WO2016204063A1 - Liquid detergent composition for clothing - Google Patents

Liquid detergent composition for clothing Download PDF

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Publication number
WO2016204063A1
WO2016204063A1 PCT/JP2016/067191 JP2016067191W WO2016204063A1 WO 2016204063 A1 WO2016204063 A1 WO 2016204063A1 JP 2016067191 W JP2016067191 W JP 2016067191W WO 2016204063 A1 WO2016204063 A1 WO 2016204063A1
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WO
WIPO (PCT)
Prior art keywords
component
mass
clothing
content
less
Prior art date
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PCT/JP2016/067191
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French (fr)
Japanese (ja)
Inventor
美野輪優
妹脊環木
庭野悠
Original Assignee
花王株式会社
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Application filed by 花王株式会社 filed Critical 花王株式会社
Priority to CN201680033884.8A priority Critical patent/CN107683325B/en
Publication of WO2016204063A1 publication Critical patent/WO2016204063A1/en

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Classifications

    • CCHEMISTRY; METALLURGY
    • C11ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11DDETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D1/00Detergent compositions based essentially on surface-active compounds; Use of these compounds as a detergent
    • C11D1/02Anionic compounds
    • C11D1/12Sulfonic acids or sulfuric acid esters; Salts thereof
    • C11D1/29Sulfates of polyoxyalkylene ethers
    • CCHEMISTRY; METALLURGY
    • C11ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11DDETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D1/00Detergent compositions based essentially on surface-active compounds; Use of these compounds as a detergent
    • C11D1/38Cationic compounds
    • C11D1/62Quaternary ammonium compounds
    • CCHEMISTRY; METALLURGY
    • C11ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11DDETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D1/00Detergent compositions based essentially on surface-active compounds; Use of these compounds as a detergent
    • C11D1/66Non-ionic compounds
    • C11D1/72Ethers of polyoxyalkylene glycols
    • CCHEMISTRY; METALLURGY
    • C11ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11DDETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D17/00Detergent materials or soaps characterised by their shape or physical properties
    • C11D17/08Liquid soap, e.g. for dispensers; capsuled
    • CCHEMISTRY; METALLURGY
    • C11ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11DDETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D3/00Other compounding ingredients of detergent compositions covered in group C11D1/00
    • C11D3/16Organic compounds
    • C11D3/20Organic compounds containing oxygen

Definitions

  • the present invention relates to a liquid detergent composition for clothing.
  • JP 2011-246585 A As means for suppressing the growth of bacteria adhering to clothing, for example, as disclosed in JP 2011-246585 A, a nonionic surfactant as a main cleaning component and a main agent exhibiting a deodorizing effect against fresh drying A liquid detergent composition containing a quaternary ammonium salt having one hydrocarbon group having 6 to 22 carbon atoms is disclosed.
  • Japanese Patent Laid-Open No. 11-43405 discloses an antibacterial processing agent for hypoallergenic fibers containing a quaternary ammonium salt having an organic carboxylic acid as a counter ion.
  • 7-53995 contains a cationic bactericidal agent, a metal chelating agent of 0.5 times mol or more of the bactericidal agent, and a nonionic surfactant and / or an amphoteric surfactant. Disinfecting and disinfecting detergent compositions that do not reduce the bactericidal effect even in compositions containing active agents are disclosed.
  • Japanese Patent Publication No. 11-512768 discloses an anionic surfactant such as alkyl polyethoxy sulfate, a quaternary ammonium surfactant, and the anionic surfactant and the quaternary ammonium salt surfactant.
  • a structured heavy duty liquid laundry detergent composition is disclosed that forms liquid crystal particles.
  • the present invention provides a liquid detergent composition for clothing that imparts antibacterial properties to clothing and is excellent in storage stability.
  • component (A) is 10 to 16% by mass
  • component (B) is 1 to 3% by mass
  • component (C) is 2 to 8% by mass
  • (D) Contains ingredients and water
  • the mass ratio of [(D) component content] / [(A) component content + (B) component content] is 0.1 or more and 0.4 or less
  • the present invention relates to a liquid cleaning composition for clothing.
  • Component (A) anionic surfactant represented by the following general formula (1) RO- (C 2 H 4 O) m SO 3 - ⁇ M + (1) [Wherein, R represents a hydrocarbon group having 10 to 16 carbon atoms, m represents an average number of added moles, is a number of 1 to 4 and M + is a cation.]
  • R 1 is an aliphatic hydrocarbon group having 12 to 16 carbon atoms
  • R 2 , R 3 and R 4 are each independently a group selected from a methyl group, an ethyl group and a hydroxyethyl group
  • X ⁇ is an anion.
  • Component a nonionic surfactant R 5 O represented by the following general formula (3) -(C 2 H 4 O) n H (3) [Wherein, R 5 represents a hydrocarbon group having 12 to 16 carbon atoms, and n represents an average added mole number, which is a number of 10 to 40. ]
  • the liquid detergent composition for clothing which provided the antimicrobial property to clothing and was excellent in storage stability is provided.
  • the two functions of washing clothes and imparting antibacterial properties are used to wash clothes with dirt and while wearing dry clothes as well as fresh dry smell generated during drying.
  • a liquid detergent composition for clothing that can effectively suppress the odor generated in the clothes.
  • the liquid detergent composition for clothing of the present invention is capable of coexistence of an anionic surfactant as component (A) and a quaternary ammonium compound as component (B). And antibacterial performance. Moreover, in order to mix
  • the liquid detergent composition for clothing of the present invention is an anionic surfactant as component (A), a cationic surfactant as component (B), a polyvalent carboxylic acid as component (C), and a component (D).
  • a composition comprising water and a nonionic surfactant having a specific average added mole number.
  • the component (A) is an anionic surfactant represented by the following general formula (1).
  • (A) component has the effect
  • R represents a hydrocarbon group having 10 to 16 carbon atoms
  • m represents an average number of added moles, is a number of 1 to 4 and M + is a cation.
  • R is a hydrocarbon group having 10 to 16 carbon atoms, and preferably includes a hydrocarbon group having 12 to 14 carbon atoms from the viewpoint of further improving the washability of clothing.
  • the proportion of the hydrocarbon group having 12 to 14 carbon atoms in the total R of the component (A) is preferably 60% by mass or more, more preferably 70% by mass or more from the viewpoint of maintaining the washability and storage stability of the clothing. More preferably, 100 mass% or less is preferable. This proportion may be 100% by weight. That is, in the component (A), the proportion of the anionic surfactant in which R is a hydrocarbon group having 12 or more and 14 or less carbon atoms is 60% by mass or more from the viewpoint of maintaining the washability and storage stability of clothing. Preferably, 70 mass% or more is more preferable, and 100 mass% or less is preferable. This proportion may be 100% by weight.
  • hydrocarbon group for R examples include an alkyl group and an alkenyl group, preferably an alkyl group, more preferably a primary alkyl group, and still more preferably a linear primary alkyl group.
  • the average added mole number of m is 1 or more, preferably 1.2 or more, more preferably 1.4 or more, from the difficulty of forming a complex with the component (B). 1.6 or more is more preferable. From the viewpoint of detergency, the average added mole number of m is 4 or less, preferably 3 or less, and more preferably 2.5 or less.
  • M + is a cation, and preferably one or more ions selected from a monovalent metal ion, a divalent metal ion, and an alkanol ammonium ion having 2 to 6 carbon atoms.
  • monovalent metal ions include potassium ions and sodium ions.
  • divalent metal ions include magnesium ions.
  • alkanol ammonium ion having 2 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.
  • the component (B) is a quaternary ammonium compound represented by the following general formula (2).
  • the liquid detergent composition for clothing of the present invention containing the component (B) can impart antibacterial properties to clothing.
  • R 1 is an aliphatic hydrocarbon group having 12 to 16 carbon atoms
  • R 2 , R 3 and R 4 are each independently a group selected from a methyl group, an ethyl group and a hydroxyethyl group.
  • X ⁇ is an anion.
  • the aliphatic hydrocarbon group of R 1 has 16 or less carbon atoms and 14 or less carbon atoms. 12 is more preferable. From the viewpoint of the persistence of the component (B) on the cloth, R 1 has 12 or more carbon atoms, preferably 14 or more, and more preferably 16.
  • the aliphatic hydrocarbon group for R 1 include an alkyl group and an alkenyl group, an alkyl group is preferable, a primary alkyl group is more preferable, and a linear primary alkyl group is still more preferable.
  • Examples of the aliphatic hydrocarbon group having 12 carbon atoms include a lauryl group. Examples of the aliphatic hydrocarbon group having 14 carbon atoms include a myristyl group.
  • the aliphatic hydrocarbon group having 16 carbon atoms include a palmityl group and a palmitoleyl group.
  • the liquid detergent composition for clothing of the present invention has the following component (b1) as the component (B) in that the storage stability at high temperatures of the liquid detergent composition for clothing of the present invention is further improved. It is preferable to contain (b2) component.
  • (B1) Component: A quaternary ammonium compound in which R 1 in the general formula (2) is an aliphatic hydrocarbon group having 12 carbon atoms.
  • the component (b2) is the fourth in which R 1 is an aliphatic hydrocarbon group having 16 carbon atoms in that the storage stability at high temperature is improved while maintaining the effect of imparting antibacterial properties to the clothing.
  • a quaternary ammonium compound is preferred.
  • the liquid detergent composition for clothing of the present invention contains the component (b1) and the component (b2) as the component (b), it is stored at a high temperature while maintaining the effect of imparting antibacterial properties to the clothing.
  • the content ratio of the component (b1) and the component (b2) is a mass ratio of [(b2) component content] / [(b1) component content] in that the stability is improved. It is preferable that it is above 90/10.
  • the mass ratio is more preferably 2/98 or more, more preferably 3/97 or more, still more preferably 4/96 or more, and more preferably 5/95 or more in that the storage stability at a high temperature is further improved. More preferably, 10/90 or more is still more preferable, 15/85 or more is more preferable, 85/15 or less is more preferable, and 80/20 or less is still more preferable.
  • R 2 , R 3 and R 4 are each independently a group selected from a methyl group, an ethyl group and a hydroxyethyl group.
  • R 2 , R 3 and R 4 are each preferably a methyl group.
  • X ⁇ is an anion, and from the viewpoint of easy availability of the raw material, one or more anions selected from halogen ions and alkyl sulfate ions having 1 to 3 carbon atoms can be mentioned. It is done.
  • the halogen ion include one or more anions selected from chloride ions and bromide ions.
  • the alkyl sulfate ion having 1 to 3 carbon atoms include one or more anions selected from methyl sulfate ion and ethyl sulfate ion.
  • the component (B) of the present invention can be used in combination with one or more quaternary ammonium compounds.
  • the component (C) is a polyvalent carboxylic acid having 4 to 6 carbon atoms and having 2 to 4 carbon atoms or a salt thereof.
  • (C) component suppresses complex formation of (A) component and (B) component by forming a complex with (B) component preferentially in water, and (A) component It is thought that the cleaning property derived from the origin and the antibacterial property derived from the component (B) are maintained.
  • the component (C) is preferably a trivalent polyvalent carboxylic acid or a salt thereof.
  • the component (C) is preferably one or more polyvalent carboxylic acids or salts thereof selected from succinic acid, malic acid, tartaric acid, citric acid and salts thereof.
  • the component (C) is more preferably citric acid or a salt thereof.
  • Examples of the salt of the polyvalent carboxylic acid (C) include alkali metals such as sodium salt and potassium salt.
  • a compound in which the carboxylic acid group having 2 or more and 4 or less is in an acid form and a compound in a salt form may coexist.
  • the component (D) is a nonionic surfactant represented by the following general formula (3).
  • R 5 O— (C 2 H 4 O) n H (3) [Wherein, R 5 represents a hydrocarbon group having 12 to 16 carbon atoms, and n represents an average added mole number, which is a number of 10 to 40. ]
  • the component (D) in the present invention not only improves the detergency but also improves the storage stability of the liquid cleaning composition for clothing of the present invention at high temperatures.
  • the complex formed by component (A) and component (B) tends to precipitate and separate in the composition during storage, especially during storage at high temperatures.
  • the composite formed by the (A) component and the (B) component is incorporated into the mixed micelle of the (A) component and the (D) component, whereby the composition It is presumed that the storage stability of
  • R 5 is a hydrocarbon group having 12 to 16 carbon atoms.
  • the hydrocarbon group for R 5 include an alkyl group and an alkenyl group. An alkyl group is preferred, a primary alkyl group is more preferred, and a linear primary alkyl group is still more preferred.
  • the hydrocarbon group for R 5 include a linear aliphatic hydrocarbon group or a branched aliphatic hydrocarbon group, and a linear aliphatic hydrocarbon group is preferable.
  • R 5 is preferably a straight-chain alkyl group, and at least one selected from a lauryl group and a myristyl group, while maintaining the antibacterial effect imparted to clothing by the component (B). Groups are more preferred.
  • the proportion of the hydrocarbon group having 12 to 14 carbon atoms in the total R 5 of the component (D) is 60% from the viewpoint of improving the storage stability of the liquid cleaning composition for clothing of the present invention at high temperature. % Or more is preferable, 70 mass% or more is more preferable, 80 mass% or more is further more preferable, and 100 mass% or less is preferable. This proportion may be 100% by weight. That is, in the component (D), the ratio of the nonionic surfactant in which R 5 is a hydrocarbon group having 12 to 14 carbon atoms is the storage stability of the liquid cleaning composition for clothing of the present invention at a high temperature. From the point of improvement, 60 mass% or more is preferable, 70 mass% or more is more preferable, 80 mass% or more is further more preferable, and 100 mass% or less is preferable. This proportion may be 100% by weight.
  • R 5 is a nonionic surfactant having a hydrocarbon group having 12 carbon atoms
  • R 5 is a non-ionic surfactant having a hydrocarbon group having 14 carbon atoms. It is preferable to contain one or more nonionic surfactants selected from ionic surfactants.
  • R 5 is a nonionic surfactant having a hydrocarbon group having 12 carbon atoms
  • R 5 is a non-ionic surfactant having a hydrocarbon group having 14 carbon atoms. It is preferable to contain an ionic surfactant.
  • the ratio is preferably 40/60 or more, more preferably 50/50 or more, still more preferably 55/45 or more, and is preferably 100 or less, that is, 100/1 or less, and more preferably 98/2 or less.
  • n represents the average number of moles of ethylene oxide added, and is a number from 10 to 40. From the viewpoint of further improving storage stability, n is preferably 12 or more, more preferably 13 or more, still more preferably 15 or more, still more preferably 16 or more, still more preferably 18 or more, and still more preferably 20 or more. And 35 or less is preferable.
  • water examples include ion-exchanged water, ion-exchanged water containing 0.1 mg / kg to 5 mg / kg of hypochlorite, and tap water.
  • the liquid detergent composition for clothing of the present invention contains the above-mentioned component (A), component (B), component (C), component (D) and water.
  • the liquid detergent composition for clothing of the present invention contains 10% by mass or more and 16% by mass or less of the component (A) from the viewpoint of improving the detergency of dirt and bacteria attached to the clothing and improving the storage stability. To do.
  • the content of the component (A) is preferably 11% by mass or more in the composition from the same viewpoint as described above. And from a viewpoint which can maintain the antimicrobial effect of the clothing by (B) component, 15 mass% or less is preferable in a composition, and, as for content of (A) component, 14 mass% or less is more preferable.
  • the content of the component (A) is calculated by mass obtained by converting M + cations to Na + . That is, content of (A) component shall be computed by the mass converted into sodium salt.
  • the garment cleaning composition of the present invention contains 1% by mass or more and 3% by mass or less of the component (B).
  • the content of the component (B) is preferably 1.5% by mass or more and more preferably 2% by mass or more in the composition from the viewpoint of further enhancing the ability to impart antibacterial properties to clothing.
  • the content of the component (B) is preferably 2.9% by mass or less, more preferably 2.8% by mass or less in the composition from the viewpoint of improving the storage stability of the liquid detergent composition for clothing. 2.7 mass% or less is still more preferable, and 2.6 mass% or less is still more preferable.
  • the clothing cleaning composition of the present invention contains 2% by mass or more and 8% by mass or less of the component (C).
  • (C) Content of component is 2.5 mass% or more in a composition at the point which can suppress the composite formation of (A) component and (B) component in water, and can improve the antimicrobial property of clothing more. Is preferably 3% by mass or more, more preferably 3.5% by mass or more, still more preferably 4% by mass or more, still more preferably 4.5% by mass or more, and preferably 7% by mass or less.
  • 0.5 mass% or less is more preferable, 6 mass% or less is still more preferable, and 5.5 mass% or less is still more preferable.
  • the garment cleaning composition of the present invention is a mass ratio of the content of the component (D) and the total content of the content of the component (A) and the content of the component (B) [component (D) Content] / [(A) component content + (B) component content] is 0.1 or more and 0.4 or less.
  • [( D) component content] / [(A) component content + (B) component content] mass ratio is preferably 0.11 or more, more preferably 0.12 or more, and 0.35 or less. Is preferable, 0.3 or less is more preferable, 0.25 or less is more preferable, and 0.2 or less is further more preferable.
  • the liquid detergent composition for clothing is a mass ratio of the content of the component (B) and the content of the component (A) from the viewpoint of imparting high antibacterial properties to the clothing and further improving the storage stability.
  • [Content of (B) component] / [Content of (A) component] is preferably 0.05 or more and 0.3 or less.
  • the mass ratio of [(B) component content] / [(A) component content] is preferably 0.06 or more, more preferably 0.07 or more, 0.08 or more is still more preferable, 0.09 or more is still more preferable, and 1.0 or more is still more preferable.
  • the mass ratio of [(B) component content] / [(A) component content] is preferably 0.25 or less, more preferably 0.23 or less. 0.2 or less is more preferable, 0.19 or less is more preferable, and 0.18 or less is still more preferable.
  • the water content is such that the sum of the contents of the components (A) to (D) and the optional component is 100% by mass.
  • the water content in the composition is preferably 60% by mass or more, more preferably 65% by mass or more, and still more preferably 70% by mass or more.
  • the liquid detergent composition for clothing of the present invention preferably has a pH of 2 or more and 7 or less at 20 ° C. from the viewpoint of suppressing odor generated from the liquid detergent composition for clothing containing the component (B).
  • the pH is preferably 6.8 or less, more preferably 6.5 or less, still more preferably 6 or less, and more preferably 3 or more, and 3.5 or more. Is more preferable, and 4 or more is more preferable.
  • the pH is measured by the following method.
  • the pH electrode in the following method is a glass electrode. ⁇ Measurement method of pH> HORIBA, Ltd.
  • pH meter D-52 pH electrode (model 6367) was calibrated with phthalate buffer solution (pH 4.01), phosphate standard solution (pH 6.84), and borate standard solution (pH 9.18) in advance. Rinse thoroughly with ion-exchanged water. Place the pH electrode calibrated and washed as described above into the liquid detergent composition for clothing adjusted to a temperature of 20 ° C. Using the HOLD mode, measure until the measured value is constant.
  • the liquid detergent composition for clothing of the present invention is excellent in appearance.
  • the liquid detergent composition for clothing of the present invention can have a transparent appearance.
  • the term “transparent” may refer to a state in which cloudiness is not recognized by visual observation.
  • transparent means that the liquid detergent composition for clothing of the present invention is put in a glass cell having an optical path length of 1 cm in an ultraviolet-visible spectrophotometer, and ion-exchanged water is used for the control side cell at 660 nm. It can be assumed that the transmittance at a wavelength of 90% or more. A higher transmittance figure is more transparent and a more preferable appearance. If the components (A) to (D) of the present invention and water are mixed so as to have the predetermined content of the present invention, a composition having a transparent appearance can be obtained.
  • the liquid detergent composition of the present invention can contain a pH adjuster as the component (E).
  • a pH adjuster as the component (E).
  • 1 or more types of pH adjusters chosen from sodium hydroxide, potassium hydroxide, and a C2-C6 alkanolamine are mentioned.
  • the alkanolamine having 2 to 6 carbon atoms include monoethanolamine, diethanolamine, methyldiethanolamine, dimethylethanolamine, and triethanolamine.
  • the pH adjusting agent can be used in such an amount that the above pH is reached.
  • the liquid detergent composition for clothing of the present invention can contain a fragrance as the component (F) in order to impart a preferable scent from the composition.
  • the component (F) include a fragrance composition known to be blended in a liquid detergent composition for clothing.
  • a composition containing a fragrance can be used as described in "Basic knowledge of fragrance and fragrance", edited by Motoki Nakajima, 1995, published by Sangyo Tosho Co., Ltd., 4th printing.
  • the content of the component (F) is preferably 0.1% by mass or more, more preferably 0.2% by mass or more, still more preferably 0.4% by mass or more, and preferably 1% by mass or less in the composition. 0.8 mass% or less is more preferable.
  • the liquid detergent composition for clothing of the present invention can contain a preservative such as 1,2-benzisothiazolin-3-one, polyhexamethylene biguanide hydrochloride, etc. as component (G).
  • a preservative such as 1,2-benzisothiazolin-3-one, polyhexamethylene biguanide hydrochloride, etc.
  • the content of the component (G) in the composition is preferably 0.001% by mass or more, more preferably 0.05% by mass or more, and preferably 0.5% by mass or less, more preferably 0.3% by mass or less. preferable.
  • the liquid detergent composition for clothing of the present invention is generally used to make the appearance of the liquid composition transparent, and the appearance is transparent even if the content of the organic solvent having one or more hydroxyl groups is small. For example, an excellent appearance can be exhibited. Specifically, the liquid detergent composition for clothing of the present invention can exhibit an excellent appearance even when the content of the organic solvent having one or more hydroxyl groups is 0% by mass or more and less than 10% by mass.
  • the organic solvent include monovalent to hexavalent alcohols having 2 to 6 carbon atoms. Examples of the monovalent alcohol having 2 to 6 carbon atoms include ethanol. Examples of the divalent alcohol having 2 to 6 carbon atoms include ethylene glycol and propylene glycol.
  • Examples of the trivalent alcohol having 2 to 6 carbon atoms include glycerin.
  • the content of the organic solvent is preferably 9% by mass or less, more preferably 8% by mass or less, still more preferably 7% by mass or less, and may be 0% by mass in the composition.
  • the liquid detergent composition for clothing of the present invention can impart antibacterial properties to clothing.
  • the liquid detergent composition for clothing of the present invention can impart more effective antibacterial properties against causative bacteria that produce odorous substances to clothing, for example, Moraxella genus described in JP2013-18971A More effective antibacterial properties can be imparted to bacteria, Escherichia coli, and Acinetobacter bacteria.
  • One or more kinds of bacteria selected from Moraxella osloensis and Moraxella sp. are more preferable as the object of the present invention. These bacteria are abundant on the used clothing, and are known as causative bacteria that produce odorous substances that make the clothing smell after washing or after dehydration.
  • the liquid detergent composition for clothing of the present invention exhibits excellent antibacterial properties against these bacteria.
  • the liquid detergent composition for clothing of the present invention can be used for applications that impart antibacterial properties to clothing.
  • the liquid detergent composition for clothes of the present invention can be used for applications that impart antibacterial properties against causative bacteria that produce odorous substances to clothes. Examples of causative bacteria that produce odorous substances include Moraxella bacteria, Escherichia coli, and Acinetobacter bacteria.
  • the liquid detergent composition for clothing of the present invention can be used for applications that impart a deodorizing effect to clothing.
  • the liquid detergent composition for clothing of the present invention can be used for applications that impart a deodorizing effect to clothing that makes it difficult for the clothing to smell after washing or after dehydration and drying.
  • liquid detergent composition for clothing of the present invention for imparting antibacterial properties to clothing is exemplified.
  • the use of the liquid detergent composition for clothing of the present invention for imparting antibacterial properties against causative bacteria producing odor substances to clothing is exemplified.
  • use of the liquid cleaning composition for clothing of the present invention for imparting a deodorizing effect to clothing is exemplified.
  • the use of the liquid detergent composition for clothing of the present invention for imparting a deodorizing effect to the clothing such that the clothing hardly smells after washing or after dehydration until drying. It is done.
  • 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.
  • Component (A) anionic surfactant represented by the following general formula (1) RO- (C 2 H 4 O) m SO 3 - ⁇ M + (1) [Wherein, R represents a hydrocarbon group having 10 to 16 carbon atoms, m represents an average number of added moles, is a number of 1 to 4 and M + is a cation.]
  • R 1 is an aliphatic hydrocarbon group having 12 to 16 carbon atoms
  • R 2 , R 3 and R 4 are each independently a group selected from a methyl group, an ethyl group and a hydroxyethyl group
  • X ⁇ is an anion.
  • Component a nonionic surfactant R 5 O represented by the following general formula (3) -(C 2 H 4 O) n H (3) [Wherein, R 5 represents a hydrocarbon group having 12 to 16 carbon atoms, and n represents an average added mole number, which is a number of 10 to 40. ]
  • the proportion of hydrocarbon groups having 12 to 14 carbon atoms in the total R of component (A) is 60% by mass or more, further 70% by mass or more, 100% by mass or less, further 95% by mass or less, and further 90%.
  • the proportion of the anionic surfactant in which R is a hydrocarbon group having 12 to 14 carbon atoms is 60% by mass or more, further 70% by mass or more, and 100% by mass or less, and further 95% by mass.
  • % Liquid detergent composition for clothes as described in ⁇ 1> which is 90 mass% or less further, or 100 mass%.
  • the liquid detergent composition for clothing according to any one of ⁇ 1> to ⁇ 4>, which comprises the following component (b1) and component (b2) as component (B): (B1)
  • the content ratio of the component (b2) and the component (b1) in the liquid detergent composition for clothing is 1/99 in the mass ratio of [(b2) component content] / [(b1) component content]. 2/98 or more, 3/97 or more, 4/96 or more, 5/95 or more, 10/90 or more, 90/10 or less, 85/15 or less, 80/20 or less.
  • the aliphatic hydrocarbon group having 12 carbon atoms is a lauryl group
  • the aliphatic hydrocarbon group having 14 carbon atoms is a myristyl group
  • the aliphatic hydrocarbon group having 16 carbon atoms is a palmityl group or a palmitoleyl group, 5.
  • a liquid detergent composition for clothing according to any one of 5> to ⁇ 7>.
  • the component (C) is one or more polyvalent carboxylic acids selected from succinic acid, malic acid, tartaric acid, citric acid and salts thereof, or a salt thereof, according to any one of ⁇ 1> to ⁇ 9>.
  • Liquid detergent composition for clothing is one or more polyvalent carboxylic acids selected from succinic acid, malic acid, tartaric acid, citric acid and salts thereof, or a salt thereof, according to any one of ⁇ 1> to ⁇ 9>.
  • liquid detergent composition for clothing according to ⁇ 10>, wherein the component (C) is one or more polyvalent carboxylic acids selected from citric acid and salts thereof or salts thereof.
  • the ratio of the hydrocarbon group having 12 to 14 carbon atoms in the total R 5 of the component (D) is 60% by mass or more, further 70% by mass or more, further 80% by mass or more, and 100% by mass or less.
  • the proportion of the nonionic surfactant in which R 5 is a hydrocarbon group having 12 to 14 carbon atoms is 60% by mass or more, further 70% by mass or more, further 80% by mass or more, and 100
  • the hydrocarbon group of R 5 is a linear aliphatic hydrocarbon group or a branched aliphatic hydrocarbon group, and further a linear aliphatic hydrocarbon group. 13> Liquid detergent composition for clothes in any one of.
  • n is 12 or more, 13 or more, 15 or more, 16 or more, 18 or more, 20 or more, and 35 or less, and any one of ⁇ 1> to ⁇ 16>
  • the content of the component (B) in the composition is 1.5% by mass or more, further 2% by mass or more, 2.9% by mass or less, further 2.8% by mass or less, and further 2.7% by mass or less. Furthermore, the liquid cleaning composition for clothes according to any one of ⁇ 1> to ⁇ 18>, which is 2.6% by mass or less.
  • the content of component (C) in the composition is 2.5% by mass or more, further 3% by mass or more, further 3.5% by mass or more, further 4% by mass or more, further 4.5% by mass or more, and
  • the liquid detergent composition for clothing according to any one of ⁇ 1> to ⁇ 18>, which is 7% by mass or less, further 6.5% by mass or less, further 6% by mass or less, and further 5.5% by mass or less.
  • (D) component content and (A) component content and (B) component content is the mass ratio of [(D) component content] / [(A) component Content + content of component (B)] is 0.11 or more, further 0.12 or more, 0.35 or less, further 0.3 or less, further 0.25 or less, and further 0.2 or less.
  • (D) component content and (A) component content and (B) component content is the mass ratio of [(D) component content] / [(A) component Content + content of component (B)] is 0.11 or more, further 0.12 or more, 0.35 or less, further 0.3 or less, further 0.25 or less, and further 0.2 or less.
  • the pH at 20 ° C. is 2 or more, 3 or more, 3.5 or more, 4 or more, 7 or less, further 6.8 or less, further 6.5 or less, and further 6 or less.
  • the content of the organic solvent having one or more hydroxyl groups is 0% by mass or more and less than 10% by mass, further 9% by mass or less, further 8% by mass or less, further 7% by mass or less, or 0% by mass, ⁇ 1
  • liquid detergent composition for clothing according to any one of ⁇ 23>, wherein the organic solvent having one or more hydroxyl groups is a monovalent to hexavalent alcohol having 2 to 6 carbon atoms.
  • composition according to any one of ⁇ 1> to ⁇ 24> is used as a liquid detergent for clothing.
  • Example ⁇ Compounding ingredients> The components used in Examples and Comparative Examples are shown below.
  • Component (A)] (A-1): In the general formula (1), R is a mixed alkyl group in which lauryl group and myristyl group are in a mass ratio, lauryl group / myristyl group 7/3 (mass ratio), and m is 2.0.
  • An anionic surfactant (a-2) in which M + is Na + :
  • (B) component] (B1-1): N-lauryl-N, N, N-trimethylammonium chloride [R 1 in the general formula (2) is a lauryl group, R 2 , R 3 and R 4 are each a methyl group, X ⁇ There Cl - quaternary ammonium compounds which are] (B2-1): N-palmityl-N, N, N-trimethylammonium chloride [in formula (2), R 1 is a palmityl group, R 2 , R 3 and R 4 are each a methyl group, X ⁇ There Cl - quaternary ammonium compounds which are]
  • (B ′) Component: Comparative Compound of Component (B)] (B′-1): N, N-didecyl-N, N-dimethylammonium chloride [For convenience, when represented by the structure of the general formula (2), R 1 and R 2 in the general formula (2) are , A decyl group, R 3 and R 4 are each a methyl group, and X ⁇ is Cl 2 — a quaternary ammonium compound] (B′-2): N-stearyl-N, N, N-trimethylammonium chloride [For the sake of convenience, R 1 in the general formula (2) is an octyl group, R 2 , R 3 and R 4 are each a methyl group, and X ⁇ is Cl 2 —.
  • Nonionic surfactant (d′-3) in which the myristyl group is a mixed alkyl group having a lauryl group / myristyl group 9/1 by mass ratio, and n is 6: For convenience, it is represented by the structure of the general formula (3) In the general formula (3), R 5 is a stearyl group, and n is 20, a nonionic surfactant
  • [(F) component] (F-1) A fragrance composition containing the following fragrance ingredients. Numbers in parentheses are parts by mass. Phenylethyl alcohol (10), camphor (20), citronellal (10), l-menthol (20), aldehyde C-9 (10), nerol (10), diphenyl oxide (20)
  • a cleaning liquid having a liquid cleaning composition concentration of 1 g / L Water and each liquid cleaning composition were mixed to prepare a cleaning liquid having a liquid cleaning composition concentration of 1 g / L.
  • a 1 liter stainless steel beaker 0.6 liter of the cleaning solution was placed, and 30 pieces of the above 6 cm ⁇ 6 cm cotton plain woven fabric were placed.
  • the washing operation was performed with a targotometer at 100 rpm for 10 minutes.
  • the cleaning liquid in the stainless beaker was discarded, and the cotton plain woven cloth was squeezed by hand to make it about 250% by weight based on the dry weight of the cotton plain woven cloth before washing.
  • the water was rinsed twice for 3 minutes under the same conditions, dehydrated for 30 seconds in a dewatering tank of a 2-tank washing machine, and naturally dried.
  • the bacteriostatic activity value was obtained by subtracting the common logarithm of the viable cell count of each Example or Comparative Example from the common logarithm of the viable cell count of Comparative Example 1 in Table 1. In this evaluation, the bacteriostatic activity value of 2.2 or more is acceptable, and the higher the bacteriostatic activity value, the higher the antibacterial effect.
  • the liquid detergent composition for clothing described in the table is No. 25 g was placed in a 6 standard bottle and allowed to stand in a constant temperature bath at 50 ° C. The appearance of the liquid detergent composition for clothing after 7 days was visually observed and evaluated according to the following criteria.
  • the following standards 1 and 2 are acceptable levels when the product form is considered, and 1 is preferable. Also, in the case of 2 below, it is preferable in terms of storage stability that the number of days until a slight cloudiness is seen is longer. 3 is a failure level.
  • composition of 1 or 2 of the following criteria is a UV-visible spectrophotometer in which the liquid detergent composition for clothing is placed in a glass cell having an optical path length of 1 cm, and ion-exchanged water is used for the control side cell.
  • the transmittance at a wavelength of 660 nm is 90% or more. 1: The transparent state is maintained and no separation is observed. 2: Although slightly cloudy, it is recognized as a transparent state and separation is not recognized. 3: Separation is observed.
  • (D) / [(A) + (B)] is a mass ratio of [content of (D) component] / [content of (A) component + content of (B) component]. (The same applies hereinafter).
  • (B) / (A) is a mass ratio of [content of (B) component] / [content of (A) component] (the same applies hereinafter).
  • composition of 1 or 2 of the following criteria is a UV-visible spectrophotometer in which the liquid detergent composition for clothing is placed in a glass cell having an optical path length of 1 cm, and ion-exchanged water is used for the control side cell.
  • the transmittance at a wavelength of 660 nm is 90% or more. 1: The transparent state is maintained and no separation is observed. 2: Although slightly cloudy, it is recognized as a transparent state and separation is not recognized. 3: Separation is observed.
  • Washing rate (%) 100 ⁇ [(reflectance after washing ⁇ reflectivity before washing) / (reflectance of base fabric ⁇ reflectivity before washing)]
  • Example 28 corresponds to Example 1
  • Example 29 corresponds to Example 2. It can be seen that any liquid detergent composition for clothing has good detergency.

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Abstract

The present invention pertains to a liquid detergent composition for clothing containing component (A): a specific anionic surfactant, component (B): a quaternary ammonium salt having a specific structure, component (C): a polycarboxylic acid or salt thereof, component (D): a nonionic surfactant having a specific average number of mol of ethylene oxide added, and water. The [content of component (D)]/[content of component (A) + content of component (B)] (mass ratio) is 0.1-0.4.

Description

衣料用液体洗浄剤組成物Liquid detergent composition for clothing
 本発明は、衣料用液体洗浄剤組成物に関する。 The present invention relates to a liquid detergent composition for clothing.
背景技術
 生活者の衛生意識の高まりに伴い、衣料のにおいや菌に対する関心も高まってきている。衣料には皮膚常在菌や環境中に存在する様々な菌が付着し繁殖していることが知られている。洗濯後の乾燥過程の生乾きの衣料や発汗時に着用している衣料は水分が多く含まれる為、菌に増殖に伴い代謝物の排出量が多くなり、臭いがより発生しやすくなっていると考えられている。
BACKGROUND ART With increasing awareness of hygiene among consumers, interest in clothing smells and fungi is also increasing. It is known that various bacterium existing in the skin and the environment are attached to the clothing and propagate. It is considered that raw clothes that are dried during washing and clothes that are worn during sweating contain a lot of moisture, so the amount of metabolites released increases with the growth of bacteria, and odors are more likely to occur. It has been.
 衣料に付着している菌の増殖を抑制する手段としては、例えば、特開2011-246585号公報のように、主たる洗浄成分である非イオン界面活性剤と、生乾きに対する消臭効果を示す主たる剤である炭素数6~22の炭化水素基を一つ有する第4級アンモニウム塩とを含有する液体洗浄剤組成物が開示されている。また、特開平11-43405号公報には、有機カルボン酸を対イオンとする第4級アンモニウム塩を含有する低刺激性繊維用抗菌加工処理剤が開示されている。 As means for suppressing the growth of bacteria adhering to clothing, for example, as disclosed in JP 2011-246585 A, a nonionic surfactant as a main cleaning component and a main agent exhibiting a deodorizing effect against fresh drying A liquid detergent composition containing a quaternary ammonium salt having one hydrocarbon group having 6 to 22 carbon atoms is disclosed. Japanese Patent Laid-Open No. 11-43405 discloses an antibacterial processing agent for hypoallergenic fibers containing a quaternary ammonium salt having an organic carboxylic acid as a counter ion.
 一方、汚れが付着した衣料を洗浄する場合に、衣料用洗浄剤組成物中に含まれる界面活性剤によって汚れが衣料から脱離した後に、汚れが再び衣料に再付着するという再汚染の課題により、洗浄性が出にくい課題がある。界面活性剤の中でノニオン界面活性剤よりもアニオン界面活性剤の方が、再汚染の課題が少ないことが知られている。
 しかしながら、第4級アンモニウム塩などのカチオン界面活性剤による殺菌作用は、アニオン界面活性剤を主成分とする組成物中で低下することが知られている。特開平7-53995号公報には、カチオン系殺菌剤、該殺菌剤の0.5倍モル以上の金属キレート剤、並びに非イオン性界面活性剤及び/又は両性界面活性剤を含有し、アニオン界面活性剤を含有する組成物中でも殺菌効果が低下しない殺菌消毒洗浄剤組成物が開示されている。特表平11-512768号公報には、アルキルポリエトキシサルフェート等の陰イオン界面活性剤、第4級アンモニウム界面活性剤を含有し、前記陰イオン界面活性剤及び第4級アンモニウム塩界面活性剤が液晶粒子を形成する、構造化ヘビーデューティ液体洗濯洗剤組成物が開示されている。
On the other hand, due to the problem of re-contamination, when dirt is attached to clothes, after the dirt is detached from the clothes by the surfactant contained in the clothes cleaning composition, the dirt is again attached to the clothes. There is a problem that the cleaning property is difficult to be obtained. It is known that among surfactants, anionic surfactants are less subject to recontamination than nonionic surfactants.
However, it is known that the bactericidal action by a cationic surfactant such as a quaternary ammonium salt is reduced in a composition containing an anionic surfactant as a main component. Japanese Patent Application Laid-Open No. 7-53995 contains a cationic bactericidal agent, a metal chelating agent of 0.5 times mol or more of the bactericidal agent, and a nonionic surfactant and / or an amphoteric surfactant. Disinfecting and disinfecting detergent compositions that do not reduce the bactericidal effect even in compositions containing active agents are disclosed. Japanese Patent Publication No. 11-512768 discloses an anionic surfactant such as alkyl polyethoxy sulfate, a quaternary ammonium surfactant, and the anionic surfactant and the quaternary ammonium salt surfactant. A structured heavy duty liquid laundry detergent composition is disclosed that forms liquid crystal particles.
発明の概要
 着用後の皮脂汚れなどの汚れが付着した衣料を洗濯しても、衣料に付着した汚れや菌が完全に落ちない課題がある。
 衣料上に残留した菌は、衣料に残留した皮脂などの汚れを代謝し、臭う代謝物を排出し、臭いを発生させることで、1日着用後の衣料から臭いが発生する課題が尚存在する。衣料に存在する菌の増殖を抑制する為に、第4級アンモニウム塩を使用しても未だ改良の余地はある。
 また、本発明者らは、アニオン界面活性剤を含有する衣料用液体洗浄剤組成物にカチオン界面活性剤と特定のキレート剤を使用すると、保存安定性が低下する、特に高温での保存により組成物の分離や曇りが生じるという課題を見出した。
 使い勝手の点から、形態が液体である衣料用液体洗浄剤組成物の割合が、洗浄剤の市場の中で増加してきている。そのため、液体組成物において、前記の課題を解決することが望まれる。
SUMMARY OF THE INVENTION There is a problem that dirt and bacteria attached to clothes are not completely removed even if clothes with attached dirt such as sebum dirt after wearing are washed.
The bacteria remaining on the clothes metabolize the dirt such as sebum remaining on the clothes, discharge the odorous metabolites, and generate odors, so that there is still a problem that odors are generated from the clothes after daily wear. . There is still room for improvement even if quaternary ammonium salts are used to suppress the growth of bacteria present in clothing.
In addition, the present inventors use a cationic surfactant and a specific chelating agent in a liquid detergent composition for clothing containing an anionic surfactant, resulting in a decrease in storage stability, particularly when stored at high temperatures. We found the problem of separation of objects and cloudiness.
In terms of ease of use, the proportion of liquid detergent compositions for clothing in liquid form has increased in the detergent market. Therefore, in the liquid composition, it is desired to solve the above problems.
 本発明は、衣料に抗菌性を付与し、保存安定性に優れた衣料用液体洗浄剤組成物を提供する。 The present invention provides a liquid detergent composition for clothing that imparts antibacterial properties to clothing and is excellent in storage stability.
 本発明は、下記(A)成分を10質量%以上16質量%以下、(B)成分を1質量%以上3質量%以下、(C)成分を2質量%以上8質量%以下、(D)成分及び水を含有し、
 〔(D)成分の含有量〕/〔(A)成分の含有量+(B)成分の含有量〕の質量比が0.1以上0.4以下である、
衣料用液体洗浄剤組成物に関する。
(A)成分:下記一般式(1)で表される陰イオン界面活性剤
     RO-(CO)SO ・M     (1)
〔式中、Rは炭素数10以上16以下の炭化水素基であり、mは平均付加モル数を示し、1以上4以下の数であり、Mは陽イオンである。〕
(B)成分:下記一般式(2)で表される第4級アンモニウム化合物
In the present invention, the following component (A) is 10 to 16% by mass, component (B) is 1 to 3% by mass, component (C) is 2 to 8% by mass, (D) Contains ingredients and water,
The mass ratio of [(D) component content] / [(A) component content + (B) component content] is 0.1 or more and 0.4 or less,
The present invention relates to a liquid cleaning composition for clothing.
Component (A): anionic surfactant represented by the following general formula (1) RO- (C 2 H 4 O) m SO 3 - · M + (1)
[Wherein, R represents a hydrocarbon group having 10 to 16 carbon atoms, m represents an average number of added moles, is a number of 1 to 4 and M + is a cation.] ]
Component (B): a quaternary ammonium compound represented by the following general formula (2)
Figure JPOXMLDOC01-appb-C000002
Figure JPOXMLDOC01-appb-C000002
〔式中、Rは、炭素数12以上16以下の脂肪族炭化水素基であり、R、R及びRは、それぞれ独立に、メチル基、エチル基及びヒドロキシエチル基から選ばれる基であり、Xは陰イオンである。〕
(C)成分:炭素数4以上6以下であり2価以上4価以下の多価カルボン酸又はその塩
(D)成分:下記一般式(3)で表される非イオン界面活性剤
     RO-(CO)H     (3)
〔式中、Rは炭素数12以上16以下の炭化水素基であり、nは平均付加モル数を示し、10以上40以下の数である。〕
Wherein R 1 is an aliphatic hydrocarbon group having 12 to 16 carbon atoms, and R 2 , R 3 and R 4 are each independently a group selected from a methyl group, an ethyl group and a hydroxyethyl group And X is an anion. ]
Component (C): a polyvalent carboxylic acid having 4 or more and 6 or less carbon atoms and having a valence of 2 to 4, or a salt thereof (D) Component: a nonionic surfactant R 5 O represented by the following general formula (3) -(C 2 H 4 O) n H (3)
[Wherein, R 5 represents a hydrocarbon group having 12 to 16 carbon atoms, and n represents an average added mole number, which is a number of 10 to 40. ]
 本発明によれば、衣料に抗菌性を付与し、保存安定性に優れた衣料用液体洗浄剤組成物が提供される。
 本発明によれば、衣料の洗浄と抗菌性の付与という二つの機能により、汚れが付着した衣料を洗濯し、乾燥中に発生する生乾き臭いだけでなく、乾燥後の衣料を着用している間に発生する臭いを効果的に抑制することができる衣料用液体洗浄剤組成物が提供される。
ADVANTAGE OF THE INVENTION According to this invention, the liquid detergent composition for clothing which provided the antimicrobial property to clothing and was excellent in storage stability is provided.
According to the present invention, the two functions of washing clothes and imparting antibacterial properties are used to wash clothes with dirt and while wearing dry clothes as well as fresh dry smell generated during drying. Provided is a liquid detergent composition for clothing that can effectively suppress the odor generated in the clothes.
発明を実施するための形態
 本発明の衣料用液体洗浄剤組成物は、(A)成分の陰イオン界面活性剤と(B)成分の第4級アンモニウム化合物の共存が可能であるため、洗浄性能と抗菌性能を両立できる。また、(B)成分のような第4級アンモニウム化合物を、十分な抗菌効果を発現する濃度で安定に配合するには、保存安定性の向上技術が必要となる。本発明では、(D)成分の、エチレンオキシド基の平均付加モル数が多い非イオン界面活性剤を配合することで、保存安定性の向上を達成できることを見出した。
MODE FOR CARRYING OUT THE INVENTION The liquid detergent composition for clothing of the present invention is capable of coexistence of an anionic surfactant as component (A) and a quaternary ammonium compound as component (B). And antibacterial performance. Moreover, in order to mix | blend the quaternary ammonium compound like (B) component stably with the density | concentration which expresses sufficient antibacterial effect, the storage stability improvement technique is needed. In this invention, it discovered that the improvement of storage stability was achieved by mix | blending the nonionic surfactant with many average added mole number of ethylene oxide group of (D) component.
 本発明の衣料用液体洗浄剤組成物は(A)成分であるアニオン界面活性剤、(B)成分であるカチオン界面活性剤、(C)成分である多価カルボン酸、(D)成分であるエチレンオキシドが特定の平均付加モル数を有するノニオン界面活性剤及び水を含む組成物である。一般に、水中で(A)成分と(B)成分が共存すると複合体を形成し洗浄性、抗菌性が共に失われてしまう。しかしながら、本発明のような、(B)成分と(C)成分の共存下では(B)成分は(A)成分よりも(C)成分と複合体を形成しやすいことから、(A)成分と(B)成分の複合体の形成が抑制され、(A)成分による洗浄作用、及び(B)成分による衣料への抗菌効果を付与する作用が維持できると考えられる。これは、後述の実施例で示したように、(C)成分の配合量が多い方が、抗菌性能が高まることからも支持される。
 また、本発明者は、(D)成分を配合することにより、保存安定性、特に高温での保存安定性が向上することを見出した。これは(A)成分と(B)成分との複合体が形成されても、(A)成分および(D)成分の混合ミセルに取り込まれることにより、可溶化されるためではないかと推察している。
The liquid detergent composition for clothing of the present invention is an anionic surfactant as component (A), a cationic surfactant as component (B), a polyvalent carboxylic acid as component (C), and a component (D). A composition comprising water and a nonionic surfactant having a specific average added mole number. In general, when the component (A) and the component (B) coexist in water, a complex is formed, and both the detergency and antibacterial properties are lost. However, in the presence of the component (B) and the component (C) as in the present invention, the component (B) is easier to form a complex with the component (C) than the component (A). It is considered that the formation of the complex of (B) and (B) is suppressed, and the cleaning action by the (A) ingredient and the action of imparting the antibacterial effect to the clothing by the (B) ingredient can be maintained. This is also supported because the antibacterial performance increases when the amount of component (C) is large, as shown in the examples described later.
Moreover, this inventor discovered that storage stability, especially the storage stability in high temperature improves by mix | blending (D) component. This is presumed that even if a complex of component (A) and component (B) is formed, it is solubilized by being incorporated into the mixed micelle of component (A) and component (D). Yes.
〔(A)成分〕
 (A)成分は下記一般式(1)で表される陰イオン界面活性剤である。(A)成分は衣料に付着した汚れや種々の菌を洗浄する作用を有する。
     RO-(CO)SO ・M     (1)
〔式中、Rは炭素数10以上16以下の炭化水素基であり、mは平均付加モル数を示し、1以上4以下の数であり、Mは陽イオンである。〕
[Component (A)]
The component (A) is an anionic surfactant represented by the following general formula (1). (A) component has the effect | action which wash | cleans the stain | pollution | contamination adhering to clothing, and various microbes.
RO- (C 2 H 4 O) m SO 3 - · M + (1)
[Wherein, R represents a hydrocarbon group having 10 to 16 carbon atoms, m represents an average number of added moles, is a number of 1 to 4 and M + is a cation.] ]
 一般式(1)において、Rは炭素数10以上16以下の炭化水素基であり、衣料の洗浄性を更に高める点から、炭素数12以上14以下の炭化水素基を含むことが好ましい。(A)成分が有する全R中の炭素数12以上14以下の炭化水素基の割合は、衣料の洗浄性と保存安定性を維持できる点から、60質量%以上が好ましく、70質量%以上がより好ましく、そして、100質量%以下が好ましい。この割合は、100質量%であってもよい。すなわち、(A)成分中、Rが炭素数12以上14以下の炭化水素基である陰イオン界面活性剤の割合は、衣料の洗浄性と保存安定性を維持できる点から、60質量%以上が好ましく、70質量%以上がより好ましく、そして、100質量%以下が好ましい。この割合は、100質量%であってもよい。 In general formula (1), R is a hydrocarbon group having 10 to 16 carbon atoms, and preferably includes a hydrocarbon group having 12 to 14 carbon atoms from the viewpoint of further improving the washability of clothing. The proportion of the hydrocarbon group having 12 to 14 carbon atoms in the total R of the component (A) is preferably 60% by mass or more, more preferably 70% by mass or more from the viewpoint of maintaining the washability and storage stability of the clothing. More preferably, 100 mass% or less is preferable. This proportion may be 100% by weight. That is, in the component (A), the proportion of the anionic surfactant in which R is a hydrocarbon group having 12 or more and 14 or less carbon atoms is 60% by mass or more from the viewpoint of maintaining the washability and storage stability of clothing. Preferably, 70 mass% or more is more preferable, and 100 mass% or less is preferable. This proportion may be 100% by weight.
 Rの炭化水素基としては、アルキル基、アルケニル基が挙げられ、アルキル基が好ましくは、1級アルキル基がより好ましく、直鎖1級アルキル基が更に好ましい。 Examples of the hydrocarbon group for R include an alkyl group and an alkenyl group, preferably an alkyl group, more preferably a primary alkyl group, and still more preferably a linear primary alkyl group.
 一般式(1)において、mの平均付加モル数は、(B)成分との複合体の形成のし難さから、1以上であり、1.2以上が好ましく、1.4以上がより好ましく、1.6以上が更に好ましい。洗浄性の観点からmの平均付加モル数は4以下であり、3以下が好ましく、2.5以下がより好ましい。 In the general formula (1), the average added mole number of m is 1 or more, preferably 1.2 or more, more preferably 1.4 or more, from the difficulty of forming a complex with the component (B). 1.6 or more is more preferable. From the viewpoint of detergency, the average added mole number of m is 4 or less, preferably 3 or less, and more preferably 2.5 or less.
 一般式(1)において、Mは陽イオンであり、1価の金属イオン、2価の金属イオン及び炭素数2以上6以下のアルカノールアンモニウムイオンから選ばれる1種以上のイオンが好ましい。
 1価の金属イオンとしては、例えばカリウムイオン、ナトリウムイオンが挙げられる。2価の金属イオンとしては、例えばマグネシウムイオンが挙げられる。炭素数2以上6以下のアルカノールアンモニウムイオンとしては、モノエタノールアンモニウムイオン、ジエタノールアンモニウムイオン、N-メチルエタノールアンモニウムイオン、N-メチルジエタノールアンモニウムイオン、トリエタノールアンモニウムイオンが挙げられる。
In the general formula (1), M + is a cation, and preferably one or more ions selected from a monovalent metal ion, a divalent metal ion, and an alkanol ammonium ion having 2 to 6 carbon atoms.
Examples of monovalent metal ions include potassium ions and sodium ions. Examples of divalent metal ions include magnesium ions. Examples of the alkanol ammonium ion having 2 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)成分〕
 (B)成分は、下記一般式(2)で表される第4級アンモニウム化合物である。(B)成分を含有する本発明の衣料用液体洗浄剤組成物は、衣料に抗菌性を付与することができる。
[(B) component]
The component (B) is a quaternary ammonium compound represented by the following general formula (2). The liquid detergent composition for clothing of the present invention containing the component (B) can impart antibacterial properties to clothing.
Figure JPOXMLDOC01-appb-C000003
Figure JPOXMLDOC01-appb-C000003
〔式中、Rは、炭素数12以上16以下の脂肪族炭化水素基であり、R、R及びRは、それぞれ独立にメチル基、エチル基及びヒドロキシエチル基から選ばれる基であり、Xは陰イオンである。〕 [Wherein, R 1 is an aliphatic hydrocarbon group having 12 to 16 carbon atoms, and R 2 , R 3 and R 4 are each independently a group selected from a methyl group, an ethyl group and a hydroxyethyl group. X is an anion. ]
 本発明の衣料用液体洗浄剤組成物の外観が透明になりやすく、また保存安定性に優れる観点から、Rの脂肪族炭化水素基の炭素数は、炭素数16以下であり、14以下が好ましく、12がより好ましい。布への(B)成分の残留性という観点から、Rは炭素数12以上であり、14以上が好ましく、16がより好ましい。
 Rの脂肪族炭化水素基は、アルキル基、アルケニル基が挙げられ、アルキル基が好ましくは、1級アルキル基がより好ましく、直鎖1級アルキル基が更に好ましい。
 炭素数12の脂肪族炭化水素基としてはラウリル基が挙げられる。炭素数14の脂肪族炭化水素基としてはミリスチル基が挙げられる。炭素数16の脂肪族炭化水素基としてはパルミチル基又はパルミトレイル基が挙げられる。
From the viewpoint of making the appearance of the liquid detergent composition for clothing of the present invention easily transparent and excellent in storage stability, the aliphatic hydrocarbon group of R 1 has 16 or less carbon atoms and 14 or less carbon atoms. 12 is more preferable. From the viewpoint of the persistence of the component (B) on the cloth, R 1 has 12 or more carbon atoms, preferably 14 or more, and more preferably 16.
Examples of the aliphatic hydrocarbon group for R 1 include an alkyl group and an alkenyl group, an alkyl group is preferable, a primary alkyl group is more preferable, and a linear primary alkyl group is still more preferable.
Examples of the aliphatic hydrocarbon group having 12 carbon atoms include a lauryl group. Examples of the aliphatic hydrocarbon group having 14 carbon atoms include a myristyl group. Examples of the aliphatic hydrocarbon group having 16 carbon atoms include a palmityl group and a palmitoleyl group.
 本発明の衣料用液体洗浄剤組成物の高温での保存安定性が更に良好になる点で、本発明の衣料用液体洗浄剤組成物は、(B)成分として、下記の(b1)成分と(b2)成分とを含有することが好ましい。
(b1)成分:一般式(2)中のRが炭素数12の脂肪族炭化水素基である第4級アンモニウム化合物。
(b2)成分:一般式(2)中のRが炭素数14の脂肪族炭化水素基である第4級アンモニウム化合物及び一般式(2)中のRが炭素数16の脂肪族炭化水素基である第4級アンモニウム化合物から選ばれる1種以上の化合物。
The liquid detergent composition for clothing of the present invention has the following component (b1) as the component (B) in that the storage stability at high temperatures of the liquid detergent composition for clothing of the present invention is further improved. It is preferable to contain (b2) component.
(B1) Component: A quaternary ammonium compound in which R 1 in the general formula (2) is an aliphatic hydrocarbon group having 12 carbon atoms.
Component (b2): General formula (2), R 1 of the quaternary ammonium compound and the general formula R 1 is an aliphatic hydrocarbon group of 14 carbon atoms (2) in the number 16 carbon atoms in the aliphatic hydrocarbon 1 or more types of compounds chosen from the quaternary ammonium compound which is group.
 衣料に対して抗菌性を付与する効果を維持しつつ、高温での保存安定性が良好になる点で、(b2)成分は、Rが炭素数16の脂肪族炭化水素基である第4級アンモニウム化合物が好ましい。
 本発明の衣料用液体洗浄剤組成物が(b)成分として(b1)成分と(b2)成分とを含有する場合、衣料に対して抗菌性を付与する効果を維持しつつ、高温での保存安定性が良好になる点で、(b1)成分と(b2)成分の含有割合は、〔(b2)成分の含有量〕/〔(b1)成分の含有量〕の質量比で、1/99以上90/10以下であることが好ましい。高温での保存安定性が更に良好になる点で、前記質量比は、2/98以上がより好ましく、3/97以上が更に好ましく、4/96以上がより更に好ましく、5/95以上がより更に好ましく、10/90以上がより更に好ましく、15/85以上がより更に好ましく、そして85/15以下がより好ましく、80/20以下がより更に好ましい。
The component (b2) is the fourth in which R 1 is an aliphatic hydrocarbon group having 16 carbon atoms in that the storage stability at high temperature is improved while maintaining the effect of imparting antibacterial properties to the clothing. A quaternary ammonium compound is preferred.
When the liquid detergent composition for clothing of the present invention contains the component (b1) and the component (b2) as the component (b), it is stored at a high temperature while maintaining the effect of imparting antibacterial properties to the clothing. The content ratio of the component (b1) and the component (b2) is a mass ratio of [(b2) component content] / [(b1) component content] in that the stability is improved. It is preferable that it is above 90/10. The mass ratio is more preferably 2/98 or more, more preferably 3/97 or more, still more preferably 4/96 or more, and more preferably 5/95 or more in that the storage stability at a high temperature is further improved. More preferably, 10/90 or more is still more preferable, 15/85 or more is more preferable, 85/15 or less is more preferable, and 80/20 or less is still more preferable.
 一般式(2)において、R、R及びRは、それぞれ独立にメチル基、エチル基及びヒドロキシエチル基から選ばれる基である。R、R及びRは、それぞれ、メチル基であることが好ましい。 In the general formula (2), R 2 , R 3 and R 4 are each independently a group selected from a methyl group, an ethyl group and a hydroxyethyl group. R 2 , R 3 and R 4 are each preferably a methyl group.
 一般式(2)において、Xは陰イオンであり、原料の入手のし易さの点から、ハロゲンイオン及び炭素数1以上3以下のアルキル硫酸イオンから選ばれる1種以上の陰イオンが挙げられる。ハロゲンイオンとしては塩化物イオン及び臭化物イオンから選ばれる1種以上の陰イオンが挙げられる。炭素数1以上3以下のアルキル硫酸イオンとしてはメチル硫酸イオン及びエチル硫酸イオンから選ばれる1種以上の陰イオンが挙げられる。本発明の(B)成分は1種又は2種以上の第4級アンモニウム化合物を併用して用いることが出来る。 In the general formula (2), X is an anion, and from the viewpoint of easy availability of the raw material, one or more anions selected from halogen ions and alkyl sulfate ions having 1 to 3 carbon atoms can be mentioned. It is done. Examples of the halogen ion include one or more anions selected from chloride ions and bromide ions. Examples of the alkyl sulfate ion having 1 to 3 carbon atoms include one or more anions selected from methyl sulfate ion and ethyl sulfate ion. The component (B) of the present invention can be used in combination with one or more quaternary ammonium compounds.
〔(C)成分〕
 (C)成分は、炭素数4以上6以下であり2価以上4価以下の多価カルボン酸又はその塩である。本発明では、(C)成分は、水中で、優先的に(B)成分と複合体を形成することで、(A)成分と(B)成分の複合体形成を抑制し、(A)成分由来の洗浄性と(B)成分由来の抗菌性の発現を維持していると考えられる。
 (B)成分による衣料への抗菌効果を維持できる観点から、(C)成分は、3価の多価カルボン酸又はその塩が好ましい。
 (C)成分は、コハク酸、リンゴ酸、酒石酸、クエン酸及びこれらの塩から選ばれる1種以上の多価カルボン酸又はその塩が好ましい。
 (C)成分は、クエン酸又はその塩がより好ましい。
 (C)成分の多価カルボン酸の塩は、ナトリウム塩、カリウム塩等のアルカリ金属が挙げられる。
 (C)成分は、2個以上4個以下有するカルボン酸基が酸型である化合物と塩型である化合物とが共存していても良い。
[Component (C)]
The component (C) is a polyvalent carboxylic acid having 4 to 6 carbon atoms and having 2 to 4 carbon atoms or a salt thereof. In this invention, (C) component suppresses complex formation of (A) component and (B) component by forming a complex with (B) component preferentially in water, and (A) component It is thought that the cleaning property derived from the origin and the antibacterial property derived from the component (B) are maintained.
From the viewpoint of maintaining the antibacterial effect on clothing by the component (B), the component (C) is preferably a trivalent polyvalent carboxylic acid or a salt thereof.
The component (C) is preferably one or more polyvalent carboxylic acids or salts thereof selected from succinic acid, malic acid, tartaric acid, citric acid and salts thereof.
The component (C) is more preferably citric acid or a salt thereof.
Examples of the salt of the polyvalent carboxylic acid (C) include alkali metals such as sodium salt and potassium salt.
In the component (C), a compound in which the carboxylic acid group having 2 or more and 4 or less is in an acid form and a compound in a salt form may coexist.
〔(D)成分〕
 (D)成分は、下記一般式(3)で表される非イオン界面活性剤である。
     RO-(CO)H     (3)
〔式中、Rは炭素数12以上16以下の炭化水素基であり、nは平均付加モル数を示し、10以上40以下の数である。〕
[Component (D)]
The component (D) is a nonionic surfactant represented by the following general formula (3).
R 5 O— (C 2 H 4 O) n H (3)
[Wherein, R 5 represents a hydrocarbon group having 12 to 16 carbon atoms, and n represents an average added mole number, which is a number of 10 to 40. ]
 本発明における(D)成分は、洗浄力を向上させるだけでなく、本発明の衣料用液体洗浄剤組成物の高温での保存安定性を向上させる。(A)成分と(B)成分が形成する複合体は、保存中、とりわけ高温での保存中に、組成物中で析出して分離する傾向がある。しかし、本発明では、(D)成分を用いることで(A)成分および(D)成分の混合ミセルに、(A)成分と(B)成分が形成する複合体が取り込まれることにより、組成物の保存安定性が向上しているのではないかと推察している。 The component (D) in the present invention not only improves the detergency but also improves the storage stability of the liquid cleaning composition for clothing of the present invention at high temperatures. The complex formed by component (A) and component (B) tends to precipitate and separate in the composition during storage, especially during storage at high temperatures. However, in the present invention, by using the (D) component, the composite formed by the (A) component and the (B) component is incorporated into the mixed micelle of the (A) component and the (D) component, whereby the composition It is presumed that the storage stability of
 一般式(3)において、Rは、炭素数12以上16以下の炭化水素基である。
 Rの炭化水素基は、アルキル基、アルケニル基が挙げられ、アルキル基が好ましくは、1級アルキル基がより好ましく、直鎖1級アルキル基が更に好ましい。また、Rの炭化水素基は、直鎖の脂肪族炭化水素基又は分岐鎖の脂肪族炭化水素基が挙げられ、直鎖の脂肪族炭化水素基が好ましい。
 (B)成分による衣類への抗菌効果の付与を維持しつつ、保存安定性をより向上させる点で、Rは直鎖アルキル基が好ましく、ラウリル基、及びミリスチル基から選ばれる1種以上の基がより好ましい。
In the general formula (3), R 5 is a hydrocarbon group having 12 to 16 carbon atoms.
Examples of the hydrocarbon group for R 5 include an alkyl group and an alkenyl group. An alkyl group is preferred, a primary alkyl group is more preferred, and a linear primary alkyl group is still more preferred. Examples of the hydrocarbon group for R 5 include a linear aliphatic hydrocarbon group or a branched aliphatic hydrocarbon group, and a linear aliphatic hydrocarbon group is preferable.
(B) R 5 is preferably a straight-chain alkyl group, and at least one selected from a lauryl group and a myristyl group, while maintaining the antibacterial effect imparted to clothing by the component (B). Groups are more preferred.
 (D)成分が有する全R中の炭素数12以上14以下の炭化水素基の割合は、本発明の衣料用液体洗浄剤組成物の高温での保存安定性の向上の点から、60質量%以上が好ましく、70質量%以上がより好ましく、80質量%以上がより更に好ましく、そして、100質量%以下が好ましい。この割合は、100質量%であってもよい。すなわち、(D)成分中、Rが炭素数12以上14以下の炭化水素基である非イオン界面活性剤の割合は、本発明の衣料用液体洗浄剤組成物の高温での保存安定性の向上の点から、60質量%以上が好ましく、70質量%以上がより好ましく、80質量%以上がより更に好ましく、そして、100質量%以下が好ましい。この割合は、100質量%であってもよい。 The proportion of the hydrocarbon group having 12 to 14 carbon atoms in the total R 5 of the component (D) is 60% from the viewpoint of improving the storage stability of the liquid cleaning composition for clothing of the present invention at high temperature. % Or more is preferable, 70 mass% or more is more preferable, 80 mass% or more is further more preferable, and 100 mass% or less is preferable. This proportion may be 100% by weight. That is, in the component (D), the ratio of the nonionic surfactant in which R 5 is a hydrocarbon group having 12 to 14 carbon atoms is the storage stability of the liquid cleaning composition for clothing of the present invention at a high temperature. From the point of improvement, 60 mass% or more is preferable, 70 mass% or more is more preferable, 80 mass% or more is further more preferable, and 100 mass% or less is preferable. This proportion may be 100% by weight.
 本発明の衣料用液体洗浄剤組成物は、(D)成分として、Rが炭素数12の炭化水素基である非イオン界面活性剤、及びRが炭素数14の炭化水素基である非イオン界面活性剤から選ばれる1種以上の非イオン界面活性剤を含有することが好ましい。
 本発明の衣料用液体洗浄剤組成物は、(D)成分として、Rが炭素数12の炭化水素基である非イオン界面活性剤、及びRが炭素数14の炭化水素基である非イオン界面活性剤を含有することが好ましい。この場合、(Rが炭素数12の炭化水素基である非イオン界面活性剤の含有量)/(Rが炭素数14の炭化水素基である非イオン界面活性剤の含有量)の質量比は、40/60以上が好ましく、50/50以上がより好ましく、55/45以上がより更に好ましく、そして、100以下、すなわち100/1以下が好ましく、98/2以下がより好ましい。
In the liquid detergent composition for clothing of the present invention, as component (D), R 5 is a nonionic surfactant having a hydrocarbon group having 12 carbon atoms, and R 5 is a non-ionic surfactant having a hydrocarbon group having 14 carbon atoms. It is preferable to contain one or more nonionic surfactants selected from ionic surfactants.
In the liquid detergent composition for clothing of the present invention, as component (D), R 5 is a nonionic surfactant having a hydrocarbon group having 12 carbon atoms, and R 5 is a non-ionic surfactant having a hydrocarbon group having 14 carbon atoms. It is preferable to contain an ionic surfactant. In this case, the mass of (content of nonionic surfactant in which R 5 is a hydrocarbon group having 12 carbon atoms) / (content of nonionic surfactant in which R 5 is a hydrocarbon group having 14 carbon atoms) The ratio is preferably 40/60 or more, more preferably 50/50 or more, still more preferably 55/45 or more, and is preferably 100 or less, that is, 100/1 or less, and more preferably 98/2 or less.
 一般式(3)において、nはエチレンオキシドの平均付加モル数を示し、10以上40以下の数である。保存安定性を更に向上させる観点から、nは、12以上が好ましく、13以上がより好ましく、15以上が更に好ましく、16以上がより更に好ましく、18以上がより更に好ましく、20以上がより更に好ましく、そして、35以下が好ましい。 In general formula (3), n represents the average number of moles of ethylene oxide added, and is a number from 10 to 40. From the viewpoint of further improving storage stability, n is preferably 12 or more, more preferably 13 or more, still more preferably 15 or more, still more preferably 16 or more, still more preferably 18 or more, and still more preferably 20 or more. And 35 or less is preferable.
〔水〕
 水はイオン交換水、次亜塩素酸塩を0.1mg/kg以上5mg/kg以下含有するイオン交換水、水道水などが挙げられる。
〔water〕
Examples of water include ion-exchanged water, ion-exchanged water containing 0.1 mg / kg to 5 mg / kg of hypochlorite, and tap water.
〔組成、任意成分等〕
 本発明の衣料用液体洗浄剤組成物は、前記の(A)成分、(B)成分、(C)成分、(D)成分及び水を含有する。
[Composition, optional components, etc.]
The liquid detergent composition for clothing of the present invention contains the above-mentioned component (A), component (B), component (C), component (D) and water.
 本発明の衣料用液体洗浄剤組成物は、衣料に付着した汚れや菌の洗浄性の向上の観点と保存安定性の向上の観点から、(A)成分を10質量%以上16質量%以下含有する。(A)成分の含有量は、前記同様の観点で、組成物中、11質量%以上が好ましい。そして、(A)成分の含有量は、(B)成分による衣料の抗菌効果を維持できる観点から、組成物中、15質量%以下が好ましく、14質量%以下がより好ましい。
 本発明において(A)成分の含有量は、Mの陽イオンをNaに換算した質量で算出するものとする。すなわち、(A)成分の含有量は、ナトリウム塩に換算した質量で算出するものとする。
The liquid detergent composition for clothing of the present invention contains 10% by mass or more and 16% by mass or less of the component (A) from the viewpoint of improving the detergency of dirt and bacteria attached to the clothing and improving the storage stability. To do. The content of the component (A) is preferably 11% by mass or more in the composition from the same viewpoint as described above. And from a viewpoint which can maintain the antimicrobial effect of the clothing by (B) component, 15 mass% or less is preferable in a composition, and, as for content of (A) component, 14 mass% or less is more preferable.
In the present invention, the content of the component (A) is calculated by mass obtained by converting M + cations to Na + . That is, content of (A) component shall be computed by the mass converted into sodium salt.
 本発明の衣料用洗浄剤組成物は、(B)成分を1質量%以上3質量%以下含有する。(B)成分の含有量は、衣料への抗菌性の付与能をより高める点から、組成物中、1.5質量%以上が好ましく、2質量%以上がより好ましい。そして、(B)成分の含有量は、衣料用液体洗浄剤組成物の保存安定性を向上させる点から、組成物中、2.9質量%以下が好ましく、2.8質量%以下がより好ましく、2.7質量%以下が更に好ましく、2.6質量%以下がより更に好ましい。 The garment cleaning composition of the present invention contains 1% by mass or more and 3% by mass or less of the component (B). The content of the component (B) is preferably 1.5% by mass or more and more preferably 2% by mass or more in the composition from the viewpoint of further enhancing the ability to impart antibacterial properties to clothing. The content of the component (B) is preferably 2.9% by mass or less, more preferably 2.8% by mass or less in the composition from the viewpoint of improving the storage stability of the liquid detergent composition for clothing. 2.7 mass% or less is still more preferable, and 2.6 mass% or less is still more preferable.
 本発明の衣料用洗浄剤組成物は、(C)成分を2質量%以上8質量%以下含有する。(C)成分の含有量は、水中での(A)成分と(B)成分の複合体形成を抑制し、衣料の抗菌性をより向上できる点で、組成物中、2.5質量%以上が好ましく、3質量%以上がより好ましく、3.5質量%以上が更に好ましく、4質量%以上がより更に好ましく、4.5質量%以上がより更に好ましく、そして7質量%以下が好ましく、6.5質量%以下がより好ましく、6質量%以下が更に好ましく、5.5質量%以下がより更に好ましい。 The clothing cleaning composition of the present invention contains 2% by mass or more and 8% by mass or less of the component (C). (C) Content of component is 2.5 mass% or more in a composition at the point which can suppress the composite formation of (A) component and (B) component in water, and can improve the antimicrobial property of clothing more. Is preferably 3% by mass or more, more preferably 3.5% by mass or more, still more preferably 4% by mass or more, still more preferably 4.5% by mass or more, and preferably 7% by mass or less. 0.5 mass% or less is more preferable, 6 mass% or less is still more preferable, and 5.5 mass% or less is still more preferable.
 本発明の衣料用洗浄剤組成物は、(D)成分の含有量と、(A)成分の含有量及び(B)成分の含有量の合計量との質量比である、〔(D)成分の含有量〕/〔(A)成分の含有量+(B)成分の含有量〕が、0.1以上0.4以下である。
 (A)成分と(B)成分が衣料用液体洗浄剤組成物中で形成する複合体を(D)成分が形成するミセル内に取り込むことで、保存安定性をより向上できる点で、〔(D)成分の含有量〕/〔(A)成分の含有量+(B)成分の含有量〕の質量比は、0.11以上が好ましく、0.12以上がより好ましく、そして0.35以下が好ましく、0.3以下がより好ましく、0.25以下が更に好ましく、0.2以下がより更に好ましい。
The garment cleaning composition of the present invention is a mass ratio of the content of the component (D) and the total content of the content of the component (A) and the content of the component (B) [component (D) Content] / [(A) component content + (B) component content] is 0.1 or more and 0.4 or less.
In the point that the storage stability can be further improved by incorporating the complex formed by the component (A) and the component (B) in the micelle formed by the component (D), in the liquid detergent composition for clothing, [( D) component content] / [(A) component content + (B) component content] mass ratio is preferably 0.11 or more, more preferably 0.12 or more, and 0.35 or less. Is preferable, 0.3 or less is more preferable, 0.25 or less is more preferable, and 0.2 or less is further more preferable.
 衣料用液体洗浄剤組成物は、衣料により高い抗菌性を付与し、且つ保存安定性をより向上させる観点から、(B)成分の含有量と(A)成分の含有量の質量比である、〔(B)成分の含有量〕/〔(A)成分の含有量〕は、0.05以上0.3以下が好ましい。
 衣料により高い抗菌性を付与できる観点から、〔(B)成分の含有量〕/〔(A)成分の含有量〕の質量比は、0.06以上が好ましく、0.07以上が更に好ましく、0.08以上がより更に好ましく、0.09以上がより更に好ましく、1.0以上がより更に好ましい。そして、保存安定性をより向上できる観点から、〔(B)成分の含有量〕/〔(A)成分の含有量〕の質量比は、0.25以下が好ましく、0.23以下がより好ましく、0.2以下が更に好ましく、0.19以下がより更に好ましく、0.18以下がより更に好ましい。
The liquid detergent composition for clothing is a mass ratio of the content of the component (B) and the content of the component (A) from the viewpoint of imparting high antibacterial properties to the clothing and further improving the storage stability. [Content of (B) component] / [Content of (A) component] is preferably 0.05 or more and 0.3 or less.
From the viewpoint of imparting high antibacterial properties to clothing, the mass ratio of [(B) component content] / [(A) component content] is preferably 0.06 or more, more preferably 0.07 or more, 0.08 or more is still more preferable, 0.09 or more is still more preferable, and 1.0 or more is still more preferable. From the viewpoint of further improving the storage stability, the mass ratio of [(B) component content] / [(A) component content] is preferably 0.25 or less, more preferably 0.23 or less. 0.2 or less is more preferable, 0.19 or less is more preferable, and 0.18 or less is still more preferable.
 水の含有量は、(A)~(D)成分及び任意成分の含有量との合計が100質量%となる量である。取り扱いの容易性の点で、水の含有量は、組成物中、60質量%以上が好ましく、65質量%以上がより好ましく、70質量%以上がより更に好ましい。 The water content is such that the sum of the contents of the components (A) to (D) and the optional component is 100% by mass. In terms of ease of handling, the water content in the composition is preferably 60% by mass or more, more preferably 65% by mass or more, and still more preferably 70% by mass or more.
 本発明の衣料用液体洗浄剤組成物は、20℃におけるpHが2以上7以下であることが、(B)成分を含有する衣料用液体洗浄剤組成物から発生する臭い抑制の観点から好ましい。
 (C)成分を利用したpH調整の容易さの観点から、該pHは6.8以下が好ましく、6.5以下がより好ましく、6以下が更に好ましく、そして3以上が好ましく、3.5以上がより好ましく、4以上が更に好ましい。
 該pHは、具体的には、以下の方法で測定されたものである。以下の方法のpH電極はガラス電極である。
<pHの測定方法>
 堀場製作所製pHメーター D-52のpH電極(型式 6367)をあらかじめフタル酸緩衝液(pH4.01)、リン酸標準液(pH6.84)、ホウ酸塩標準液(pH9.18)で校正し、イオン交換水で十分すすいでおく。温度を20℃に調整した衣料用液体洗浄剤組成物に、上記の通り校正、洗浄したpH電極を入れ、pHメーターのAUTO
 HOLDモードを用いて、測定値が一定になるまで測定する。
The liquid detergent composition for clothing of the present invention preferably has a pH of 2 or more and 7 or less at 20 ° C. from the viewpoint of suppressing odor generated from the liquid detergent composition for clothing containing the component (B).
From the viewpoint of ease of pH adjustment using the component (C), the pH is preferably 6.8 or less, more preferably 6.5 or less, still more preferably 6 or less, and more preferably 3 or more, and 3.5 or more. Is more preferable, and 4 or more is more preferable.
Specifically, the pH is measured by the following method. The pH electrode in the following method is a glass electrode.
<Measurement method of pH>
HORIBA, Ltd. pH meter D-52 pH electrode (model 6367) was calibrated with phthalate buffer solution (pH 4.01), phosphate standard solution (pH 6.84), and borate standard solution (pH 9.18) in advance. Rinse thoroughly with ion-exchanged water. Place the pH electrode calibrated and washed as described above into the liquid detergent composition for clothing adjusted to a temperature of 20 ° C.
Using the HOLD mode, measure until the measured value is constant.
 本発明の衣料用液体洗浄剤組成物は、外観に優れる。本発明の衣料用液体洗浄剤組成物は、透明な外観を有することができる。ここで、透明とは、目視観察で曇りが認められない状態であってよい。更に、透明とは、紫外可視分光光度計において、光路長が1cmのガラス製セルに本発明の衣料用液体洗浄剤組成物を入れ、対照側セルにはイオン交換水を用いた時の、660nmの波長における透過率が90%以上であるとすることができる。透過率の数字が高い方がより透明であり、より好ましい外観である。本発明の(A)~(D)成分及び水を、本発明の所定の含有量となるように混合すれば、外観が透明な組成物を得ることができる。 The liquid detergent composition for clothing of the present invention is excellent in appearance. The liquid detergent composition for clothing of the present invention can have a transparent appearance. Here, the term “transparent” may refer to a state in which cloudiness is not recognized by visual observation. Furthermore, transparent means that the liquid detergent composition for clothing of the present invention is put in a glass cell having an optical path length of 1 cm in an ultraviolet-visible spectrophotometer, and ion-exchanged water is used for the control side cell at 660 nm. It can be assumed that the transmittance at a wavelength of 90% or more. A higher transmittance figure is more transparent and a more preferable appearance. If the components (A) to (D) of the present invention and water are mixed so as to have the predetermined content of the present invention, a composition having a transparent appearance can be obtained.
 本発明の液体洗浄剤組成物には、(E)成分として、pH調整剤を含有することができる。(E)成分としては、水酸化ナトリウム、水酸化カリウム、及び炭素数2以上6以下のアルカノールアミンから選ばれる1種以上のpH調整剤が挙げられる。炭素数2以上6以下のアルカノールアミンとしては、モノエタノールアミン、ジエタノールアミン、メチルジエタノールアミン、ジメチルエタノールアミン、トリエタノールアミンが挙げられる。pH調整剤の含有量は前記のpHになるような量を使用することができる。 The liquid detergent composition of the present invention can contain a pH adjuster as the component (E). (E) As a component, 1 or more types of pH adjusters chosen from sodium hydroxide, potassium hydroxide, and a C2-C6 alkanolamine are mentioned. Examples of the alkanolamine having 2 to 6 carbon atoms include monoethanolamine, diethanolamine, methyldiethanolamine, dimethylethanolamine, and triethanolamine. The pH adjusting agent can be used in such an amount that the above pH is reached.
 本発明の衣料用液体洗浄剤組成物は、組成物から好ましい香りを香らせるために、(F)成分として香料を含有することができる。(F)成分は、衣料用液体洗浄剤組成物に配合することが知られている香料組成物が挙げられる。例えば、「香料と調香の基礎知識」、中島基貴編著、1995年、産業図書株式会社発行、第4刷に記載に香料を含有する組成物を使用することができる。
 (F)成分の含有量は、組成物中、0.1質量%以上が好ましく、0.2質量%以上がより好ましく、0.4質量%以上が更に好ましく、そして1質量%以下が好ましく、0.8質量%以下がより好ましい。
The liquid detergent composition for clothing of the present invention can contain a fragrance as the component (F) in order to impart a preferable scent from the composition. Examples of the component (F) include a fragrance composition known to be blended in a liquid detergent composition for clothing. For example, a composition containing a fragrance can be used as described in "Basic knowledge of fragrance and fragrance", edited by Motoki Nakajima, 1995, published by Sangyo Tosho Co., Ltd., 4th printing.
The content of the component (F) is preferably 0.1% by mass or more, more preferably 0.2% by mass or more, still more preferably 0.4% by mass or more, and preferably 1% by mass or less in the composition. 0.8 mass% or less is more preferable.
 本発明の衣料用液体洗浄剤組成物は、(G)成分として、防腐剤、例えば1,2-ベンゾイソチアゾリン-3-オン、ポリヘキサメチレンビグアニド塩酸塩等を含有することが出来る。(G)成分の含有量は、組成物中、0.001質量%以上が好ましく、0.05質量%以上がより好ましく、そして0.5質量%以下が好ましく、0.3質量%以下がより好ましい。 The liquid detergent composition for clothing of the present invention can contain a preservative such as 1,2-benzisothiazolin-3-one, polyhexamethylene biguanide hydrochloride, etc. as component (G). The content of the component (G) in the composition is preferably 0.001% by mass or more, more preferably 0.05% by mass or more, and preferably 0.5% by mass or less, more preferably 0.3% by mass or less. preferable.
 本発明の衣料用液体洗浄剤組成物は、一般的に液体組成物の外観を透明にしやすくする為に用いられる、水酸基を一つ以上有する有機溶媒の含有量が少なくても、外観が透明である等、優れた外観を呈することが出来る。具体的には、本発明の衣料用液体洗浄剤組成物は、水酸基を一つ以上有する有機溶媒の含有量が0質量%以上10質量%未満であっても優れた外観を呈することが出来る。
 前記有機溶媒としては、炭素数2以上6以下の1価以上6価以下のアルコールが挙げられる。炭素数2以上6以下の1価のアルコールとしては、例えばエタノールが挙げられる。炭素数2以上6以下の2価のアルコールとして、例えばエチレングリコール、プロピレングリコールが挙げられる。炭素数2以上6以下の3価のアルコールとしては、例えばグリセリンが挙げられる。
 前記有機溶媒の含有量は、組成物中、9質量%以下が好ましく、8質量%以下がより好ましく、7質量%以下が更に好ましく、そして、0質量%であってもよい。
The liquid detergent composition for clothing of the present invention is generally used to make the appearance of the liquid composition transparent, and the appearance is transparent even if the content of the organic solvent having one or more hydroxyl groups is small. For example, an excellent appearance can be exhibited. Specifically, the liquid detergent composition for clothing of the present invention can exhibit an excellent appearance even when the content of the organic solvent having one or more hydroxyl groups is 0% by mass or more and less than 10% by mass.
Examples of the organic solvent include monovalent to hexavalent alcohols having 2 to 6 carbon atoms. Examples of the monovalent alcohol having 2 to 6 carbon atoms include ethanol. Examples of the divalent alcohol having 2 to 6 carbon atoms include ethylene glycol and propylene glycol. Examples of the trivalent alcohol having 2 to 6 carbon atoms include glycerin.
The content of the organic solvent is preferably 9% by mass or less, more preferably 8% by mass or less, still more preferably 7% by mass or less, and may be 0% by mass in the composition.
 本発明の衣料用液体洗浄剤組成物は、衣料に抗菌性を付与することができる。
本発明の衣料用液体洗浄剤組成物は、におい物質を産生する原因菌に対する、より効果的な抗菌性を、衣料に付与することが出来る、例えば特開2013-18971号公報に記載のモラクセラ属の細菌、大腸菌、又はアシネトバクター菌に対して、より効果的な抗菌性を付与することができる。モラクセラ・オスロエンシス及びモラクセラ・エスピーから選ばれる1種以上の細菌が、本発明の対象として、より好ましい。これらの細菌は、使用した衣料上に多く存在し、洗浄後又は脱水後から乾くまでの間に衣料を臭わせるにおい物質を産生する原因菌として知られている。本発明の衣料用液体洗浄剤組成物は、これらの細菌に対して優れた抗菌性を発現する。
The liquid detergent composition for clothing of the present invention can impart antibacterial properties to clothing.
The liquid detergent composition for clothing of the present invention can impart more effective antibacterial properties against causative bacteria that produce odorous substances to clothing, for example, Moraxella genus described in JP2013-18971A More effective antibacterial properties can be imparted to bacteria, Escherichia coli, and Acinetobacter bacteria. One or more kinds of bacteria selected from Moraxella osloensis and Moraxella sp. Are more preferable as the object of the present invention. These bacteria are abundant on the used clothing, and are known as causative bacteria that produce odorous substances that make the clothing smell after washing or after dehydration. The liquid detergent composition for clothing of the present invention exhibits excellent antibacterial properties against these bacteria.
 本発明の衣料用液体洗浄剤組成物は、衣料に抗菌性を付与する用途に用いることができる。
 本発明の衣料用液体洗浄剤組成物は、におい物質を産生する原因菌に対する抗菌性を、衣料に付与する用途に用いることができる。におい物質を産生する原因菌として、モラクセラ属の細菌、大腸菌、又はアシネトバクター菌が挙げられる。
 本発明の衣料用液体洗浄剤組成物は、衣料に防臭効果を付与する用途に用いることができる。
 本発明の衣料用液体洗浄剤組成物は、衣料に洗浄後又は脱水後から乾くまでの間に衣料が臭いにくくする防臭効果を付与する用途に用いることができる。
The liquid detergent composition for clothing of the present invention can be used for applications that impart antibacterial properties to clothing.
The liquid detergent composition for clothes of the present invention can be used for applications that impart antibacterial properties against causative bacteria that produce odorous substances to clothes. Examples of causative bacteria that produce odorous substances include Moraxella bacteria, Escherichia coli, and Acinetobacter bacteria.
The liquid detergent composition for clothing of the present invention can be used for applications that impart a deodorizing effect to clothing.
The liquid detergent composition for clothing of the present invention can be used for applications that impart a deodorizing effect to clothing that makes it difficult for the clothing to smell after washing or after dehydration and drying.
 本発明の態様の例として、本発明の衣料用液体洗浄剤組成物の、衣料に抗菌性を付与するための使用が挙げられる。
 本発明の態様の他の例として、本発明の衣料用液体洗浄剤組成物の、におい物質を産生する原因菌に対する抗菌性を衣料に付与するための使用が挙げられる。
 本発明の態様の他の例として、本発明の衣料用液体洗浄剤組成物の、衣料に防臭効果を付与するための使用が挙げられる。
 本発明の態様の他の例として、本発明の衣料用液体洗浄剤組成物の、衣料に洗浄後又は脱水後から乾くまでの間に衣料が臭いにくくする防臭効果を付与するための使用が挙げられる。
As an example of the aspect of the present invention, use of the liquid detergent composition for clothing of the present invention for imparting antibacterial properties to clothing is exemplified.
As another example of the embodiment of the present invention, the use of the liquid detergent composition for clothing of the present invention for imparting antibacterial properties against causative bacteria producing odor substances to clothing.
As another example of the embodiment of the present invention, use of the liquid cleaning composition for clothing of the present invention for imparting a deodorizing effect to clothing is exemplified.
As another example of the embodiment of the present invention, the use of the liquid detergent composition for clothing of the present invention for imparting a deodorizing effect to the clothing such that the clothing hardly smells after washing or after dehydration until drying. It is done.
 本発明の衣料用液体洗浄剤組成物は、衣類、タオル、寝具、寝具用の繊維製品(シーツ、枕カバーなど)などの衣料の洗浄に用いられる。これら以外の洗濯が可能な繊維製品も対象とすることができる。 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.
 本発明のより具体的な態様を以下に示す。以下の態様には、本発明の衣料用液体洗浄剤組成物で述べた事項を適宜適用することができる。
<1>
 下記(A)成分を10質量%以上16質量%以下、(B)成分を1質量%以上3質量%以下、(C)成分を2質量%以上8質量%以下、(D)成分及び水を含有し、
 〔(D)成分の含有量〕/〔(A)成分の含有量+(B)成分の含有量〕の質量比が0.1以上0.4以下である、
衣料用液体洗浄剤組成物。
(A)成分:下記一般式(1)で表される陰イオン界面活性剤
     RO-(CO)SO ・M     (1)
〔式中、Rは炭素数10以上16以下の炭化水素基であり、mは平均付加モル数を示し、1以上4以下の数であり、Mは陽イオンである。〕
(B)成分:下記一般式(2)で表される第4級アンモニウム化合物
More specific embodiments of the present invention are shown below. The matters described in the liquid cleaning composition for clothing of the present invention can be appropriately applied to the following embodiments.
<1>
The following (A) component is 10% by mass to 16% by mass, (B) component is 1% by mass to 3% by mass, (C) component is 2% by mass to 8% by mass, (D) component and water Contains,
The mass ratio of [(D) component content] / [(A) component content + (B) component content] is 0.1 or more and 0.4 or less,
Liquid detergent composition for clothing.
Component (A): anionic surfactant represented by the following general formula (1) RO- (C 2 H 4 O) m SO 3 - · M + (1)
[Wherein, R represents a hydrocarbon group having 10 to 16 carbon atoms, m represents an average number of added moles, is a number of 1 to 4 and M + is a cation.] ]
Component (B): a quaternary ammonium compound represented by the following general formula (2)
Figure JPOXMLDOC01-appb-C000004
Figure JPOXMLDOC01-appb-C000004
〔式中、Rは、炭素数12以上16以下の脂肪族炭化水素基であり、R、R及びRは、それぞれ独立に、メチル基、エチル基及びヒドロキシエチル基から選ばれる基であり、Xは陰イオンである。〕
(C)成分:炭素数4以上6以下であり2価以上4価以下の多価カルボン酸又はその塩
(D)成分:下記一般式(3)で表される非イオン界面活性剤
     RO-(CO)H     (3)
〔式中、Rは炭素数12以上16以下の炭化水素基であり、nは平均付加モル数を示し、10以上40以下の数である。〕
Wherein R 1 is an aliphatic hydrocarbon group having 12 to 16 carbon atoms, and R 2 , R 3 and R 4 are each independently a group selected from a methyl group, an ethyl group and a hydroxyethyl group And X is an anion. ]
Component (C): a polyvalent carboxylic acid having 4 or more and 6 or less carbon atoms and having a valence of 2 to 4, or a salt thereof (D) Component: a nonionic surfactant R 5 O represented by the following general formula (3) -(C 2 H 4 O) n H (3)
[Wherein, R 5 represents a hydrocarbon group having 12 to 16 carbon atoms, and n represents an average added mole number, which is a number of 10 to 40. ]
<2>
 (A)成分が有する全R中の炭素数12以上14以下の炭化水素基の割合が、60質量%以上、更に70質量%以上、そして、100質量%以下、更に95質量%以下、更に90質量%以下である、あるいは、100質量%である、<1>に記載の衣料用液体洗浄剤組成物。
<2>
The proportion of hydrocarbon groups having 12 to 14 carbon atoms in the total R of component (A) is 60% by mass or more, further 70% by mass or more, 100% by mass or less, further 95% by mass or less, and further 90%. The liquid detergent composition for clothes according to <1>, which is not more than mass% or is 100 mass%.
<3>
 (A)成分中、Rが炭素数12以上14以下の炭化水素基である陰イオン界面活性剤の割合が、60質量%以上、更に70質量%以上、そして、100質量%以下、更に95質量%以下、更に90質量%以下である、あるいは、100質量%である、<1>に記載の衣料用液体洗浄剤組成物。
<3>
In the component (A), the proportion of the anionic surfactant in which R is a hydrocarbon group having 12 to 14 carbon atoms is 60% by mass or more, further 70% by mass or more, and 100% by mass or less, and further 95% by mass. % Liquid detergent composition for clothes as described in <1> which is 90 mass% or less further, or 100 mass%.
<4>
 (A)成分の含有量と(B)成分の含有量との質量比である〔(B)成分の含有量〕/〔(A)成分の含有量〕が0.05以上、更に0.06以上、更に0.07以上、更に0.08以上、更に0.09以上、更に1.0以上、そして、0.3以下、更に0.25以下、更に0.23以下、更に0.2以下、更に0.19以下、更に0.18以下である、<1>~<3>の何れかに記載の衣料用液体洗浄剤組成物。
<4>
[A content of component (B)] / [Content of component (A)] which is a mass ratio of the content of component (A) and the content of component (B) is 0.05 or more, and further 0.06 In addition, 0.07 or more, further 0.08 or more, further 0.09 or more, further 1.0 or more, and 0.3 or less, further 0.25 or less, further 0.23 or less, further 0.2 or less. The liquid detergent composition for clothing according to any one of <1> to <3>, further 0.19 or less, further 0.18 or less.
<5>
 (B)成分として、下記の(b1)成分と(b2)成分とを含有する、<1>~<4>の何れかに記載の衣料用液体洗浄剤組成物。
(b1)成分:一般式(2)中のRが炭素数12の脂肪族炭化水素基である第4級アンモニウム化合物。
(b2)成分:一般式(2)中のRが炭素数14の脂肪族炭化水素基である第4級アンモニウム化合物及び一般式(2)中のRが炭素数16の脂肪族炭化水素基である第4級アンモニウム化合物から選ばれる1種以上の化合物。
<5>
The liquid detergent composition for clothing according to any one of <1> to <4>, which comprises the following component (b1) and component (b2) as component (B):
(B1) Component: A quaternary ammonium compound in which R 1 in the general formula (2) is an aliphatic hydrocarbon group having 12 carbon atoms.
Component (b2): General formula (2), R 1 of the quaternary ammonium compound and the general formula R 1 is an aliphatic hydrocarbon group of 14 carbon atoms (2) in the number 16 carbon atoms in the aliphatic hydrocarbon 1 or more types of compounds chosen from the quaternary ammonium compound which is group.
<6>
 衣料用液体洗浄剤組成物中の(b2)成分と(b1)成分の含有割合が、〔(b2)成分の含有量〕/〔(b1)成分の含有量〕の質量比で、1/99以上、更に2/98以上、更に3/97以上、更に4/96以上、更に5/95以上、更に10/90以上、そして、90/10以下、更に85/15以下、更に80/20以下である、<5>に記載の衣料用液体洗浄剤組成物。
<6>
The content ratio of the component (b2) and the component (b1) in the liquid detergent composition for clothing is 1/99 in the mass ratio of [(b2) component content] / [(b1) component content]. 2/98 or more, 3/97 or more, 4/96 or more, 5/95 or more, 10/90 or more, 90/10 or less, 85/15 or less, 80/20 or less The liquid cleaning composition for clothing according to <5>.
<7>
 (b2)成分が、Rが炭素数16の脂肪族炭化水素基である第4級アンモニウム化合物である、<5>又は<6>に記載の衣料用液体洗浄剤組成物。
<7>
(B2) The liquid detergent composition for clothing according to <5> or <6>, wherein the component is a quaternary ammonium compound in which R 1 is an aliphatic hydrocarbon group having 16 carbon atoms.
<8>
 炭素数12の脂肪族炭化水素基がラウリル基であり、炭素数14の脂肪族炭化水素基がミリスチル基であり、炭素数16の脂肪族炭化水素基がパルミチル基又はパルミトレイル基である、<5>~<7>の何れかに記載の衣料用液体洗浄剤組成物。
<8>
The aliphatic hydrocarbon group having 12 carbon atoms is a lauryl group, the aliphatic hydrocarbon group having 14 carbon atoms is a myristyl group, and the aliphatic hydrocarbon group having 16 carbon atoms is a palmityl group or a palmitoleyl group, 5. A liquid detergent composition for clothing according to any one of 5> to <7>.
<9>
 一般式(2)中のR、R及びRが、それぞれ、メチル基である、<1>~<8>の何れかに記載の衣料用液体洗浄剤組成物。
<9>
The liquid detergent composition for clothing according to any one of <1> to <8>, wherein R 2 , R 3 and R 4 in the general formula (2) are each a methyl group.
<10>
 (C)成分が、コハク酸、リンゴ酸、酒石酸、クエン酸及びこれらの塩から選ばれる1種以上の多価カルボン酸又はその塩である、<1>~<9>の何れかに記載の衣料用液体洗浄剤組成物。
<10>
The component (C) is one or more polyvalent carboxylic acids selected from succinic acid, malic acid, tartaric acid, citric acid and salts thereof, or a salt thereof, according to any one of <1> to <9>. Liquid detergent composition for clothing.
<11>
 (C)成分が、クエン酸及びその塩から選ばれる1種以上の多価カルボン酸又はその塩である、<10>に記載の衣料用液体洗浄剤組成物。
<11>
The liquid detergent composition for clothing according to <10>, wherein the component (C) is one or more polyvalent carboxylic acids selected from citric acid and salts thereof or salts thereof.
<12>
 (D)成分が有する全R中の炭素数12以上14以下の炭化水素基の割合が、60質量%以上、更に70質量%以上、更に80質量%以上、そして、100質量%以下である、あるいは、100質量%である、<1>~<11>の何れかに記載の衣料用液体洗浄剤組成物。
<12>
The ratio of the hydrocarbon group having 12 to 14 carbon atoms in the total R 5 of the component (D) is 60% by mass or more, further 70% by mass or more, further 80% by mass or more, and 100% by mass or less. Alternatively, the liquid detergent composition for clothing according to any one of <1> to <11>, which is 100% by mass.
<13>
 (D)成分中、Rが炭素数12以上14以下の炭化水素基である非イオン界面活性剤の割合が、60質量%以上、更に70質量%以上、更に80質量%以上、そして、100質量%以下である、あるいは、100質量%である、<1>~<11>の何れかに記載の衣料用液体洗浄剤組成物。
<13>
In the component (D), the proportion of the nonionic surfactant in which R 5 is a hydrocarbon group having 12 to 14 carbon atoms is 60% by mass or more, further 70% by mass or more, further 80% by mass or more, and 100 The liquid detergent composition for clothing according to any one of <1> to <11>, wherein the composition is 100% by mass or less or 100% by mass.
<14>
 一般式(3)中、Rの炭化水素基が、直鎖の脂肪族炭化水素基又は分岐鎖の脂肪族炭化水素基、更に直鎖の脂肪族炭化水素基である、<1>~<13>の何れかに記載の衣料用液体洗浄剤組成物。
<14>
In the general formula (3), the hydrocarbon group of R 5 is a linear aliphatic hydrocarbon group or a branched aliphatic hydrocarbon group, and further a linear aliphatic hydrocarbon group. 13> Liquid detergent composition for clothes in any one of.
<15>
 一般式(3)中、Rの炭化水素基が、アルキル基又はアルケニル基である、<1>~<14>に記載の、衣料用液体洗浄剤組成物。
<15>
The liquid detergent composition for clothing according to <1> to <14>, wherein in formula (3), the hydrocarbon group of R 5 is an alkyl group or an alkenyl group.
<16>
 アルキル基が、1級アルキル基、更に直鎖1級アルキル基である、<15>に記載の衣料用液体洗浄剤組成物。
<16>
The liquid detergent composition for clothes according to <15>, wherein the alkyl group is a primary alkyl group, and further a linear primary alkyl group.
<17>
 一般式(3)中、nが12以上、更に13以上、更に15以上、更に16以上、更に18以上、更に20以上、そして、35以下である、<1>~<16>の何れかに記載の衣料用液体洗浄剤組成物。
<17>
In the general formula (3), n is 12 or more, 13 or more, 15 or more, 16 or more, 18 or more, 20 or more, and 35 or less, and any one of <1> to <16> The liquid detergent composition for clothes as described.
<18>
 (A)成分の含有量が、組成物中、11質量%以上、そして、15質量%以下、更に14質量%以下である、<1>~<17>の何れかに記載の衣料用液体洗浄剤組成物。
<18>
The liquid washing for clothing according to any one of <1> to <17>, wherein the content of the component (A) is 11% by mass or more and 15% by mass or less, and further 14% by mass or less in the composition. Agent composition.
<19>
 (B)成分の含有量が、組成物中、1.5質量%以上、更に2質量%以上、そして、2.9質量%以下、更に2.8質量%以下、更に2.7質量%以下、更に2.6質量%以下である、<1>~<18>の何れかに記載の衣料用液体洗浄剤組成物。
<19>
The content of the component (B) in the composition is 1.5% by mass or more, further 2% by mass or more, 2.9% by mass or less, further 2.8% by mass or less, and further 2.7% by mass or less. Furthermore, the liquid cleaning composition for clothes according to any one of <1> to <18>, which is 2.6% by mass or less.
<20>
 (C)成分の含有量が、組成物中、2.5質量%以上、更に3質量%以上、更に3.5質量%以上、更に4質量%以上、更に4.5質量%以上、そして、7質量%以下、更に6.5質量%以下、更に6質量%以下、更に5.5質量%以下である、<1>~<18>の何れかに記載の衣料用液体洗浄剤組成物。
<20>
The content of component (C) in the composition is 2.5% by mass or more, further 3% by mass or more, further 3.5% by mass or more, further 4% by mass or more, further 4.5% by mass or more, and The liquid detergent composition for clothing according to any one of <1> to <18>, which is 7% by mass or less, further 6.5% by mass or less, further 6% by mass or less, and further 5.5% by mass or less.
<21>
 (D)成分の含有量と、(A)成分の含有量及び(B)成分の含有量の合計量との質量比である、〔(D)成分の含有量〕/〔(A)成分の含有量+(B)成分の含有量〕が、0.11以上、更に0.12以上、そして、0.35以下、更に0.3以下、更に0.25以下、更に0.2以下である、<1>~<20>の何れかに記載の衣料用液体洗浄剤組成物。
<21>
(D) component content and (A) component content and (B) component content is the mass ratio of [(D) component content] / [(A) component Content + content of component (B)] is 0.11 or more, further 0.12 or more, 0.35 or less, further 0.3 or less, further 0.25 or less, and further 0.2 or less. <1>-<20> The liquid cleaning composition for clothing according to any one of <1> to <20>.
<22>
 20℃におけるpHが2以上、更に3以上、更に3.5以上、更に4以上、そして、7以下、更に6.8以下、更に6.5以下、更に6以下である、<1>~<21>のいずれか1項に記載の衣料用液体洗浄剤組成物。
<22>
The pH at 20 ° C. is 2 or more, 3 or more, 3.5 or more, 4 or more, 7 or less, further 6.8 or less, further 6.5 or less, and further 6 or less. 21> The liquid cleaning composition for clothes according to any one of 21>.
<23>
 水酸基を一つ以上有する有機溶媒の含有量が0質量%以上10質量%未満、更に9質量%以下、更に8質量%以下、更に7質量%以下である、あるいは0質量%である、<1>~<22>のいずれか1項に記載の衣料用液体洗浄剤組成物。
<23>
The content of the organic solvent having one or more hydroxyl groups is 0% by mass or more and less than 10% by mass, further 9% by mass or less, further 8% by mass or less, further 7% by mass or less, or 0% by mass, <1 The liquid cleaning composition for clothing according to any one of> to <22>.
<24>
 水酸基を一つ以上有する有機溶媒が、炭素数2以上6以下の1価以上6価以下のアルコールである、<23>の何れかに記載の衣料用液体洗浄剤組成物。
<24>
The liquid detergent composition for clothing according to any one of <23>, wherein the organic solvent having one or more hydroxyl groups is a monovalent to hexavalent alcohol having 2 to 6 carbon atoms.
<25>
 <1>~<24>の何れかに記載の衣料用液体洗浄剤組成物の、におい物質を産生する原因菌に対する抗菌性を衣料に付与するための使用。
<25>
Use of the liquid cleaning composition for clothing according to any one of <1> to <24> for imparting antibacterial properties against causative bacteria producing odorous substances to clothing.
<26>
 <1>~<24>の何れかに記載の衣料用液体洗浄剤組成物の、衣料に防臭効果を付与するための使用。
<26>
Use of the liquid detergent composition for clothing according to any one of <1> to <24> for imparting a deodorizing effect to clothing.
<27>
 <1>~<24>の何れかに記載の組成物を、衣料用液体洗浄剤として使用する用途。
<27>
Use wherein the composition according to any one of <1> to <24> is used as a liquid detergent for clothing.
<28>
 <1>~<24>の何れかに記載の組成物を、衣料の洗浄に使用する用途。
<28>
Use in which the composition according to any one of <1> to <24> is used for washing clothes.
<29>
 <1>~<24>の何れかに記載の衣料用液体洗浄剤組成物を、におい物質を産生する原因菌に対する抗菌性を衣料に付与するために使用する用途。
<29>
Use of the liquid detergent composition for clothing according to any one of <1> to <24> for imparting antibacterial properties against causative bacteria producing odor substances to clothing.
<30>
 <1>~<24>の何れかに記載の衣料用液体洗浄剤組成物を、衣料に防臭効果を付与するために使用する用途。
<30>
Use of the liquid cleaning composition for clothing according to any one of <1> to <24> for imparting a deodorizing effect to clothing.
実施例
<配合成分>
 以下に、実施例、比較例で用いた成分を示す。
〔(A)成分〕
(a-1):一般式(1)において、Rがラウリル基とミリスチル基が質量比で、ラウリル基/ミリスチル基=7/3(質量比)の混合アルキル基であり、mが2.0であり、MがNaである陰イオン界面活性剤
(a-2):一般式(1)において、Rがラウリル基とミリスチル基が質量比で、ラウリル基/ミリスチル基=7/3(質量比)の混合アルキル基であり、mが1.5であり、MがNaである陰イオン界面活性剤
Example <Compounding ingredients>
The components used in Examples and Comparative Examples are shown below.
[Component (A)]
(A-1): In the general formula (1), R is a mixed alkyl group in which lauryl group and myristyl group are in a mass ratio, lauryl group / myristyl group = 7/3 (mass ratio), and m is 2.0. An anionic surfactant (a-2) in which M + is Na + : In the general formula (1), R is a lauryl group and a myristyl group in a mass ratio, and a lauryl group / myristyl group = 7/3 ( Anionic surfactant having a mixed alkyl group (mass ratio), m is 1.5, and M + is Na +
〔(B)成分〕
(b1-1):N-ラウリル-N,N,N-トリメチルアンモニウムクロリド〔一般式(2)中のRがラウリル基、R、R及びRが、それぞれ、メチル基、XがClである第4級アンモニウム化合物〕
(b2-1):N-パルミチル-N,N,N-トリメチルアンモニウムクロリド〔一般式(2)中のRがパルミチル基、R、R及びRが、それぞれ、メチル基、XがClである第4級アンモニウム化合物〕
[(B) component]
(B1-1): N-lauryl-N, N, N-trimethylammonium chloride [R 1 in the general formula (2) is a lauryl group, R 2 , R 3 and R 4 are each a methyl group, X There Cl - quaternary ammonium compounds which are]
(B2-1): N-palmityl-N, N, N-trimethylammonium chloride [in formula (2), R 1 is a palmityl group, R 2 , R 3 and R 4 are each a methyl group, X There Cl - quaternary ammonium compounds which are]
〔(B’)成分:(B)成分の比較化合物〕
(b’-1):N,N-ジデシル-N,N-ジメチルアンモニウムクロリド〔便宜的に一般式(2)の構造で表すと、一般式(2)中のR及びRが、それぞれ、デシル基、R及びRが、それぞれ、メチル基、XがClである第4級アンモニウム化合物〕
(b’-2):N-ステアリル-N,N,N-トリメチルアンモニウムクロリド〔便宜的に一般式(2)の構造で表すと、一般式(2)中のRがオクチル基、R、R及びRが、それぞれ、メチル基、XがClである第4級アンモニウム化合物〕
[(B ′) Component: Comparative Compound of Component (B)]
(B′-1): N, N-didecyl-N, N-dimethylammonium chloride [For convenience, when represented by the structure of the general formula (2), R 1 and R 2 in the general formula (2) are , A decyl group, R 3 and R 4 are each a methyl group, and X is Cl 2 a quaternary ammonium compound]
(B′-2): N-stearyl-N, N, N-trimethylammonium chloride [For the sake of convenience, R 1 in the general formula (2) is an octyl group, R 2 , R 3 and R 4 are each a methyl group, and X is Cl 2 —.
〔(C)成分〕
(c-1):クエン酸
[Component (C)]
(C-1): Citric acid
〔(D)成分〕
(d-1):一般式(3)において、Rは、ラウリル基とミリスチル基が質量比でラウリル基/ミリスチル基=9/1の混合アルキル基、nは21である非イオン界面活性剤
(d-2):一般式(3)において、Rは、ラウリル基とミリスチル基が質量比でラウリル基/ミリスチル基=9/1の混合アルキル基、nは18である非イオン界面活性剤
(d-3):一般式(3)において、Rは、ラウリル基とミリスチル基が質量比でラウリル基/ミリスチル基=9/1の混合アルキル基、nは15である非イオン界面活性剤
(d-4):一般式(3)において、Rは、ラウリル基とミリスチル基が質量比でラウリル基/ミリスチル基=9/1の混合アルキル基、nは12である非イオン界面活性剤
(d-5):一般式(3)において、Rは、ラウリル基とミリスチル基が質量比でラウリル基/ミリスチル基=9/1の混合アルキル基、nは10である非イオン界面活性剤
[Component (D)]
(D-1): In the general formula (3), R 5 is a mixed alkyl group in which lauryl group and myristyl group are in a mass ratio of lauryl group / myristyl group = 9/1, and n is 21 (D-2): In the general formula (3), R 5 is a mixed alkyl group in which lauryl group and myristyl group are in a mass ratio of lauryl group / myristyl group = 9/1, and n is 18. (D-3): In the general formula (3), R 5 is a mixed alkyl group in which lauryl group and myristyl group are lauryl group / myristyl group = 9/1 by mass ratio, and n is 15. (D-4): In the general formula (3), R 5 is a mixed alkyl group in which lauryl group and myristyl group are in a mass ratio of lauryl group / myristyl group = 9/1, and n is 12. (D-5): In general formula (3) , R 5 is a mixed alkyl group in which lauryl group and myristyl group are lauryl group / myristyl group = 9/1 by mass ratio, and n is 10. Nonionic surfactant
〔(D’)成分:(D)成分の比較化合物〕
(d’-1):便宜的に一般式(3)の構造で表すと、一般式(3)において、Rは、ラウリル基とミリスチル基が質量比でラウリル基/ミリスチル基=9/1の混合アルキル基、nは8である非イオン界面活性剤
(d’-2):便宜的に一般式(3)の構造で表すと、一般式(3)において、Rは、ラウリル基とミリスチル基が質量比でラウリル基/ミリスチル基=9/1の混合アルキル基、nは6である非イオン界面活性剤
(d’-3):便宜的に一般式(3)の構造で表すと、一般式(3)において、Rはステアリル基、nは20である非イオン界面活性剤
[(D ′) Component: Comparative Compound of (D) Component]
(D′-1): For the sake of convenience, the structure represented by the general formula (3) is represented. In the general formula (3), R 5 is a lauryl group / myristyl group in a mass ratio of lauryl group / myristyl group = 9/1. A nonionic surfactant (d′-2) wherein n is 8; for convenience, in the structure of the general formula (3), in the general formula (3), R 5 is a lauryl group Nonionic surfactant (d′-3) in which the myristyl group is a mixed alkyl group having a lauryl group / myristyl group = 9/1 by mass ratio, and n is 6: For convenience, it is represented by the structure of the general formula (3) In the general formula (3), R 5 is a stearyl group, and n is 20, a nonionic surfactant
〔水〕
 次亜塩素酸ナトリウムを1mg/kg含有するイオン交換水
〔water〕
Ion exchange water containing 1mg / kg sodium hypochlorite
〔(E)成分〕
(e-1):水酸化ナトリウム(22質量%水酸化ナトリウム水溶液として使用した。)
[(E) component]
(E-1): Sodium hydroxide (used as a 22% by mass aqueous sodium hydroxide solution)
〔(F)成分〕
(f-1):下記の香料成分を含有する香料組成物。( )内の数字は質量部。
フェニルエチルアルコール(10)、カンファー(20)、シトロネラール(10)、l-メントール(20)、アルデヒドC-9(10)、ネロール(10)、ジフェニルオキサイド(20)
[(F) component]
(F-1): A fragrance composition containing the following fragrance ingredients. Numbers in parentheses are parts by mass.
Phenylethyl alcohol (10), camphor (20), citronellal (10), l-menthol (20), aldehyde C-9 (10), nerol (10), diphenyl oxide (20)
〔(G)成分〕
(g-1):防腐剤、ポリヘキサメチレンビグアニド塩酸塩
[(G) component]
(G-1): Preservative, polyhexamethylene biguanide hydrochloride
<衣料用液体洗浄剤組成物の調製方法>
 以下に、実施例、比較例で用いた衣料用液体洗浄剤組成物の調製方法を示す。
 表1~4の実施例又は比較例の各組成において、出来上がり質量が100gになるのに必要な30℃のイオン交換水に対して、各成分を添加し衣料用液体洗浄剤組成物を調製した。実施例の衣料用液体洗浄剤組成物は、いずれも、調製直後は透明な外観を有していた。
<Method for Preparing Liquid Cleaning Composition for Clothing>
Below, the preparation method of the liquid cleaning composition for clothes used by the Example and the comparative example is shown.
In each of the compositions of Examples and Comparative Examples in Tables 1 to 4, a liquid detergent composition for clothing was prepared by adding each component to 30 ° C. ion-exchanged water necessary for a finished mass of 100 g. . All of the liquid detergent compositions for clothing of the examples had a transparent appearance immediately after preparation.
<pHの測定方法>
 以下に、実施例、比較例の衣料用液体洗浄剤組成物のpHの測定方法を示す。
 堀場製作所製pHメーター D-52のpH電極(型式 6367)をあらかじめフタル酸緩衝液(pH4.01)、リン酸標準液(pH6.84)、ホウ酸塩標準液(pH9.18)で校正し、イオン交換水で十分すすいだ。温度を20℃に調整した衣料用液体洗浄剤組成物に、上記の通り校正、洗浄したpH電極を入れ、pHメーターのAUTO HOLDモードを用いて、測定値が一定になるまで測定した。
<Measurement method of pH>
Below, the measuring method of pH of the liquid cleaning composition for clothes of an Example and a comparative example is shown.
HORIBA, Ltd. pH meter D-52 pH electrode (model 6367) was calibrated with phthalate buffer solution (pH 4.01), phosphate standard solution (pH 6.84), and borate standard solution (pH 9.18) in advance. Rinse with ion exchange water. The pH electrode calibrated and washed as described above was placed in the liquid detergent composition for clothing adjusted to a temperature of 20 ° C., and measurement was performed using the AUTO HOLD mode of the pH meter until the measured value became constant.
<実施例1~7、比較例1~4>
 表1に記載の衣料用液体洗浄剤組成物を用い、以下の方法で、衣料に対する抗菌性の付与効果を評価した。また、以下の方法で、保存安定性を評価した。結果を表1に示す。
<Examples 1 to 7, Comparative Examples 1 to 4>
Using the liquid detergent composition for clothing shown in Table 1, antibacterial imparting effect on clothing was evaluated by the following method. The storage stability was evaluated by the following method. The results are shown in Table 1.
〔衣料の抗菌性の評価方法〕
(1)試験布の作製
 6cm×6cmの木綿平織布(谷頭商店より購入した綿布2003布)を、表1に記載の各液体洗浄剤組成物にて洗浄し、抗菌試験に供する試験布を作製した。水は、100℃で120分間煮沸滅菌したイオン交換水に硬度成分を5DH°(Ca/Mg=7/3、質量比)になるように加え、アルカリ度が80mg/Lになるように炭酸水素ナトリウムを加え、塩酸でpHを7に調整した水を用いた。水と各液体洗浄剤組成物とを混合し、液体洗浄剤組成物の濃度が1g/Lである洗浄液を調製した。1リットルのステンレスビーカーに、洗浄液を0.6リットル入れ、前記の6cm×6cmの木綿平織布を30枚入れた。前記洗浄液の容量(リットル)と木綿平織布の質量(g)との比である、容量(リットル)/木綿平織布の質量(g)は50であった。ターゴトメーターで、100回転、10分間の洗浄操作を行った。次にステンレスビーカー内の洗浄液を捨て、木綿平織布を手で絞り木綿平織布の洗浄前の乾燥質量に対し、250質量%程度にした。水を用いて同様の条件で3分間のすすぎを2回行い、2槽式洗濯機の脱水槽で30秒間脱水し、自然乾燥させた。
[Method of evaluating antibacterial properties of clothing]
(1) Preparation of test cloth A 6 cm x 6 cm cotton plain woven cloth (cotton cloth 2003 cloth purchased from Tanigami Shoten) was washed with each liquid detergent composition described in Table 1, and a test cloth for use in antibacterial tests was prepared. Produced. Water is added to ion-exchanged water sterilized by boiling at 100 ° C. for 120 minutes so that the hardness component is 5 DH ° (Ca / Mg = 7/3, mass ratio), and hydrogen carbonate so that the alkalinity is 80 mg / L. Sodium was added, and water adjusted to pH 7 with hydrochloric acid was used. Water and each liquid cleaning composition were mixed to prepare a cleaning liquid having a liquid cleaning composition concentration of 1 g / L. In a 1 liter stainless steel beaker, 0.6 liter of the cleaning solution was placed, and 30 pieces of the above 6 cm × 6 cm cotton plain woven fabric were placed. The volume (liter) / mass of cotton plain woven fabric (g), which is the ratio of the volume of the cleaning liquid (liter) to the mass of cotton plain woven fabric (g), was 50. The washing operation was performed with a targotometer at 100 rpm for 10 minutes. Next, the cleaning liquid in the stainless beaker was discarded, and the cotton plain woven cloth was squeezed by hand to make it about 250% by weight based on the dry weight of the cotton plain woven cloth before washing. The water was rinsed twice for 3 minutes under the same conditions, dehydrated for 30 seconds in a dewatering tank of a 2-tank washing machine, and naturally dried.
(2)抗菌効果
 モラクセラ・オスロエンシスに対する抗菌効果を評価した。菌は、衣料から単離したMoraxella osloensis 41を使用した。
 試験布0.4gに菌液(初発菌数1.0×10CFU/mL)を0.2mL植菌し、37℃にて18時間静置培養を行った。20mLのLP希釈液(日本製薬(株)製)を加えて超音波を10分間照射し、菌の抽出を行った。抽出液の段階希釈を行い、SCD-LP寒天培地(日本製薬(株)製)にて混釈後、37℃にて静置培養(1日)を行い、得られたコロニー数を計測し、表1の比較例1の生菌数の常用対数値から、各実施例又は比較例の生菌数の常用対数値を引いたもの(対数値)を静菌活性値とした。この評価では、静菌活性値が、2.2以上が合格であり、静菌活性値は高いほど抗菌効果が高いことを意味する。
(2) Antibacterial effect The antibacterial effect against Moraxella osloensis was evaluated. The fungus used was Moraxella osloensis 41 isolated from clothing.
0.2 g of the bacterial solution (initial bacterial count 1.0 × 10 5 CFU / mL) was inoculated on 0.4 g of the test cloth, and static culture was performed at 37 ° C. for 18 hours. 20 mL of LP diluent (manufactured by Nippon Pharmaceutical Co., Ltd.) was added and irradiated with ultrasonic waves for 10 minutes to extract bacteria. Perform serial dilution of the extract, pour in SCD-LP agar medium (manufactured by Nippon Pharmaceutical Co., Ltd.), perform static culture at 37 ° C (1 day), count the number of colonies obtained, The bacteriostatic activity value was obtained by subtracting the common logarithm of the viable cell count of each Example or Comparative Example from the common logarithm of the viable cell count of Comparative Example 1 in Table 1. In this evaluation, the bacteriostatic activity value of 2.2 or more is acceptable, and the higher the bacteriostatic activity value, the higher the antibacterial effect.
〔保存安定性の評価方法〕
 表に記載の衣料用液体洗浄剤組成物を、No.6の規格瓶に25g入れ、50℃の恒温槽内に静置した。7日後の衣料用液体洗浄剤組成物の外観を、それぞれ目視で観察し、以下の基準で評価した。下記基準の1と2は、製品形態などを考慮した場合に合格レベルであり、1が好ましい。また、下記基準の2の場合も、僅かな曇りが見られるまでの日数がより長い方が、保存安定性の点で好ましい。3は不合格のレベルである。また、下記基準の1又は2の組成物は、紫外可視分光光度計において、光路長が1cmのガラス製セルに当該衣料用液体洗浄剤組成物を入れ、対照側セルにはイオン交換水を用いた時の、660nmの波長における透過率が90%以上となっている。
  1:透明状態を維持し、分離が認められない。
  2:僅かに曇っているが、透明状態と認められ、分離が認められない。
  3:分離が認められる。
[Method for evaluating storage stability]
The liquid detergent composition for clothing described in the table is No. 25 g was placed in a 6 standard bottle and allowed to stand in a constant temperature bath at 50 ° C. The appearance of the liquid detergent composition for clothing after 7 days was visually observed and evaluated according to the following criteria. The following standards 1 and 2 are acceptable levels when the product form is considered, and 1 is preferable. Also, in the case of 2 below, it is preferable in terms of storage stability that the number of days until a slight cloudiness is seen is longer. 3 is a failure level. The composition of 1 or 2 of the following criteria is a UV-visible spectrophotometer in which the liquid detergent composition for clothing is placed in a glass cell having an optical path length of 1 cm, and ion-exchanged water is used for the control side cell. The transmittance at a wavelength of 660 nm is 90% or more.
1: The transparent state is maintained and no separation is observed.
2: Although slightly cloudy, it is recognized as a transparent state and separation is not recognized.
3: Separation is observed.
Figure JPOXMLDOC01-appb-T000005
Figure JPOXMLDOC01-appb-T000005
 表中、(D)/[(A)+(B)]は、〔(D)成分の含有量〕/〔(A)成分の含有量+(B)成分の含有量〕の質量比である(以下同様)。
 また、表中、(B)/(A)は、〔(B)成分の含有量〕/〔(A)成分の含有量〕の質量比である(以下同様)。
In the table, (D) / [(A) + (B)] is a mass ratio of [content of (D) component] / [content of (A) component + content of (B) component]. (The same applies hereinafter).
In the table, (B) / (A) is a mass ratio of [content of (B) component] / [content of (A) component] (the same applies hereinafter).
<実施例8~19、比較例5~12>
 表2に記載の衣料用液体洗浄剤組成物を用い、以下の方法で、保存安定性を評価した。結果を表2に示す。
〔保存安定性の評価方法〕
 表に記載の衣料用液体洗浄剤組成物を、No.6の規格瓶に25g入れ、50℃の恒温槽内に静置した。7日後、14日後及び21日後の衣料用液体洗浄剤組成物の外観を、それぞれ目視で観察し、以下の基準で評価した。下記基準の1と2は、製品形態などを考慮した場合に合格レベルであり、1が好ましい。また、下記基準の2の場合も、僅かな曇りが見られるまでの日数がより長い方が、保存安定性の点で好ましい。3は不合格のレベルである。また、下記基準の1又は2の組成物は、紫外可視分光光度計において、光路長が1cmのガラス製セルに当該衣料用液体洗浄剤組成物を入れ、対照側セルにはイオン交換水を用いた時の、660nmの波長における透過率が90%以上となっている。
  1:透明状態を維持し、分離が認められない。
  2:僅かに曇っているが、透明状態と認められ、分離が認められない。
  3:分離が認められる。
<Examples 8 to 19 and Comparative Examples 5 to 12>
Storage stability was evaluated by the following method using the liquid detergent composition for clothing described in Table 2. The results are shown in Table 2.
[Method for evaluating storage stability]
The liquid detergent composition for clothing described in the table is No. 25 g was placed in a 6 standard bottle and allowed to stand in a constant temperature bath at 50 ° C. The appearance of the liquid detergent composition for clothing after 7 days, 14 days and 21 days was visually observed and evaluated according to the following criteria. The following standards 1 and 2 are acceptable levels when the product form is considered, and 1 is preferable. Also, in the case of 2 below, it is preferable in terms of storage stability that the number of days until a slight cloudiness is seen is longer. 3 is a failure level. The composition of 1 or 2 of the following criteria is a UV-visible spectrophotometer in which the liquid detergent composition for clothing is placed in a glass cell having an optical path length of 1 cm, and ion-exchanged water is used for the control side cell. The transmittance at a wavelength of 660 nm is 90% or more.
1: The transparent state is maintained and no separation is observed.
2: Although slightly cloudy, it is recognized as a transparent state and separation is not recognized.
3: Separation is observed.
Figure JPOXMLDOC01-appb-T000006
Figure JPOXMLDOC01-appb-T000006
<実施例20~27>
 表3に記載の衣料用液体洗浄剤組成物を用い、以下の方法で、臭いの評価を行った。結果を表3に示す。
<Examples 20 to 27>
Using the liquid cleaning composition for clothing described in Table 3, the odor was evaluated by the following method. The results are shown in Table 3.
〔衣料用液体洗浄剤組成物の臭いの評価方法〕
 表3に記載の衣料用液体洗浄剤組成物を、No.6の規格瓶に20g入れてふたを閉め、ウォーターバスに入れて内容物の温度を30℃に調整した。30℃で3時間維持した後の衣料用液体洗浄剤組成物について、評価パネラー10名が、それぞれ臭いを評価し、以下の基準により点数を付けた。10人の点数の平均点により、臭いを評価した。平均点が高い方が好ましく、平均点が1.0を超える値を合格とした。
評価基準
  0:実施例27(基準)と同等のアミン臭を感じる。
  1:実施例27よりアミン臭が弱いが、僅かにアミン臭を感じる。
  2:アミン臭を殆ど感じない。
[Method for evaluating odor of liquid detergent composition for clothing]
The liquid detergent composition for clothing described in Table 3 20g was put into the 6 standard bottle, the lid was closed, it put into the water bath, and the temperature of the contents was adjusted to 30 degreeC. About the liquid cleaning composition for clothes after maintaining at 30 degreeC for 3 hours, ten evaluation panelists evaluated the odor, respectively, and gave the score by the following references | standards. The odor was evaluated by the average score of 10 people. A higher average score is preferred, and a value with an average score exceeding 1.0 was considered acceptable.
Evaluation criteria 0: An amine odor equivalent to that in Example 27 (standard) is felt.
1: Although the amine odor was weaker than Example 27, a slight amine odor is felt.
2: Almost no amine odor is felt.
Figure JPOXMLDOC01-appb-T000007
Figure JPOXMLDOC01-appb-T000007
<実施例28、29>
 表4に記載の衣料用液体洗浄剤組成物を用い、以下の方法で、洗浄力を評価した。結果を表4に示す。
<Examples 28 and 29>
Using the liquid cleaning composition for clothing described in Table 4, the cleaning power was evaluated by the following method. The results are shown in Table 4.
〔洗浄力評価〕
<人工汚染布の作製>
 使用した人工汚染布は、6cm×6cmの木綿/ポリエステルブロード混紡布(木綿/ポリエステル比=35/65 谷頭商店より購入)に、下記組成から成るモデル皮脂汚れを1枚当り100mgになるようグラビア塗工して調製した。
[Detergency evaluation]
<Production of artificially contaminated cloth>
The artificial soiling cloth used was a 6cm x 6cm cotton / polyester broad blended fabric (cotton / polyester ratio = 35/65 purchased from Tanigami Shoten) with a gravure coating so that the model sebum soil consisting of the following composition was 100 mg per sheet. Prepared.
・モデル皮脂汚れ
 以下の組成を有するモデル皮脂汚れを使用した。
ラウリン酸0.44質量%、ミリスチン酸3.15質量%、ペンタデカン酸2.35質量%、パルチミチン酸6.31質量%、ヘプタデカン酸0.44質量%、ステアリン酸1.6質量%、オレイン酸7.91質量%、トリオレイン13.33質量%、パルミチン酸n-ヘキサデシル2.22質量%、スクアレン6.66質量%、及び残部の水(合計100質量%)
-Model sebum stain A model sebum stain having the following composition was used.
Lauric acid 0.44%, myristic acid 3.15%, pentadecanoic acid 2.35%, palmitic acid 6.31%, heptadecanoic acid 0.44%, stearic acid 1.6%, oleic acid 7.91% by mass, 13.33% by mass of triolein, 2.22% by mass of n-hexadecyl palmitate, 6.66% by mass of squalene, and the balance water (total of 100% by mass)
<洗浄条件>
 モデル水道水として、イオン交換水に硬度成分を5DH°(Ca/Mg=7/3、質量比)になるように加えた水を使用した。このモデル水道水0.6リットルに、表4の衣料用液体洗浄剤組成物を0.6g加え、人工汚染布を4枚入れた。ターゴトメーターで、100回転、10分間の条件で洗浄した。
 洗浄力は、汚染前の原布、及び洗浄前後の550nmにおける反射率を測色色差計(日本電色株式会社製Z-300A)にて測定し、次式によって洗浄率(%)を求めた。汚染布4枚についてそれぞれ測定し平均値を求めた。洗浄率は30%以上が合格ラインであり、数値が高い方がより好ましい。
<Cleaning conditions>
As model tap water, water obtained by adding hardness components to ion exchange water so as to be 5 DH ° (Ca / Mg = 7/3, mass ratio) was used. To 0.6 liters of this model tap water, 0.6 g of the liquid cleaning composition for clothing shown in Table 4 was added, and four artificially contaminated cloths were placed. Washing was performed with a targotometer at 100 rpm for 10 minutes.
The cleaning power was determined by measuring the reflectance at 550 nm before and after cleaning with a colorimetric color difference meter (Nippon Denshoku Co., Ltd. Z-300A), and calculating the cleaning rate (%) by the following formula. . Each of the four soiled cloths was measured to obtain an average value. A cleaning rate of 30% or more is an acceptable line, and a higher numerical value is more preferable.
 洗浄率(%)=100×[(洗浄後の反射率-洗浄前の反射率)/(原布の反射率-洗浄前の反射率)] Washing rate (%) = 100 × [(reflectance after washing−reflectivity before washing) / (reflectance of base fabric−reflectivity before washing)]
Figure JPOXMLDOC01-appb-T000008
Figure JPOXMLDOC01-appb-T000008
 実施例28は実施例1に、実施例29は実施例2に対応する。いずれの衣料用液体洗浄剤組成物も、良好な洗浄力を有することがわかる。 Example 28 corresponds to Example 1, and Example 29 corresponds to Example 2. It can be seen that any liquid detergent composition for clothing has good detergency.

Claims (7)

  1.  下記(A)成分を10質量%以上16質量%以下、(B)成分を1質量%以上3質量%以下、(C)成分を2質量%以上8質量%以下、(D)成分及び水を含有し、
     〔(D)成分の含有量〕/〔(A)成分の含有量+(B)成分の含有量〕の質量比が0.1以上0.4以下である、
    衣料用液体洗浄剤組成物。
    (A)成分:下記一般式(1)で表される陰イオン界面活性剤
         RO-(CO)SO ・M     (1)
    〔式中、Rは炭素数10以上16以下の炭化水素基であり、mは平均付加モル数を示し、1以上4以下の数であり、Mは陽イオンである。〕
    (B)成分:下記一般式(2)で表される第4級アンモニウム化合物
    Figure JPOXMLDOC01-appb-C000001
    〔式中、Rは、炭素数12以上16以下の脂肪族炭化水素基であり、R、R及びRは、それぞれ独立に、メチル基、エチル基及びヒドロキシエチル基から選ばれる基であり、Xは陰イオンである。〕
    (C)成分:炭素数4以上6以下であり2価以上4価以下の多価カルボン酸又はその塩
    (D)成分:下記一般式(3)で表される非イオン界面活性剤
         RO-(CO)H     (3)
    〔式中、Rは炭素数12以上16以下の炭化水素基であり、nは平均付加モル数を示し、10以上40以下の数である。〕
    The following (A) component is 10% by mass to 16% by mass, (B) component is 1% by mass to 3% by mass, (C) component is 2% by mass to 8% by mass, (D) component and water Contains,
    The mass ratio of [(D) component content] / [(A) component content + (B) component content] is 0.1 or more and 0.4 or less,
    Liquid detergent composition for clothing.
    Component (A): anionic surfactant represented by the following general formula (1) RO- (C 2 H 4 O) m SO 3 - · M + (1)
    [Wherein, R represents a hydrocarbon group having 10 to 16 carbon atoms, m represents an average number of added moles, is a number of 1 to 4 and M + is a cation.] ]
    Component (B): a quaternary ammonium compound represented by the following general formula (2)
    Figure JPOXMLDOC01-appb-C000001
    Wherein R 1 is an aliphatic hydrocarbon group having 12 to 16 carbon atoms, and R 2 , R 3 and R 4 are each independently a group selected from a methyl group, an ethyl group and a hydroxyethyl group And X is an anion. ]
    Component (C): a polyvalent carboxylic acid having 4 or more and 6 or less carbon atoms and having a valence of 2 to 4, or a salt thereof (D) Component: a nonionic surfactant R 5 O represented by the following general formula (3) -(C 2 H 4 O) n H (3)
    [Wherein, R 5 represents a hydrocarbon group having 12 to 16 carbon atoms, and n represents an average added mole number, which is a number of 10 to 40. ]
  2.  (A)成分の含有量と(B)成分の含有量との質量比である〔(B)成分の含有量〕/〔(A)成分の含有量〕が0.05以上0.3以下である、請求項1に記載の衣料用液体洗浄剤組成物。 [A content of (B)] / [Content of (A) component] which is a mass ratio of the content of (A) component and the content of (B) component is 0.05 or more and 0.3 or less The liquid cleaning composition for clothes according to claim 1.
  3.  (B)成分として、下記の(b1)成分と(b2)成分とを含有する、請求項1又は2に記載の衣料用液体洗浄剤組成物。
    (b1)成分:一般式(2)中のRが炭素数12の脂肪族炭化水素基である第4級アンモニウム化合物。
    (b2)成分:一般式(2)中のRが炭素数14の脂肪族炭化水素基である第4級アンモニウム化合物及び一般式(2)中のRが炭素数16の脂肪族炭化水素基である第4級アンモニウム化合物から選ばれる1種以上の化合物。
    (B) The liquid cleaning composition for clothes of Claim 1 or 2 containing the following (b1) component and (b2) component as a component.
    (B1) Component: A quaternary ammonium compound in which R 1 in the general formula (2) is an aliphatic hydrocarbon group having 12 carbon atoms.
    Component (b2): General formula (2), R 1 of the quaternary ammonium compound and the general formula R 1 is an aliphatic hydrocarbon group of 14 carbon atoms (2) in the number 16 carbon atoms in the aliphatic hydrocarbon 1 or more types of compounds chosen from the quaternary ammonium compound which is group.
  4.  20℃におけるpHが2以上7以下である、請求項1~3のいずれか1項に記載の衣料用液体洗浄剤組成物。 The liquid detergent composition for clothing according to any one of claims 1 to 3, wherein the pH at 20 ° C is 2 or more and 7 or less.
  5.  水酸基を一つ以上有する有機溶媒の含有量が0質量%以上10質量%未満である、請求項1~4のいずれか1項に記載の衣料用液体洗浄剤組成物。 The liquid detergent composition for clothing according to any one of claims 1 to 4, wherein the content of the organic solvent having one or more hydroxyl groups is 0% by mass or more and less than 10% by mass.
  6.  請求項1~5の何れかに記載の衣料用液体洗浄剤組成物の、におい物質を産生する原因菌に対する抗菌性を衣料に付与するための使用。 Use of the liquid detergent composition for clothing according to any one of claims 1 to 5 for imparting antibacterial properties against causative bacteria producing odor substances to clothing.
  7.  請求項1~5の何れかに記載の衣料用液体洗浄剤組成物の、衣料に防臭効果を付与するための使用。 Use of the liquid cleaning composition for clothing according to any one of claims 1 to 5 for imparting a deodorizing effect to clothing.
PCT/JP2016/067191 2015-06-19 2016-06-09 Liquid detergent composition for clothing WO2016204063A1 (en)

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JP7190823B2 (en) * 2017-05-09 2022-12-16 ライオン株式会社 Liquid detergent composition for clothes
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