a sulfate ester salt in which m is 0 and a sulfate ester salt in which m is more than 0 and not more than 5, are contained in the liquid detergent composition for clothing of the present invention. . In (a3) of the present invention, m in the general formula (2) is represented by a value calculated by adding all (a3) contained in the composition.

  In the general formula (2), examples of the counter ion represented by M include a counter ion selected from an alkali metal ion and an alkanol ammonium ion having 1 to 6 carbon atoms. Examples of alkali metal ions include sodium ions and potassium ions. Examples of the alkanol ammonium ion having 1 to 6 carbon atoms include monoethanol ammonium ion, diethanol ammonium ion, N-methyl ethanol ammonium ion, N-methyl diethanol ammonium ion, and triethanol ammonium ion.

<(B) component>
The component (b) of the present invention is selected from a quaternary ammonium salt having one hydrocarbon group having 12 to 16 carbon atoms and a quaternary ammonium salt having two hydrocarbon groups having 8 to 10 carbon atoms. One or more compounds. (B) component of this invention wash | cleans clothing with the liquid cleaning composition for clothing of this invention, (b) component adsorb | sucks to clothing, and can provide a deodorizing effect to clothing.

  As the component (b), a compound represented by the following general formula (b-1) [hereinafter referred to as component (b1)] and a compound represented by the general formula (b-2) [hereinafter referred to as component (b2) ] 1 or more types of compounds chosen from these are mentioned.

[In the formula, R ^11b is a hydrocarbon group having 12 to 16 carbon atoms, and R ^12b , R ^13b and R ^14b are each an alkyl group having 1 to 3 carbon atoms, and a carbon group having 1 to 3 carbon atoms. A group selected from a hydroxyalkyl group, — (A ³ O) _k —H, and a benzyl group, A ³ O is an ethyleneoxy group or a propyleneoxy group, k is a number from 1 to 5, and X ^- is a halogen ion, and anions selected from the number 1 to 3 of alkyl sulfate ion carbon. ]

[Wherein, R ^21b and R ^22b are each a hydrocarbon group having 8 to 10 carbon atoms, and R ^23b and R ^24b are each an alkyl group having 1 to 3 carbon atoms and a carbon number 1 to 3 It is a group selected from the following hydroxyalkyl groups, — (A ³ O) _k —H, or a benzyl group, A ³ O is an ethyleneoxy group or a propyleneoxy group, and k is a number of 1 or more and 5 or less. , X ⁻ is an anion selected from a halogen ion and an alkyl sulfate ion having 1 to 3 carbon atoms. ]

(B1) in the general formula of component ^{(b1), R 11b} is a hydrocarbon group having 12 to 16 carbon atoms, in that the effect of imparting deodorizing effect on clothing becomes ^higher, the ^{R 11b} The number of carbon atoms is preferably 13 or more, more preferably 14 or more, still more preferably 15 or more, and still more preferably 16. The number of carbon atoms of R ^11b is preferably 15 or less, more preferably 14 or less, still more preferably 13 or less, and even more preferably 12 in that the appearance of the liquid detergent composition for clothes of the present invention is likely to become more transparent. Examples of the hydrocarbon group for R ^11b include an alkyl group and an alkenyl group, and an alkyl group is preferable. Specific examples of the hydrocarbon group for R ^11b include a dodecyl group, a tridecyl group, a tetradecyl group, a pentadecyl group, and a hexadecyl group.

In General Formula (b-1), R ^12b , R ^13b , and R ^14b are each independently selected from an alkyl group having 1 to 3 carbon atoms, a hydroxyalkyl group having 1 to 3 carbon atoms, or a benzyl group. It is a group. Specific examples of the alkyl group having 1 to 3 carbon atoms include a methyl group, an ethyl group, and a propyl group. Specific examples of the hydroxyalkyl group having 1 to 3 carbon atoms include a hydroxymethyl group, a hydroxyethyl group, and a hydroxypropyl group.

In the general formula (b-1), X ^- is a halogen ion, and anions selected from the number 1 to 3 of alkyl sulfate ion carbon. Specific examples of the halogen ion are chloro ion and bromo ion, and chloro ion is preferable from the viewpoint of suppressing yellowing of clothes. Specific examples of the alkyl sulfate ion having 1 to 3 carbon atoms include methyl sulfate ion, ethyl sulfate ion, and propyl sulfate ion. From the viewpoint of ease of production, methyl sulfate ion and ethyl sulfate ion are preferred.

More preferable specific component (b1) includes one or more compounds selected from the following (b1-1) to (b1-4).
(B1-1): In the general formula (b-1), R ^11b is a hydrocarbon group having 12 to 16 carbon atoms, and R ^12b , R ^13b , and R ^14b each have 1 to 3 carbon atoms. the following is an alkyl group, X ^- is a halogen ion, and the compound is an anion selected from C 1 to 3 alkyl sulfate ion carbon.
More specific compounds of (b1-1) include N-dodecyl-N, N, N-trimethylammonium salt, N-tetradecyl-N, N, N-trimethylammonium salt, and N-hexadecyl-N, N, One or more compounds selected from N-trimethylammonium salts. These salts are preferably chloro salt, methyl sulfate, or ethyl sulfate.
(B1-2): In the general formula (b-1), R ^11b is a hydrocarbon group having 12 to 16 carbon atoms, and R ^12b and R ^13b are each an alkyl having 1 to 3 carbon atoms. A compound wherein R ^14b is a hydroxyalkyl group having 1 to 3 carbon atoms, and X ⁻ is an anion selected from a halogen ion and an alkyl sulfate ion having 1 to 3 carbon atoms.
More specific compounds of (b1-2) are N-dodecyl-N-hydroxyethyl-N, N-dimethylammonium salt, N-tetradecyl-N-hydroxyethyl-N, N-dimethylammonium salt, and N- One or more compounds selected from hexadecyl-N-hydroxyethyl-N, N-dimethylammonium salt. These salts include chlor salt, methyl sulfate, or ethyl sulfate.
(B1-3): In the general formula (b-1), R ^11b is a hydrocarbon group having 12 to 16 carbon atoms, and R ^12b and R ^13b are each an alkyl having 1 to 3 carbon atoms. A compound in which R ^14b is a benzyl group, and X ⁻ is an anion selected from a halogen ion and an alkyl sulfate ion having 1 to 3 carbon atoms.
More specific compounds of (b1-3) include N-dodecyl-N, N-dimethyl-N-benzylammonium salt, N-tetradecyl-N, N-dimethyl-N-benzylammonium salt, and N-hexadecyl- One or more compounds selected from N, N-dimethyl-N-benzylammonium salts. These salts are preferably chloro salt, methyl sulfate, or ethyl sulfate.
(B1-4): In the general formula (b-1), R ^11b is a hydrocarbon group having 12 to 16 carbon atoms, and R ^12b and R ^13b are each an alkyl having 1 to 3 carbon atoms. R ^14b is — (A ³ O) _k —H, A ³ O is an ethyleneoxy group or a propyleneoxy group, k is a number from 1 to 5, and X ⁻ is a halogen atom. A compound which is an anion selected from ions and alkyl sulfate ions having 1 to 3 carbon atoms.

In the general formula (b-2) of the component (b2), R ^21b and R ^22b each preferably have 9 or more carbon atoms, and more preferably 10 in terms of enhancing the effect of imparting a deodorizing effect to clothing. Specific examples of R ^21b and R ^22b are each independently an octyl group, a nonyl group, and a decyl group, and are preferably a nonyl group and a decyl group in terms of further enhancing the effect of imparting a deodorizing effect to clothing. Is more preferable. R ^23b and R ^24b are each independently a group selected from an alkyl group having 1 to 3 carbon atoms, a hydroxyalkyl group having 1 to 3 carbon atoms, — (A ³ O) _k —H, or a benzyl group. Yes, A ³ O is an ethyleneoxy group or a propyleneoxy group, and k is a number of 1 or more and 5 or less. Specific examples of the alkyl group having 1 to 3 carbon atoms include a methyl group, an ethyl group, and a propyl group. Specific examples of the hydroxyalkyl group having 1 to 3 carbon atoms include a hydroxymethyl group, a hydroxyethyl group, and a hydroxypropyl group.

  More specific compounds of the component (b2) include N, N-dioctyl-N, N-dimethylammonium salt, N, N-dinonyl-N, N-dimethylammonium salt, N, N-didecyl-N, N- Dimethylammonium salt, N, N-dioctyl-N-ethyl-N-methylammonium salt, N, N-dinonyl-N-ethyl-N-methylammonium salt, and N, N-didecyl-N-ethyl-N-methyl 1 or more types of compounds chosen from ammonium salt are mentioned. These salts include chloro ion, methyl sulfate ion, and ethyl sulfate ion.

  The component (b2) is composed of N, N-didecyl-N, N-dimethylammonium salt and N, N-didecyl-N-ethyl-N-methylammonium salt in that the effect of imparting a deodorizing effect to clothing is high. One or more selected compounds are preferred. These salts are preferably chloro ion, methyl sulfate ion, or ethyl sulfate ion.

<(C) component>
The component (c) is a salt represented by the following general formula (c1). (C) component has the effect | action which further raises the smell suppression effect of the clothing by (b) component.
(M ^{x +} ) _y SO ₄ ²⁻ (c1)
[Wherein, (M ^{x +} ) is one or more ions selected from sodium ions, potassium ions, magnesium ions, ammonium ions, and alkanol ammonium ions having 2 to 6 carbon atoms. x is the valence of the ion and is a number of 1 or 2. When x is 1, y is a number of 2, and when x is 2, y is a number of 1. ]

Examples of the alkanol ammonium ion having 2 to 6 carbon atoms in (M ^{x +} ) in the general formula (c1) include monoethanol ammonium ion, diethanol ammonium ion, triethanol ammonium ion, methyl ethanol ammonium ion, methyl diethanol ammonium ion. Is mentioned.
When (M ^{x +} ) is one or more ions selected from sodium ions, potassium ions, ammonium ions, and alkanol ammonium ions having 2 to 6 carbon atoms, x is 1 and y is 2. . When (M ^{x +} ) is a magnesium ion, x is 2 and y is 1.

When the liquid detergent composition for clothing of the present invention contains a protease, (M ^{x +} ) is sodium ion, potassium in that the protease further enhances the effect of imparting an excellent deodorizing effect to the clothing by the component (b). One or more ions selected from ions and alkanol ammonium ions having 2 to 6 carbon atoms are preferred, one or more ions selected from sodium ions and potassium ions are more preferred, and sodium ions are still more preferred.

(C) As a preferable salt of a component, 1 or more types of salts chosen from sodium sulfate, potassium sulfate, and a monoethanolammonium sulfate salt are mentioned.
(C) As a more preferable salt of a component, 1 or more types of salts chosen from sodium sulfate and potassium sulfate are mentioned.

  The component (c) can be contained in the composition by blending the salt compound together with other components when preparing the liquid detergent composition for clothing of the present invention. Moreover, the mixture used as the composition of this invention using 1 or more types of alkali agents chosen from sodium hydroxide, potassium hydroxide, magnesium hydroxide, ammonia, and C2-C6 alkanolamine, and a sulfuric acid. By carrying out the neutralization reaction therein, the component (c) can be formed and contained in the composition.

  The component (c) may be one or more compounds selected from sodium sulfate, potassium sulfate, magnesium sulfate, ammonium sulfate, and a salt of sulfuric acid and an alkanolamine having 2 to 6 carbon atoms.

  When the liquid detergent composition for clothing of the present invention contains a protease (d), which will be described later, the ingredient (c) is a detergent composition containing a specific surfactant composition and water. It has the effect | action which raises the effect | action which provides the deodorizing effect excellent in the clothing by the (b) component in cooperation with d) component.

<Water>
The liquid detergent composition for clothes of the present invention contains water. As water, ion-exchanged water, distilled water, tap water, water containing 1 to 5 mg / kg of sodium hypochlorite, or the like can be used.

<Optional component>
[Component (d)]
The liquid detergent composition for clothing of the present invention preferably contains a protease as the component (d). By using the component (d) in combination with the component (b) and the component (c), the deodorizing effect of the clothing can be further enhanced.

Proteolytic enzymes are sometimes called proteases. Examples of proteases include proteases that can act in neutral or alkaline aqueous solutions.
Specific examples of preferable protease include alkaline protease. Furthermore, the alkaline protease described in International Publication No. 99/018218, wherein 70% or more of the amino acid sequence represented by SEQ ID NO: 1 or 2 is preferably preserved, described in JP-A-5-25492 Alkaline protease K-16 or alkaline protease K-14 is preferable.
In addition, they are sold under the trade names Novazymes Sabinase (registered trademark), Cannase (registered trademark), Evalase (registered trademark), Alcalase (registered trademark), Polarzyme (registered trademark), and Esperase (registered trademark). Protease produced by Bacillus subtilisins, FN2 (registered trademark), FN3 (registered trademark) and FN4 (registered trademark) manufactured by DuPont, Perfect (registered trademark), Perfect Prime (registered trademark), manufactured by Kao Corporation Proteases supplied under the trade name of alkaline protease, for example, KAP4.3G (registered trademark, manufactured by Kao Corporation), KAP8.0Q-L (produced by Kao Corporation) or KAP11.1G (registered trademark, Kao Corporation) Or the variant etc. are mentioned.

  Among them, an enzyme in which 80% or more of the amino acid sequence represented by SEQ ID NO: 1 or 2 described in International Publication No. 99/018218 is conserved, sabinase manufactured by Novozymes, Everase, Alcalase, manufactured by DuPont Of these, the alkaline protease manufactured by Kao Corporation is more preferable.

  From the viewpoint of the deodorizing effect of clothing, the protease (d) component has an activity per gram of enzyme protein, that is, a specific activity, preferably 5000 mPU / g or more, more preferably 20000 mPU / g or more.

[(E) component]
The liquid detergent composition for clothing of the present invention preferably contains, as component (e), a carboxylic acid having 4 to 12 carbon atoms and having 2 to 4 carbon atoms or a salt thereof. (E) A component can further improve the deodorizing effect of clothing by using together with (b) component.

More specifically, the component (e) includes one or more compounds selected from the following components (e1) and (e2). One or more compounds selected from the following components (e1) are preferred.
(E1) Component: a divalent to tetravalent or lower carboxylic acid having 4 to 10 carbon atoms, or a salt thereof, which does not contain an amino group, or (e1) In terms of further enhancing the deodorizing effect of the clothing by the component (b) A trivalent or tetravalent carboxylic acid having 4 to 10 carbon atoms or a salt thereof is preferable.
Specific examples of the component (e1) include one or more carboxylic acids or salts thereof selected from citric acid, tartaric acid, succinic acid, and malic acid. Citric acid or a salt thereof is preferable in that the effect of imparting a deodorizing effect to clothing can be further enhanced.
(E2) component: a divalent to tetravalent carboxylic acid having an amino group and having 4 to 10 carbon atoms or a salt thereof (e2) Specifically, as the component, nitrilotriacetic acid, ethylenediaminetetraacetic acid, 3- Examples thereof include one or more carboxylic acids selected from hydroxy-2,2′-iminodisuccinic acid, diethylenetriaminepentaacetic acid and hydroxymethylethylenediaminetriacetic acid or salts thereof.

[Component (f)]
The liquid detergent composition for clothing of the present invention can contain a fatty acid having 10 to 20 carbon atoms or a salt thereof as the component (f). The component (f) is preferably a fatty acid having 12 or more and 14 or less carbon atoms or a salt thereof from the viewpoint of suppressing foaming of the liquid cleaning composition for clothing of the present invention.

[(G) component]
The liquid detergent composition for clothing of the present invention can contain a water-miscible organic solvent containing one or more hydroxyl groups as the component (g). (G) It is preferable to contain a component from the solubility point of surfactant. (G) About a component, water miscibility refers to melt | dissolving 50g or more in 1L of ion-exchange water of 25 degreeC. As the component (g), specifically, (g1) one or more compounds selected from ethanol and 2-propanol, (g2) one or more compounds selected from ethylene glycol, propylene glycol, and hexylene glycol (G3) one or more compounds selected from diethylene glycol monomethyl ether, triethylene glycol monomethyl ether, diethylene glycol monoethyl ether, dipropylene glycol monomethyl ether, dipropylene glycol monoethyl ether, tripropylene glycol monomethyl ether, and diethylene glycol monobutyl ether (G4) selected from 2-phenoxyethanol, diethylene glycol monophenyl ether, and triethylene glycol monophenyl ether One or more compounds.

[(H) component]
The liquid detergent composition for clothing of the present invention can contain a calcium ion donor as the component (h). The component (h) is a compound having the property of ion dissociation in water and is used as a protease stabilizer. Component (h) is preferably composed of an inorganic compound, and specific examples include calcium chloride.

[Other ingredients]
The liquid detergent composition for clothing of the present invention contains an acid agent such as glycolic acid, lactic acid or citric acid, an alkali agent such as sodium hydroxide or an alkanolamine having 2 to 6 carbon atoms as a pH adjuster. Can do. Examples of the alkanolamine having 2 to 6 carbon atoms include monoethanolamine, methyldiethanolamine, and triethanolamine. Further, it may contain a carboxylic acid polymer such as polyacrylic acid having a weight average molecular weight of 5000 to 30000 as measured by gel permeation chromatography using polyethylene glycol as a standard substance.

<Composition etc. of liquid detergent composition for clothing>
The liquid detergent composition for clothing of the present invention preferably contains 10% by mass or more and 60% by mass or less of the component (a). From the viewpoint of suppressing the generation of odor from clothing, the content of the component (a) in the composition is more preferably 12% by mass or more, further preferably 14% by mass or more, and still more preferably 16% by mass or more. In terms of economy, the content of the component (a) is more preferably 55% by mass or less, further preferably 50% by mass or less, and further preferably 40% by mass or less.
Of the component (a), a sulfonate having a hydrocarbon group having 8 to 18 carbon atoms, and an alkylbenzene sulfonate having an alkyl group having 9 to 18 carbon atoms are regarded as acid type compounds. The content in the case of being used shall be adopted.

The liquid detergent composition for clothing of the present invention contains (b) component in an amount of 0.5% by mass to 5% by mass. The content of the component (b) is preferably 0.6% by mass or more, more preferably 0.7% by mass or more in the composition from the viewpoint of imparting a high deodorizing effect to the clothing and suppressing the generation of odor from the clothing. More preferably, 0.8 mass% or more is more preferable, 1.0 mass% or more is more preferable, 1.3 mass% or more is more preferable, and 1.5 mass% or more is more preferable. And content of (b) component is 4.5 mass% or less in a composition, 4.0 mass% or less is more preferable, 3.5 mass% or less is further more preferable, 3.0 mass% or less Is still more preferable, 2.5 mass% or less is still more preferable, and 2.0 mass% or less is especially preferable. In the present invention, in the liquid detergent composition for clothing, an anion (for example, X ⁻ in the general formulas (b-1) and (b-2)) which is a counter ion of the component (b) is contained in the composition. The content of the component (b) is regarded as synonymous with the amount of the component (b) used for the preparation of the composition.

The liquid detergent composition for clothing of the present invention further enhances the odor control effect of the component (b) by containing the component (c) in a specific ratio with respect to the content of the component (b). I can do it. The mass ratio of the content of the component (c) and the content of the component (b) is 0.2 to 5 in terms of [content of the component (c)] / [content of the component (b)], From the viewpoint of further suppressing the generation of odor from the clothing due to the component (b), 0.25 or more is preferable, 0.3 or more is more preferable, 0.35 or more is more preferable, 0.4 or more is more preferable, and 5 or more is more preferable, 0.6 or more is more preferable, 0.7 or more is more preferable, 0.8 or more is more preferable, 1 or more is more preferable, and 2 or more is more preferable. 4.5 or less is preferable at the point which the external appearance of the liquid cleaning composition for clothes of this invention becomes transparent easily, 4 or less is preferable and 3 or less is more preferable.
The liquid detergent composition for clothes of the present invention contains (c) component in an amount of 0.5% by mass to 7% by mass. Content of (c) component is adjusted so that the said mass ratio may be satisfy | filled.

When the liquid detergent composition for clothing of the present invention contains the component (d), the content of the component (d) in the composition is the amount of enzyme protein in that the generation of odor from the clothing can be further suppressed. Is preferably 0.1% by mass or more, more preferably 0.2% by mass or more, and preferably 3% by mass or less, more preferably 2% by mass or less, and further preferably 1.5% by mass or less.
In the present invention, the amount of enzyme protein of component (d) is determined according to the method of Lowry et al. (Lowry, OH et al., J. Biol. Chem., 193, 265 (1951)). It is expressed in terms of serum albumin (Bovine Serum Albumin, manufactured by SIGMA, product number A-7030).

  When the liquid detergent composition for clothes of this invention contains (e) component, 0.5 to 5 mass% of content of (e) component in this composition is preferable. The content of the component (e) is preferably 0.6% by mass or more, more preferably 0.7% by mass or more, and more preferably 0.8% by mass or more from the viewpoint of further improving the deodorizing effect on the clothing by the component (b). Is more preferably 4.5% by mass or less, more preferably 4.0% by mass or less, still more preferably 3.5% by mass or less, still more preferably 3.0% by mass or less, and even more preferably 2.5% by mass. The following is even more preferable, and 2.0% by mass or less is particularly preferable. The content of the component (e) in the liquid cleaning composition for clothing of the present invention is calculated as the content as a compound that is acid type, that is, —COOH.

  When the liquid detergent composition for clothing of the present invention contains the component (f), the content of the component (f) is preferably 0.1% by mass or more in the composition from the viewpoint of defoaming. 2 mass% or more is more preferable, and 1 mass% or less is preferable from the point of the storage stability of liquid feeling, and 0.9 mass% or less is more preferable. The content of the component (f) in the liquid cleaning composition for clothing of the present invention is calculated as the content as a compound that is an acid type, that is, —COOH.

  When the liquid cleaning composition for clothing of the present invention contains the component (g), the content of the component (g) is preferably 1% by mass or more in the composition from the viewpoint of the solubility of the surfactant. 2 mass% or more is more preferable, and 10 mass% or less is preferable from an economical point, and 8 mass% or less is more preferable.

  When the liquid cleaning composition for clothing of the present invention contains the component (h), the content of the component (h) is 0.01 mass% or more and 0.15 mass% or less in the composition as calcium ions. preferable. (D) The content of the component (h) is preferably 0.02% by mass or more as a calcium ion in terms of improving the stability of the protease in the case of containing the component protease. The mass% or more is preferable. From the viewpoint of detergency, the content of the component (h) is preferably 0.12% by mass or less, preferably 0.1% by mass or less, and more preferably 0.08% by mass or less in the composition as calcium ions. .

  The water content is the remainder excluding optional components such as the (a) component, the (b) component, the (c) component, the (d) component, and the (e) component.

The viewpoint that the liquid detergent composition for clothing of the present invention has a pH at 20 ° C. of 3 or more and less than 10 is more easily understood by the (c) component to further enhance the deodorizing effect of the component (b) on the clothing. To preferred. The pH is preferably 9.5 or less, more preferably 9.0 or less, still more preferably 8.5 or less, and preferably 3.5 or more, more preferably 4.0 or more, and even more preferably 4.5 or more.
The pH is a value measured at 20 ° C. using a glass electrode. Specifically, it was measured by the following method.
<Measurement method of pH>
A pH electrode (model 6367) is pre-calibrated with a phthalate buffer solution (pH 4.01), a phosphate standard solution (pH 6.84), and a borate standard solution (pH 9.18) on a pH meter D-52 manufactured by HORIBA, Ltd. Rinse thoroughly with ion-exchanged water. A pH electrode that has been calibrated and washed as described above is placed in a liquid detergent composition for clothing adjusted to a temperature of 20 ° C., and measured until the measured value becomes constant using the AUTO HOLD mode of the pH meter.

  The liquid detergent composition for clothing of the present invention is used for washing clothing such as clothing, towels, bedding, and textile products (sheets, pillow covers, etc.) for bedding. Textile products that can be washed other than these can also be targeted.

<Examples 1-15, Comparative Examples 1-2>
A liquid detergent composition for clothing shown in Table 1 was prepared using the following components, and the deodorizing effect was evaluated by the following method using the obtained composition. The results are shown in Table 1. In addition, the 20 degreeC pH of the liquid cleaning composition for clothes in Table 1 was 7.5.

[(A) component]
A1-1: Polyoxyethylene alkyl ether obtained by adding an average of 10 moles of ethylene oxide to a linear primary alcohol having 12 to 14 carbon atoms.
A1-2: A polyoxyalkylene alkyl ether obtained by adding an average of 8 moles of ethylene oxide, an average of 2 moles of propylene oxide, and an average of 10 moles of ethylene oxide in this order to a linear primary alcohol having 12 to 14 carbon atoms.
A2-1: Sodium alkylbenzenesulfonate having an alkyl group having 9 to 14 carbon atoms (mixed with an acid type compound, neutralized with monoethanolamine as a pH adjuster and contained as a salt in the composition)
A3-1: Polyoxyethylene (average number of moles added 2) sodium lauryl ether sulfate (manufactured by Kao Corporation)

[Component (b)]
B1-1: N-lauryl-N, N, N-trimethylammonium chloride b1-2: N-myristyl-N, N-dimethyl-N-ethylammonium ethyl sulfate b1-3: N-myristyl-N N, N-trimethylammonium chloride, b2-1: N, N-dioctyl-N, N-dimethylammonium methyl chloride, b2-2: N, N-didecyl-N-methyl-N-ethylammonium ethyl sulfate

[(C) component]
・ Sodium sulfate: Wako Pure Chemical Industries, Ltd., reagent special grade ・ Potassium sulfate: Wako Pure Chemical Industries, Ltd., reagent special grade

〔water〕
Water: ion-exchanged water containing 3 mg / kg sodium hypochlorite

[Component (d)]
D-1: KAP 8.0Q-L (manufactured by Kao Corporation)
D-2: Sabinase Ultra 16L (Novozyme)

[(E) component]
・ Citric acid, succinic acid, malic acid, tartaric acid

[Component (f)]
Fatty acid: Mixed fatty acid (fatty acid with lauric acid and myristic acid in a mass ratio of lauric acid / myristic acid = 60/40) (manufactured by Kao Corporation)

[(G) component]
・ Ethanol: 95 degree ethanol (Wako Pure Chemical Industries, Ltd.)
・ Diethylene glycol-mono-butyl ether: Nippon Emulsifier Co., Ltd.

[(H) component]
・ Calcium chloride: The content of calcium ions in 1 mol of calcium chloride is 36% by mass.

[Other ingredients]
-Carboxylic acid polymer: Polyacrylic acid having a weight average molecular weight of 5000-pH adjuster: Glycolic acid (manufactured by Wako Pure Chemical Industries, Ltd.) and / or monoethanolamine (manufactured by Wako Pure Chemical Industries, Ltd.)

<Deodorization effect>
A commercial sports towel (90 cm × 20 cm, 100% cotton) that was used and washed for one month was used as evaluation clothing. The evaluation clothing had an oily odor. Evaluation clothing was cut into a size of 10 cm × 10 cm.
Five cut evaluation clothes were washed with the liquid cleaning composition for clothes described in the table. Washing was performed with a washing liquid having a concentration of 0.67 g / L, using a stirring-type cleaning tester (Target-o-Meter) under conditions of a water temperature of 25 ° C., a stirring speed of 85 rpm, a stirring time of 10 minutes, and a bath ratio of 15. . The washed apparel was thoroughly rinsed with tap water and immediately left for 24 hours in an environment of 40 ° C. and 80% relative humidity, and then left for 1 hour in an environment of 30 ° C. and 65% RH.
Based on the strength of the odor from the evaluation clothing washed in Comparative Example 1, the score was given in 1 point increments from 0 to 5 according to the following criteria. 0 is the lowest point and 5 is the highest point. Five expert evaluators respectively compared and evaluated odors, and scored 0 points, 1 point, 2 points, 3 points, 4 points, and 5 points. The score from 1 point to 4 points was assigned to a score closer to 0 to 5 points. The deodorizing effect was evaluated by the average value of the total score. Table 1 shows the average evaluation score. A higher score means better deodorization effect.
0: The same odor intensity as the clothes washed with the composition of Comparative Example 1.
1: The same oily odor as the clothes washed with the composition of Comparative Example 1 but slightly weaker.
The odor intensity between 2: 0 and 5 is close to the odor intensity from the clothes washed with the composition of Comparative Example 1.
3: Slightly oily odor, but at a level that does not matter.
4: Slightly oily odor, but at a level that does not matter.
5: No oily odor from clothes before washing.

<Formulation Examples 1-7>
A liquid detergent composition for clothing shown in Table 2 was prepared using the above components. In addition, 20 degreeC pH of the liquid cleaning composition for clothes in Table 2 was 7.5. It is thought that the liquid cleaning composition for clothes described in Table 2 also has the effect of the present invention.

Claims (4)

The following (a) component, (b) component 0.5 mass% or more and 5 mass% or less, (c) component 0.5 mass% or more and 7 mass% or less, and water are contained, (b) content of component The liquid cleaning composition for clothing, wherein the mass ratio of the amount and the content of component (c) is [content of component (c)] / [content of component (b)] of 0.2 to 5 object.
Component (a): Nonionic surfactant having a polyoxyalkylene group, sulfonate having a hydrocarbon group having 8 to 18 carbon atoms, and sulfate ester salt having a hydrocarbon group having 10 to 18 carbon atoms One or more anionic surfactants selected from the group consisting of one or more surfactants (b) selected from: a quaternary ammonium salt having one hydrocarbon group having 12 to 16 carbon atoms and 8 carbon atoms One or more compounds (c) selected from quaternary ammonium salts having two or more hydrocarbon groups of 10 or less: a salt represented by the following general formula (c1)
(M ^{x +} ) _y SO ₄ ²⁻ (c1)
[Wherein, (M ^{x +} ) is one or more ions selected from sodium ions, potassium ions, magnesium ions, ammonium ions, and alkanol ammonium ions having 2 to 6 carbon atoms. x is the valence of the ion and is a number of 1 or 2. When x is 1, y is a number of 2, and when x is 2, y is a number of 1. ]   Furthermore, the liquid cleaning composition for clothing of Claim 1 which contains protease as (d) component.   The component (e) further contains 0.5 to 5% by mass of a polyvalent carboxylic acid having 3 to 8 carbon atoms in total and having a valence of 2 to 4 and a salt thereof. The liquid detergent composition for clothes as described. The liquid cleaning composition for clothes according to any one of claims 1 to 3, wherein the nonionic surfactant having a polyoxyalkylene group is a nonionic surfactant represented by the following general formula (a1).
_{^{R 1 (CO) m O- (}} A 1 O) n -R 2 (a1)
[Wherein, R ¹ is a primary aliphatic hydrocarbon group having 9 to 16 carbon atoms, R ² is a hydrogen atom or a methyl group, CO is a carbonyl group, and m is 0 or 1. The A ¹ O group is one or more groups selected from an ethyleneoxy group and a propyleneoxy group, n is the average number of moles added, and is a number from 2 to 30. ]