WO2017051776A1 - Liquid cleaning agent composition - Google Patents

Liquid cleaning agent composition Download PDF

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Publication number
WO2017051776A1
WO2017051776A1 PCT/JP2016/077444 JP2016077444W WO2017051776A1 WO 2017051776 A1 WO2017051776 A1 WO 2017051776A1 JP 2016077444 W JP2016077444 W JP 2016077444W WO 2017051776 A1 WO2017051776 A1 WO 2017051776A1
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WIPO (PCT)
Prior art keywords
component
group
carbon atoms
liquid detergent
detergent composition
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PCT/JP2016/077444
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French (fr)
Japanese (ja)
Inventor
圭輔 森
真嘉 大石
神藤　宏明
Original Assignee
ライオン株式会社
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Priority to JP2017541540A priority Critical patent/JP6770964B2/en
Publication of WO2017051776A1 publication Critical patent/WO2017051776A1/en

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Classifications

    • C—CHEMISTRY; METALLURGY
    • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D1/00—Detergent compositions based essentially on surface-active compounds; Use of these compounds as a detergent
    • C11D1/66—Non-ionic compounds
    • C11D1/72—Ethers of polyoxyalkylene glycols
    • C—CHEMISTRY; METALLURGY
    • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D1/00—Detergent compositions based essentially on surface-active compounds; Use of these compounds as a detergent
    • C11D1/66—Non-ionic compounds
    • C11D1/722—Ethers of polyoxyalkylene glycols having mixed oxyalkylene groups; Polyalkoxylated fatty alcohols or polyalkoxylated alkylaryl alcohols with mixed oxyalkylele groups
    • C—CHEMISTRY; METALLURGY
    • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D1/00—Detergent compositions based essentially on surface-active compounds; Use of these compounds as a detergent
    • C11D1/66—Non-ionic compounds
    • C11D1/74—Carboxylates or sulfonates esters of polyoxyalkylene glycols
    • C—CHEMISTRY; METALLURGY
    • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D1/00—Detergent compositions based essentially on surface-active compounds; Use of these compounds as a detergent
    • C11D1/66—Non-ionic compounds
    • C11D1/83—Mixtures of non-ionic with anionic compounds
    • C—CHEMISTRY; METALLURGY
    • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D1/00—Detergent compositions based essentially on surface-active compounds; Use of these compounds as a detergent
    • C11D1/86—Mixtures of anionic, cationic, and non-ionic compounds
    • C—CHEMISTRY; METALLURGY
    • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D17/00—Detergent materials or soaps characterised by their shape or physical properties
    • C11D17/08—Liquid soap, e.g. for dispensers; capsuled
    • C—CHEMISTRY; METALLURGY
    • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D3/00—Other compounding ingredients of detergent compositions covered in group C11D1/00
    • C11D3/16—Organic compounds
    • C11D3/24—Organic compounds containing halogen
    • C—CHEMISTRY; METALLURGY
    • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D3/00—Other compounding ingredients of detergent compositions covered in group C11D1/00
    • C11D3/16—Organic compounds
    • C11D3/37—Polymers
    • C—CHEMISTRY; METALLURGY
    • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D3/00—Other compounding ingredients of detergent compositions covered in group C11D1/00
    • C11D3/48—Medical, disinfecting agents, disinfecting, antibacterial, germicidal or antimicrobial compositions

Definitions

  • the present invention relates to a liquid detergent composition.
  • This application claims priority based on Japanese Patent Application No. 2015-186892 filed in Japan on September 24, 2015, the contents of which are incorporated herein by reference.
  • liquid detergent compositions are often used as household laundry detergents.
  • the frequency of picking and washing is increased with the increase in the size of a washing machine, so that a high cleaning power is required for the liquid detergent composition.
  • re-contamination that is, a phenomenon in which some of the dirt that has separated from the fibers of the item to be washed and dispersed in the washing liquid adheres to the fibers again.
  • the liquid detergent composition must also have excellent liquid stability.
  • liquid cleaning composition what mix
  • blended antibacterial agents such as a cationic surfactant
  • blended antibacterial agents such as a cationic surfactant
  • an anionic surfactant is combined with a cationic surfactant as a cleaning component in order to enhance the cleaning effect, re-contamination is likely to occur during cleaning, and the cleaning effect is hardly exhibited.
  • clothing containing synthetic fibers other than cotton has become mainstream due to the diversification of clothing products.
  • cationic surfactants are not sufficiently adsorbed on synthetic fibers, so antibacterial properties against clothing containing synthetic fibers are antibacterial. It is difficult to demonstrate its properties.
  • liquid detergent compositions containing an antibacterial agent having an aromatic ring have also been proposed (for example, Patent Documents 2 to 4).
  • JP 2014-28942 A JP-T-2004-515642 JP 2001-146681 A Japanese Patent Laying-Open No. 2015-7220
  • the present invention is a liquid detergent that can exhibit high detergency, excellent liquid stability, and high anti-recontamination effect, can impart excellent antibacterial properties to the object to be washed, and is excellent in the effect of suppressing the occurrence of room-dried odor
  • An object is to provide a composition.
  • the present invention has the following configuration.
  • component (B) A liquid detergent composition containing at least one selected from the group consisting of component: anionic surfactant and component (C): an antibacterial agent having a phenol structure.
  • component (D) a water-soluble polymer having one or both of an alkylene terephthalate unit and an alkylene isophthalate unit, and one or both of an oxyalkylene unit and a polyoxyalkylene unit;
  • the liquid detergent composition according to any one of [1] to [3], which is contained in an amount of 1 to 5% by mass.
  • a liquid detergent composition according to any one of the above.
  • component (F) a cationic surfactant.
  • R 1 in the formula (I) is an alkyl group having 11 carbon atoms and an alkyl group having 13 carbon atoms
  • R 2 is a methyl group
  • s 15, and t
  • the liquid detergent composition of the present invention can exhibit high detergency, excellent liquid stability, and a high anti-recontamination effect, and can impart excellent antibacterial properties to the object to be washed, thereby suppressing the occurrence of room drying odor. Is excellent.
  • the liquid detergent composition of the present invention is a liquid detergent composition containing the components (A) to (C) described later.
  • the component (A) includes a compound represented by the following formula (I) (hereinafter also referred to as compound (I)) and a compound represented by the following formula (II) (hereinafter also referred to as compound (II)).
  • a nonionic surfactant containing at least one selected from the group consisting of R 1 —C ( ⁇ O) O — [(EO) s / (PO) t ] — (EO) u —R 2 (I) R 3 —O — [(EO) v / (PO) w ] — (EO) x —H (II)
  • EO is an ethyleneoxy group and PO is a propyleneoxy group.
  • R 1 is a hydrocarbon group having 7 to 22 carbon atoms
  • R 2 is a methyl group or an ethyl group
  • R 3 is a hydrocarbon group having 7 to 22 carbon atoms.
  • s, v, u, and x are the average number of repetitions of EO
  • t and w are the average number of repetitions of PO.
  • s is a number from 6 to 20
  • t is a number from 0 to 6
  • u is a number from 0 to 20.
  • v is a number from 8 to 20
  • w is a number from 0 to 6
  • x is a number from 0 to 20.
  • the hydrocarbon group for R 1 in formula (I) may be linear or branched.
  • the hydrocarbon group of R 1 has 7 to 22 carbon atoms. If the number of carbon atoms is at least the lower limit, a sufficient drape maintaining effect can be obtained. If the carbon number is not more than the upper limit value, excellent liquid stability can be obtained.
  • the number of carbon atoms of the hydrocarbon group for R 1 is preferably 9 to 21, and more preferably 11 to 21, from the viewpoint of improving detergency.
  • R 1 is preferably an alkyl group or an alkenyl group.
  • alkyl group or alkenyl group examples include alkyl groups derived from raw materials such as primary or secondary higher alcohols having 7 to 22 carbon atoms, higher fatty acids having 8 to 23 carbon atoms, and higher fatty acid amides having 8 to 23 carbon atoms.
  • An alkenyl group is mentioned.
  • S + u in the formula (I) is preferably 6 to 20, more preferably 6 to 18, and still more preferably 11 to 18. If s + u is not less than the lower limit, the hydrophilicity will be sufficient, and free water in the system will be reduced, thereby improving the enzyme stability. If s + u is less than or equal to the upper limit, the hydrophilicity does not become too high and sufficient detergency can be easily obtained.
  • T in the formula (I) is a number of 0 to 6, preferably 0 to 3. If t is less than or equal to the upper limit value, the liquid stability is improved.
  • the ethyleneoxy group and propyleneoxy group in [(EO) s / (PO) t ] may form a random chain or may form a block chain.
  • the hydrocarbon group for R 3 in formula (II) may be linear or branched.
  • the hydrocarbon group of R 3 has 7 to 22 carbon atoms. If the number of carbon atoms is at least the lower limit, a sufficient drape maintaining effect can be obtained. If the carbon number is not more than the upper limit value, excellent liquid stability can be obtained. From the viewpoint of improving detergency, the number of carbon atoms in the hydrocarbon group of R 3 is preferably 10-22, more preferably 10-20, and even more preferably 10-18.
  • R 3 is preferably an alkyl group or an alkenyl group. Examples of the alkyl group or alkenyl group are the same as those described for R 1 .
  • V + x in the formula (II) is preferably 8 to 20, more preferably 9 to 18, further preferably 10 to 18, and particularly preferably 13 to 18.
  • v + x is equal to or greater than the lower limit, the hydrophilicity is sufficient, and the enzyme stability is improved by reducing the amount of free water in the system. If v + x is less than or equal to the upper limit value, the hydrophilicity does not become too high and sufficient detergency is easily obtained.
  • w is 0 to 6, preferably 0 to 3. If w is not more than the upper limit value, the liquid stability is improved.
  • the ethyleneoxy group and propyleneoxy group in [(EO) v / (PO) w ] may form a random chain or may form a block chain.
  • polyoxyethylene fatty acid alkyl ester is preferable, and polyoxyethylene fatty acid methyl ester (hereinafter, also referred to as MEE) in which R 2 is a methyl group is more preferable.
  • MEE polyoxyethylene fatty acid methyl ester
  • the solubility of the liquid detergent composition in water can be increased and the cleaning power can be increased.
  • the content of the component (B) in the liquid cleaning composition is increased, a concentrated liquid cleaning composition having a good fluidity is obtained without causing a significant increase in viscosity (gelation). It is done.
  • a polyoxyethylene fatty acid alkyl ester is a nonionic surfactant having a weak molecular orientation and an unstable micelle in an aqueous solution system. For this reason, it is speculated that polyoxyethylene fatty acid alkyl ester does not cause gelation or the like at a high concentration, and can increase solubility in water even if it is blended in a liquid detergent composition in a large amount alone.
  • the narrow ratio indicating the distribution ratio of compounds having different numbers of added moles of ethylene oxide is preferably 20% by mass or more.
  • the upper limit of the narrow ratio is preferably substantially 80% by mass.
  • the narrow ratio is more preferably 20 to 60% by mass. The higher the narrow ratio, the better the detergency can be obtained, but if it is too high, the liquid stability at low temperatures may be lowered, so 30 to 45% by mass is more preferable.
  • the narrow rate of polyoxyalkylene type nonionic surfactants such as polyoxyethylene fatty acid alkyl esters is a value determined by the following mathematical formula (S).
  • S max represents the number of added moles of alkylene oxide (value of s + t + u) in the alkylene oxide adduct most frequently present in the polyoxyalkylene type nonionic surfactant.
  • i represents the number of added moles of alkylene oxide.
  • Yi represents the proportion (% by mass) of an alkylene oxide adduct having an added mole number of alkylene oxide present in the entire component represented by the formula (S).
  • the narrow rate can be controlled by, for example, a method for producing a polyoxyethylene fatty acid alkyl ester.
  • the distribution of EO or PO in compound (I) and compound (II) varies depending on the reaction method in production. For example, when ethylene oxide or propylene oxide is added to a raw material using sodium hydroxide, potassium hydroxide or the like, which is a general alkali catalyst, the distribution of s or t becomes relatively wide.
  • a specific alkoxylation catalyst such as magnesium oxide to which metal ions such as Al 3+ , Ga 3+ , In 3+ , Tl 3+ , Co 3+ , Sc 3+ , La 3+ , Mn 2+ and the like described in JP-B-6-15038 is added.
  • metal ions such as Al 3+ , Ga 3+ , In 3+ , Tl 3+ , Co 3+ , Sc 3+ , La 3+ , Mn 2+ and the like described in JP-B-6-15038 is added.
  • the distribution of EO or PO becomes relatively narrow.
  • an alkylene oxide is added to a fatty acid alkyl ester with an alkoxylation catalyst prepared from a mixture of an alkaline earth metal compound and oxyacid.
  • alkoxylation catalysts are disclosed in Japanese Patent No. 04977609, International Publication No. 1993/004030, International Publication No. 2002/038269, International Publication No. 2012/028435, and the like. Examples include an alkoxylation catalyst prepared from a mixture of an earth metal salt and / or an alkaline earth metal salt of hydroxycarboxylic acid and sulfuric acid.
  • (A) component may contain other nonionic surfactants other than compound (I) and compound (II).
  • nonionic surfactants include known ones used in liquid detergent compositions, such as polyoxyalkylene type nonionic surfactants other than compound (I) and compound (II), alkylphenols, Alkylene oxide adducts such as higher amines, polyoxyethylene polyoxypropylene block copolymers, fatty acid alkanolamines, fatty acid alkanolamides, polyhydric alcohol fatty acid esters or alkylene oxide adducts thereof, polyhydric alcohol fatty acid ethers, alkyl (or alkenyl) amines Examples thereof include oxides, alkylene oxide adducts of hydrogenated castor oil, sugar fatty acid esters, N-alkyl polyhydroxy fatty acid amides, and alkyl glycosides.
  • the component (A) one type may be used alone, or two or more types may be used in combination. By combining two or more types may
  • the content of the component (A) in the liquid detergent composition (100% by mass) of the present invention is preferably 5 to 80% by mass, more preferably 10 to 70% by mass. If content of (A) component is more than a lower limit, the cleaning power of a liquid detergent composition will increase. If content of (A) component is below an upper limit, the liquid stability of a liquid detergent composition will increase.
  • Component (B) is at least one selected from the group consisting of anionic surfactants.
  • Examples of the component (B) include the following compounds (B1) to (B12).
  • B1 A methyl ester salt, ethyl ester salt or propyl ester salt of a saturated or unsaturated ⁇ -sulfo fatty acid having 8 to 20 carbon atoms.
  • B2 A linear or branched alkylbenzene sulfonate (LAS or ABS) having an alkyl group having 8 to 18 carbon atoms. Of these, those having a linear alkyl group are preferred.
  • the linear alkyl group preferably has 8 to 16 carbon atoms, and more preferably 10 to 14 carbon atoms.
  • B3 Alkane sulfonate having 10 to 20 carbon atoms.
  • B4) ⁇ -olefin sulfonate (AOS) having 10 to 20 carbon atoms.
  • B5) Alkyl sulfate or alkenyl sulfate (AS) having 10 to 20 carbon atoms.
  • the average added mole number of alkylene oxide or ethylene oxide and propylene oxide is preferably 1 to 5.
  • Alkyl polyhydric alcohol ether sulfates such as alkyl glyceryl ether sulfonic acids having 10 to 20 carbon atoms.
  • B10 Long chain monoalkyl phosphate, long chain dialkyl phosphate, or long chain sesquialkyl phosphate.
  • B11 Polyoxyethylene monoalkyl phosphate, polyoxyethylene dialkyl phosphate, or polyoxyethylene sesquialkyl phosphate.
  • an anionic surfactant other than the compounds (B1) to (B12) may be used.
  • carboxylic acid type anionic surfactants such as alkyl ether carboxylates, polyoxyalkylene ether carboxylates, alkylamide ether carboxylates or alkenylamide ether carboxylates, acylaminocarboxylates; alkyl phosphate ester salts And phosphoric acid ester type anionic surfactants such as polyoxyalkylene alkyl phosphoric acid ester salt, polyoxyalkylene alkyl phenyl phosphoric acid ester salt and glycerin fatty acid ester monophosphoric acid ester salt.
  • salt form of the anionic surfactant examples include alkali metal salts such as sodium salts and potassium salts; alkaline earth metal salts such as magnesium salts; alkanolamine salts such as monoethanolamine salts and diethanolamine salts; ammonium salts and the like. It is done. Of these, alkali metal salts are preferred.
  • surfactants having high hard water resistance are preferable from the viewpoint of detergency, and those having low hard water resistance are preferable from the viewpoint of improving antibacterial power.
  • one type may be used alone, or two or more types may be used in combination.
  • the component (B) is composed of a polyoxyalkylene alkyl ether sulfate having a linear or branched alkyl group having 10 to 20 carbon atoms and a linear alkylbenzene sulfonate having an alkyl group having 8 to 18 carbon atoms. It is preferable to include at least one selected from the group consisting of: Further, from the viewpoint of detergency and enzyme stability, the component (B) preferably contains at least one or both of LAS and AES.
  • the LAS / AES ratio (mass ratio) of LAS and AES is preferably 0.1 to 2, and more preferably 0.5 to 1. If the LAS / AES ratio is not more than the upper limit, the enzyme stability is improved. If the LAS / AES ratio is at least the lower limit, the liquid stability will be improved.
  • the content of the component (B) in the liquid detergent composition (100% by mass) of the present invention is preferably 3 to 40% by mass, more preferably 5 to 30% by mass, further preferably 7 to 20% by mass, 10 to 20% by mass is particularly preferable. If content of (B) component exists in the said range, the outstanding recontamination prevention property and detergency will be easy to be obtained.
  • a part of the anionic surfactant in the component (B) is combined with calcium ions in tap water to form a salt, thereby increasing the hydrophobicity in the detergent liquid, and the highly hydrophobic component (C) And form a complex. Thereby, the adsorption amount to the clothing which has surfaces with high hydrophobicity, such as the surface of a synthetic fiber, increases, and antibacterial property (bacteriostatic activity) improves.
  • the (A) / (B) ratio (mass ratio) between the component (A) and the component (B) is preferably 0.1 to 5, more preferably 0.3 to 3, and particularly preferably 1 to 3. If (A) / (B) ratio is more than a lower limit, the liquid stability of a liquid cleaning composition will increase. If the ratio (A) / (B) is less than or equal to the upper limit, the amount of the component (B) that forms a composite with the component (C) is increased, and the garment having a surface having high hydrophobicity such as the surface of synthetic fiber is applied. Adsorption amount increases and antibacterial properties (bacteriostatic activity) are improved. Moreover, if (A) / (B) ratio is 1 or more, enzyme stability will improve.
  • the total amount of the active agent in the liquid detergent composition (100% by mass) of the present invention is preferably 25 to 80% by mass, and more preferably 30 to 60% by mass. If the total amount of the activator is at least the lower limit, the detergency of the liquid detergent is further improved, and the (C) component having high hydrophobicity is easily solubilized and the liquid stability is enhanced. If the total amount of activator is below an upper limit, the liquid stability of a liquid detergent composition will increase.
  • the total amount of an active agent means the total amount of (A) component, (B) component, and (F) component.
  • the component (C) is an antibacterial agent having a phenol structure.
  • the phenol structure means a structure in which one or more hydrogen atoms of the aromatic hydrocarbon nucleus are substituted with a hydroxy group.
  • Component (C) is a component that imparts antibacterial properties to textiles such as clothes after washing.
  • the antibacterial agent having a phenol structure can exhibit antibacterial properties without impairing the detergency due to the anionic surfactant even if it coexists with the anionic surfactant in the liquid detergent composition.
  • Component includes phenol derivatives or diphenyl compounds known as antibacterial agents. Specifically, 5-chloro-2- (2,4-dichlorophenoxy) phenol (common name: triclosan), 4,4′-dichloro-2-hydroxydiphenyl ether (common name: dichrosan), o-benzyl- Examples thereof include p-chlorophenol (chlorophen), isopropylmethylphenol, parachlorometaxylenol and the like. Of these, diphenyl compounds are preferred.
  • 5-chloro-2- (2,4-dichlorophenoxy) phenol (common name: triclosan), 4,4′-dichloro-2-hydroxydiphenyl ether (common name: Diclosan) and o-benzyl-p-chlorophenol (chlorophene) are preferred.
  • a 2-hydroxydiphenyl compound represented by the following formula (III) (hereinafter referred to as the compound (III) is used because it has a high adsorption amount on the hydrophobic fiber and has a large effect by applying the present invention. )) Is preferred.
  • X is an oxygen atom or an alkylene group having 1 to 4 carbon atoms
  • Y is a chlorine atom or a bromine atom
  • Z is SO 2 H, NO 2 , or a carbon atom having 1 to 4 carbon atoms.
  • An alkyl group, a, b and c are each independently 0 or an integer of 1 to 3, d is 0 or 1, m is 0 or 1, and n is 0 or 1.
  • -(Y) b means that b hydrogen atoms in the benzene ring are substituted with Y. The same applies to-(Y) c,-(Z) d,-(OH) m and-(OH) n.
  • X is an oxygen atom or a methylene group
  • Y is a chlorine atom or a bromine atom
  • m is 0, n is 0 or 1
  • a is 1, and b is 0.
  • the compound is 1 or 2
  • c is 0, 1 or 2
  • d is 0.
  • preferred compound (III) include, for example, monochlorohydroxydiphenyl ether (wherein X is an oxygen atom, a is 1, Y is a chlorine atom, one of b or c is 1 and the other is 0) , D is 0, m is 0, and n is 0), dichlorohydroxydiphenyl ether (X is an oxygen atom, a is 1, Y is a chlorine atom, and b is 1) , C is 1, d is 0, m is 0, and n is 0), trichlorohydroxydiphenyl ether (X is an oxygen atom, a is 1, Y is a chlorine atom) , B or c is 1 and the other is 2, d is 0, m is 0 and n is 0), benzylchlorophenol (X is a methylene group, a is 1) Y is a chlorine atom, b is In it, c is 1, d is 0, m is 0, compounds wherein n is 0
  • Particularly preferred compounds (III) are 5-chloro-2- (2,4-dichlorophenoxy) phenol (common name: triclosan), 4,4′-dichloro-2-hydroxydiphenyl ether (common name: dichrosan), o-Benzyl-p-chlorophenol (common name: chlorophene), and 4,4′-dichloro-2-hydroxydiphenyl ether (common name: dichrosan) is most preferred.
  • the component (C) one type may be used alone, or two or more types may be used in combination.
  • the ratio of the total amount of the compound (III) to the total amount (100% by mass) of the component (C) is preferably 60% by mass or more, more preferably 80% by mass or more, and further preferably 90% by mass or more.
  • the upper limit of the ratio of the total amount of the compound (III) is 100% by mass.
  • the content of the component (C) in the liquid detergent composition (100% by mass) of the present invention is preferably 0.01 to 3% by mass, more preferably 0.05 to 1% by mass, and 0.1 to 0%. More preferably, 5% by mass. If content of (C) component is more than a lower limit, the outstanding antimicrobial property will be easy to be obtained. If content of (C) component is below an upper limit, it will become easily a liquid detergent composition which has favorable storage stability.
  • the (B) / (C) ratio (mass ratio) between the component (B) and the component (C) is preferably 3 or more, more preferably 5 or more, and more than 10 Is more preferable.
  • the (B) / (C) ratio is preferably 300 or less, more preferably 200 or less, and even more preferably 100 or less, from the viewpoint of enhancing antibacterial properties.
  • the ratio (B) / (C) is preferably 3 to 300.
  • the premix may be formed by premixing the component (C) and the fragrance before blending them into the liquid detergent composition.
  • the highly hydrophobic component (C) can be more stably blended in the liquid detergent composition.
  • the mixing method may be a general method, and the mixing temperature is preferably 5 to 30 ° C.
  • the premix can be stored for a long period of time, but when stored at a low temperature, the component (C) may be precipitated.
  • the liquid detergent composition of the present invention has a component (D): a water-soluble solution having one or both of an alkylene terephthalate unit and an alkylene isophthalate unit, and one or both of an oxyalkylene unit and a polyoxyalkylene unit. It is preferable that a functional polymer is further contained.
  • Water-soluble polymer means that 10 g of polymer was added to 1000 g of water under the condition of 40 ° C. and stirred (200 rpm) for 12 hours with a stirrer (thickness 8 mm, length 50 mm, 1 liter beaker). Sometimes it completely dissolves.
  • alkylene terephthalate unit and the alkylene isophthalate unit are collectively referred to as a unit (d1).
  • the oxyalkylene unit and the polyoxyalkylene unit are collectively referred to as a unit (d2).
  • the alkylene terephthalate unit is a unit represented by the following formula (IV).
  • R 21 is a lower alkylene group.
  • the lower alkylene group for R 21 has 1 to 4 carbon atoms, preferably 2 to 4 carbon atoms.
  • alkylene terephthalate unit examples include, for example, ethylene terephthalate unit, n-propylene terephthalate unit, isopropylene terephthalate unit, n-butylene terephthalate unit, isobutylene terephthalate unit, sec-butylene terephthalate unit, tert-butylene terephthalate unit and the like. It is done. Of these, isopropylene terephthalate units are preferred.
  • the unit (d1) a single type of alkylene terephthalate unit may be used, or a plurality of types of alkylene terephthalate units may be used in combination.
  • the alkylene isophthalate unit is a unit represented by the following formula (V).
  • R 22 is a lower alkylene group.
  • the lower alkylene group for R 22 has 1 to 4 carbon atoms, preferably 2 to 4 carbon atoms.
  • alkylene isophthalate unit examples include, for example, an ethylene isophthalate unit, a propylene isophthalate unit, an n-butylene isophthalate unit, a sec-butylene isophthalate unit, and a tert-butylene isophthalate unit. Of these, propylene isophthalate units are preferred.
  • the unit (d1) a single type of alkylene isophthalate unit may be used, or a plurality of types of alkylene isophthalate units may be used in combination.
  • the unit (d1) may be only an alkylene terephthalate unit, only an alkylene isophthalate unit, or both an alkylene terephthalate unit and an alkylene isophthalate unit.
  • the unit (d2) is a unit represented by the following formula (VI). -(R 23 O) e- (VI) R 23 is a lower alkylene group, and e is an integer of 1 to 100.
  • the lower alkylene group for R 23 has 1 to 4 carbon atoms, preferably 2 to 4 carbon atoms.
  • e when e is 1, it is an oxyalkylene unit, and when e is 2 or more, it is a polyoxyalkylene unit.
  • e is preferably an integer of 1 to 80, and more preferably an integer of 1 to 50.
  • the unit (d2) include, for example, oxyethylene units and polyoxyethylene units; oxypropylene units and polyoxypropylene units; polyoxyethylene polyoxypropylene units. Of these, oxyethylene units and polyoxyethylene units are preferred.
  • the unit (d2) may be an oxyalkylene unit only, a polyoxyalkylene unit only, or both an oxyalkylene unit and a polyoxyalkylene unit.
  • the component (D) is preferably a polymer compound in which the unit (d1) and the unit (d2) are polymerized randomly or in blocks, and more preferably a polymer compound polymerized in blocks.
  • the component may contain units other than unit (d1) and unit (d2). Examples of other units include units derived from a polymerization initiator, a polymerization terminator and the like, and other copolymerizable units.
  • the total ratio of the unit (d1) and the unit (d2) to the total units of the component (D) is preferably 80 mol% or more, more preferably 90 mol% or more. .
  • component (D) a compound represented by the following formula (VII) and a compound represented by the following formula (VIII) are preferable.
  • a 1 and B 1 are each independently a hydrogen atom or a methyl group
  • R 11 and R 12 are each independently an alkylene group having 2 to 4 carbon atoms.
  • f is the average number of repeating alkylene terephthalate units represented by —CO— (C 6 H 4 ) —COO—R 12 O—, and is 0 to 10.
  • g is the average number of repetitions of R 11 O, and is 1 to 100.
  • a 2 and B 2 are each independently a hydrogen atom or a methyl group
  • R 13 and R 14 are each independently an alkylene group having 2 to 4 carbon atoms.
  • h is an average repeating number of alkylene isophthalate units represented by —CO— (C 6 H 4 ) —COO—R 14 O—, and is 0 to 10.
  • i is the average number of repetitions of R 13 O, and is 1 to 100.
  • a 1 and B 1 in formula (VII) are preferably both methyl groups.
  • R 11 and R 12 are preferably alkylene groups having 2 to 3 carbon atoms.
  • f is preferably 0.5 to 5, and more preferably 0.5 to 2.5.
  • g is preferably 1 to 80, more preferably 1 to 50, still more preferably 10 to 50, and particularly preferably 20 to 30.
  • the ratio of f and g in formula (VII) is preferably 1: 5 to 1:20, more preferably 1: 8 to 1:18. If the ratio of f and g is in the above range, the soil release performance is sufficiently exhibited and the solubility in water is improved.
  • Both A 2 and B 2 in formula (VIII) are preferably methyl groups.
  • R 13 and R 14 are preferably alkylene groups having 2 to 3 carbon atoms.
  • h is preferably 0.5 to 5, and more preferably 0.5 to 2.5.
  • i is preferably 1 to 80, more preferably 1 to 50, further preferably 10 to 50, and particularly preferably 20 to 30.
  • the ratio of h to i in formula (VIII) is preferably 1: 5 to 1:20, more preferably 1: 8 to 1:18, for the same reason as the ratio of f to g in formula (VII). .
  • the weight average molecular weight of the component (D) is preferably 500 to 10,000, more preferably 800 to 9000, and still more preferably 1000 to 8000. If the weight average molecular weight is within the above range, the solubility and dispersibility in water will be improved, and the effect of improving the water absorption of hydrophobic fibers (especially polyester) will be sufficiently exhibited, and the liquid appearance of the liquid detergent composition Will be better.
  • the weight average molecular weight in this invention says the value which converted the value measured by GPC (gel permeation chromatography) using THF (tetrahydrofuran) as a solvent using PEG (polyethylene glycol) for the calibration curve.
  • (D) As a component a commercial item can be used.
  • the trade name “TexCare SRN-100” (manufactured by Clariant, weight average molecular weight: 2000 to 3000), the trade name “TexCare SRN-300” (manufactured by Clariant, weight average molecular weight: 7000), and the trade name “Repel-O”.
  • -Tex Crystal (manufactured by Rhodia)
  • trade name Repel-O-Tex QC "(manufactured by Rhodia) and the like.
  • TexCare SRN-170 (Clariant), which is a 70% by mass aqueous solution of TexCare SRN-100 or TexCare SRN-100, is highly soluble in water and has little deterioration in cleaning performance after storage. Manufactured by the company), and TexCare SRN-170 is particularly preferable.
  • Component (D) is, for example, Journal of Polymer Science, Volume 3, pages 609 to 630 (1948), Journal of Polymer Science, Volume 8, pages 1 to 22 (1951), JP-A-61-218699. It is also possible to synthesize by the method described in the publication number. As the component (D), one type may be used alone, or two or more types may be used in combination.
  • the content of the component (D) in the liquid cleaning composition (100% by mass) of the present invention is preferably 0.1 to 5% by mass, and more preferably 0.3 to 3% by mass. If content of (D) component is more than a lower limit, the stain
  • the liquid detergent composition of the present invention preferably further contains (E) component: a polyalkyleneamine alkylene oxide copolymer having an alkyleneamine structural unit containing a polyalkyleneoxide chain.
  • component (D) and the component (E) particularly increases the antibacterial effect on the cotton and synthetic fiber blended garment and the effect of suppressing the generation of room-dried odor.
  • the component (E) is a polyalkyleneamine alkylene oxide copolymer having an alkyleneamine structural unit containing a polyalkyleneoxide chain, that is, an alkyleneoxide adduct of polyalkyleneimine.
  • the polyalkyleneimine is represented by the following formula (IX).
  • NH 2 —R 31 — (NA 3 —R 32 ) j NH 2 (IX)
  • R 31 and R 32 are each independently an alkylene group having 2 to 6 carbon atoms
  • a 3 is a hydrogen atom or another polyamine chain formed by branching.
  • j is the average number of repetitions of NA 3 -R 32 , and is a number of 1 or more. It is assumed that not all of A 3 are hydrogen atoms.
  • the alkylene group for R 31 and R 32 may be linear or branched.
  • the number of carbon atoms of the alkylene group of R 31 and R 32 is preferably 2 to 4, and 2 is particularly preferable.
  • the polyalkyleneimine can be obtained by polymerizing one or more of alkyleneimines having 2 to 6 carbon atoms by a conventional method.
  • alkyleneimine having 2 to 6 carbon atoms include ethyleneimine, propyleneimine, 1,2-butyleneimine, 2,3-butyleneimine, 1,1-dimethylethyleneimine and the like.
  • polyethyleneimine (PEI) and polypropyleneimine are preferable, and PEI is more preferable.
  • PEI is obtained by polymerizing ethyleneimine and has a branched chain structure containing primary, secondary and tertiary amine nitrogen atoms in the structure.
  • the weight average molecular weight of the polyalkyleneimine is preferably 200 to 2000, more preferably 300 to 1500, still more preferably 400 to 1000, and particularly preferably 500 to 800.
  • the number of active hydrogens possessed by one polyalkyleneimine molecule is preferably 5 to 30, more preferably 7 to 25, and even more preferably 10 to 20.
  • alkylene oxide added to the polyalkyleneimine examples include alkylene oxides having 2 to 4 carbon atoms. Of these, ethylene oxide and propylene oxide are preferable, and ethylene oxide is more preferable.
  • a method for adding an alkylene oxide to a polyalkyleneimine for example, in the presence of a basic catalyst such as sodium hydroxide, potassium hydroxide, sodium methylate, etc., 100 to 180 ° C. with respect to the starting polyalkyleneimine. And a method of adding an alkylene oxide such as ethylene oxide.
  • component (E) examples include polyalkyleneimine ethylene oxide adducts, polyalkyleneimine propylene oxide adducts, polyalkyleneimine ethylene oxide-propylene oxide adducts, and the like.
  • the ethylene oxide-propylene oxide adduct of polyalkyleneimine is obtained by adding ethylene oxide and propylene oxide to polyalkyleneimine, and the order of addition or form of addition of ethylene oxide and propylene oxide to polyalkyleneimine (block or random) Is optional.
  • an ethylene oxide adduct of polyalkyleneimine and an ethylene oxide-propylene oxide adduct of polyalkyleneimine are preferable, and an ethylene oxide adduct of polyalkyleneimine is more preferable.
  • the average number of alkylene oxides added per active hydrogen atom of the starting polyalkyleneimine is preferably 5 to 40, and more preferably 10 to 30. That is, the average number of added moles of alkylene oxide per mole of active hydrogen contained in the starting polyalkylenimine is preferably 5 to 40 moles, and more preferably 10 to 30 moles.
  • the weight average molecular weight of the component (E) is preferably 1000 to 80000, more preferably 2000 to 50000, still more preferably 5000 to 30000, and particularly preferably 10,000 to 20000.
  • component (E) a synthetic product or a commercially available product may be used.
  • a commercial item the brand name "Sokalan HP20" by BASF Corporation etc. are mentioned, for example.
  • component (E) one type may be used alone, or two or more types may be used in combination.
  • the content of the component (E) in the liquid detergent composition (100% by mass) of the present invention is preferably 0.1 to 5% by mass, and more preferably 0.3 to 3% by mass. If the content of the component (E) is equal to or higher than the lower limit, the component (E) is adsorbed to the cotton fiber, so that the dirt and the amount of bacteria in the washing solution to be adhered can be suppressed, and the number of initial bacteria is further reduced. Can do. Thereby, since the increase amount of the number of microbes during room drying can be reduced more, it becomes easy to obtain the suppression effect of room drying odor generation. If content of (E) component is below an upper limit, the stability of the external appearance of a liquid detergent composition will become more favorable.
  • the liquid detergent composition of the present invention preferably further contains (F) component: a cationic surfactant.
  • F a cationic surfactant.
  • component (F) component for example, a quaternary ammonium salt can be used.
  • a quaternary ammonium salt the conventionally well-known thing normally used for the detergent for clothes is mentioned, for example.
  • preferred quaternary ammonium salts include the compound (f1), the compound (f2), and the compound (f3) described later because a high antibacterial effect or bactericidal effect is easily obtained.
  • R 41 to R 44 are each independently an alkyl group having 1 to 3 carbon atoms or a hydroxyalkyl group having 1 to 3 carbon atoms; Is a linear or branched alkyl group having 8 to 22 carbon atoms or a linear or branched alkenyl group having 8 to 22 carbon atoms.
  • Q A - is a halogen ion or an alkyl sulfate ion.
  • the compound (f1) the following compound (f1-1) and compound (f1-2) are preferable.
  • R 41 to R 43 are each independently an alkyl group having 1 to 3 carbon atoms or a hydroxyalkyl group having 1 to 3 carbon atoms
  • R 44 is an alkyl group having 8 to A compound having a linear or branched alkyl group having 22 or a linear or branched alkenyl group having 8 to 22 carbon atoms
  • R 41 to R 43 in the compound (f1-1) are each preferably an alkyl group having 1 to 3 carbon atoms, and more preferably a methyl group. In particular, it is particularly preferable that all of R 41 to R 43 are methyl groups.
  • the carbon number in the alkyl group or alkenyl group of R 44 is 8 to 22, preferably 10 to 22, and more preferably 16 to 18.
  • R 44 is preferably a linear or branched alkyl group, and more preferably a linear alkyl group.
  • R 41 and R 42 are each independently a linear or branched alkyl group having 8 to 22 carbon atoms, or a linear or branched chain group having 8 to 22 carbon atoms.
  • R 43 and R 44 are each independently an alkyl group having 1 to 3 carbon atoms or a hydroxyalkyl group having 1 to 3 carbon atoms.
  • the number of carbon atoms in the alkyl group or alkenyl group of R 41 and R 42 of the compound (f1-2) is independently 8 to 22, preferably 8 to 12, and more preferably 8 to 10.
  • R 41 and R 42 are each preferably a linear or branched alkyl group, and more preferably a linear alkyl group.
  • both R 41 and R 42 are linear alkyl groups.
  • R 43 and R 44 are each preferably an alkyl group having 1 to 3 carbon atoms, and more preferably a methyl group. Among these, it is particularly preferable that R 43 and R 44 are both methyl groups.
  • examples of Q A constituting the halogen ion include a fluorine atom, a chlorine atom, a bromine atom, and an iodine atom, and a chlorine atom is preferable.
  • Q A constituting the alkyl sulfate ion is preferably one having an alkyl group having 1 to 3 carbon atoms, such as methyl sulfate.
  • compound (f1) examples include alkyl chloride (C12-16) trimethylammonium, didecyldimethylammonium chloride and the like.
  • R 45 is a linear or branched alkyl group having 8 to 22 carbon atoms or a linear or branched alkenyl group having 8 to 22 carbon atoms.
  • R 46 is a methyl group or a tolyl group.
  • p and q represent the average number of repeating ethyleneoxy groups, each independently a number of 0 or more, and p + q is 10 or more.
  • Q B - is a halogen ion or an alkyl sulfate ion.
  • the number of carbon atoms in the alkyl group or alkenyl group of R 45 in the formula (f2) is 8 to 22, and preferably 10 to 18.
  • R 45 is preferably a linear or branched alkyl group, and more preferably a linear alkyl group.
  • R 46 in formula (f2) is a methyl group or a tolyl group.
  • p + q is 10 or more, preferably 10-50. When p + q is less than 10, the effect of dispersing dirt adhering to the article to be washed is small, and the effect of removing dirt from the article to be washed may be difficult to obtain.
  • Q B - is, Q A in the formula (f1) - include the same one.
  • R 45 is a linear or branched alkyl group having 10 to 18 carbon atoms, or a linear or branched alkenyl group having 10 to 18 carbon atoms
  • R 46 is And a compound in which it is a methyl group or a tolyl group, p + q is 10 or more, and Q B ⁇ is a halogen ion or an alkyl sulfate ion.
  • the compound (f3) is a compound represented by the following formula (f3).
  • R 47 and R 48 are each independently an alkyl group having 1 to 3 carbon atoms or a hydroxyalkyl group having 1 to 3 carbon atoms
  • R 49 is an alkyl group having 8 to 22 carbon atoms.
  • R 50 is an alkylene group having 1 to 3 carbon atoms.
  • Q C - is a halogen ion or an alkyl sulfate ion.
  • R 47 and R 48 in formula (f3) are each preferably an alkyl group having 1 to 3 carbon atoms, and more preferably a methyl group. Among these, it is particularly preferable that both R 47 and R 48 are methyl groups.
  • the number of carbon atoms in the alkyl group or alkenyl group of R 49 is from 8 to 22, preferably from 10 to 18, and more preferably from 12 to 14.
  • R 49 is preferably a linear or branched alkyl group, and more preferably a linear alkyl group.
  • R 50 is an alkylene group having 1 to 3 carbon atoms, preferably a methylene group.
  • Q C - is, Q A in the formula (f1) - like can be mentioned and, among them halogen ion are preferred.
  • compound (f3) examples include coconut alkyldimethylbenzylammonium chloride.
  • component (F) one type may be used alone, or two or more types may be used in combination.
  • the content of the component (F) in the liquid detergent composition (100% by mass) of the present invention is preferably 0.3 to 5% by mass, more preferably 1 to 3% by mass, and 1.5 to 2% by mass. Is more preferable. If content of (F) component is more than the said lower limit, the effect which suppresses generation
  • the (C) / (F) ratio (mass ratio) between the component (C) and the component (F) is preferably 0.002 to 5, more preferably 0.05 to 1, and 0.1 to 0.75. Further preferred. If (C) / (F) ratio is more than the said lower limit, the effect which suppresses generation
  • the liquid detergent composition of the present invention preferably contains water from the viewpoint of ease of handling during production, solubility in water during use, and the like.
  • the liquid detergent composition of the present invention may contain optional components commonly used in liquid detergent compositions.
  • Optional components include, for example, enzymes (proteases, etc.), solvents, hydrotropes, chelating agents, bactericides, antiseptics, antifungal agents, dyes, antioxidants, ultraviolet absorbers, fragrances, pH adjusters, alkaline agents Etc.
  • the liquid detergent composition of the present invention may contain a solvent.
  • the solvent may be any solvent conventionally used in liquid detergent compositions for clothing and the like, and examples thereof include monohydric alcohols having 2 to 4 carbon atoms, polyhydric alcohols having 2 to 4 carbon atoms, and glycol ethers. Examples thereof include system solvents and alcohols having a methoxy group.
  • Examples of the monohydric alcohol having 2 to 4 carbon atoms include ethanol, 1-propanol, 2-propanol, 1-butanol and the like.
  • Examples of the polyhydric alcohol having 2 to 4 carbon atoms include ethylene glycol, propylene glycol, butylene glycol, glycerin and the like.
  • Examples of the glycol ether solvent include ethylene glycol monobutyl ether, ethylene glycol monohexyl ether, ethylene glycol monophenyl ether, propylene glycol monophenyl ether, diethylene glycol monomethyl ether, diethylene glycol monobutyl ether (butyl carbitol) and the like.
  • Examples of the alcohol having a methoxy group include 3-methoxybutanol, 3-methoxy-3-methylbutanol, 3-methoxy-3-ethylbutanol, 3-methoxy-3-propylbutanol, 3-methoxy- 2-methylbutanol, 3-methoxy-2-ethylbutanol, 3-methoxy-2-propylbutanol, 3-methoxy-1-methylbutanol, 3-methoxy-1-ethylbutanol, 3-methoxy- 1-propylbutanol, 3-methoxybutyl acetate, 3-methoxy-3-methylbutyl acetate, 3-methoxy-3-ethylbutyl acetate, 3-methoxy-3-propylbutyl acetate, 3-methoxy-2-methylbutyl Acetate, 3-methoxy-2-ethylbutyl acetate, 3-methoxy-2-propi Butyl acetate, 3-methoxy-1-methyl
  • the liquid detergent composition of the present invention may contain a fragrance precursor.
  • the perfume precursor itself is an odorless or nearly odorless component, but means a component that generates a scent by an oxidation reaction or the like in a liquid detergent composition or on a fiber.
  • the strength of the fragrance felt from the synthetic clothing and the like after washing and drying can be further increased.
  • the actual feeling effect of the soft touch of synthetic fiber clothing etc. after performing a washing process can be further enhanced, and the comfort is easily improved.
  • the fragrance derived from the fragrance precursor is gradually released, the actual feeling effect can be further sustained.
  • the perfume precursor is not particularly limited as long as it has the above-mentioned effect, and those generally used in liquid detergent compositions can be used. Examples of such a fragrance precursor include a fragrance precursor containing sulfur (a sulfur-containing fragrance precursor).
  • the pH of the liquid detergent composition of the present invention at 25 ° C. is preferably 5-9, more preferably 7-9. If the pH is within the above range, good detergency is easily maintained.
  • the pH of the liquid detergent composition of the present invention at 25 ° C. is measured by adjusting the sample to 25 ° C. and using a pH meter (for example, using the product name “HM-30G” manufactured by Toa DKK Corporation). Indicates the value to be processed.
  • liquid detergent composition of the present invention by combining the components (A) to (C), a high detergency, excellent liquid stability, and a high recontamination preventing effect can be exhibited.
  • the antibacterial property which was excellent in the to-be-washed object can be provided, and room dry odor generation can fully be suppressed.
  • Such an effect is obtained because the anionic surfactant of the component (B) and the compound having a phenol structure of the component (C) form a complex to improve the adsorption to the fiber, and (C) This is because the antibacterial power of the component is sufficiently exhibited.
  • antibacterial property can further be improved by using together (D) component, (E) component, and (F) component.
  • the liquid detergent composition of the present invention contains the components (A) to (C), and the component (B) is a polyoxyalkylene alkyl having a linear or branched alkyl group having 10 to 20 carbon atoms.
  • the liquid detergent composition of the present invention contains the components (A) to (C), and the component (C) contains at least one selected from the group consisting of dichlorohydroxydiphenyl ether, trichlorohydroxydiphenyl ether, and benzylchlorophenol. It is preferable.
  • An autoclave was charged with 2.2 g of calcined alumina / magnesium hydroxide (unmodified) catalyst, 2.9 mL of 0.5N potassium hydroxide ethanol solution, 280 g of lauric acid methyl ester, and 70 g of myristic acid methyl ester in a 4 L autoclave.
  • the catalyst was reformed inside.
  • 1052 g of ethylene oxide was introduced and reacted while stirring while maintaining the temperature at 180 ° C. and the pressure at 0.3 MPa.
  • the resulting reaction solution was cooled to 80 ° C., 159 g of water, 5 g of activated clay and 5 g of diatomaceous earth as filter aids were added and mixed, and then the catalyst was filtered off to obtain A-1.
  • A-1 ′ MEE.
  • a compound obtained by adding 15 mol of ethylene oxide to coconut fatty acid methyl (mixture of methyl laurate / methyl myristate 8/2 by mass ratio) using an alkoxylation catalyst.
  • R 1 is an alkyl group having 11 carbon atoms and an alkyl group having 13 carbon atoms
  • R 2 methyl group
  • IPA isopropyl alcohol
  • primary reagent manufactured by Kanto Chemical Co., Ltd.
  • calcium acetate monohydrate special grade reagent, manufactured by Kanto Chemical Co., Ltd.
  • disper stirring blade To obtain a dispersion (dispersing step). While stirring the dispersion at 3000 rpm, 75 g of sulfuric acid (special grade reagent, manufactured by Kanto Chemical Co., Inc.) was added and mixed with a dropping funnel over 60 minutes (mixing step).
  • A-2 LMAO. Polyoxyethylene alkyl ether, a compound obtained by adding 15 moles of ethylene oxide to a natural alcohol (primary alcohol) having 12 and 14 carbon atoms.
  • ⁇ LMAO synthesis method> 861.2 g of CO-1214 (trade name, natural alcohols having 12 and 14 carbon atoms) manufactured by Procter & Gamble Co., Ltd. and 2.0 g of 30% by mass NaOH aqueous solution were charged into a pressure-resistant reaction vessel, and the reaction vessel The inside was replaced with nitrogen. Next, after dehydrating for 30 minutes at a temperature of 100 ° C. and a pressure of 2.0 kPa or less, the temperature was raised to 160 ° C.
  • ethylene oxide gaseous
  • ethylene oxide was added through the blowing tube while adjusting the addition rate so that the reaction temperature did not exceed 180 ° C.
  • aging was performed at a temperature of 180 ° C. and a pressure of 0.3 MPa or less for 30 minutes, and then unreacted ethylene oxide was distilled off at a temperature of 180 ° C. and a pressure of 6.0 kPa or less for 10 minutes.
  • 70% by mass p-toluenesulfonic acid was added to neutralize so that the pH of the 1% by mass aqueous solution of the reaction product was about 7, thereby obtaining LMAO.
  • A-3 EOPO nonion.
  • R 3 is an alkyl group having 12 carbon atoms and an alkyl group having 14 carbon atoms
  • ⁇ Method of synthesizing EOPO nonion> 224.4 g of “CO-1270” manufactured by P & G Co. and 2.0 g of 30 mass% NaOH aqueous solution were charged into a pressure-resistant reaction vessel, and the inside of the reaction vessel was purged with nitrogen.
  • ((B) component) B-1 Sodium polyoxyethylene alkyl ether sulfate (AES).
  • a compound represented by the following formula (b1-1), wherein R 51 is a linear alkyl group having 12 to 14 carbon atoms, k 1.0, and M is sodium.
  • EO is an ethyleneoxy group, and k is the average number of repetitions of EO.
  • B-2 Sodium linear alkylbenzene sulfonate (LAS), manufactured by Lion Corporation, trade name “Lypon LH-200”.
  • B-3 ⁇ -sulfo fatty acid methyl ester salt (MES), trade name “MIZULAN FL-80”, manufactured by Lion Eco Chemicals Co., Ltd.
  • B-4 Soap, trade name “Zushi fatty acid”, manufactured by NOF Corporation.
  • ((C) component) C-1 4,4′-dichloro-2-hydroxydiphenyl ether, trade name “Tinosan HP100”, manufactured by BASF Corporation.
  • C-2 5-chloro-2- (2,4-dichlorophenoxy) phenol, trade name “Triclosan”, manufactured by Wako Pure Chemical Industries, Ltd.
  • C-3 o-benzyl-p-chlorophenol, trade name “Chlorophen”, manufactured by Clariant Japan KK
  • ((D) component) D-1 TexCare SRN-170C (trade name, manufactured by Clariant Japan, weight average molecular weight: 2000 to 3000, pH (5 mass% aqueous solution at 20 ° C.): 4, viscosity (20 ° C.): 300 mPa ⁇ s).
  • TexCare SRN-170C is a 70% by mass aqueous solution of trade name: TexCare SRN-100 (manufactured by Clariant Japan, weight average molecular weight: 2000 to 3000).
  • ((E) component) E-1 An ethylene oxide adduct of polyethyleneimine (trade name “Sokalan HP20” manufactured by BASF). The average number of moles of ethylene oxide added per mole of active hydrogen possessed by polyethyleneimine is 20 moles.
  • F-1 Dodecyltrimethylammonium chloride, trade name “Lipoguard 12-37W”, manufactured by Lion Specialty Chemicals Co., Ltd. (in the formula (f1), R 41 to R 43 are methyl groups, and R 44 has 12 carbon atoms. A compound which is a linear alkyl group).
  • F-2 Didecyldimethylammonium chloride, trade name “ARCARD 210”, manufactured by Lion Specialty Chemicals Co., Ltd.
  • F-3 Cocoyldimethylbenzylammonium chloride, trade name “Lipocard CB-50”, manufactured by Lion Specialty Chemicals Co., Ltd.
  • Water Purified water
  • Ethanol Water miscible organic solvent, trade name “specific alcohol 95 degree synthesis”, manufactured by Nippon Alcohol Sales Co.
  • BC Butyl carbitol (water-miscible organic solvent), trade name “butyl carbitol”, manufactured by Tokyo Chemical Industry Co., Ltd.
  • MMB 3-methoxy-3-methylbutanol (water-miscible organic solvent), trade name “Solfit”, manufactured by Kuraray Co., Ltd.
  • Sodium benzoate manufactured by Toa Gosei Co., Ltd.
  • Protease Coronase, trade name “Coronase 48L”, manufactured by Novozymes.
  • MEA monoethanolamine (alkali agent), trade name “monoethanolamine”, manufactured by Nippon Shokubai Co., Ltd.
  • BHT Dibutylhydroxytoluene (antioxidant), trade name “SUMILZER BHT-R”, manufactured by Sumitomo Chemical Co., Ltd.
  • Sodium lactate manufactured by Kanto Chemical Co., Ltd., trade name “sodium lactate”.
  • Perfume Perfume composition A described in Tables 11 to 18 of JP-A-2002-146399.
  • Examples 1 to 28, Comparative Examples 1 to 3 Each component was mixed according to the composition shown in Tables 1 to 4 to obtain a liquid detergent composition.
  • Tables 1 to 4 show the composition (formulation component, content (%)) of the liquid detergent composition of each example.
  • a blank in Tables 1 to 4 means that the blending component is not blended.
  • Content of a compounding component shows a pure conversion amount.
  • “Balance” indicating the content of purified water means the balance added so that the total amount (%) of all the components included in the liquid detergent composition is 100%. Note that only in Example 6, a premix was prepared in which the fragrance and C-1 were mixed in advance so as to achieve the mass ratio described in the Examples, and was added to the liquid detergent composition.
  • component (C) was mixed with other components without forming a premix with the fragrance.
  • the compounding quantity in an Example is described as an active ingredient amount.
  • the liquid detergent composition (manufactured immediately after production) immediately after production in each example was used.
  • EMPA117 EMPA Testmateliaien, Polyester / cotton, 65/35, soiled with blood / milk / ink) cut into 5 cm ⁇ 5 cm square was used.
  • a Terg-O-meter (manufactured by UNITED STATES TESTING) was used as a cleaning tester.
  • As a cleaning solution a solution prepared by adding 300 ⁇ L of a liquid cleaning composition to 900 mL of water and stirring for 30 seconds was used.
  • the cleaning tester was charged with 900 mL of cleaning liquid, 10 soiled cloths, and a cleaning knitted cloth, and washed at 120 rpm and 15 ° C. for 10 minutes in accordance with the bath ratio of 20 times. Then, it was transferred to a two-tank washing machine (product name: CW-C30A1-H1 manufactured by Mitsubishi Electric Corporation), dehydrated for 1 minute, rinsed in 30 L of tap water (15 ° C., 4 ° DH) for 3 minutes, and air-dried.
  • CW-C30A1-H1 manufactured by Mitsubishi Electric Corporation
  • the color difference meter (Nippon Denshoku Co., Ltd.) reflects the reflectance of unstained cloth (here, unstained cloth refers to a reference white cloth that is not soiled), unwashed EMPA117, and washed EMPA117.
  • the evaluation criteria for the cleaning power were ⁇ (passed) when the cleaning rate (%) was 55% or more, and ⁇ (failed) when the cleaning rate was less than 55%.
  • a solution obtained by diluting 1 g of the liquid detergent composition obtained in each example 25 times with calcium chloride (calcium chloride (special grade), manufactured by Kanto Chemical Co., Inc.) 3 ° DH hard water was used as a sample solution.
  • 5 g of the protease substrate was added to 1 g of the sample solution, and the mixture was stirred for 10 seconds with a vortex mixer, and then allowed to stand at 37 ° C. for 30 minutes to proceed the enzyme reaction. Thereafter, 5 g of a 0.44M aqueous solution of TCA (trichloroacetic acid (special grade), manufactured by Kanto Chemical Co., Inc.), an enzyme reaction terminator, was added to this solution and stirred for 10 seconds with a vortex mixer.
  • TCA trichloroacetic acid
  • TCA as an enzyme reaction stopper was separately added to 1 g of each sample solution, stirred for 10 seconds with a vortex mixer, then 5 g of protease substrate was added, and 10 times with a vortex mixer. Stir for 2 seconds and remove with a 0.45 ⁇ m filter to collect the filtrate. Thereafter, the absorbance (absorbance ⁇ ) at a wavelength of 275 nm of the filtrate was measured using UV-160.
  • protease activity remaining rate (%) was determined by the following formula.
  • the absorbance value at 275 nm of each sample assigned to the following formula was used by dividing the absorbance value at 600 nm measured at the same time in order to exclude scattered light such as bubbles from the absorbance.
  • Protease activity remaining rate (absorbance of 35 ° C. stored product ⁇ absorbance ⁇ of 35 ° C.
  • -Wet artificial contamination cloth Contamination cloth manufactured by Japan Association for Laundry Science (28.3% oleic acid, 15.6% triolein, 12.2% cholesterol oleate, 2.5% liquid paraffin, 2.5% squalene, 20 sheets of soil with a composition of 1.6% cholesterol, 7.0% gelatin, 29.8% mud, and 0.5% carbon mass (mass ratio).
  • -Skin shirt A skin shirt (LL size, manufactured by DVD) cut into pieces (about 3 cm x 3 cm). In a Terg-o-meter (manufactured by UNITED STATES TESTING), 900 mL of 3 ° DH hard water at 25 ° C.
  • ⁇ : ⁇ Z is 7 or more and less than 9.
  • X: ⁇ Z is 9 or more.
  • Criteria for PE cloth A: ⁇ Z is less than 3.
  • ⁇ : ⁇ Z is 3 or more and less than 4.
  • ⁇ : ⁇ Z is 4 or more and less than 5.
  • X: ⁇ Z is 5 or more.
  • washing-out physiological saline means that 1,000 mL of purified water and 8.5 g of sodium chloride are sufficiently dissolved in a flask, and polyoxyethylene sorbitan monooleate (Kanto Chemical Co., Ltd.) as a nonionic surfactant. 2 g of a trade name “Polysorbate 80, Tween 80”) manufactured by Co., Ltd.
  • Activity value (B) was calculated. From the calculated antibacterial activity value (A) and antibacterial activity value (B), the difference between the antibacterial activity values ⁇ antibacterial activity value (A)-antibacterial activity value (B) ⁇ is obtained, and the antibacterial properties are evaluated according to the following evaluation criteria. went. ⁇ and X were rejected. Evaluation criteria A: Difference in antibacterial activity value was 2.5 or more. A: The difference in antibacterial activity value was 2.0 or more and less than 2.5. ⁇ : The difference in antibacterial activity value was 1.0 or more and less than 2.0. X: The difference in antibacterial activity value was less than 1.0.
  • washing treatment (JW-Z23A type, made by Haier Co., Ltd.) using a blended T-shirt (60% cotton, 40% polyester) with a commercially available detergent top (manufactured by Lion Corporation) and a detergent usage of 25g / 30L of tap water , Water temperature 20 ° C., 10 minutes).
  • 10 males in their 20s to 40s wear a blended T-shirt for 12 hours, and then wash them in the normal course of a washing machine (JW-Z23A, manufactured by Haier) using the liquid detergent composition of each example.
  • the treatment water temperature of about 20 ° C. and hardness of about 3 ° DH was poured into the water, bath ratio 20 times).
  • the washing treatment was performed by setting the amount of the liquid detergent composition to the washing machine as 10 mL / 30 L of tap water.
  • a new 100% cotton skin shirt (manufactured by BVD) was washed 5 times with a fully automatic washing machine (NA-F70SD1 manufactured by Panasonic Corporation) with a water temperature of about 20 ° C and a hardness of about 3 ° DH. What was injected with tap water was used as clothing for bath ratio matching.
  • the blended T-shirt was dried in a room at room temperature (about 23 ° C.) and a relative humidity of 90% RH and dried (room dried) for 5 hours.

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Abstract

The purpose of the present invention is to provide a liquid cleaning agent composition capable of exhibiting high cleaning ability, excellent liquid stability, and high effectiveness at preventing resoiling, as well as being capable of imparting excellent antimicrobial properties to a cleaning object and having excellent indoor drying odor suppressing effects. A liquid cleaning agent composition containing as component (A) a nonionic surfactant including at least one species selected from a specific group of compounds, as component (B) at least one species selected from the group consisting of an anionic surfactant and a salt of an anionic surfactant, and as component (C) an antimicrobial agent having a phenol structure.

Description

液体洗浄剤組成物Liquid detergent composition
　本発明は、液体洗浄剤組成物に関する。
　本願は、２０１５年９月２４日に、日本に出願された特願２０１５－１８６８９２号に基づき優先権を主張し、その内容をここに援用する。 The present invention relates to a liquid detergent composition.
This application claims priority based on Japanese Patent Application No. 2015-186892 filed in Japan on September 24, 2015, the contents of which are incorporated herein by reference.
　例えば家庭における衣料用洗剤として、液体洗浄剤組成物が多く用いられている。近年では洗濯機の大型化に伴ってつめこみ洗いの頻度が高くなっていることから、液体洗浄剤組成物には高い洗浄力が求められる。また、洗浄剤を用いて衣類等の繊維製品の洗濯を行う際には、再汚染（つまり被洗物の繊維から離脱して洗濯液に分散した汚れの一部が、再び繊維に付着する現象）を抑制することも重要である。また、液体洗浄剤組成物は優れた液安定性を有していることも必要である。 For example, liquid detergent compositions are often used as household laundry detergents. In recent years, the frequency of picking and washing is increased with the increase in the size of a washing machine, so that a high cleaning power is required for the liquid detergent composition. In addition, when washing textile products such as clothing using a cleaning agent, re-contamination (that is, a phenomenon in which some of the dirt that has separated from the fibers of the item to be washed and dispersed in the washing liquid adheres to the fibers again) ) Is also important. The liquid detergent composition must also have excellent liquid stability.
　ところで、液体洗浄剤組成物としては、衛生意識の高まりから、カチオン界面活性剤等の抗菌剤を配合したものが提案されている（例えば、特許文献１）。しかし、カチオン界面活性剤に、洗浄効果を高めるために洗浄成分としてアニオン界面活性剤を組み合わせると、洗浄中に再汚染を生じやすくなり、洗浄効果が発揮されにくくなる。また、近年では衣類製品の多様化により綿以外の化繊を含む衣類が主流となっているが、カチオン界面活性剤は化繊への吸着が不十分なために、化繊を含む衣類に対しては抗菌性が発揮されにくい。抗菌性が不十分になると、特に衣料等の部屋干しの際に微生物が増殖し、衣料等から発生する不快な臭気が発生する。
　そこで、芳香環を有する抗菌剤を配合した液体洗浄剤組成物も提案されている（例えば、特許文献２～４）。 By the way, as liquid cleaning composition, what mix | blended antibacterial agents, such as a cationic surfactant, is proposed from the heightened hygiene awareness (for example, patent document 1). However, when an anionic surfactant is combined with a cationic surfactant as a cleaning component in order to enhance the cleaning effect, re-contamination is likely to occur during cleaning, and the cleaning effect is hardly exhibited. In recent years, clothing containing synthetic fibers other than cotton has become mainstream due to the diversification of clothing products. However, cationic surfactants are not sufficiently adsorbed on synthetic fibers, so antibacterial properties against clothing containing synthetic fibers are antibacterial. It is difficult to demonstrate its properties. If the antibacterial property is insufficient, microorganisms grow especially when clothes are dried, and an unpleasant odor generated from the clothes is generated.
Thus, liquid detergent compositions containing an antibacterial agent having an aromatic ring have also been proposed (for example, Patent Documents 2 to 4).
特開２０１４－２８９４２号公報JP 2014-28942 A 特表２００４－５１５６４２号公報JP-T-2004-515642 特開２００１－１４６６８１号公報JP 2001-146681 A 特開２０１５－７２２０号公報Japanese Patent Laying-Open No. 2015-7220
　しかし、特許文献２～４のような芳香環を有する抗菌剤を配合した液体洗浄剤組成物を用いても、化繊を含む衣類に汚れが再汚染してしまい、優れた抗菌性を得ることができても、部屋干し臭抑制効果を得ることは難しい。 However, even when a liquid detergent composition containing an antibacterial agent having an aromatic ring as in Patent Documents 2 to 4 is used, stains are recontaminated on clothes containing synthetic fibers, and excellent antibacterial properties can be obtained. Even if it is possible, it is difficult to obtain the effect of suppressing room-dried odor.
　本発明は、高い洗浄力、優れた液安定性、及び高い再汚染防止効果を発揮できるうえ、被洗物に優れた抗菌性を付与でき、部屋干し臭発生の抑制効果に優れた液体洗浄剤組成物を提供することを目的とする。 The present invention is a liquid detergent that can exhibit high detergency, excellent liquid stability, and high anti-recontamination effect, can impart excellent antibacterial properties to the object to be washed, and is excellent in the effect of suppressing the occurrence of room-dried odor An object is to provide a composition.
　本発明は、以下の構成を有する。
［１］（Ａ）成分：下式（Ｉ）で表される化合物、及び下式（ＩＩ）で表される化合物からなる群から選ばれる少なくとも１種を含むノニオン界面活性剤と、（Ｂ）成分：アニオン界面活性剤からなる群から選ばれる少なくとも１種と、（Ｃ）成分：フェノール構造を有する抗菌剤と、を含有する、液体洗浄剤組成物。
　Ｒ１－Ｃ（＝Ｏ）Ｏ－［（ＥＯ）ｓ／（ＰＯ）ｔ］－（ＥＯ）ｕ－Ｒ２　・・・（Ｉ）
　Ｒ３－Ｏ－［（ＥＯ）ｖ／（ＰＯ）ｗ］－（ＥＯ）ｘ－Ｈ　・・・（ＩＩ）
（ただし、式中、ＥＯはエチレンオキシ基であり、ＰＯはプロピレンオキシ基である。Ｒ１は炭素数７～２２の炭化水素基であり、Ｒ２はメチル基又はエチル基であり、Ｒ３は炭素数７～２２の炭化水素基である。ｓ、ｖ、ｕ、ｘはＥＯの平均繰り返し数であり、ｔ、ｗはＰＯの平均繰り返し数である。ｓは６～２０の数であり、ｔは０～６の数であり、ｕは０～２０の数である。ｖは８～２０の数であり、ｗは０～６の数であり、ｘは０～２０の数である。）
［２］前記（Ａ）成分と前記（Ｂ）成分との（Ａ）／（Ｂ）比（質量比）が１以上である、［１］に記載の液体洗浄剤組成物。
［３］前記（Ｂ）成分と前記（Ｃ）成分との（Ｂ）／（Ｃ）比（質量比）が３以上である、［１］又は［２］に記載の液体洗浄剤組成物。
［４］さらに、（Ｄ）成分：アルキレンテレフタレート単位及びアルキレンイソフタレート単位のいずれか一方もしくは両方と、オキシアルキレン単位及びポリオキシアルキレン単位のいずれか一方もしくは両方とを有する水溶性ポリマーを、０．１～５質量％含有する、［１］～［３］のいずれかに記載の液体洗浄剤組成物。
［５］さらに、（Ｅ）成分：ポリアルキレンオキシド鎖を含むアルキレンアミン構造単位を有するポリアルキレンアミンアルキレンオキシド系共重合体を、０．１～５質量％含有する、［１］～［４］のいずれかに記載の液体洗浄剤組成物。
［６］さらに、（Ｆ）成分：カチオン界面活性剤からなる群から選ばれる少なくとも１種を含有する、［１］～［５］のいずれかに記載の液体洗浄剤組成物。
［７］前記（Ａ）成分が、前記式（Ｉ）におけるＲ１が炭素数１１のアルキル基及び炭素数１３のアルキル基であり、Ｒ２がメチル基であり、ｓ＝１５であり、ｔ＝０である化合物を含む、［１］～［６］のいずれかに記載の液体洗浄剤組成物。
［８］前記（Ａ）成分の含有量が５～８０質量％である、［１］～［７］のいずれかに記載の液体洗浄剤組成物。
［９］前記（Ｂ）成分が、炭素数１０～２０の直鎖状又は分岐鎖状のアルキル基を有するポリオキシアルキレンアルキルエーテル硫酸塩、及び炭素数８～１８のアルキル基を有する直鎖アルキルベンゼンスルホン酸塩からなる群から選ばれる少なくとも１種を含む、［１］～［８］のいずれかに記載の液体洗浄剤組成物。
［１０］前記（Ｂ）成分の含有量が３～４０質量％である、［１］～［９］のいずれかに記載の液体洗浄剤組成物。
［１１］前記（Ｃ）成分が、ジクロロヒドロキシジフェニルエーテル、トリクロロヒドロキシジフェニルエーテル及びベンジルクロロフェノールからなる群から選ばれる少なくとも１種を含む、［１］～［１０］のいずれかに記載の液体洗浄剤組成物。
［１２］前記（Ｃ）成分の含有量が０．０１～３質量％である、［１］～［１１］のいずれかに記載の液体洗浄剤組成物。 The present invention has the following configuration.
[1] Component (A): a nonionic surfactant containing at least one selected from the group consisting of a compound represented by the following formula (I) and a compound represented by the following formula (II); and (B) A liquid detergent composition containing at least one selected from the group consisting of component: anionic surfactant and component (C): an antibacterial agent having a phenol structure.
R 1 —C (═O) O — [(EO) s / (PO) t ] — (EO) u —R 2 (I)
R 3 —O — [(EO) v / (PO) w ] — (EO) x —H (II)
(In the formula, EO is an ethyleneoxy group, PO is a propyleneoxy group, R 1 is a hydrocarbon group having 7 to 22 carbon atoms, R 2 is a methyl group or an ethyl group, and R 3 Is a hydrocarbon group having 7 to 22 carbon atoms, s, v, u and x are the average number of repetitions of EO, t and w are the average number of repetitions of PO, and s is a number of 6 to 20 , T is a number from 0 to 6, u is a number from 0 to 20, v is a number from 8 to 20, w is a number from 0 to 6, and x is a number from 0 to 20. .)
[2] The liquid detergent composition according to [1], wherein the (A) / (B) ratio (mass ratio) between the component (A) and the component (B) is 1 or more.
[3] The liquid detergent composition according to [1] or [2], wherein the (B) / (C) ratio (mass ratio) between the component (B) and the component (C) is 3 or more.
[4] Further, component (D): a water-soluble polymer having one or both of an alkylene terephthalate unit and an alkylene isophthalate unit, and one or both of an oxyalkylene unit and a polyoxyalkylene unit; The liquid detergent composition according to any one of [1] to [3], which is contained in an amount of 1 to 5% by mass.
[5] Furthermore, component (E): containing 0.1 to 5% by mass of a polyalkyleneamine alkylene oxide copolymer having an alkyleneamine structural unit containing a polyalkyleneoxide chain, [1] to [4] A liquid detergent composition according to any one of the above.
[6] The liquid detergent composition according to any one of [1] to [5], further comprising at least one selected from the group consisting of component (F): a cationic surfactant.
[7] In the component (A), R 1 in the formula (I) is an alkyl group having 11 carbon atoms and an alkyl group having 13 carbon atoms, R 2 is a methyl group, s = 15, and t The liquid detergent composition according to any one of [1] to [6], which comprises a compound where = 0.
[8] The liquid detergent composition according to any one of [1] to [7], wherein the content of the component (A) is 5 to 80% by mass.
[9] A polyoxyalkylene alkyl ether sulfate having a linear or branched alkyl group having 10 to 20 carbon atoms and a linear alkylbenzene having an alkyl group having 8 to 18 carbon atoms, wherein the component (B) is The liquid detergent composition according to any one of [1] to [8], comprising at least one selected from the group consisting of sulfonates.
[10] The liquid detergent composition according to any one of [1] to [9], wherein the content of the component (B) is 3 to 40% by mass.
[11] The liquid detergent composition according to any one of [1] to [10], wherein the component (C) includes at least one selected from the group consisting of dichlorohydroxydiphenyl ether, trichlorohydroxydiphenyl ether, and benzylchlorophenol. object.
[12] The liquid detergent composition according to any one of [1] to [11], wherein the content of the component (C) is 0.01 to 3% by mass.
　本発明の液体洗浄剤組成物は、高い洗浄力、優れた液安定性、及び高い再汚染防止効果を発揮できるうえ、被洗物に優れた抗菌性を付与でき、部屋干し臭発生の抑制効果に優れている。 The liquid detergent composition of the present invention can exhibit high detergency, excellent liquid stability, and a high anti-recontamination effect, and can impart excellent antibacterial properties to the object to be washed, thereby suppressing the occurrence of room drying odor. Is excellent.
　本発明の液体洗浄剤組成物は、後述する（Ａ）～（Ｃ）成分を含有する液体洗浄剤組成物である。 The liquid detergent composition of the present invention is a liquid detergent composition containing the components (A) to (C) described later.
［（Ａ）成分］
　（Ａ）成分は、下式（Ｉ）で表される化合物（以下、化合物（Ｉ）ともいう。）、及び下式（ＩＩ）で表される化合物（以下、化合物（ＩＩ）ともいう。）からなる群から選ばれる少なくとも１種を含むノニオン界面活性剤である。
　Ｒ１－Ｃ（＝Ｏ）Ｏ－［（ＥＯ）ｓ／（ＰＯ）ｔ］－（ＥＯ）ｕ－Ｒ２　・・・（Ｉ）
　Ｒ３－Ｏ－［（ＥＯ）ｖ／（ＰＯ）ｗ］－（ＥＯ）ｘ－Ｈ　・・・（ＩＩ） [(A) component]
The component (A) includes a compound represented by the following formula (I) (hereinafter also referred to as compound (I)) and a compound represented by the following formula (II) (hereinafter also referred to as compound (II)). A nonionic surfactant containing at least one selected from the group consisting of
R 1 —C (═O) O — [(EO) s / (PO) t ] — (EO) u —R 2 (I)
R 3 —O — [(EO) v / (PO) w ] — (EO) x —H (II)
　ただし、式（Ｉ）、（ＩＩ）中、ＥＯはエチレンオキシ基であり、ＰＯはプロピレンオキシ基である。Ｒ１は炭素数７～２２の炭化水素基であり、Ｒ２はメチル基又はエチル基であり、Ｒ３は炭素数７～２２の炭化水素基である。ｓ、ｖ、ｕ、ｘはＥＯの平均繰り返し数であり、ｔ、ｗはＰＯの平均繰り返し数である。ｓは６～２０の数であり、ｔは０～６の数であり、ｕは０～２０の数である。ｖは８～２０の数であり、ｗは０～６の数であり、ｘは０～２０の数である。 However, in the formulas (I) and (II), EO is an ethyleneoxy group and PO is a propyleneoxy group. R 1 is a hydrocarbon group having 7 to 22 carbon atoms, R 2 is a methyl group or an ethyl group, and R 3 is a hydrocarbon group having 7 to 22 carbon atoms. s, v, u, and x are the average number of repetitions of EO, and t and w are the average number of repetitions of PO. s is a number from 6 to 20, t is a number from 0 to 6, and u is a number from 0 to 20. v is a number from 8 to 20, w is a number from 0 to 6, and x is a number from 0 to 20.
　式（Ｉ）におけるＲ１の炭化水素基は、直鎖状であってもよく、分岐鎖状であってもよい。
　Ｒ１の炭化水素基の炭素数は、７～２２である。炭素数が下限値以上であれば、充分なドレープ維持効果が得られる。炭素数が上限値以下であれば、優れた液安定性が得られる。Ｒ１の炭化水素基の炭素数は、洗浄力向上の観点から、９～２１が好ましく、１１～２１がより好ましい。
　Ｒ１としては、アルキル基又はアルケニル基が好ましい。アルキル基又はアルケニル基としては、炭素数７～２２の１級又は２級の高級アルコール、炭素数８～２３の高級脂肪酸、炭素数８～２３の高級脂肪酸アミド等の原料に由来するアルキル基又はアルケニル基が挙げられる。 The hydrocarbon group for R 1 in formula (I) may be linear or branched.
The hydrocarbon group of R 1 has 7 to 22 carbon atoms. If the number of carbon atoms is at least the lower limit, a sufficient drape maintaining effect can be obtained. If the carbon number is not more than the upper limit value, excellent liquid stability can be obtained. The number of carbon atoms of the hydrocarbon group for R 1 is preferably 9 to 21, and more preferably 11 to 21, from the viewpoint of improving detergency.
R 1 is preferably an alkyl group or an alkenyl group. Examples of the alkyl group or alkenyl group include alkyl groups derived from raw materials such as primary or secondary higher alcohols having 7 to 22 carbon atoms, higher fatty acids having 8 to 23 carbon atoms, and higher fatty acid amides having 8 to 23 carbon atoms. An alkenyl group is mentioned.
　式（Ｉ）におけるｓ＋ｕは、６～２０が好ましく、６～１８がより好ましく、１１～１８がさらに好ましい。ｓ＋ｕが下限値以上であれば、親水性が充分となり、系中の自由水が少なくなることで酵素安定性が向上する。ｓ＋ｕが上限値以下であれば、親水性が高くなりすぎず、充分な洗浄力が得られやすい。 S + u in the formula (I) is preferably 6 to 20, more preferably 6 to 18, and still more preferably 11 to 18. If s + u is not less than the lower limit, the hydrophilicity will be sufficient, and free water in the system will be reduced, thereby improving the enzyme stability. If s + u is less than or equal to the upper limit, the hydrophilicity does not become too high and sufficient detergency can be easily obtained.
　式（Ｉ）におけるｔは、０～６の数であり、０～３が好ましい。ｔが上限値以下であれば、液安定性が向上する。
　［（ＥＯ）ｓ／（ＰＯ）ｔ］におけるエチレンオキシ基とプロピレンオキシ基とは、ランダム鎖を形成していてもよく、ブロック鎖を形成していてもよい。 T in the formula (I) is a number of 0 to 6, preferably 0 to 3. If t is less than or equal to the upper limit value, the liquid stability is improved.
The ethyleneoxy group and propyleneoxy group in [(EO) s / (PO) t ] may form a random chain or may form a block chain.
　式（ＩＩ）におけるＲ３の炭化水素基は、直鎖状であってもよく、分岐鎖状であってもよい。
　Ｒ３の炭化水素基の炭素数は、７～２２である。炭素数が下限値以上であれば、充分なドレープ維持効果が得られる。炭素数が上限値以下であれば、優れた液安定性が得られる。Ｒ３の炭化水素基の炭素数は、洗浄力向上の観点から、１０～２２が好ましく、１０～２０がより好ましく、１０～１８がさらに好ましい。
　Ｒ３としては、アルキル基又はアルケニル基が好ましい。アルキル基又はアルケニル基としては、Ｒ１で挙げたものと同じものが挙げられる。 The hydrocarbon group for R 3 in formula (II) may be linear or branched.
The hydrocarbon group of R 3 has 7 to 22 carbon atoms. If the number of carbon atoms is at least the lower limit, a sufficient drape maintaining effect can be obtained. If the carbon number is not more than the upper limit value, excellent liquid stability can be obtained. From the viewpoint of improving detergency, the number of carbon atoms in the hydrocarbon group of R 3 is preferably 10-22, more preferably 10-20, and even more preferably 10-18.
R 3 is preferably an alkyl group or an alkenyl group. Examples of the alkyl group or alkenyl group are the same as those described for R 1 .
　式（ＩＩ）におけるｖ＋ｘは、８～２０が好ましく、９～１８がより好ましく、１０～１８がさらに好ましく、１３～１８が特に好ましい。ｖ＋ｘが下限値以上であれば、親水性が充分となり、系中の自由水が少なくなることで酵素安定性が向上する。ｖ＋ｘが上限値以下であれば、親水性が高くなりすぎず、充分な洗浄力が得られやすい。 V + x in the formula (II) is preferably 8 to 20, more preferably 9 to 18, further preferably 10 to 18, and particularly preferably 13 to 18. When v + x is equal to or greater than the lower limit, the hydrophilicity is sufficient, and the enzyme stability is improved by reducing the amount of free water in the system. If v + x is less than or equal to the upper limit value, the hydrophilicity does not become too high and sufficient detergency is easily obtained.
　式（ＩＩ）におけるｗは、０～６であり、０～３が好ましい。ｗが上限値以下であれば、液安定性が向上する。
　［（ＥＯ）ｖ／（ＰＯ）ｗ］におけるエチレンオキシ基とプロピレンオキシ基とは、ランダム鎖を形成していてもよく、ブロック鎖を形成していてもよい。 In the formula (II), w is 0 to 6, preferably 0 to 3. If w is not more than the upper limit value, the liquid stability is improved.
The ethyleneoxy group and propyleneoxy group in [(EO) v / (PO) w ] may form a random chain or may form a block chain.
　化合物（Ｉ）としては、ポリオキシエチレン脂肪酸アルキルエステルが好ましく、Ｒ２がメチル基であるポリオキシエチレン脂肪酸メチルエステル（以下、ＭＥＥともいう。）がより好ましい。ポリオキシエチレン脂肪酸アルキルエステルを用いることで、液体洗浄剤組成物の水への溶解性を高め、洗浄力を高められる。加えて、液体洗浄剤組成物中の（Ｂ）成分の含有量を高めても、粘度の著しい増大（ゲル化）が生じにくく、良好な流動性を有する濃縮型の液体洗浄剤組成物が得られる。
　ポリオキシエチレン脂肪酸アルキルエステル、特にＭＥＥは、水溶液系中で分子同士の配向性が弱く、ミセルが不安定なノニオン界面活性剤である。このため、ポリオキシエチレン脂肪酸アルキルエステルは、高濃度でゲル化等を生じず、１種単独で多量に液体洗浄剤組成物中に配合されても、水への溶解性を高められると推測される。従って、ポリオキシエチレン脂肪酸アルキルエステルを含む液体洗浄剤組成物が水に分散されると、洗浄液中のポリオキシエチレン脂肪酸アルキルエステルの濃度が速やかに均一となり、洗浄初期から任意の濃度で被洗物と接して高い洗浄力を発揮すると考えられる。 As compound (I), polyoxyethylene fatty acid alkyl ester is preferable, and polyoxyethylene fatty acid methyl ester (hereinafter, also referred to as MEE) in which R 2 is a methyl group is more preferable. By using polyoxyethylene fatty acid alkyl ester, the solubility of the liquid detergent composition in water can be increased and the cleaning power can be increased. In addition, even if the content of the component (B) in the liquid cleaning composition is increased, a concentrated liquid cleaning composition having a good fluidity is obtained without causing a significant increase in viscosity (gelation). It is done.
A polyoxyethylene fatty acid alkyl ester, particularly MEE, is a nonionic surfactant having a weak molecular orientation and an unstable micelle in an aqueous solution system. For this reason, it is speculated that polyoxyethylene fatty acid alkyl ester does not cause gelation or the like at a high concentration, and can increase solubility in water even if it is blended in a liquid detergent composition in a large amount alone. The Accordingly, when the liquid cleaning composition containing polyoxyethylene fatty acid alkyl ester is dispersed in water, the concentration of polyoxyethylene fatty acid alkyl ester in the cleaning liquid becomes uniform quickly, and the object to be cleaned is at an arbitrary concentration from the initial stage of cleaning. It is thought that it exerts a high cleaning power in contact with.
　ポリオキシエチレン脂肪酸アルキルエステルにおいて、エチレンオキシドの付加モル数が異なる化合物の分布の割合を示すナロー率は、２０質量％以上が好ましい。ナロー率の上限値は実質的に８０質量％が好ましい。ナロー率は、２０～６０質量％がより好ましい。ナロー率が高いほど良好な洗浄力が得られるが、高すぎると低温での液安定性が低下するおそれがあるため、３０～４５質量％がさらに好ましい。 In the polyoxyethylene fatty acid alkyl ester, the narrow ratio indicating the distribution ratio of compounds having different numbers of added moles of ethylene oxide is preferably 20% by mass or more. The upper limit of the narrow ratio is preferably substantially 80% by mass. The narrow ratio is more preferably 20 to 60% by mass. The higher the narrow ratio, the better the detergency can be obtained, but if it is too high, the liquid stability at low temperatures may be lowered, so 30 to 45% by mass is more preferable.
　ポリオキシエチレン脂肪酸アルキルエステル等のポリオキシアルキレン型ノニオン界面活性剤のナロー率は、下記の数式（Ｓ）で求められる値である。 The narrow rate of polyoxyalkylene type nonionic surfactants such as polyoxyethylene fatty acid alkyl esters is a value determined by the following mathematical formula (S).
Figure JPOXMLDOC01-appb-M000001
Figure JPOXMLDOC01-appb-M000001
　（Ｓ）式において、Ｓｍａｘは、ポリオキシアルキレン型ノニオン界面活性剤中に最も多く存在するアルキレンオキシド付加体におけるアルキレンオキシドの付加モル数（ｓ＋ｔ＋ｕの値）を示す。
　ｉはアルキレンオキシドの付加モル数を示す。
　Ｙｉは、（Ｓ）式で表される成分全体の中に存在するアルキレンオキシドの付加モル数がｉであるアルキレンオキシド付加体の割合（質量％）を示す。 In the formula (S), S max represents the number of added moles of alkylene oxide (value of s + t + u) in the alkylene oxide adduct most frequently present in the polyoxyalkylene type nonionic surfactant.
i represents the number of added moles of alkylene oxide.
Yi represents the proportion (% by mass) of an alkylene oxide adduct having an added mole number of alkylene oxide present in the entire component represented by the formula (S).
　前記ナロー率は、例えば、ポリオキシエチレン脂肪酸アルキルエステルの製造方法等によって制御することができる。 The narrow rate can be controlled by, for example, a method for producing a polyoxyethylene fatty acid alkyl ester.
　化合物（Ｉ）及び化合物（ＩＩ）におけるＥＯ又はＰＯの分布は、製造する際の反応方法によって変動する。例えば、一般的なアルカリ触媒である水酸化ナトリウムや水酸化カリウム等を用いて、エチレンオキシドやプロピレンオキシドを原料に付加した場合には、ｓ又はｔの分布は、比較的広くなる。特公平６－１５０３８号公報に記載のＡｌ３＋、Ｇａ３＋、Ｉｎ３＋、Ｔｌ３＋、Ｃｏ３＋、Ｓｃ３＋、Ｌａ３＋、Ｍｎ２＋等の金属イオンを添加した酸化マグネシウム等の特定のアルコキシル化触媒を用いてエチレンオキシドやプロピレンオキシドを原料に付加した場合には、ＥＯ又はＰＯの分布は、比較的狭くなる。 The distribution of EO or PO in compound (I) and compound (II) varies depending on the reaction method in production. For example, when ethylene oxide or propylene oxide is added to a raw material using sodium hydroxide, potassium hydroxide or the like, which is a general alkali catalyst, the distribution of s or t becomes relatively wide. A specific alkoxylation catalyst such as magnesium oxide to which metal ions such as Al 3+ , Ga 3+ , In 3+ , Tl 3+ , Co 3+ , Sc 3+ , La 3+ , Mn 2+ and the like described in JP-B-6-15038 is added. When ethylene oxide or propylene oxide is added to the raw material, the distribution of EO or PO becomes relatively narrow.
　また、その他の（Ａ）成分の製造法としては、アルカリ土類金属化合物とオキシ酸等の混合物より調製されるアルコキシル化触媒により、脂肪酸アルキルエステルにアルキレンオキシドを付加する方法がある。上記のアルコキシル化触媒については、特許第０４９７７６０９号公報、国際公開第１９９３／００４０３０号、国際公開第２００２／０３８２６９号、国際公開第２０１２／０２８４３５号等で開示されており、例えば、カルボン酸のアルカリ土類金属塩及び／又はヒドロキシカルボン酸のアルカリ土類金属塩と硫酸等の混合物より調製したアルコキシル化触媒等が挙げられる。 As another method for producing the component (A), there is a method in which an alkylene oxide is added to a fatty acid alkyl ester with an alkoxylation catalyst prepared from a mixture of an alkaline earth metal compound and oxyacid. The above alkoxylation catalysts are disclosed in Japanese Patent No. 04977609, International Publication No. 1993/004030, International Publication No. 2002/038269, International Publication No. 2012/028435, and the like. Examples include an alkoxylation catalyst prepared from a mixture of an earth metal salt and / or an alkaline earth metal salt of hydroxycarboxylic acid and sulfuric acid.
　（Ａ）成分としては、洗浄力や液体洗浄剤組成物の溶解性の向上の点から、式（Ｉ）におけるＲ１が炭素数１１のアルキル基及び炭素数１３のアルキル基であり、Ｒ２がメチル基であり、ｓ＝１５であり、ｔ＝０である化合物（ＭＥＥ）が特に好ましい。ＭＥＥは他のノニオン界面活性剤やアニオン界面活性剤に比べ、衣類に残りにくく、（Ｃ）成分を効率良く衣類上に吸着させることができる。 As the component (A), R 1 in the formula (I) is an alkyl group having 11 carbon atoms and an alkyl group having 13 carbon atoms, from the viewpoint of improving detergency and solubility of the liquid detergent composition, and R 2 Is particularly preferably a compound (MEE) in which is a methyl group, s = 15 and t = 0. Compared with other nonionic surfactants and anionic surfactants, MEE is less likely to remain on clothing and can efficiently adsorb component (C) onto clothing.
　また、（Ａ）成分は化合物（Ｉ）及び化合物（ＩＩ）以外の他のノニオン界面活性剤を含有してもよい。他のノニオン界面活性剤としては、液体洗浄剤組成物に用いられている公知のものが挙げられ、例えば、化合物（Ｉ）及び化合物（ＩＩ）以外のポリオキシアルキレン型ノニオン界面活性剤、アルキルフェノール、高級アミン等のアルキレンオキシド付加体、ポリオキシエチレンポリオキシプロピレンブロックコポリマー、脂肪酸アルカノールアミン、脂肪酸アルカノールアミド、多価アルコール脂肪酸エステル又はそのアルキレンオキシド付加体、多価アルコール脂肪酸エーテル、アルキル（又はアルケニル）アミンオキシド、硬化ヒマシ油のアルキレンオキシド付加体、糖脂肪酸エステル、Ｎ－アルキルポリヒドロキシ脂肪酸アミド、アルキルグリコシド等が挙げられる。
　（Ａ）成分は、１種が単独で用いられてもよく、２種以上が組み合わされて用いられてもよい。（Ａ）成分を２種以上組み合わせることで、洗浄力が向上し、部屋干し臭発生の抑制効果が得られやすくなる。 Moreover, (A) component may contain other nonionic surfactants other than compound (I) and compound (II). Examples of other nonionic surfactants include known ones used in liquid detergent compositions, such as polyoxyalkylene type nonionic surfactants other than compound (I) and compound (II), alkylphenols, Alkylene oxide adducts such as higher amines, polyoxyethylene polyoxypropylene block copolymers, fatty acid alkanolamines, fatty acid alkanolamides, polyhydric alcohol fatty acid esters or alkylene oxide adducts thereof, polyhydric alcohol fatty acid ethers, alkyl (or alkenyl) amines Examples thereof include oxides, alkylene oxide adducts of hydrogenated castor oil, sugar fatty acid esters, N-alkyl polyhydroxy fatty acid amides, and alkyl glycosides.
As the component (A), one type may be used alone, or two or more types may be used in combination. By combining two or more types of component (A), the detergency is improved, and the effect of suppressing the generation of room-dried odor is easily obtained.
　本発明の液体洗浄剤組成物（１００質量％）中の（Ａ）成分の含有量は、５～８０質量％が好ましく、１０～７０質量％がより好ましい。（Ａ）成分の含有量が下限値以上であれば、液体洗浄剤組成物の洗浄力が高まる。（Ａ）成分の含有量が上限値以下であれば、液体洗浄剤組成物の液安定性が高まる。 The content of the component (A) in the liquid detergent composition (100% by mass) of the present invention is preferably 5 to 80% by mass, more preferably 10 to 70% by mass. If content of (A) component is more than a lower limit, the cleaning power of a liquid detergent composition will increase. If content of (A) component is below an upper limit, the liquid stability of a liquid detergent composition will increase.
［（Ｂ）成分］
　（Ｂ）成分は、アニオン界面活性剤からなる群から選ばれる少なくとも１種である。 [Component (B)]
The component (B) is at least one selected from the group consisting of anionic surfactants.
　（Ｂ）成分としては、例えば、以下の化合物（Ｂ１）～（Ｂ１２）が挙げられる。
　（Ｂ１）炭素数８～２０の飽和又は不飽和α－スルホ脂肪酸のメチルエステル塩、エチルエステル塩もしくはプロピルエステル塩。
　（Ｂ２）炭素数８～１８のアルキル基を有する直鎖状又は分岐鎖状のアルキルベンゼンスルホン酸塩（ＬＡＳ又はＡＢＳ）。なかでも、直鎖アルキル基を有するものが好ましい。該直鎖アルキル基の炭素数は、８～１６が好ましく、１０～１４がより好ましい。
　（Ｂ３）炭素数１０～２０のアルカンスルホン酸塩。
　（Ｂ４）炭素数１０～２０のα－オレフィンスルホン酸塩（ＡＯＳ）。
　（Ｂ５）炭素数１０～２０のアルキル硫酸塩又はアルケニル硫酸塩（ＡＳ）。 Examples of the component (B) include the following compounds (B1) to (B12).
(B1) A methyl ester salt, ethyl ester salt or propyl ester salt of a saturated or unsaturated α-sulfo fatty acid having 8 to 20 carbon atoms.
(B2) A linear or branched alkylbenzene sulfonate (LAS or ABS) having an alkyl group having 8 to 18 carbon atoms. Of these, those having a linear alkyl group are preferred. The linear alkyl group preferably has 8 to 16 carbon atoms, and more preferably 10 to 14 carbon atoms.
(B3) Alkane sulfonate having 10 to 20 carbon atoms.
(B4) α-olefin sulfonate (AOS) having 10 to 20 carbon atoms.
(B5) Alkyl sulfate or alkenyl sulfate (AS) having 10 to 20 carbon atoms.
　（Ｂ６）炭素数２～４のアルキレンオキシドのいずれか、又はエチレンオキシド（ＥＯ）とプロピレンオキシド（ＰＯ）（モル比ＥＯ／ＰＯ＝０．１／９．９～９．９／０．１）を平均０．５～１０モル付加した炭素数１０～２０の直鎖状又は分岐鎖状のアルキル基（又はアルケニル基）を有する、ポリオキシアルキレンアルキル（又はアルケニル）エーテル硫酸塩（ＡＥＳ）。アルキレンオキシド、又はエチレンオキシドとプロピレンオキシドの平均付加モル数は、１～５が好ましい。
　（Ｂ７）炭素数２～４のアルキレンオキシドのいずれか、又はエチレンオキシドとプロピレンオキシド（モル比ＥＯ／ＰＯ＝０．１／９．９～９．９／０．１）を平均３～３０モル付加した炭素数１０～２０の直鎖状又は分岐鎖状のアルキル基（又はアルケニル基）を有する、ポリオキシアルキレンアルキル（又はアルケニル）フェニルエーテル硫酸塩。
　（Ｂ８）炭素数２～４のアルキレンオキシドのいずれか、又はエチレンオキシドとプロピレンオキシド（モル比ＥＯ／ＰＯ＝０．１／９．９～９．９／０．１）を、平均０．５～１０モル付加した炭素数１０～２０の直鎖状又は分岐鎖状のアルキル基（又はアルケニル基）を有する、ポリオキシアルキレンアルキル（又はアルケニル）エーテルカルボン酸塩。 (B6) Any one of alkylene oxides having 2 to 4 carbon atoms, or ethylene oxide (EO) and propylene oxide (PO) (molar ratio EO / PO = 0.1 / 9.9 to 9.9 / 0.1) Polyoxyalkylene alkyl (or alkenyl) ether sulfate (AES) having a linear or branched alkyl group (or alkenyl group) having 10 to 20 carbon atoms added with an average of 0.5 to 10 moles. The average added mole number of alkylene oxide or ethylene oxide and propylene oxide is preferably 1 to 5.
(B7) Addition of any one of alkylene oxides having 2 to 4 carbon atoms or ethylene oxide and propylene oxide (molar ratio EO / PO = 0.1 / 9.9 to 9.9 / 0.1) on average 3 to 30 mol A polyoxyalkylene alkyl (or alkenyl) phenyl ether sulfate having a linear or branched alkyl group (or alkenyl group) having 10 to 20 carbon atoms.
(B8) Any one of alkylene oxides having 2 to 4 carbon atoms, or ethylene oxide and propylene oxide (molar ratio EO / PO = 0.1 / 9.9 to 9.9 / 0.1), an average of 0.5 to A polyoxyalkylene alkyl (or alkenyl) ether carboxylate having 10 to 20 carbon atoms and a linear or branched alkyl group (or alkenyl group) having 10 to 20 carbon atoms.
　（Ｂ９）炭素数１０～２０のアルキルグリセリルエーテルスルホン酸等のアルキル多価アルコールエーテル硫酸塩。
　（Ｂ１０）長鎖モノアルキルリン酸塩、長鎖ジアルキルリン酸塩、又は長鎖セスキアルキルリン酸塩。
　（Ｂ１１）ポリオキシエチレンモノアルキルリン酸塩、ポリオキシエチレンジアルキルリン酸塩、又はポリオキシエチレンセスキアルキルリン酸塩。
　（Ｂ１２）石鹸。平均炭素数が１０～２０（好ましくは１２～１８）の高級脂肪酸塩。 (B9) Alkyl polyhydric alcohol ether sulfates such as alkyl glyceryl ether sulfonic acids having 10 to 20 carbon atoms.
(B10) Long chain monoalkyl phosphate, long chain dialkyl phosphate, or long chain sesquialkyl phosphate.
(B11) Polyoxyethylene monoalkyl phosphate, polyoxyethylene dialkyl phosphate, or polyoxyethylene sesquialkyl phosphate.
(B12) Soap. A higher fatty acid salt having an average carbon number of 10 to 20 (preferably 12 to 18).
　（Ｂ）成分としては、化合物（Ｂ１）～（Ｂ１２）以外のアニオン界面活性剤を用いてもよい。例えば、アルキルエーテルカルボン酸塩、ポリオキシアルキレンエーテルカルボン酸塩、アルキルアミドエーテルカルボン酸塩又はアルケニルアミドエーテルカルボン酸塩、アシルアミノカルボン酸塩等のカルボン酸型アニオン界面活性剤；アルキルリン酸エステル塩、ポリオキシアルキレンアルキルリン酸エステル塩、ポリオキシアルキレンアルキルフェニルリン酸エステル塩、グリセリン脂肪酸エステルモノリン酸エステル塩等のリン酸エステル型アニオン界面活性剤等が挙げられる。 As the component (B), an anionic surfactant other than the compounds (B1) to (B12) may be used. For example, carboxylic acid type anionic surfactants such as alkyl ether carboxylates, polyoxyalkylene ether carboxylates, alkylamide ether carboxylates or alkenylamide ether carboxylates, acylaminocarboxylates; alkyl phosphate ester salts And phosphoric acid ester type anionic surfactants such as polyoxyalkylene alkyl phosphoric acid ester salt, polyoxyalkylene alkyl phenyl phosphoric acid ester salt and glycerin fatty acid ester monophosphoric acid ester salt.
　アニオン界面活性剤の塩の形態としては、ナトリウム塩、カリウム塩等のアルカリ金属塩；マグネシウム塩等のアルカリ土類金属塩；モノエタノールアミン塩、ジエタノールアミン塩等のアルカノールアミン塩；アンモニウム塩等が挙げられる。なかでも、アルカリ金属塩が好ましい。 Examples of the salt form of the anionic surfactant include alkali metal salts such as sodium salts and potassium salts; alkaline earth metal salts such as magnesium salts; alkanolamine salts such as monoethanolamine salts and diethanolamine salts; ammonium salts and the like. It is done. Of these, alkali metal salts are preferred.
　（Ｂ）成分としては、洗浄力の観点からは耐硬水性が高い界面活性剤が好ましく、抗菌力向上の観点からは耐硬水性が低いものが好ましい。
　（Ｂ）成分は、１種が単独で用いられてもよく、２種以上が組み合わされて用いられてもよい。 As the component (B), surfactants having high hard water resistance are preferable from the viewpoint of detergency, and those having low hard water resistance are preferable from the viewpoint of improving antibacterial power.
As the component (B), one type may be used alone, or two or more types may be used in combination.
　（Ｂ）成分は、炭素数１０～２０の直鎖状又は分岐鎖状のアルキル基を有するポリオキシアルキレンアルキルエーテル硫酸塩、及び炭素数８～１８のアルキル基を有する直鎖アルキルベンゼンスルホン酸塩からなる群から選ばれる少なくとも１種を含むことが好ましい。また、洗浄力及び酵素安定性の観点から、（Ｂ）成分は、ＬＡＳ及びＡＥＳの少なくとも一方もしくは両方を含むことがより好ましい。 The component (B) is composed of a polyoxyalkylene alkyl ether sulfate having a linear or branched alkyl group having 10 to 20 carbon atoms and a linear alkylbenzene sulfonate having an alkyl group having 8 to 18 carbon atoms. It is preferable to include at least one selected from the group consisting of: Further, from the viewpoint of detergency and enzyme stability, the component (B) preferably contains at least one or both of LAS and AES.
　（Ｂ）成分としてＬＡＳ及びＡＥＳの両方を用いる場合、ＬＡＳとＡＥＳのＬＡＳ／ＡＥＳ比（質量比）は、０．１～２が好ましく、０．５～１がさらに好ましい。ＬＡＳ／ＡＥＳ比が上限値以下であれば、酵素安定性が向上する。ＬＡＳ／ＡＥＳ比が下限値以上であれば液安定性が向上する。 When both LAS and AES are used as the component (B), the LAS / AES ratio (mass ratio) of LAS and AES is preferably 0.1 to 2, and more preferably 0.5 to 1. If the LAS / AES ratio is not more than the upper limit, the enzyme stability is improved. If the LAS / AES ratio is at least the lower limit, the liquid stability will be improved.
　本発明の液体洗浄剤組成物（１００質量％）中の（Ｂ）成分の含有量は、３～４０質量％が好ましく、５～３０質量％がより好ましく、７～２０質量％がさらに好ましく、１０～２０質量％が特に好ましい。（Ｂ）成分の含有量が前記範囲内であれば、優れた再汚染防止性及び洗浄力が得られやすい。加えて、（Ｂ）成分における一部のアニオン界面活性剤が水道水中のカルシウムイオンと結合して塩を形成することで、洗剤液中の疎水性が増加し、疎水性の高い（Ｃ）成分と複合体を形成する。これにより、化繊の表面等の疎水性が高い表面を有する衣類への吸着量が増加し、抗菌性（静菌活性）が向上する。 The content of the component (B) in the liquid detergent composition (100% by mass) of the present invention is preferably 3 to 40% by mass, more preferably 5 to 30% by mass, further preferably 7 to 20% by mass, 10 to 20% by mass is particularly preferable. If content of (B) component exists in the said range, the outstanding recontamination prevention property and detergency will be easy to be obtained. In addition, a part of the anionic surfactant in the component (B) is combined with calcium ions in tap water to form a salt, thereby increasing the hydrophobicity in the detergent liquid, and the highly hydrophobic component (C) And form a complex. Thereby, the adsorption amount to the clothing which has surfaces with high hydrophobicity, such as the surface of a synthetic fiber, increases, and antibacterial property (bacteriostatic activity) improves.
　（Ａ）成分と（Ｂ）成分との（Ａ）／（Ｂ）比（質量比）は、０．１～５が好ましく、０．３～３がより好ましく、１～３が特に好ましい。（Ａ）／（Ｂ）比が下限値以上であれば、液体洗浄剤組成物の液安定性が高まる。（Ａ）／（Ｂ）比が上限値以下であれば、（Ｃ）成分と複合体を形成する（Ｂ）成分量が増加し、化繊の表面等の疎水性が高い表面を有する衣類への吸着量が増加し、抗菌性（静菌活性）が向上する。また、（Ａ）／（Ｂ）比が１以上であれば、酵素安定性が向上する。 The (A) / (B) ratio (mass ratio) between the component (A) and the component (B) is preferably 0.1 to 5, more preferably 0.3 to 3, and particularly preferably 1 to 3. If (A) / (B) ratio is more than a lower limit, the liquid stability of a liquid cleaning composition will increase. If the ratio (A) / (B) is less than or equal to the upper limit, the amount of the component (B) that forms a composite with the component (C) is increased, and the garment having a surface having high hydrophobicity such as the surface of synthetic fiber is applied. Adsorption amount increases and antibacterial properties (bacteriostatic activity) are improved. Moreover, if (A) / (B) ratio is 1 or more, enzyme stability will improve.
　本発明の液体洗浄剤組成物（１００質量％）中の活性剤の総量は、２５～８０質量％が好ましく、３０～６０質量％がより好ましい。活性剤の総量が下限値以上であれば、液体洗浄剤の洗浄力がより向上し、さらに疎水性の高い（Ｃ）成分が可溶化されやすくなり、液安定性が高まる。活性剤の総量が上限値以下であれば、液体洗浄剤組成物の液安定性が高まる。
　なお、活性剤の総量とは、（Ａ）成分、（Ｂ）成分及び（Ｆ）成分の合計量を意味する。 The total amount of the active agent in the liquid detergent composition (100% by mass) of the present invention is preferably 25 to 80% by mass, and more preferably 30 to 60% by mass. If the total amount of the activator is at least the lower limit, the detergency of the liquid detergent is further improved, and the (C) component having high hydrophobicity is easily solubilized and the liquid stability is enhanced. If the total amount of activator is below an upper limit, the liquid stability of a liquid detergent composition will increase.
In addition, the total amount of an active agent means the total amount of (A) component, (B) component, and (F) component.
［（Ｃ）成分］
　（Ｃ）成分は、フェノール構造を有する抗菌剤である。なお、フェノール構造とは、芳香族炭化水素核の水素原子の１以上がヒドロキシ基で置換された構造を意味する。
　（Ｃ）成分は、洗濯後の衣類等の繊維製品に抗菌性を付与する成分である。フェノール構造をもつ抗菌剤は、液体洗浄剤組成物中においてアニオン界面活性剤と共存させても、アニオン界面活性剤による洗浄性を損なわずに抗菌性を発揮できる。 [Component (C)]
The component (C) is an antibacterial agent having a phenol structure. The phenol structure means a structure in which one or more hydrogen atoms of the aromatic hydrocarbon nucleus are substituted with a hydroxy group.
Component (C) is a component that imparts antibacterial properties to textiles such as clothes after washing. The antibacterial agent having a phenol structure can exhibit antibacterial properties without impairing the detergency due to the anionic surfactant even if it coexists with the anionic surfactant in the liquid detergent composition.
　（Ｃ）成分としては、抗菌剤として公知のフェノール誘導体又はジフェニル化合物が挙げられる。具体的には、５－クロロ－２－（２，４－ジクロロフェノキシ）フェノール（慣用名：トリクロサン）、４，４’－ジクロロ－２－ヒドロキシジフェニルエーテル（慣用名：ダイクロサン）、ｏ－ベンジル－ｐ－クロロフェノール（クロロフェン）、イソプロピルメチルフェノール、パラクロロメタキシレノール等が挙げられる。なかでも、ジフェニル化合物が好ましく、具体的には、５－クロロ－２－（２，４－ジクロロフェノキシ）フェノール（慣用名：トリクロサン）、４，４’－ジクロロ－２－ヒドロキシジフェニルエーテル（慣用名：ダイクロサン）、ｏ－ベンジル－ｐ－クロロフェノール（クロロフェン）が好ましい。 (C) Component includes phenol derivatives or diphenyl compounds known as antibacterial agents. Specifically, 5-chloro-2- (2,4-dichlorophenoxy) phenol (common name: triclosan), 4,4′-dichloro-2-hydroxydiphenyl ether (common name: dichrosan), o-benzyl- Examples thereof include p-chlorophenol (chlorophen), isopropylmethylphenol, parachlorometaxylenol and the like. Of these, diphenyl compounds are preferred. Specifically, 5-chloro-2- (2,4-dichlorophenoxy) phenol (common name: triclosan), 4,4′-dichloro-2-hydroxydiphenyl ether (common name: Diclosan) and o-benzyl-p-chlorophenol (chlorophene) are preferred.
　（Ｃ）成分としては、疎水性繊維への吸着量が高く、本発明を適用することによる効果が大きい点から、下式（ＩＩＩ）で表される２－ヒドロキシジフェニル化合物（以下、化合物（ＩＩＩ）という。）が好ましい。 As the component (C), a 2-hydroxydiphenyl compound represented by the following formula (III) (hereinafter referred to as the compound (III) is used because it has a high adsorption amount on the hydrophobic fiber and has a large effect by applying the present invention. )) Is preferred.
Figure JPOXMLDOC01-appb-C000002
Figure JPOXMLDOC01-appb-C000002
　ただし、式（ＩＩＩ）中、Ｘは酸素原子又は炭素数１～４のアルキレン基であり、Ｙは塩素原子又は臭素原子であり、ＺはＳＯ２Ｈ、ＮＯ２、又は炭素数１～４のアルキル基であり、ａ、ｂ、ｃはそれぞれ独立に０又は１～３の整数であり、ｄは０又は１であり、ｍは０又は１であり、ｎは０又は１である。
　なお、－（Ｙ）ｂは、ベンゼン環の水素原子のｂ個がＹに置換されていることを意味する。－（Ｙ）ｃ、－（Ｚ）ｄ、－（ＯＨ）ｍ及び－（ＯＨ）ｎについても同様である。 In the formula (III), X is an oxygen atom or an alkylene group having 1 to 4 carbon atoms, Y is a chlorine atom or a bromine atom, Z is SO 2 H, NO 2 , or a carbon atom having 1 to 4 carbon atoms. An alkyl group, a, b and c are each independently 0 or an integer of 1 to 3, d is 0 or 1, m is 0 or 1, and n is 0 or 1.
In addition,-(Y) b means that b hydrogen atoms in the benzene ring are substituted with Y. The same applies to-(Y) c,-(Z) d,-(OH) m and-(OH) n.
　化合物（ＩＩＩ）としては、Ｘが酸素原子又はメチレン基であり、Ｙが塩素原子又は臭素原子であり、ｍが０であり、ｎが０又は１であり、ａが１であり、ｂが０、１又は２であり、ｃが０、１又は２であり、かつｄが０である化合物がより好ましい。
　好ましい化合物（ＩＩＩ）の具体例としては、例えば、モノクロロヒドロキシジフェニルエーテル（Ｘが酸素原子であり、ａが１であり、Ｙが塩素原子であり、ｂ又はｃの一方が１で他方が０であり、ｄが０であり、ｍが０であり、ｎが０である化合物）、ジクロロヒドロキシジフェニルエーテル（Ｘが酸素原子であり、ａが１であり、Ｙが塩素原子であり、ｂが１であり、ｃが１であり、ｄが０であり、ｍが０であり、ｎが０である化合物）、トリクロロヒドロキシジフェニルエーテル（Ｘが酸素原子であり、ａが１であり、Ｙが塩素原子であり、ｂ又はｃの一方が１で他方が２であり、ｄが０であり、ｍが０であり、ｎが０である化合物）、ベンジルクロロフェノール（Ｘがメチレン基であり、ａが１であり、Ｙが塩素原子であり、ｂが０であり、ｃが１であり、ｄが０であり、ｍが０であり、ｎが０である化合物）が挙げられる。 As compound (III), X is an oxygen atom or a methylene group, Y is a chlorine atom or a bromine atom, m is 0, n is 0 or 1, a is 1, and b is 0. More preferably, the compound is 1 or 2, c is 0, 1 or 2, and d is 0.
Specific examples of preferred compound (III) include, for example, monochlorohydroxydiphenyl ether (wherein X is an oxygen atom, a is 1, Y is a chlorine atom, one of b or c is 1 and the other is 0) , D is 0, m is 0, and n is 0), dichlorohydroxydiphenyl ether (X is an oxygen atom, a is 1, Y is a chlorine atom, and b is 1) , C is 1, d is 0, m is 0, and n is 0), trichlorohydroxydiphenyl ether (X is an oxygen atom, a is 1, Y is a chlorine atom) , B or c is 1 and the other is 2, d is 0, m is 0 and n is 0), benzylchlorophenol (X is a methylene group, a is 1) Y is a chlorine atom, b is In it, c is 1, d is 0, m is 0, compounds wherein n is 0) and the like.
　特に好適な化合物（ＩＩＩ）は、５－クロロ－２－（２，４－ジクロロフェノキシ）フェノール（慣用名：トリクロサン）、４，４’－ジクロロ－２－ヒドロキシジフェニルエーテル（慣用名：ダイクロサン）、ｏ－ベンジル－ｐ－クロロフェノール（慣用名：クロロフェン）であり、４，４’－ジクロロ－２－ヒドロキシジフェニルエーテル（慣用名：ダイクロサン）が最も好ましい。
　（Ｃ）成分は、１種が単独で用いられてもよく、２種以上が組み合わされて用いられてもよい。 Particularly preferred compounds (III) are 5-chloro-2- (2,4-dichlorophenoxy) phenol (common name: triclosan), 4,4′-dichloro-2-hydroxydiphenyl ether (common name: dichrosan), o-Benzyl-p-chlorophenol (common name: chlorophene), and 4,4′-dichloro-2-hydroxydiphenyl ether (common name: dichrosan) is most preferred.
As the component (C), one type may be used alone, or two or more types may be used in combination.
　（Ｃ）成分の合計量（１００質量％）に対する化合物（ＩＩＩ）の合計量の割合は、６０質量％以上が好ましく、８０質量％以上がより好ましく、９０質量％以上がさらに好ましい。該化合物（ＩＩＩ）の合計量の割合の上限値は、１００質量％である。 The ratio of the total amount of the compound (III) to the total amount (100% by mass) of the component (C) is preferably 60% by mass or more, more preferably 80% by mass or more, and further preferably 90% by mass or more. The upper limit of the ratio of the total amount of the compound (III) is 100% by mass.
　本発明の液体洗浄剤組成物（１００質量％）中の（Ｃ）成分の含有量は、０．０１～３質量％が好ましく、０．０５～１質量％がより好ましく、０．１～０．５質量％がさらに好ましい。（Ｃ）成分の含有量が下限値以上であれば、優れた抗菌性が得られやすい。（Ｃ）成分の含有量が上限値以下であれば、良好な保存安定性を有する液体洗浄剤組成物となりやすい。 The content of the component (C) in the liquid detergent composition (100% by mass) of the present invention is preferably 0.01 to 3% by mass, more preferably 0.05 to 1% by mass, and 0.1 to 0%. More preferably, 5% by mass. If content of (C) component is more than a lower limit, the outstanding antimicrobial property will be easy to be obtained. If content of (C) component is below an upper limit, it will become easily a liquid detergent composition which has favorable storage stability.
　洗浄力と再汚染防止能を高める観点から、（Ｂ）成分と（Ｃ）成分との（Ｂ）／（Ｃ）比（質量比）は、３以上が好ましく、５以上がより好ましく、１０以上がさらに好ましい。また、（Ｂ）／（Ｃ）比は、抗菌性を高める観点から、３００以下が好ましく、２００以下がより好ましく、１００以下がさらに好ましい。
　（Ｂ）／（Ｃ）比は、３～３００が好ましい。 From the viewpoint of enhancing the detergency and ability to prevent recontamination, the (B) / (C) ratio (mass ratio) between the component (B) and the component (C) is preferably 3 or more, more preferably 5 or more, and more than 10 Is more preferable. In addition, the (B) / (C) ratio is preferably 300 or less, more preferably 200 or less, and even more preferably 100 or less, from the viewpoint of enhancing antibacterial properties.
The ratio (B) / (C) is preferably 3 to 300.
　本発明においては、（Ｃ）成分と香料を液体洗浄剤組成物中に配合する前に予備混合してプレミックスを形成させてもよい。プレミックスを形成することで、疎水性の高い（Ｃ）成分を液体洗浄剤組成物中により安定的に配合することができる。混合方法は一般的な方法で差し支えなく、混合時の温度は５～３０℃が好ましい。プレミックスは長時間貯蔵しても問題ないが、低温で貯蔵した場合には（Ｃ）成分が析出する恐れがあるため、貯蔵する場合には２０～３０℃が望ましい。 In the present invention, the premix may be formed by premixing the component (C) and the fragrance before blending them into the liquid detergent composition. By forming the premix, the highly hydrophobic component (C) can be more stably blended in the liquid detergent composition. The mixing method may be a general method, and the mixing temperature is preferably 5 to 30 ° C. The premix can be stored for a long period of time, but when stored at a low temperature, the component (C) may be precipitated.
［（Ｄ）成分］
　本発明の液体洗浄剤組成物には、（Ｄ）成分：アルキレンテレフタレート単位及びアルキレンイソフタレート単位のいずれか一方もしくは両方と、オキシアルキレン単位及びポリオキシアルキレン単位のいずれか一方もしくは両方とを有する水溶性ポリマーがさらに含有されていることが好ましい。
　なお、「水溶性ポリマー」とは、１０ｇのポリマーを、４０℃の条件で、１０００ｇの水に添加し、スターラー（太さ８ｍｍ、長さ５０ｍｍ、１リットルビーカー）で１２時間撹拌（２００ｒｐｍ）したときに完全に溶解するものをいう。 [(D) component]
The liquid detergent composition of the present invention has a component (D): a water-soluble solution having one or both of an alkylene terephthalate unit and an alkylene isophthalate unit, and one or both of an oxyalkylene unit and a polyoxyalkylene unit. It is preferable that a functional polymer is further contained.
“Water-soluble polymer” means that 10 g of polymer was added to 1000 g of water under the condition of 40 ° C. and stirred (200 rpm) for 12 hours with a stirrer (thickness 8 mm, length 50 mm, 1 liter beaker). Sometimes it completely dissolves.
　以下、アルキレンテレフタレート単位及びアルキレンイソフタレート単位をまとめて単位（ｄ１）という。また、オキシアルキレン単位及びポリオキシアルキレン単位をまとめて単位（ｄ２）という。
　アルキレンテレフタレート単位は下式（ＩＶ）で表される単位である。 Hereinafter, the alkylene terephthalate unit and the alkylene isophthalate unit are collectively referred to as a unit (d1). The oxyalkylene unit and the polyoxyalkylene unit are collectively referred to as a unit (d2).
The alkylene terephthalate unit is a unit represented by the following formula (IV).
Figure JPOXMLDOC01-appb-C000003
Figure JPOXMLDOC01-appb-C000003
　ただし、式（ＩＶ）中、Ｒ２１は低級アルキレン基である。
　Ｒ２１の低級アルキレン基の炭素数は、１～４であり、２～４が好ましい。 However, in formula (IV), R 21 is a lower alkylene group.
The lower alkylene group for R 21 has 1 to 4 carbon atoms, preferably 2 to 4 carbon atoms.
　アルキレンテレフタレート単位の具体例としては、例えば、エチレンテレフタレート単位、ｎ－プロピレンテレフタレート単位、イソプロピレンテレフタレート単位、ｎ－ブチレンテレフタレート単位、イソブチレンテレフタレート単位、ｓｅｃ－ブチレンテレフタレート単位、ｔｅｒｔ－ブチレンテレフタレート単位等が挙げられる。なかでも、イソプロピレンテレフタレート単位が好ましい。
　単位（ｄ１）としては、単一種類のアルキレンテレフタレート単位を用いてもよく、複数種類のアルキレンテレフタレート単位を組み合わせて用いてもよい。 Specific examples of the alkylene terephthalate unit include, for example, ethylene terephthalate unit, n-propylene terephthalate unit, isopropylene terephthalate unit, n-butylene terephthalate unit, isobutylene terephthalate unit, sec-butylene terephthalate unit, tert-butylene terephthalate unit and the like. It is done. Of these, isopropylene terephthalate units are preferred.
As the unit (d1), a single type of alkylene terephthalate unit may be used, or a plurality of types of alkylene terephthalate units may be used in combination.
　アルキレンイソフタレート単位は、下式（Ｖ）で表される単位である。 The alkylene isophthalate unit is a unit represented by the following formula (V).
Figure JPOXMLDOC01-appb-C000004
Figure JPOXMLDOC01-appb-C000004
　式（Ｖ）中、Ｒ２２は低級アルキレン基である。
　Ｒ２２の低級アルキレン基の炭素数は、１～４であり、２～４が好ましい。 In the formula (V), R 22 is a lower alkylene group.
The lower alkylene group for R 22 has 1 to 4 carbon atoms, preferably 2 to 4 carbon atoms.
　アルキレンイソフタレート単位の具体例としては、例えば、エチレンイソフタレート単位、プロピレンイソフタレート単位、ｎ－ブチレンイソフタレート単位、ｓｅｃ－ブチレンイソフタレート単位、ｔｅｒｔ－ブチレンイソフタレート単位等が挙げられる。これらの中ではプロピレンイソフタレート単位が好ましい。
　単位（ｄ１）としては、単一種類のアルキレンイソフタレート単位を用いてもよく、複数種類のアルキレンイソフタレート単位を組み合わせて用いてもよい。 Specific examples of the alkylene isophthalate unit include, for example, an ethylene isophthalate unit, a propylene isophthalate unit, an n-butylene isophthalate unit, a sec-butylene isophthalate unit, and a tert-butylene isophthalate unit. Of these, propylene isophthalate units are preferred.
As the unit (d1), a single type of alkylene isophthalate unit may be used, or a plurality of types of alkylene isophthalate units may be used in combination.
　単位（ｄ１）としては、アルキレンテレフタレート単位のみであってもよく、アルキレンイソフタレート単位のみであってもよく、アルキレンテレフタレート単位とアルキレンイソフタレート単位の両方であってもよい。 The unit (d1) may be only an alkylene terephthalate unit, only an alkylene isophthalate unit, or both an alkylene terephthalate unit and an alkylene isophthalate unit.
　単位（ｄ２）は、下式（ＶＩ）で表される単位である。
　－（Ｒ２３Ｏ）ｅ－　・・・（ＶＩ）
　ただし、Ｒ２３は低級アルキレン基であり、ｅは１～１００の整数である。 The unit (d2) is a unit represented by the following formula (VI).
-(R 23 O) e- (VI)
R 23 is a lower alkylene group, and e is an integer of 1 to 100.
　Ｒ２３の低級アルキレン基の炭素数は、１～４であり、２～４が好ましい。
　式（ＶＩ）において、ｅが１の場合はオキシアルキレン単位であり、ｅが２以上の場合はポリオキシアルキレン単位である。ｅは、１～８０の整数が好ましく、１～５０の整数がより好ましい。 The lower alkylene group for R 23 has 1 to 4 carbon atoms, preferably 2 to 4 carbon atoms.
In the formula (VI), when e is 1, it is an oxyalkylene unit, and when e is 2 or more, it is a polyoxyalkylene unit. e is preferably an integer of 1 to 80, and more preferably an integer of 1 to 50.
　単位（ｄ２）の具体例としては、例えば、オキシエチレン単位及びポリオキシエチレン単位；オキシプロピレン単位及びポリオキシプロピレン単位；ポリオキシエチレンポリオキシプロピレン単位等が挙げられる。なかでも、オキシエチレン単位及びポリオキシエチレン単位が好ましい。
　単位（ｄ２）としては、オキシアルキレン単位のみであってもよく、ポリオキシアルキレン単位のみであってもよく、オキシアルキレン単位とポリオキシアルキレン単位の両方であってもよい。 Specific examples of the unit (d2) include, for example, oxyethylene units and polyoxyethylene units; oxypropylene units and polyoxypropylene units; polyoxyethylene polyoxypropylene units. Of these, oxyethylene units and polyoxyethylene units are preferred.
The unit (d2) may be an oxyalkylene unit only, a polyoxyalkylene unit only, or both an oxyalkylene unit and a polyoxyalkylene unit.
　（Ｄ）成分は、単位（ｄ１）と単位（ｄ２）とが、ランダム又はブロックで重合している高分子化合物であることが好ましく、ブロックで重合している高分子化合物がより好ましい。 The component (D) is preferably a polymer compound in which the unit (d1) and the unit (d2) are polymerized randomly or in blocks, and more preferably a polymer compound polymerized in blocks.
　（Ｄ）成分は、単位（ｄ１）及び単位（ｄ２）以外の他の単位を含んでいてもよい。他の単位としては、例えば、重合開始剤や重合停止剤等に由来する単位や、その他共重合可能な単位が挙げられる。（Ｄ）成分が他の単位を含む場合、（Ｄ）成分の全単位に対する単位（ｄ１）と単位（ｄ２）との合計の割合は、８０モル％以上が好ましく、９０モル％以上がより好ましい。 (D) The component may contain units other than unit (d1) and unit (d2). Examples of other units include units derived from a polymerization initiator, a polymerization terminator and the like, and other copolymerizable units. When the component (D) contains other units, the total ratio of the unit (d1) and the unit (d2) to the total units of the component (D) is preferably 80 mol% or more, more preferably 90 mol% or more. .
　（Ｄ）成分としては、下式（ＶＩＩ）で表される化合物、下式（ＶＩＩＩ）で表される化合物が好ましい。 As the component (D), a compound represented by the following formula (VII) and a compound represented by the following formula (VIII) are preferable.
Figure JPOXMLDOC01-appb-C000005
Figure JPOXMLDOC01-appb-C000005
　ただし、式（ＶＩＩ）中、Ａ１及びＢ１はそれぞれ独立して水素原子又はメチル基であり、Ｒ１１及びＲ１２はそれぞれ独立して炭素数２～４のアルキレン基である。ｆは、－ＣＯ－（Ｃ６Ｈ４）－ＣＯＯ－Ｒ１２Ｏ－で表されるアルキレンテレフタレート単位の平均繰り返し数であり、０～１０である。ｇは、Ｒ１１Ｏの平均繰り返し数であり、１～１００である。
　また、式（ＶＩＩＩ）中、Ａ２及びＢ２はそれぞれ独立して水素原子又はメチル基であり、Ｒ１３及びＲ１４はそれぞれ独立して炭素数２～４のアルキレン基である。ｈは、－ＣＯ－（Ｃ６Ｈ４）－ＣＯＯ－Ｒ１４Ｏ－で表されるアルキレンイソフタレート単位の平均繰り返し数であり、０～１０である。ｉは、Ｒ１３Ｏの平均繰り返し数であり、１～１００である。 However, in formula (VII), A 1 and B 1 are each independently a hydrogen atom or a methyl group, and R 11 and R 12 are each independently an alkylene group having 2 to 4 carbon atoms. f is the average number of repeating alkylene terephthalate units represented by —CO— (C 6 H 4 ) —COO—R 12 O—, and is 0 to 10. g is the average number of repetitions of R 11 O, and is 1 to 100.
In formula (VIII), A 2 and B 2 are each independently a hydrogen atom or a methyl group, and R 13 and R 14 are each independently an alkylene group having 2 to 4 carbon atoms. h is an average repeating number of alkylene isophthalate units represented by —CO— (C 6 H 4 ) —COO—R 14 O—, and is 0 to 10. i is the average number of repetitions of R 13 O, and is 1 to 100.
　式（ＶＩＩ）におけるＡ１及びＢ１は、ともにメチル基であることが好ましい。
　Ｒ１１及びＲ１２は、炭素数２～３のアルキレン基であることが好ましい。
　ｆは、０．５～５が好ましく、０．５～２．５がより好ましい。
　ｇは、１～８０が好ましく、１～５０がより好ましく、１０～５０がさらに好ましく、２０～３０が特に好ましい。
　式（ＶＩＩ）におけるｆとｇとの比率は、１：５～１：２０が好ましく、１：８～１：１８がより好ましい。ｆとｇとの比率が前記範囲であれば、ソイルリリース性能が十分に発揮されやすく、また水に対する溶解性が向上する。 A 1 and B 1 in formula (VII) are preferably both methyl groups.
R 11 and R 12 are preferably alkylene groups having 2 to 3 carbon atoms.
f is preferably 0.5 to 5, and more preferably 0.5 to 2.5.
g is preferably 1 to 80, more preferably 1 to 50, still more preferably 10 to 50, and particularly preferably 20 to 30.
The ratio of f and g in formula (VII) is preferably 1: 5 to 1:20, more preferably 1: 8 to 1:18. If the ratio of f and g is in the above range, the soil release performance is sufficiently exhibited and the solubility in water is improved.
　式（ＶＩＩＩ）におけるＡ２及びＢ２は、ともにメチル基であることが好ましい。
　Ｒ１３及びＲ１４は、炭素数２～３のアルキレン基であることが好ましい。
　ｈは、０．５～５が好ましく、０．５～２．５がより好ましい。
　ｉは、１～８０が好ましく、１～５０がより好ましく、１０～５０がさらに好ましく、２０～３０が特に好ましい。
　式（ＶＩＩＩ）におけるｈとｉとの比率は、式（ＶＩＩ）におけるｆとｇとの比率と同様の理由から、１：５～１：２０が好ましく、１：８～１：１８がより好ましい。 Both A 2 and B 2 in formula (VIII) are preferably methyl groups.
R 13 and R 14 are preferably alkylene groups having 2 to 3 carbon atoms.
h is preferably 0.5 to 5, and more preferably 0.5 to 2.5.
i is preferably 1 to 80, more preferably 1 to 50, further preferably 10 to 50, and particularly preferably 20 to 30.
The ratio of h to i in formula (VIII) is preferably 1: 5 to 1:20, more preferably 1: 8 to 1:18, for the same reason as the ratio of f to g in formula (VII). .
　（Ｄ）成分の重量平均分子量は、５００～１００００が好ましく、８００～９０００がより好ましく、１０００～８０００がさらに好ましい。重量平均分子量が前記範囲内であれば、水への溶解分散性が向上し、かつ疎水性繊維（特にポリエステル）の吸水性向上効果が十分に発現しやすく、また液体洗浄剤組成物の液外観が良好になる。
　なお、本発明における重量平均分子量は、溶媒としてＴＨＦ（テトラヒドロフラン）を用いてＧＰＣ（ゲルパーミネーションクロマトグラフィー）により測定した値を、ＰＥＧ（ポリエチレングリコール）を較正曲線に用いて換算した値をいう。 The weight average molecular weight of the component (D) is preferably 500 to 10,000, more preferably 800 to 9000, and still more preferably 1000 to 8000. If the weight average molecular weight is within the above range, the solubility and dispersibility in water will be improved, and the effect of improving the water absorption of hydrophobic fibers (especially polyester) will be sufficiently exhibited, and the liquid appearance of the liquid detergent composition Will be better.
In addition, the weight average molecular weight in this invention says the value which converted the value measured by GPC (gel permeation chromatography) using THF (tetrahydrofuran) as a solvent using PEG (polyethylene glycol) for the calibration curve.
　（Ｄ）成分としては、市販品を使用することができる。例えば、商品名「ＴｅｘＣａｒｅ　ＳＲＮ－１００」（クラリアント社製、重量平均分子量：２０００～３０００）、商品名「ＴｅｘＣａｒｅ　ＳＲＮ－３００」（クラリアント社製、重量平均分子量：７０００）、商品名「Ｒｅｐｅｌ－Ｏ－Ｔｅｘ　Ｃｒｙｓｔａｌ」（ローディア社製）、商品名「Ｒｅｐｅｌ－Ｏ－Ｔｅｘ　ＱＣ」（ローディア社製）等が挙げられる。なかでも、水への溶解性が高く、保存後の洗浄性能の低下が少ない点から、ＴｅｘＣａｒｅ　ＳＲＮ－１００や、ＴｅｘＣａｒｅ　ＳＲＮ－１００の７０質量％水溶液である商品名「ＴｅｘＣａｒｅ　ＳＲＮ－１７０」（クラリアント社製）が好ましく、ＴｅｘＣａｒｅ　ＳＲＮ－１７０が特に好ましい。 (D) As a component, a commercial item can be used. For example, the trade name “TexCare SRN-100” (manufactured by Clariant, weight average molecular weight: 2000 to 3000), the trade name “TexCare SRN-300” (manufactured by Clariant, weight average molecular weight: 7000), and the trade name “Repel-O”. -Tex Crystal "(manufactured by Rhodia), trade name" Repel-O-Tex QC "(manufactured by Rhodia) and the like. Among them, the trade name “TexCare SRN-170” (Clariant), which is a 70% by mass aqueous solution of TexCare SRN-100 or TexCare SRN-100, is highly soluble in water and has little deterioration in cleaning performance after storage. Manufactured by the company), and TexCare SRN-170 is particularly preferable.
　（Ｄ）成分は、例えば、Ｊｏｕｒｎａｌ　ｏｆ　Ｐｏｌｙｍｅｒ　Ｓｃｉｅｎｃｅ，第３巻，６０９～６３０ページ（１９４８年）、Ｊｏｕｒｎａｌ　ｏｆ　Ｐｏｌｙｍｅｒ　Ｓｃｉｅｎｃｅ，第８巻，１～２２ページ（１９５１年）、特開昭６１－２１８６９９号公報等に記載の方法で合成することもできる。
　（Ｄ）成分は、１種が単独で用いられてもよく、２種以上が組み合わされて用いられてもよい。 Component (D) is, for example, Journal of Polymer Science, Volume 3, pages 609 to 630 (1948), Journal of Polymer Science, Volume 8, pages 1 to 22 (1951), JP-A-61-218699. It is also possible to synthesize by the method described in the publication number.
As the component (D), one type may be used alone, or two or more types may be used in combination.
　本発明の液体洗浄体組成物（１００質量％）中の（Ｄ）成分の含有量は、０．１～５質量％が好ましく、０．３～３質量％がより好ましい。（Ｄ）成分の含有量が下限値以上であれば、化繊に付着する洗液中の汚れ及び菌量が抑えられ、初発菌数をより減少させることができる。これにより、部屋干し中の菌数の増加量をより低減できるため、部屋干し臭発生の抑制効果が得られやすくなる。（Ｄ）成分の含有量が上限値以下であれば、液体洗浄剤組成物の外観の安定性がより良好になる。 The content of the component (D) in the liquid cleaning composition (100% by mass) of the present invention is preferably 0.1 to 5% by mass, and more preferably 0.3 to 3% by mass. If content of (D) component is more than a lower limit, the stain | pollution | contamination in washing | cleaning liquid and the amount of bacteria which adhere to a chemical fiber will be suppressed, and the number of initial germs can be reduced more. Thereby, since the increase amount of the number of microbes during room drying can be reduced more, it becomes easy to obtain the suppression effect of room drying odor generation. If content of (D) component is below an upper limit, the stability of the external appearance of a liquid cleaning composition will become more favorable.
［（Ｅ）成分］
　本発明の液体洗浄剤組成物は、（Ｅ）成分：ポリアルキレンオキシド鎖を含むアルキレンアミン構造単位を有するポリアルキレンアミンアルキレンオキシド系共重合体がさらに含有されていることが好ましい。
　本発明では、（Ｄ）成分と（Ｅ）成分とを併用することで、綿と化繊の混紡衣類への抗菌効果、部屋干し臭発生の抑制効果が特に高くなる。 [(E) component]
The liquid detergent composition of the present invention preferably further contains (E) component: a polyalkyleneamine alkylene oxide copolymer having an alkyleneamine structural unit containing a polyalkyleneoxide chain.
In the present invention, the combined use of the component (D) and the component (E) particularly increases the antibacterial effect on the cotton and synthetic fiber blended garment and the effect of suppressing the generation of room-dried odor.
　（Ｅ）成分は、ポリアルキレンオキシド鎖を含むアルキレンアミン構造単位を有するポリアルキレンアミンアルキレンオキシド系共重合体であり、すなわちポリアルキレンイミンのアルキレンオキシド付加体である。 The component (E) is a polyalkyleneamine alkylene oxide copolymer having an alkyleneamine structural unit containing a polyalkyleneoxide chain, that is, an alkyleneoxide adduct of polyalkyleneimine.
　ポリアルキレンイミンは、下式（ＩＸ）で表される。
　ＮＨ２－Ｒ３１－（ＮＡ３－Ｒ３２）ｊ－ＮＨ２　・・・（ＩＸ）
　ただし、式（ＩＸ）中、Ｒ３１及びＲ３２は、それぞれ独立して炭素数２～６のアルキレン基であり、Ａ３は、水素原子又は分岐による別のポリアミン鎖である。ｊは、ＮＡ３－Ｒ３２の平均繰り返し数であり、１以上の数である。Ａ３のすべてが水素原子となることはないものとする。
　Ｒ３１及びＲ３２のアルキレン基は、直鎖状であってもよく、分岐鎖状であってもよい。Ｒ３１及びＲ３２のアルキレン基の炭素数は、２～４が好ましく、２が特に好ましい。 The polyalkyleneimine is represented by the following formula (IX).
NH 2 —R 31 — (NA 3 —R 32 ) j —NH 2 (IX)
However, in formula (IX), R 31 and R 32 are each independently an alkylene group having 2 to 6 carbon atoms, and A 3 is a hydrogen atom or another polyamine chain formed by branching. j is the average number of repetitions of NA 3 -R 32 , and is a number of 1 or more. It is assumed that not all of A 3 are hydrogen atoms.
The alkylene group for R 31 and R 32 may be linear or branched. The number of carbon atoms of the alkylene group of R 31 and R 32 is preferably 2 to 4, and 2 is particularly preferable.
　ポリアルキレンイミンは、炭素数２～６のアルキレンイミンの１種又は２種以上を常法により重合することで得られる。炭素数２～６のアルキレンイミンとしては、エチレンイミン、プロピレンイミン、１，２－ブチレンイミン、２，３－ブチレンイミン、１，１－ジメチルエチレンイミン等が挙げられる。
　ポリアルキレンイミンとしては、ポリエチレンイミン（ＰＥＩ）、ポリプロピレンイミンが好ましく、ＰＥＩがより好ましい。ＰＥＩは、エチレンイミンを重合することによって得られ、その構造中に、１級、２級及び３級アミン窒素原子を含む分岐鎖構造を有している。 The polyalkyleneimine can be obtained by polymerizing one or more of alkyleneimines having 2 to 6 carbon atoms by a conventional method. Examples of the alkyleneimine having 2 to 6 carbon atoms include ethyleneimine, propyleneimine, 1,2-butyleneimine, 2,3-butyleneimine, 1,1-dimethylethyleneimine and the like.
As polyalkyleneimine, polyethyleneimine (PEI) and polypropyleneimine are preferable, and PEI is more preferable. PEI is obtained by polymerizing ethyleneimine and has a branched chain structure containing primary, secondary and tertiary amine nitrogen atoms in the structure.
　ポリアルキレンイミンの重量平均分子量は、２００～２０００が好ましく、３００～１５００がより好ましく、４００～１０００がさらに好ましく、５００～８００が特に好ましい。
　ポリアルキレンイミン１分子が有する活性水素の数は、５～３０個が好ましく、７～２５個がより好ましく、１０～２０個がさらに好ましい。 The weight average molecular weight of the polyalkyleneimine is preferably 200 to 2000, more preferably 300 to 1500, still more preferably 400 to 1000, and particularly preferably 500 to 800.
The number of active hydrogens possessed by one polyalkyleneimine molecule is preferably 5 to 30, more preferably 7 to 25, and even more preferably 10 to 20.
　ポリアルキレンイミンに付加するアルキレンオキシドとしては、例えば、炭素数２～４のアルキレンオキシドが挙げられる。なかでも、エチレンオキシド、プロピレンオキシドが好ましく、エチレンオキシドがより好ましい。
　ポリアルキレンイミンにアルキレンオキシドを付加する方法としては、例えば、水酸化ナトリウム、水酸化カリウム、ナトリウムメチラート等の塩基性触媒の存在下、出発物質であるポリアルキレンイミンに対して、１００～１８０℃でエチレンオキシド等のアルキレンオキシドを付加させる方法等が挙げられる。 Examples of the alkylene oxide added to the polyalkyleneimine include alkylene oxides having 2 to 4 carbon atoms. Of these, ethylene oxide and propylene oxide are preferable, and ethylene oxide is more preferable.
As a method for adding an alkylene oxide to a polyalkyleneimine, for example, in the presence of a basic catalyst such as sodium hydroxide, potassium hydroxide, sodium methylate, etc., 100 to 180 ° C. with respect to the starting polyalkyleneimine. And a method of adding an alkylene oxide such as ethylene oxide.
　（Ｅ）成分としては、例えば、ポリアルキレンイミンのエチレンオキシド付加体、ポリアルキレンイミンのプロピレンオキシド付加体、ポリアルキレンイミンのエチレンオキシド－プロピレンオキシド付加体等が挙げられる。なお、ポリアルキレンイミンのエチレンオキシド－プロピレンオキシド付加体は、ポリアルキレンイミンにエチレンオキシド及びプロピレンオキシドを付加したものであり、ポリアルキレンイミンに対するエチレンオキシドとプロピレンオキシドの付加順序や付加形態（ブロック状、ランダム状）は任意である。
　（Ｅ）成分としては、ポリアルキレンイミンのエチレンオキシド付加体、ポリアルキレンイミンのエチレンオキシド－プロピレンオキシド付加体が好ましく、ポリアルキレンイミンのエチレンオキシド付加体がより好ましい。 Examples of the component (E) include polyalkyleneimine ethylene oxide adducts, polyalkyleneimine propylene oxide adducts, polyalkyleneimine ethylene oxide-propylene oxide adducts, and the like. The ethylene oxide-propylene oxide adduct of polyalkyleneimine is obtained by adding ethylene oxide and propylene oxide to polyalkyleneimine, and the order of addition or form of addition of ethylene oxide and propylene oxide to polyalkyleneimine (block or random) Is optional.
As the component (E), an ethylene oxide adduct of polyalkyleneimine and an ethylene oxide-propylene oxide adduct of polyalkyleneimine are preferable, and an ethylene oxide adduct of polyalkyleneimine is more preferable.
　ポリアルキレンイミンのアルキレンオキシド付加体における、原料であるポリアルキレンイミンが有する活性水素１原子に対するアルキレンオキシドの平均付加数は、５～４０個が好ましく、１０～３０個がより好ましい。すなわち、原料であるポリアルキレンイミンが有する活性水素１モルあたりのアルキレンオキシドの平均付加モル数は、５～４０モルが好ましく、１０～３０モルがより好ましい。 In the alkylene oxide adduct of polyalkyleneimine, the average number of alkylene oxides added per active hydrogen atom of the starting polyalkyleneimine is preferably 5 to 40, and more preferably 10 to 30. That is, the average number of added moles of alkylene oxide per mole of active hydrogen contained in the starting polyalkylenimine is preferably 5 to 40 moles, and more preferably 10 to 30 moles.
　（Ｅ）成分の重量平均分子量は、１０００～８００００が好ましく、２０００～５００００がより好ましく、５０００～３００００がさらに好ましく、１００００～２００００が特に好ましい。 The weight average molecular weight of the component (E) is preferably 1000 to 80000, more preferably 2000 to 50000, still more preferably 5000 to 30000, and particularly preferably 10,000 to 20000.
　（Ｅ）成分としては、合成品を用いてもよく、市販品を用いてもよい。
　市販品としては、例えば、ＢＡＳＦ社製の商品名「Ｓｏｋａｌａｎ　ＨＰ２０」等が挙げられる。
　（Ｅ）成分は、１種が単独で用いられてもよく、２種以上が組み合わされて用いられてもよい。 As the component (E), a synthetic product or a commercially available product may be used.
As a commercial item, the brand name "Sokalan HP20" by BASF Corporation etc. are mentioned, for example.
As the component (E), one type may be used alone, or two or more types may be used in combination.
　本発明の液体洗浄剤組成物（１００質量％）中の（Ｅ）成分の含有量は、０．１～５質量％が好ましく、０．３～３質量％がより好ましい。（Ｅ）成分の含有量が下限値以上であれば、（Ｅ）成分が綿繊維に吸着することで、付着する洗液中の汚れ及び菌量が抑えられ、初発菌数をより減少させることができる。これにより、部屋干し中の菌数の増加量をより低減できるため、部屋干し臭発生の抑制効果が得られやすくなる。（Ｅ）成分の含有量が上限値以下であれば、液体洗浄剤組成物の外観の安定性がより良好になる。 The content of the component (E) in the liquid detergent composition (100% by mass) of the present invention is preferably 0.1 to 5% by mass, and more preferably 0.3 to 3% by mass. If the content of the component (E) is equal to or higher than the lower limit, the component (E) is adsorbed to the cotton fiber, so that the dirt and the amount of bacteria in the washing solution to be adhered can be suppressed, and the number of initial bacteria is further reduced. Can do. Thereby, since the increase amount of the number of microbes during room drying can be reduced more, it becomes easy to obtain the suppression effect of room drying odor generation. If content of (E) component is below an upper limit, the stability of the external appearance of a liquid detergent composition will become more favorable.
［（Ｆ）成分］
　本発明の液体洗浄剤組成物には、（Ｆ）成分：カチオン界面活性剤がさらに含有されていることが好ましい。（Ｆ）成分が含有されていることで、部屋干し臭の発生を抑制する効果がより高くなる。また、（Ｃ）成分と（Ｆ）成分とを併用することで、綿と化繊の混紡衣類への抗菌効果、部屋干し臭発生の抑制効果が特に高くなる。
　（Ｆ）成分としては、例えば、第４級アンモニウム塩を用いることができる。第４級アンモニウム塩としては、例えば、通常、衣料用洗剤に用いられている従来公知のものが挙げられる。なかでも、好ましい第４級アンモニウム塩としては、高い抗菌効果又は殺菌効果が得られやすいことから、後述する化合物（ｆ１）、化合物（ｆ２）、化合物（ｆ３）が挙げられる。 [(F) component]
The liquid detergent composition of the present invention preferably further contains (F) component: a cationic surfactant. By containing (F) component, the effect which suppresses generation | occurrence | production of room drying odor becomes higher. Moreover, by using together (C) component and (F) component, the antibacterial effect to the mixed clothing of cotton and a synthetic fiber, and the suppression effect of room-drying odor generation become especially high.
As the component (F), for example, a quaternary ammonium salt can be used. As a quaternary ammonium salt, the conventionally well-known thing normally used for the detergent for clothes is mentioned, for example. Among these, preferred quaternary ammonium salts include the compound (f1), the compound (f2), and the compound (f3) described later because a high antibacterial effect or bactericidal effect is easily obtained.
（化合物（ｆ１））
　化合物（ｆ１）は、下式（ｆ１）で表される化合物である。 (Compound (f1))
The compound (f1) is a compound represented by the following formula (f1).
Figure JPOXMLDOC01-appb-C000006
Figure JPOXMLDOC01-appb-C000006
　ただし、式（ｆ１）中、Ｒ４１～Ｒ４４のうちの２つ以上は、それぞれ独立して、炭素数１～３のアルキル基、又は炭素数１～３のヒドロキシアルキル基であり、それ以外は、炭素数８～２２の直鎖状もしくは分岐鎖状のアルキル基、又は炭素数８～２２の直鎖状もしくは分岐鎖状のアルケニル基である。ＱＡ －は、ハロゲンイオン又はアルキル硫酸イオンである。 However, in formula (f1), two or more of R 41 to R 44 are each independently an alkyl group having 1 to 3 carbon atoms or a hydroxyalkyl group having 1 to 3 carbon atoms; Is a linear or branched alkyl group having 8 to 22 carbon atoms or a linear or branched alkenyl group having 8 to 22 carbon atoms. Q A - is a halogen ion or an alkyl sulfate ion.
　化合物（ｆ１）としては、下記の化合物（ｆ１－１）、化合物（ｆ１－２）が好ましい。 As the compound (f1), the following compound (f1-1) and compound (f1-2) are preferable.
　化合物（ｆ１－１）：Ｒ４１～Ｒ４３の３つが、それぞれ独立して、炭素数１～３のアルキル基又は炭素数１～３のヒドロキシアルキル基であり、Ｒ４４が、炭素数８～２２の直鎖状もしくは分岐鎖状のアルキル基、又は炭素数８～２２の直鎖状もしくは分岐鎖状のアルケニル基である化合物。
　化合物（ｆ１－１）におけるＲ４１～Ｒ４３は、それぞれ炭素数１～３のアルキル基であることが好ましく、それぞれメチル基であることがより好ましい。なかでも、Ｒ４１～Ｒ４３がいずれもメチル基であることが特に好ましい。
　Ｒ４４のアルキル基又はアルケニル基における炭素数は、８～２２であり、１０～２２が好ましく、１６～１８がより好ましい。また、Ｒ４４は、直鎖状もしくは分岐鎖状のアルキル基であることが好ましく、直鎖状のアルキル基であることがより好ましい。 Compound (f1-1): three of R 41 to R 43 are each independently an alkyl group having 1 to 3 carbon atoms or a hydroxyalkyl group having 1 to 3 carbon atoms, and R 44 is an alkyl group having 8 to A compound having a linear or branched alkyl group having 22 or a linear or branched alkenyl group having 8 to 22 carbon atoms.
R 41 to R 43 in the compound (f1-1) are each preferably an alkyl group having 1 to 3 carbon atoms, and more preferably a methyl group. In particular, it is particularly preferable that all of R 41 to R 43 are methyl groups.
The carbon number in the alkyl group or alkenyl group of R 44 is 8 to 22, preferably 10 to 22, and more preferably 16 to 18. R 44 is preferably a linear or branched alkyl group, and more preferably a linear alkyl group.
　化合物（ｆ１－２）：Ｒ４１及びＲ４２が、それぞれ独立して、炭素数８～２２の直鎖状もしくは分岐鎖状のアルキル基、又は炭素数８～２２の直鎖状もしくは分岐鎖状のアルケニル基であり、Ｒ４３及びＲ４４が、それぞれ独立して、炭素数１～３のアルキル基又は炭素数１～３のヒドロキシアルキル基である化合物。
　化合物（ｆ１－２）のＲ４１及びＲ４２のアルキル基又はアルケニル基における炭素数は、それぞれ独立に８～２２であり、８～１２が好ましく、８～１０がより好ましい。また、Ｒ４１及びＲ４２は、それぞれ直鎖状もしくは分岐鎖状のアルキル基であることが好ましく、それぞれ直鎖状のアルキル基であることがより好ましい。なかでも、Ｒ４１及びＲ４２がいずれも直鎖状のアルキル基であることが特に好ましい。
　Ｒ４３及びＲ４４は、それぞれ炭素数１～３のアルキル基であることが好ましく、それぞれメチル基であることがより好ましい。なかでも、Ｒ４３及びＲ４４がいずれもメチル基であることが特に好ましい。 Compound (f1-2): R 41 and R 42 are each independently a linear or branched alkyl group having 8 to 22 carbon atoms, or a linear or branched chain group having 8 to 22 carbon atoms. Wherein R 43 and R 44 are each independently an alkyl group having 1 to 3 carbon atoms or a hydroxyalkyl group having 1 to 3 carbon atoms.
The number of carbon atoms in the alkyl group or alkenyl group of R 41 and R 42 of the compound (f1-2) is independently 8 to 22, preferably 8 to 12, and more preferably 8 to 10. R 41 and R 42 are each preferably a linear or branched alkyl group, and more preferably a linear alkyl group. Among these, it is particularly preferable that both R 41 and R 42 are linear alkyl groups.
R 43 and R 44 are each preferably an alkyl group having 1 to 3 carbon atoms, and more preferably a methyl group. Among these, it is particularly preferable that R 43 and R 44 are both methyl groups.
　前記式（ｆ１）中、ハロゲンイオンを構成するＱＡとしては、フッ素原子、塩素原子、臭素原子、ヨウ素原子等が挙げられ、塩素原子が好ましい。アルキル硫酸イオンを構成するＱＡとしては、炭素数１～３のアルキル基を有するものが好ましく、例えばメチル硫酸等が挙げられる。 In the formula (f1), examples of Q A constituting the halogen ion include a fluorine atom, a chlorine atom, a bromine atom, and an iodine atom, and a chlorine atom is preferable. Q A constituting the alkyl sulfate ion is preferably one having an alkyl group having 1 to 3 carbon atoms, such as methyl sulfate.
　化合物（ｆ１）の具体例としては、塩化アルキル（炭素数１２～１６）トリメチルアンモニウム、塩化ジデシルジメチルアンモニウム等が挙げられる。 Specific examples of the compound (f1) include alkyl chloride (C12-16) trimethylammonium, didecyldimethylammonium chloride and the like.
（化合物（ｆ２））
　化合物（ｆ２）は、下式（ｆ２）で表される化合物である。 (Compound (f2))
The compound (f2) is a compound represented by the following formula (f2).
Figure JPOXMLDOC01-appb-C000007
Figure JPOXMLDOC01-appb-C000007
　ただし、式（ｆ２）中、Ｒ４５は、炭素数８～２２の直鎖状もしくは分岐鎖状のアルキル基、又は炭素数８～２２の直鎖状もしくは分岐鎖状のアルケニル基である。Ｒ４６は、メチル基又はトリル基である。ｐ及びｑは、エチレンオキシ基の平均繰り返し数を示し、それぞれ独立して０以上の数であって、ｐ＋ｑが１０以上である。ＱＢ －は、ハロゲンイオン又はアルキル硫酸イオンである。 However, in the formula (f2), R 45 is a linear or branched alkyl group having 8 to 22 carbon atoms or a linear or branched alkenyl group having 8 to 22 carbon atoms. R 46 is a methyl group or a tolyl group. p and q represent the average number of repeating ethyleneoxy groups, each independently a number of 0 or more, and p + q is 10 or more. Q B - is a halogen ion or an alkyl sulfate ion.
　式（ｆ２）のＲ４５のアルキル基又はアルケニル基における炭素数は、８～２２であり、１０～１８が好ましい。Ｒ４５は、直鎖状もしくは分岐鎖状のアルキル基であることが好ましく、直鎖状のアルキル基であることがより好ましい。
　式（ｆ２）のＲ４６は、メチル基又はトリル基である。
　前記式（ｆ２）中、ｐ＋ｑは、１０以上であり、１０～５０が好ましい。ｐ＋ｑが１０未満では、被洗物に付着している汚れの分散効果が小さく、被洗物からの汚れ除去効果が得られにくくなることがある。
　ＱＢ －は、前記式（ｆ１）におけるＱＡ －と同様のものが挙げられる。 The number of carbon atoms in the alkyl group or alkenyl group of R 45 in the formula (f2) is 8 to 22, and preferably 10 to 18. R 45 is preferably a linear or branched alkyl group, and more preferably a linear alkyl group.
R 46 in formula (f2) is a methyl group or a tolyl group.
In the formula (f2), p + q is 10 or more, preferably 10-50. When p + q is less than 10, the effect of dispersing dirt adhering to the article to be washed is small, and the effect of removing dirt from the article to be washed may be difficult to obtain.
Q B - is, Q A in the formula (f1) - include the same one.
　化合物（ｆ２）としては、Ｒ４５が炭素数１０～１８の直鎖状もしくは分岐鎖状のアルキル基、又は炭素数１０～１８の直鎖状もしくは分岐鎖状のアルケニル基であり、Ｒ４６がメチル基又はトリル基であり、ｐ＋ｑが１０以上であり、ＱＢ －がハロゲンイオン又はアルキル硫酸イオンである化合物等が挙げられる。 In the compound (f2), R 45 is a linear or branched alkyl group having 10 to 18 carbon atoms, or a linear or branched alkenyl group having 10 to 18 carbon atoms, and R 46 is And a compound in which it is a methyl group or a tolyl group, p + q is 10 or more, and Q B − is a halogen ion or an alkyl sulfate ion.
（化合物（ｆ３））
　化合物（ｆ３）は、下式（ｆ３）で表される化合物である。 (Compound (f3))
The compound (f3) is a compound represented by the following formula (f3).
Figure JPOXMLDOC01-appb-C000008
Figure JPOXMLDOC01-appb-C000008
　ただし、式（ｆ３）中、Ｒ４７及びＲ４８は、それぞれ独立して、炭素数１～３のアルキル基又は炭素数１～３のヒドロキシアルキル基であり、Ｒ４９は、炭素数８～２２の直鎖状もしくは分岐鎖状のアルキル基又はアルケニル基であり、Ｒ５０は、炭素数１～３のアルキレン基である。ＱＣ －は、ハロゲンイオン又はアルキル硫酸イオンである。 However, in the formula (f3), R 47 and R 48 are each independently an alkyl group having 1 to 3 carbon atoms or a hydroxyalkyl group having 1 to 3 carbon atoms, and R 49 is an alkyl group having 8 to 22 carbon atoms. A linear or branched alkyl group or alkenyl group, and R 50 is an alkylene group having 1 to 3 carbon atoms. Q C - is a halogen ion or an alkyl sulfate ion.
　式（ｆ３）中のＲ４７及びＲ４８は、それぞれ炭素数１～３のアルキル基であることが好ましく、それぞれメチル基であることがより好ましい。なかでも、Ｒ４７及びＲ４８がいずれもメチル基であることが特に好ましい。
　Ｒ４９のアルキル基又はアルケニル基における炭素数は、８～２２であり、１０～１８が好ましく、１２～１４がより好ましい。Ｒ４９は、直鎖状もしくは分岐鎖状のアルキル基であることが好ましく、直鎖状のアルキル基であることがより好ましい。
　Ｒ５０は、炭素数１～３のアルキレン基であり、メチレン基であることが好ましい。
　ＱＣ －は、前記式（ｆ１）におけるＱＡ －と同様のものが挙げられ、なかでもハロゲンイオンが好ましい。 R 47 and R 48 in formula (f3) are each preferably an alkyl group having 1 to 3 carbon atoms, and more preferably a methyl group. Among these, it is particularly preferable that both R 47 and R 48 are methyl groups.
The number of carbon atoms in the alkyl group or alkenyl group of R 49 is from 8 to 22, preferably from 10 to 18, and more preferably from 12 to 14. R 49 is preferably a linear or branched alkyl group, and more preferably a linear alkyl group.
R 50 is an alkylene group having 1 to 3 carbon atoms, preferably a methylene group.
Q C - is, Q A in the formula (f1) - like can be mentioned and, among them halogen ion are preferred.
　化合物（ｆ３）の具体例としては、椰子アルキルジメチルベンジルアンモニウムクロライド等が挙げられる。 Specific examples of the compound (f3) include coconut alkyldimethylbenzylammonium chloride.
　（Ｆ）成分は、１種が単独で用いられてもよく、２種以上が組み合わされて用いられてもよい。
　（Ｆ）成分としては、化合物（ｆ１）、化合物（ｆ２）及び化合物（ｆ３）からなる群から選ばれる少なくとも１種が好ましい。なかでも、（Ｃ）成分と併用した際に、より部屋干し臭の発生を抑制する効果が高くなることから、化合物（ｆ１）がより好ましい。 As the component (F), one type may be used alone, or two or more types may be used in combination.
(F) As a component, at least 1 sort (s) chosen from the group which consists of a compound (f1), a compound (f2), and a compound (f3) is preferable. Especially, since the effect which suppresses generation | occurrence | production of room drying odor becomes high when used together with (C) component, a compound (f1) is more preferable.
　本発明の液体洗浄剤組成物（１００質量％）中の（Ｆ）成分の含有量は、０．３～５質量％が好ましく、１～３質量％がより好ましく、１．５～２質量％がさらに好ましい。（Ｆ）成分の含有量が、前記下限値以上であれば、部屋干し臭の発生を抑制する効果がより得られやすくなる。（Ｆ）成分の含有量が前記上限値以下であれば、液体洗浄剤組成物の液安定性（着色の抑制、粘度低下の防止効果、香気安定化等）がより向上する。また、被洗物に対する移染や再汚染等が抑制されやすい。さらに、経済的にも有利となる。 The content of the component (F) in the liquid detergent composition (100% by mass) of the present invention is preferably 0.3 to 5% by mass, more preferably 1 to 3% by mass, and 1.5 to 2% by mass. Is more preferable. If content of (F) component is more than the said lower limit, the effect which suppresses generation | occurrence | production of room-drying odor will become easier to be acquired. If content of (F) component is below the said upper limit, liquid stability (suppression of a coloring, the prevention effect of a viscosity fall, aroma stabilization, etc.) of a liquid detergent composition will improve more. In addition, transfer and recontamination of the object to be washed are easily suppressed. Furthermore, it becomes economically advantageous.
　（Ｃ）成分と（Ｆ）成分との（Ｃ）／（Ｆ）比（質量比）は、０．００２～５が好ましく、０．０５～１がより好ましく、０．１～０．７５がさらに好ましい。（Ｃ）／（Ｆ）比が前記下限値以上であれば、部屋干し臭の発生を抑制する効果が得られやすい。また、被洗物への再汚染の点で不具合を生じるおそれが少ない。（Ｃ）／（Ｆ）比が前記上限値以下であれば、外観安定性を損なうおそれが少ない。
　なお、（Ｃ）／（Ｆ）比（質量比）とは、液体洗浄剤組成物に含まれる（Ｆ）成分の含有量（質量％）に対する、（Ｃ）成分の含有量（質量％）の割合を意味する。 The (C) / (F) ratio (mass ratio) between the component (C) and the component (F) is preferably 0.002 to 5, more preferably 0.05 to 1, and 0.1 to 0.75. Further preferred. If (C) / (F) ratio is more than the said lower limit, the effect which suppresses generation | occurrence | production of room-drying odor will be easy to be acquired. In addition, there is little risk of problems in terms of recontamination of the object to be washed. If the ratio (C) / (F) is less than or equal to the upper limit, there is little risk of impairing appearance stability.
In addition, (C) / (F) ratio (mass ratio) is the content (mass%) of the component (C) with respect to the content (mass%) of the component (F) contained in the liquid detergent composition. Mean percentage.
［水］
　本発明の液体洗浄剤組成物は、製造時のハンドリングのし易さ、使用する際の水への溶解性等の点から、水を含有することが好ましい。 [water]
The liquid detergent composition of the present invention preferably contains water from the viewpoint of ease of handling during production, solubility in water during use, and the like.
［任意成分］
　本発明の液体洗浄剤組成物は、（Ａ）～（Ｆ）成分以外に、液体洗浄剤組成物に通常用いられる任意成分を含有してもよい。
　任意成分としては、例えば、酵素（プロテアーゼ等）、溶剤、ハイドロトロープ剤、キレート剤、殺菌剤、防腐剤、抗カビ剤、色素、酸化防止剤、紫外線吸収剤、香料、ｐＨ調整剤、アルカリ剤等が挙げられる。 [Optional ingredients]
In addition to the components (A) to (F), the liquid detergent composition of the present invention may contain optional components commonly used in liquid detergent compositions.
Optional components include, for example, enzymes (proteases, etc.), solvents, hydrotropes, chelating agents, bactericides, antiseptics, antifungal agents, dyes, antioxidants, ultraviolet absorbers, fragrances, pH adjusters, alkaline agents Etc.
（溶剤）
　本発明の液体洗浄剤組成物は、溶剤を含有していてもよい。溶剤としては、従来、衣料用等の液体洗浄剤組成物に用いられている溶剤であればよく、例えば、炭素数２～４の１価アルコール、炭素数２～４の多価アルコール、グリコールエーテル系溶剤、メトキシ基を有するアルコールが挙げられる。 (solvent)
The liquid detergent composition of the present invention may contain a solvent. The solvent may be any solvent conventionally used in liquid detergent compositions for clothing and the like, and examples thereof include monohydric alcohols having 2 to 4 carbon atoms, polyhydric alcohols having 2 to 4 carbon atoms, and glycol ethers. Examples thereof include system solvents and alcohols having a methoxy group.
　炭素数２～４の１価アルコールとしては、例えば、エタノール、１－プロパノール、２－プロパノール、１－ブタノール等が挙げられる。
　炭素数２～４の多価アルコールとしては、例えば、エチレングリコール、プロピレングリコール、ブチレングリコール、グリセリン等が挙げられる。
　グリコールエーテル系溶剤としては、例えば、エチレングリコールモノブチルエーテル、エチレングリコールモノヘキシルエーテル、エチレングリコールモノフェニルエーテル、プロピレングリコールモノフェニルエーテル、ジエチレングリコールモノメチルエーテル、ジエチレングリコールモノブチルエーテル（ブチルカルビトール）等が挙げられる。 Examples of the monohydric alcohol having 2 to 4 carbon atoms include ethanol, 1-propanol, 2-propanol, 1-butanol and the like.
Examples of the polyhydric alcohol having 2 to 4 carbon atoms include ethylene glycol, propylene glycol, butylene glycol, glycerin and the like.
Examples of the glycol ether solvent include ethylene glycol monobutyl ether, ethylene glycol monohexyl ether, ethylene glycol monophenyl ether, propylene glycol monophenyl ether, diethylene glycol monomethyl ether, diethylene glycol monobutyl ether (butyl carbitol) and the like.
　メトキシ基を有するアルコールとしては、例えば、３－メトキシブタノ－ル、３－メトキシ－３－メチルブタノ－ル、３－メトキシ－３－エチルブタノ－ル、３－メトキシ－３－プロピルブタノ－ル、３－メトキシ－２－メチルブタノ－ル、３－メトキシ－２－エチルブタノ－ル、３－メトキシ－２－プロピルブタノ－ル、３－メトキシ－１－メチルブタノ－ル、３－メトキシ－１－エチルブタノ－ル、３－メトキシ－１－プロピルブタノ－ル、３－メトキシブチルアセテート、３－メトキシ－３－メチルブチルアセテート、３－メトキシ－３－エチルブチルアセテート、３－メトキシ－３－プロピルブチルアセテート、３－メトキシ－２－メチルブチルアセテート、３－メトキシ－２－エチルブチルアセテート、３－メトキシ－２－プロピルブチルアセテート、３－メトキシ－１－メチルブチルアセテート、３－メトキシ－１－エチルブチルアセテート、３－メトキシ－１－プロピルブチルアセテートが挙げられる。
　これらの溶剤は１種を単独で用いてもよく、２種以上を適宜組み合わせて用いてもよい。 Examples of the alcohol having a methoxy group include 3-methoxybutanol, 3-methoxy-3-methylbutanol, 3-methoxy-3-ethylbutanol, 3-methoxy-3-propylbutanol, 3-methoxy- 2-methylbutanol, 3-methoxy-2-ethylbutanol, 3-methoxy-2-propylbutanol, 3-methoxy-1-methylbutanol, 3-methoxy-1-ethylbutanol, 3-methoxy- 1-propylbutanol, 3-methoxybutyl acetate, 3-methoxy-3-methylbutyl acetate, 3-methoxy-3-ethylbutyl acetate, 3-methoxy-3-propylbutyl acetate, 3-methoxy-2-methylbutyl Acetate, 3-methoxy-2-ethylbutyl acetate, 3-methoxy-2-propi Butyl acetate, 3-methoxy-1-methyl-butyl acetate, 3-methoxy-1-ethyl butyl acetate, and 3-methoxy-1-propyl-butyl acetate.
One of these solvents may be used alone, or two or more thereof may be used in appropriate combination.
（香料前駆体）
　本発明の液体洗浄剤組成物は、香料前駆体を含んでいてもよい。香料前駆体とは、それ自体は無臭又は無臭に近いものであるが、液体洗浄剤組成物中又は繊維上で酸化反応等をすることによって、香りを発生させる成分のことを意味する。
　本発明の液体洗浄剤組成物が香料前駆体を含有することにより、洗濯処理・乾燥後の化繊衣類等から感じられる香りの強さ（香気強度）をより高められる。これにより、洗濯処理を施した後の化繊衣類等のさらっとした触感の実感効果をより高められ、着心地が向上しやすい。さらに、香料前駆体由来の香気が徐々に放出されることで、前記実感効果をより持続させられる。
　香料前駆体としては、前記効果を有する限り特に限定されず、液体洗浄剤組成物に一般的に用いられているものを使用することができる。このような香料前駆体としては、例えば、硫黄を含有する香料前駆体（硫黄含有香料前駆体）等が挙げられる。 (Fragrance precursor)
The liquid detergent composition of the present invention may contain a fragrance precursor. The perfume precursor itself is an odorless or nearly odorless component, but means a component that generates a scent by an oxidation reaction or the like in a liquid detergent composition or on a fiber.
By containing the fragrance precursor in the liquid detergent composition of the present invention, the strength of the fragrance (fragrance strength) felt from the synthetic clothing and the like after washing and drying can be further increased. Thereby, the actual feeling effect of the soft touch of synthetic fiber clothing etc. after performing a washing process can be further enhanced, and the comfort is easily improved. Furthermore, since the fragrance derived from the fragrance precursor is gradually released, the actual feeling effect can be further sustained.
The perfume precursor is not particularly limited as long as it has the above-mentioned effect, and those generally used in liquid detergent compositions can be used. Examples of such a fragrance precursor include a fragrance precursor containing sulfur (a sulfur-containing fragrance precursor).
　本発明の液体洗浄剤組成物の２５℃におけるｐＨは、５～９が好ましく、７～９がより好ましい。ｐＨが前記範囲内であれば、良好な洗浄力が維持されやすい。
　なお、本発明における液体洗浄剤組成物の２５℃でのｐＨは、試料を２５℃に調整し、ｐＨメーター（例えば、東亜ディーケーケー株式会社製の製品名「ＨＭ－３０Ｇ」を使用）等により測定される値を示す。 The pH of the liquid detergent composition of the present invention at 25 ° C. is preferably 5-9, more preferably 7-9. If the pH is within the above range, good detergency is easily maintained.
The pH of the liquid detergent composition of the present invention at 25 ° C. is measured by adjusting the sample to 25 ° C. and using a pH meter (for example, using the product name “HM-30G” manufactured by Toa DKK Corporation). Indicates the value to be processed.
　以上説明した本発明の液体洗浄剤組成物においては、（Ａ）～（Ｃ）成分を組み合わせていることで、高い洗浄力、優れた液安定性、及び高い再汚染防止効果を発揮できるうえ、被洗物に優れた抗菌性を付与でき、部屋干し臭発生の十分に抑制することができる。このような効果が得られるのは、（Ｂ）成分のアニオン界面活性剤と（Ｃ）成分のフェノール構造を有する化合物とが複合体を形成することで化繊への吸着が向上し、（Ｃ）成分の抗菌力が充分に発揮されるためである。
　また、本発明の液体洗浄剤組成物においては、（Ｄ）成分や（Ｅ）成分、（Ｆ）成分を併用することで、抗菌性をさらに高めることができる。 In the liquid detergent composition of the present invention described above, by combining the components (A) to (C), a high detergency, excellent liquid stability, and a high recontamination preventing effect can be exhibited. The antibacterial property which was excellent in the to-be-washed object can be provided, and room dry odor generation can fully be suppressed. Such an effect is obtained because the anionic surfactant of the component (B) and the compound having a phenol structure of the component (C) form a complex to improve the adsorption to the fiber, and (C) This is because the antibacterial power of the component is sufficiently exhibited.
Moreover, in the liquid cleaning composition of this invention, antibacterial property can further be improved by using together (D) component, (E) component, and (F) component.
　本発明の液体洗浄剤組成物は、（Ａ）～（Ｃ）成分を含有し、（Ａ）成分が、化合物（Ｉ）を含むことが好ましく、式（Ｉ）におけるＲ１が炭素数１１のアルキル基及び炭素数１３のアルキル基であり、Ｒ２がメチル基であり、ｓ＝１５であり、ｔ＝０である化合物を含むことがより好ましい。
　本発明の液体洗浄剤組成物は、（Ａ）～（Ｃ）成分を含有し、（Ｂ）成分が、炭素数１０～２０の直鎖状又は分岐鎖状のアルキル基を有するポリオキシアルキレンアルキルエーテル硫酸塩、及び炭素数８～１８のアルキル基を有する直鎖アルキルベンゼンスルホン酸塩からなる群から選ばれる少なくとも１種を含むことが好ましい。
　本発明の液体洗浄剤組成物は、（Ａ）～（Ｃ）成分を含有し、（Ｃ）成分が、ジクロロヒドロキシジフェニルエーテル、トリクロロヒドロキシジフェニルエーテル及びベンジルクロロフェノールからなる群から選ばれる少なくとも１種を含むことが好ましい。 The liquid detergent composition of the present invention contains the components (A) to (C), the component (A) preferably contains the compound (I), and R 1 in the formula (I) has 11 carbon atoms. More preferably, it includes an alkyl group and an alkyl group having 13 carbon atoms, R 2 is a methyl group, s = 15, and t = 0.
The liquid detergent composition of the present invention contains the components (A) to (C), and the component (B) is a polyoxyalkylene alkyl having a linear or branched alkyl group having 10 to 20 carbon atoms. It is preferable to include at least one selected from the group consisting of ether sulfates and linear alkylbenzene sulfonates having an alkyl group having 8 to 18 carbon atoms.
The liquid detergent composition of the present invention contains the components (A) to (C), and the component (C) contains at least one selected from the group consisting of dichlorohydroxydiphenyl ether, trichlorohydroxydiphenyl ether, and benzylchlorophenol. It is preferable.
　以下、実施例によって本発明を詳細に説明するが、本発明は以下の記載によっては限定されない。本実施例において、「％」は特に断りがない限り「質量％」を示す。
［原料］
　本実施例において使用した原料は下記の通りである。
（（Ａ）成分）
　Ａ－１：ＭＥＥ。ヤシ脂肪酸メチル（質量比でラウリン酸メチル／ミリスチン酸メチル＝８／２の混合物）に対して、アルコキシル化触媒を用いて、１５モル相当のエチレンオキシドを付加した化合物。式（Ｉ）において、Ｒ１が炭素数１１のアルキル基及び炭素数１３のアルキル基であり、Ｒ２がメチル基であり、ｓ＝１５であり、ｔ＝０である。ナロー率は３３％であった。
　＜Ａ－１の合成方法＞
　特開２０００－１４４１７９号公報に記載の合成方法に準じて合成した。
　組成が２．５ＭｇＯ・Ａｌ２Ｏ３・ｗＨ２Ｏである水酸化アルミナ・マグネシウム（キョーワード３００（商品名）、協和化学工業株式会社製）を６００℃で１時間、窒素雰囲気下で焼成して、焼成水酸化アルミナ・マグネシウム（未改質）触媒を得た。焼成水酸化アルミナ・マグネシウム（未改質）触媒２．２ｇと、０．５Ｎ水酸化カリウムエタノール溶液２．９ｍＬと、ラウリン酸メチルエステル２８０ｇと、ミリスチン酸メチルエステル７０ｇとを４Ｌオートクレーブに仕込み、オートクレーブ内で触媒の改質を行った。次いで、オートクレーブ内を窒素で置換した後、温度を１８０℃、圧力を０．３ＭＰａに維持しつつ、エチレンオキシド１０５２ｇを導入し、撹拌しながら反応させた。
　得られた反応液を８０℃に冷却し、水１５９ｇと、濾過助剤として活性白土５ｇ及び珪藻土５ｇとを添加して混合した後、触媒を濾別してＡ－１を得た。 EXAMPLES Hereinafter, although an Example demonstrates this invention in detail, this invention is not limited by the following description. In this example, “%” indicates “% by mass” unless otherwise specified.
[material]
The raw materials used in this example are as follows.
((A) component)
A-1: MEE. A compound obtained by adding 15 mol of ethylene oxide to coconut fatty acid methyl (mixture of methyl laurate / methyl myristate = 8/2 by mass ratio) using an alkoxylation catalyst. In the formula (I), R 1 is an alkyl group having 11 carbon atoms and an alkyl group having 13 carbon atoms, R 2 is a methyl group, s = 15, and t = 0. The narrow rate was 33%.
<Synthesis Method of A-1>
Synthesis was performed according to the synthesis method described in JP-A No. 2000-144179.
Alumina-magnesium hydroxide (Kyoward 300 (trade name), manufactured by Kyowa Chemical Industry Co., Ltd.) having a composition of 2.5 MgO.Al 2 O 3 .wH 2 O was calcined at 600 ° C. for 1 hour in a nitrogen atmosphere. Thus, a calcined alumina / magnesium hydroxide (unmodified) catalyst was obtained. An autoclave was charged with 2.2 g of calcined alumina / magnesium hydroxide (unmodified) catalyst, 2.9 mL of 0.5N potassium hydroxide ethanol solution, 280 g of lauric acid methyl ester, and 70 g of myristic acid methyl ester in a 4 L autoclave. The catalyst was reformed inside. Next, after the inside of the autoclave was replaced with nitrogen, 1052 g of ethylene oxide was introduced and reacted while stirring while maintaining the temperature at 180 ° C. and the pressure at 0.3 MPa.
The resulting reaction solution was cooled to 80 ° C., 159 g of water, 5 g of activated clay and 5 g of diatomaceous earth as filter aids were added and mixed, and then the catalyst was filtered off to obtain A-1.
　Ａ－１’：ＭＥＥ。ヤシ脂肪酸メチル（質量比でラウリン酸メチル／ミリスチン酸メチル＝８／２の混合物）に対して、アルコキシル化触媒を用いて、１５モル相当のエチレンオキシドを付加した化合物。式（Ｉ）において、Ｒ１が炭素数１１のアルキル基及び炭素数１３のアルキル基、Ｒ２＝メチル基、ｓ＝１５、ｔ＝０、ナロー率３３％。下記合成方法により合成されたもの。
　＜Ａ－１’の合成方法＞
　Ａ－１’を以下の合成方法に準じて合成した。
　１Ｌセパラブルフラスコに、イソプロピルアルコール（ＩＰＡ）（一級試薬、関東化学株式会社製）５２５ｇと、酢酸カルシウム一水和物（特級試薬、関東化学株式会社製）１５０ｇを入れ、ディスパー撹拌翼により２０℃で混合して分散物を得た（分散工程）。前記分散物を３０００ｒｐｍで撹拌しながら、滴下ロートによって、硫酸（特級試薬、関東化学株式会社製）７５ｇを６０分間かけて添加し混合した（混合工程）。混合工程では硫酸の添加で発熱するので、セパラブルフラスコを温浴で、反応温度を１５～２５℃に制御した。硫酸を添加した後、２０℃に保ちながら、さらに２時間撹拌し（触媒熟成工程）、アルコキシル化触媒を得た。
　オートクレーブに、上記アルコキシル化触媒２．１ｇと、ラウリン酸メチル（パステルＭ１２、ライオンケミカル株式会社製）４６２ｇと、ミリスチン酸メチル（パステルＭ１４、ライオンケミカル株式会社製）１６６ｇとを入れ、撹拌した。撹拌しながら、オートクレーブ内を窒素置換し、１６０℃に昇温し、０．１～０．５ＭＰａの条件で、エチレンオキシド（ＥＯ）１８７６ｇ（ラウリン酸メチルとミリスチン酸メチルとの合計の１５倍モル）を導入して撹拌した（付加反応工程）。さらに、付加反応温度で０．５時間撹拌した（熟成工程）後、８０℃に冷却し、反応粗製物（脂肪酸メチルエステルエトキシレート（ＭＥＥ）、ＥＯ平均付加モル数＝１５）２５１６ｇを得た。前記反応粗製物をろ過して触媒を除去したものをＡ－１’とした。 A-1 ′: MEE. A compound obtained by adding 15 mol of ethylene oxide to coconut fatty acid methyl (mixture of methyl laurate / methyl myristate = 8/2 by mass ratio) using an alkoxylation catalyst. In the formula (I), R 1 is an alkyl group having 11 carbon atoms and an alkyl group having 13 carbon atoms, R 2 = methyl group, s = 15, t = 0, and a narrow ratio of 33%. Synthesized by the following synthesis method.
<Synthesis Method of A-1 '>
A-1 ′ was synthesized according to the following synthesis method.
Into a 1 L separable flask, 525 g of isopropyl alcohol (IPA) (primary reagent, manufactured by Kanto Chemical Co., Ltd.) and 150 g of calcium acetate monohydrate (special grade reagent, manufactured by Kanto Chemical Co., Ltd.) are placed, and 20 ° C. with a disper stirring blade. To obtain a dispersion (dispersing step). While stirring the dispersion at 3000 rpm, 75 g of sulfuric acid (special grade reagent, manufactured by Kanto Chemical Co., Inc.) was added and mixed with a dropping funnel over 60 minutes (mixing step). In the mixing step, heat was generated by the addition of sulfuric acid, so the reaction flask was controlled with a warm bath and the reaction temperature was controlled at 15-25 ° C. After adding sulfuric acid, the mixture was further stirred for 2 hours while maintaining at 20 ° C. (catalyst aging step) to obtain an alkoxylation catalyst.
In an autoclave, 2.1 g of the alkoxylation catalyst, 462 g of methyl laurate (Pastel M12, manufactured by Lion Chemical Co., Ltd.) and 166 g of methyl myristate (Pastel M14, manufactured by Lion Chemical Co., Ltd.) were added and stirred. While stirring, the inside of the autoclave was purged with nitrogen, heated to 160 ° C., and under conditions of 0.1 to 0.5 MPa, ethylene oxide (EO) 1876 g (15 times mol of the total of methyl laurate and methyl myristate) And stirred (addition reaction step). Furthermore, after stirring at the addition reaction temperature for 0.5 hours (aging step), the mixture was cooled to 80 ° C. to obtain 2516 g of a crude reaction product (fatty acid methyl ester ethoxylate (MEE), EO average addition mole number = 15). The product obtained by filtering the crude reaction product to remove the catalyst was designated as A-1 ′.
　Ａ－２：ＬＭＡＯ。ポリオキシエチレンアルキルエーテル、炭素数１２及び１４の天然アルコール（第１級アルコール）に１５モル相当のエチレンオキシドを付加した化合物。
　＜ＬＭＡＯ合成方法＞
　プロクター・アンド・ギャンブル社製のＣＯ－１２１４（商品名、炭素数１２及び１４の天然アルコール）８６１．２ｇと、３０質量％ＮａＯＨ水溶液２．０ｇとを耐圧型反応容器内に仕込み、該反応容器内を窒素置換した。次に、温度１００℃、圧力２．０ｋＰａ以下で３０分間脱水した後、温度を１６０℃まで昇温した。次いで、反応液を撹拌しながら、エチレンオキシド（ガス状）７６０．６ｇを反応液中に徐々に加えた。この時、反応温度が１８０℃を超えないように添加速度を調節しながら、エチレンオキシドを吹き込み管で加えた。
　エチレンオキシドの添加終了後、温度１８０℃、圧力０．３ＭＰａ以下で３０分間熟成した後、温度１８０℃、圧力６．０ｋＰａ以下で１０分間、未反応のエチレンオキシドを留去した。
　次に、温度を１００℃以下まで冷却した後、反応物の１質量％水溶液のｐＨが約７になるように、７０質量％ｐ－トルエンスルホン酸を加えて中和し、ＬＭＡＯを得た。 A-2: LMAO. Polyoxyethylene alkyl ether, a compound obtained by adding 15 moles of ethylene oxide to a natural alcohol (primary alcohol) having 12 and 14 carbon atoms.
<LMAO synthesis method>
861.2 g of CO-1214 (trade name, natural alcohols having 12 and 14 carbon atoms) manufactured by Procter & Gamble Co., Ltd. and 2.0 g of 30% by mass NaOH aqueous solution were charged into a pressure-resistant reaction vessel, and the reaction vessel The inside was replaced with nitrogen. Next, after dehydrating for 30 minutes at a temperature of 100 ° C. and a pressure of 2.0 kPa or less, the temperature was raised to 160 ° C. Next, while stirring the reaction solution, 760.6 g of ethylene oxide (gaseous) was gradually added to the reaction solution. At this time, ethylene oxide was added through the blowing tube while adjusting the addition rate so that the reaction temperature did not exceed 180 ° C.
After completion of the addition of ethylene oxide, aging was performed at a temperature of 180 ° C. and a pressure of 0.3 MPa or less for 30 minutes, and then unreacted ethylene oxide was distilled off at a temperature of 180 ° C. and a pressure of 6.0 kPa or less for 10 minutes.
Next, after cooling the temperature to 100 ° C. or lower, 70% by mass p-toluenesulfonic acid was added to neutralize so that the pH of the 1% by mass aqueous solution of the reaction product was about 7, thereby obtaining LMAO.
　Ａ－３：ＥＯＰＯノニオン。炭素数１２の第２級アルコール及び炭素数１４の第２級アルコールに、８モル相当のエチレンオキシドと、２モル相当のプロピレンオキシドと、を付加したもの。式（ＩＩ）においては、Ｒ３が炭素数１２のアルキル基及び炭素数１４のアルキル基であり、ｖ＝８であり、ｗ＝２であり、ｘ＝０である。
　＜ＥＯＰＯノニオンの合成方法＞
　Ｐ＆Ｇ社製の「ＣＯ－１２７０」２２４．４ｇと、３０質量％ＮａＯＨ水溶液２．０ｇと、を耐圧型反応容器内に仕込み、該反応容器内を窒素置換した。次いで、温度１００℃、圧力２．０ｋＰａ以下で３０分間脱水した後、温度を１６０℃まで昇温した。次いで、撹拌しつつ、エチレンオキシド（ガス状）３５２ｇを、吹き込み管を使って、反応温度が１８０℃を超えないように添加速度を調整しながら、アルコール液中に徐々に加えて反応させた。次いで、プロピレンオキシド１１６ｇを導入してさらに反応させた。
　次いで、温度１８０℃、圧力０．３ＭＰａ以下で３０分間熟成した後、温度１８０℃、圧力６．０ｋＰａ以下で１０分間、未反応のエチレンオキシドとプロピレンオキシドとを留去した。次いで、温度を１００℃以下まで冷却した後、反応物の１質量％水溶液のｐＨが約７になるように、７０質量％ｐ－トルエンスルホン酸を加えて中和し、ＥＯＰＯノニオンを得た。 A-3: EOPO nonion. A product obtained by adding 8 moles of ethylene oxide and 2 moles of propylene oxide to a secondary alcohol having 12 carbon atoms and a secondary alcohol having 14 carbon atoms. In the formula (II), R 3 is an alkyl group having 12 carbon atoms and an alkyl group having 14 carbon atoms, v = 8, w = 2, and x = 0.
<Method of synthesizing EOPO nonion>
224.4 g of “CO-1270” manufactured by P & G Co. and 2.0 g of 30 mass% NaOH aqueous solution were charged into a pressure-resistant reaction vessel, and the inside of the reaction vessel was purged with nitrogen. Subsequently, after dehydrating for 30 minutes at a temperature of 100 ° C. and a pressure of 2.0 kPa or less, the temperature was raised to 160 ° C. Next, while stirring, 352 g of ethylene oxide (gaseous) was gradually added to the alcohol liquid and reacted while adjusting the addition rate so that the reaction temperature did not exceed 180 ° C. using a blowing tube. Next, 116 g of propylene oxide was introduced and further reacted.
Subsequently, after aging at a temperature of 180 ° C. and a pressure of 0.3 MPa or less for 30 minutes, unreacted ethylene oxide and propylene oxide were distilled off at a temperature of 180 ° C. and a pressure of 6.0 kPa or less for 10 minutes. Next, after cooling the temperature to 100 ° C. or lower, 70% by mass p-toluenesulfonic acid was added to neutralize so that the pH of the 1% by mass aqueous solution of the reaction product was about 7, thereby obtaining EOPO nonion.
（（Ｂ）成分）
　Ｂ－１：ポリオキシエチレンアルキルエーテル硫酸ナトリウム（ＡＥＳ）。下式（ｂ１－１）で表され、Ｒ５１が炭素数１２～１４の直鎖アルキル基であり、ｋ＝１．０であり、Ｍがナトリウムである化合物。ただし、式（ｂ１－１）中、ＥＯは、エチレンオキシ基であり、ｋはＥＯの平均繰り返し数である。
　Ｒ５１－Ｏ－（ＥＯ）ｋ－ＳＯ３Ｍ　・・・（ｂ１－１）
　＜ＡＥＳの合成方法＞
　容量４Ｌのオートクレーブ中に、原料アルコールとしてＰ＆Ｇ社製の商品名ＣＯ１２７０アルコール（炭素数１２のアルコールと炭素数１４のアルコールとの質量比７５／２５の混合物）４００ｇと、反応用触媒として水酸化カリウム０．８ｇとを仕込み、該オートクレーブ内を窒素で置換した後、撹拌しながら昇温した。続いて、温度を１８０℃、圧力を０．３ＭＰａ以下に維持しながらエチレンオキシド９１ｇを導入し、反応させることによりアルコールエトキシレートを得た。
　ガスクロマトグラフ質量分析（分析計：Ｈｅｗｌｅｔｔ－Ｐａｃｋａｒｄ社製のＧＣ－５８９０、検出器：水素炎イオン化型検出器（ＦＩＤ）、カラム：Ｕｌｔｒａ－１（ＨＰ社製、Ｌ２５ｍ×φ０．２ｍｍ×Ｔ０．１１μｍ。）により分析した結果、得られたアルコールエトキシレートは、エチレンオキシドの平均付加モル数が１．０であった。また、エチレンオキシドが付加していない化合物は、得られたアルコールエトキシレートの総質量に対して４３質量％であった。
　次に、上記で得たアルコールエトキシレート２３７ｇを、撹拌装置付の５００ｍＬフラスコに採り、窒素で置換した後、液体無水硫酸（サルファン）９６ｇを、反応温度４０℃に保ちながらゆっくりと滴下した。滴下終了後、１時間撹拌を続け（硫酸化反応）、ポリオキシエチレンアルキルエーテル硫酸を得た。次いで、これを水酸化ナトリウム水溶液で中和することによりＡＥＳを得た。 ((B) component)
B-1: Sodium polyoxyethylene alkyl ether sulfate (AES). A compound represented by the following formula (b1-1), wherein R 51 is a linear alkyl group having 12 to 14 carbon atoms, k = 1.0, and M is sodium. However, in formula (b1-1), EO is an ethyleneoxy group, and k is the average number of repetitions of EO.
R 51 —O— (EO) k —SO 3 M (b1-1)
<Synthesis method of AES>
In an autoclave with a capacity of 4 L, 400 g of a trade name CO1270 alcohol (mixture of 75/25 mass ratio of 12-carbon alcohol and 14-carbon alcohol) manufactured by P & G as raw material alcohol and potassium hydroxide as a reaction catalyst After charging 0.8 g and replacing the inside of the autoclave with nitrogen, the temperature was raised with stirring. Subsequently, while maintaining the temperature at 180 ° C. and the pressure at 0.3 MPa or less, 91 g of ethylene oxide was introduced and reacted to obtain an alcohol ethoxylate.
Gas chromatograph mass spectrometry (analyzer: GC-5890 manufactured by Hewlett-Packard Co., detector: flame ionization detector (FID), column: Ultra-1 (manufactured by HP, L25m × φ0.2mm × T0.11 μm) As a result, the alcohol ethoxylate obtained had an average number of moles of ethylene oxide added of 1.0, and the compound to which no ethylene oxide was added was added to the total mass of the alcohol ethoxylate obtained. It was 43 mass% with respect to.
Next, 237 g of the alcohol ethoxylate obtained above was placed in a 500 mL flask equipped with a stirrer and replaced with nitrogen, and 96 g of liquid sulfuric anhydride (sulfane) was slowly added dropwise while maintaining the reaction temperature at 40 ° C. After completion of the dropping, stirring was continued for 1 hour (sulfation reaction) to obtain polyoxyethylene alkyl ether sulfuric acid. Next, this was neutralized with an aqueous sodium hydroxide solution to obtain AES.
　Ｂ－２：直鎖アルキルベンゼンスルホン酸ナトリウム（ＬＡＳ）、ライオン株式会社製、商品名「ライポンＬＨ－２００」。
　Ｂ－３：α－スルホ脂肪酸メチルエステル塩（ＭＥＳ）、商品名「ＭＩＺＵＬＡＮ　ＦＬ－８０」、ライオンエコケミカルズ有限公司製。
　Ｂ－４：石鹸、商品名「椰子脂肪酸」、日油株式会社製。 B-2: Sodium linear alkylbenzene sulfonate (LAS), manufactured by Lion Corporation, trade name “Lypon LH-200”.
B-3: α-sulfo fatty acid methyl ester salt (MES), trade name “MIZULAN FL-80”, manufactured by Lion Eco Chemicals Co., Ltd.
B-4: Soap, trade name “Zushi fatty acid”, manufactured by NOF Corporation.
（（Ｃ）成分）
　Ｃ－１：４，４’－ジクロロ－２－ヒドロキシジフェニルエーテル、商品名「Ｔｉｎｏｓａｎ　ＨＰ１００」、ＢＡＳＦ社製。
　Ｃ－２：５－クロロ－２－（２，４－ジクロロフェノキシ）フェノール、商品名「トリクロサン」、和光純薬工業株式会社製。
　Ｃ－３：ｏ－ベンジル－ｐ－クロロフェノール、商品名「クロロフェン」、クラリアントジャパン株式会社製。 ((C) component)
C-1: 4,4′-dichloro-2-hydroxydiphenyl ether, trade name “Tinosan HP100”, manufactured by BASF Corporation.
C-2: 5-chloro-2- (2,4-dichlorophenoxy) phenol, trade name “Triclosan”, manufactured by Wako Pure Chemical Industries, Ltd.
C-3: o-benzyl-p-chlorophenol, trade name “Chlorophen”, manufactured by Clariant Japan KK
（（Ｄ）成分）
　Ｄ－１：ＴｅｘＣａｒｅ　ＳＲＮ－１７０Ｃ（商品名、クラリアントジャパン社製、重量平均分子量：２０００～３０００、ｐＨ（２０℃の５質量％水溶液）：４、粘度（２０℃）：３００ｍＰａ・ｓ）。ＴｅｘＣａｒｅ　ＳＲＮ－１７０Ｃは、商品名：ＴｅｘＣａｒｅ　ＳＲＮ－１００（クラリアントジャパン社製、重量平均分子量：２０００～３０００）の７０質量％水溶液である。 ((D) component)
D-1: TexCare SRN-170C (trade name, manufactured by Clariant Japan, weight average molecular weight: 2000 to 3000, pH (5 mass% aqueous solution at 20 ° C.): 4, viscosity (20 ° C.): 300 mPa · s). TexCare SRN-170C is a 70% by mass aqueous solution of trade name: TexCare SRN-100 (manufactured by Clariant Japan, weight average molecular weight: 2000 to 3000).
（（Ｅ）成分）
　Ｅ－１：ポリエチレンイミンのエチレンオキシド付加体（ＢＡＳＦ社製、商品名「Ｓｏｋａｌａｎ　ＨＰ２０」）。ポリエチレンイミンが有する活性水素１モルあたりのエチレンオキシドの平均付加モル数は２０モルである。 ((E) component)
E-1: An ethylene oxide adduct of polyethyleneimine (trade name “Sokalan HP20” manufactured by BASF). The average number of moles of ethylene oxide added per mole of active hydrogen possessed by polyethyleneimine is 20 moles.
（（Ｆ）成分）
　Ｆ－１：塩化ドデシルトリメチルアンモニウム、商品名「リポガード１２－３７Ｗ」、ライオンスペシャリティケミカルズ株式会社製、（式（ｆ１）中、Ｒ４１～Ｒ４３がメチル基であり、Ｒ４４が炭素数１２の直鎖状アルキル基である化合物）。
　Ｆ－２：塩化ジデシルジメチルアンモニウム、商品名「アーカード２１０」、ライオンスペシャリティケミカルズ株式会社製。
　Ｆ－３：塩化ココイルジメチルベンジルアンモニウム、商品名「リポカード　ＣＢ－５０」、ライオンスペシャリティケミカルズ株式会社製。 ((F) component)
F-1: Dodecyltrimethylammonium chloride, trade name “Lipoguard 12-37W”, manufactured by Lion Specialty Chemicals Co., Ltd. (in the formula (f1), R 41 to R 43 are methyl groups, and R 44 has 12 carbon atoms. A compound which is a linear alkyl group).
F-2: Didecyldimethylammonium chloride, trade name “ARCARD 210”, manufactured by Lion Specialty Chemicals Co., Ltd.
F-3: Cocoyldimethylbenzylammonium chloride, trade name “Lipocard CB-50”, manufactured by Lion Specialty Chemicals Co., Ltd.
（その他の成分）
　水：精製水
　エタノール：水混和性有機溶剤、商品名「特定アルコール９５度合成」、日本アルコール販売株式会社製。
　ＢＣ：ブチルカルビトール（水混和性有機溶剤）、商品名「ブチルカルビトール」、東京化成工業株式会社製。
　ＭＭＢ：３－メトキシ－３－メチルブタノール（水混和性有機溶剤）、商品名「ソルフィット」、クラレ株式会社製。
　安息香酸ナトリウム：東亜合成株式会社製。
　プロテアーゼ：コロナーゼ、商品名「Ｃｏｒｏｎａｓｅ　４８Ｌ」、ノボザイムズ社製。
　ＭＥＡ：モノエタノールアミン（アルカリ剤）、商品名「モノエタノールアミン」、株式会社日本触媒製。
　ＢＨＴ：ジブチルヒドロキシトルエン（酸化防止剤）、商品名「ＳＵＭＩＬＺＥＲ　ＢＨＴ－Ｒ」、住友化学株式会社製。
　乳酸ナトリウム：関東化学株式会社製、商品名「乳酸ナトリウム」。
　香料：特開２００２－１４６３９９号公報の表１１～１８に記載の香料組成物Ａ。 (Other ingredients)
Water: Purified water Ethanol: Water miscible organic solvent, trade name “specific alcohol 95 degree synthesis”, manufactured by Nippon Alcohol Sales Co.
BC: Butyl carbitol (water-miscible organic solvent), trade name “butyl carbitol”, manufactured by Tokyo Chemical Industry Co., Ltd.
MMB: 3-methoxy-3-methylbutanol (water-miscible organic solvent), trade name “Solfit”, manufactured by Kuraray Co., Ltd.
Sodium benzoate: manufactured by Toa Gosei Co., Ltd.
Protease: Coronase, trade name “Coronase 48L”, manufactured by Novozymes.
MEA: monoethanolamine (alkali agent), trade name “monoethanolamine”, manufactured by Nippon Shokubai Co., Ltd.
BHT: Dibutylhydroxytoluene (antioxidant), trade name “SUMILZER BHT-R”, manufactured by Sumitomo Chemical Co., Ltd.
Sodium lactate: manufactured by Kanto Chemical Co., Ltd., trade name “sodium lactate”.
Perfume: Perfume composition A described in Tables 11 to 18 of JP-A-2002-146399.
［実施例１～２８、比較例１～３］
　表１～４に示す組成に従って各成分を混合して液体洗浄剤組成物を得た。
　表１～４に、各例の液体洗浄剤組成物の組成（配合成分、含有量（％））を示す。表１～４中の空欄はその配合成分が配合されていないことを意味する。配合成分の含有量は純分換算量を示す。精製水の含有量を示す「バランス」は、液体洗浄剤組成物に含まれる全配合成分の合計の配合量（％）が１００％となるように加えられる残部を意味する。
　なお、実施例６においてのみ、香料とＣ－１を実施例記載の質量比となるように事前に混合したプレミックスを調製し、それを液体洗浄剤組成物に配合した。他の例では、（Ｃ）成分は香料とプレミックスを形成させずに他の成分と混合した。
　また、実施例中の配合量は有効成分量として記載している。 [Examples 1 to 28, Comparative Examples 1 to 3]
Each component was mixed according to the composition shown in Tables 1 to 4 to obtain a liquid detergent composition.
Tables 1 to 4 show the composition (formulation component, content (%)) of the liquid detergent composition of each example. A blank in Tables 1 to 4 means that the blending component is not blended. Content of a compounding component shows a pure conversion amount. “Balance” indicating the content of purified water means the balance added so that the total amount (%) of all the components included in the liquid detergent composition is 100%.
Note that only in Example 6, a premix was prepared in which the fragrance and C-1 were mixed in advance so as to achieve the mass ratio described in the Examples, and was added to the liquid detergent composition. In another example, component (C) was mixed with other components without forming a premix with the fragrance.
Moreover, the compounding quantity in an Example is described as an active ingredient amount.
［評価方法］
　各例の液体洗浄剤組成物について、以下に示す評価方法により「洗浄力」、「酵素安定性」、「再汚染防止効果」、「液安定性」、「抗菌性」及び「部屋干し臭発生の抑制効果」の評価をそれぞれ行った。 [Evaluation methods]
For the liquid detergent composition of each example, "detergency", "enzyme stability", "anti-contamination effect", "liquid stability", "antibacterial", and "dry room odor" are generated according to the evaluation methods shown below. Was evaluated.
（洗浄力）
　洗浄力の評価には、各例における製造直後の液体洗浄剤組成物（製造直後品）を用いた。汚垢布として、タンパク汚れ布であるＥＭＰＡ１１７（ＥＭＰＡ　Ｔｅｓｔｍａｔｅｒｉａｌｉｅｎ社製、Ｐｏｌｙｅｓｔｅｒ／ｃｏｔｔｏｎ，６５／３５，ｓｏｉｌｅｄ　ｗｉｔｈ　ｂｌｏｏｄ／ｍｉｌｋ／ｉｎｋ）を５ｃｍ×５ｃｍ角に裁断したものを用いた。洗浄試験機として、Ｔｅｒｇ－Ｏ－ｔｏｍｅｔｅｒ（ＵＮＩＴＥＤ　ＳＴＡＴＥＳ　ＴＥＳＴＩＮＧ社製）を用いた。洗浄液として、水９００ｍＬに対して、液体洗浄剤組成物３００μＬを加え、３０秒間撹拌して調製したものを用いた。
　洗浄試験器に、洗浄液９００ｍＬと、汚垢布１０枚と、洗浄メリヤス布とを投入し、浴比２０倍に合わせて、１２０ｒｐｍ、１５℃で１０分間洗浄した。その後、二槽式洗濯機（三菱電機株式会社製：製品名ＣＷ－Ｃ３０Ａ１－Ｈ１）に移し、１分間脱水後、水道水（１５℃、４゜ＤＨ）３０Ｌ中で３分間濯ぎ、風乾した。未汚れ布（ここで未汚れ布とは、汚れの付着していない、基準となる白布をいう）、未洗浄のＥＭＰＡ１１７、及び洗浄後のＥＭＰＡ１１７について、それぞれ反射率を色差計（日本電色株式会社製：製品名ＳＥ２００型）で測定し、下式により洗浄率（％）を求めた。
　　洗浄率（％）＝（洗浄前の汚垢布のＫ／Ｓ－洗浄後の汚垢布のＫ／Ｓ）／（洗浄前の汚垢布のＫ／Ｓ－未汚れ布のＫ／Ｓ）×１００
　ただし、Ｋ／Ｓは、（１－Ｒ／１００）２／（２Ｒ／１００）である（Ｒは、未洗浄布、洗浄前後のＥＭＰＡ１１７の反射率（％）を示す）。
　洗浄力の評価基準は、洗浄率（％）が５５％以上のものを○（合格）、５５％未満のものを×（不合格）とした。 (Detergency)
For the evaluation of the cleaning power, the liquid detergent composition (manufactured immediately after production) immediately after production in each example was used. As the soiled cloth, EMPA117 (EMPA Testmateliaien, Polyester / cotton, 65/35, soiled with blood / milk / ink) cut into 5 cm × 5 cm square was used. A Terg-O-meter (manufactured by UNITED STATES TESTING) was used as a cleaning tester. As a cleaning solution, a solution prepared by adding 300 μL of a liquid cleaning composition to 900 mL of water and stirring for 30 seconds was used.
The cleaning tester was charged with 900 mL of cleaning liquid, 10 soiled cloths, and a cleaning knitted cloth, and washed at 120 rpm and 15 ° C. for 10 minutes in accordance with the bath ratio of 20 times. Then, it was transferred to a two-tank washing machine (product name: CW-C30A1-H1 manufactured by Mitsubishi Electric Corporation), dehydrated for 1 minute, rinsed in 30 L of tap water (15 ° C., 4 ° DH) for 3 minutes, and air-dried. The color difference meter (Nippon Denshoku Co., Ltd.) reflects the reflectance of unstained cloth (here, unstained cloth refers to a reference white cloth that is not soiled), unwashed EMPA117, and washed EMPA117. The washing rate (%) was determined by the following formula.
Washing rate (%) = (K / S of dirty cloth before washing−K / S of dirty cloth after washing) / (K / S of dirty cloth before washing−K / S of unclean cloth) × 100
However, K / S is (1-R / 100) 2 / (2R / 100) (R represents the reflectance (%) of the unwashed cloth and EMPA 117 before and after washing).
The evaluation criteria for the cleaning power were ○ (passed) when the cleaning rate (%) was 55% or more, and × (failed) when the cleaning rate was less than 55%.
（酵素安定性）
　＜プロテアーゼ活性の測定＞
　ミルクカゼイン（Ｃａｓｅｉｎ、Ｂｏｖｉｎｅ　Ｍｉｌｋ、Ｃａｒｂｏｈｙｄｒａｔｅ　ａｎｄ　Ｆａｔｔｙ　Ａｃｉｄ　Ｆｒｅｅ／Ｃａｌｂｉｏｃｈｅｍ（登録商標））を１Ｎ水酸化ナトリウム（１ｍｏｌ／Ｌ水酸化ナトリウム溶液（１Ｎ）、関東化学社製）に溶解し、ｐＨを１０．５とし、０．０５Ｍホウ酸（ホウ酸（特級）、関東化学社製）水溶液でミルクカゼインの濃度が０．６％になるよう希釈し、プロテアーゼ基質とした。
　各例で得た液体洗浄剤組成物１ｇを、塩化カルシウム（塩化カルシウム（特級）、関東化学社製）３°ＤＨ硬水で２５倍希釈した溶液をサンプル溶液とした。
　サンプル溶液１ｇに、上記プロテアーゼ基質５ｇを添加し、ボルテックスミキサーで１０秒間撹拌した後、３７℃、３０分間静置して酵素反応を進めた。その後、この溶液に酵素反応停止剤のＴＣＡ（トリクロロ酢酸（特級）、関東化学社製）の０．４４Ｍ水溶液５ｇを添加し、ボルテックスミキサーで１０秒間撹拌した。その後、この溶液を２０℃、３０分間静置して、析出する未反応基質を０．４５μｍフィルターで除去し、ろ液を回収した。
　回収したろ液の波長２７５ｎｍにおける吸光度（吸光度α）を、島津製作所社製紫外可視分光光度計ＵＶ－１６０を用いて測定した。吸光度αが大きいほど、ろ液中に存在するチロシン（プロテアーゼがプロテアーゼ基質を分解することにより産生）の量が多かったことを示す。
　目的成分以外の吸収の影響を除くため、別途、各サンプル溶液１ｇに、酵素反応停止剤であるＴＣＡ５ｇを添加し、ボルテックスミキサーで１０秒間撹拌した後、プロテアーゼ基質を５ｇ添加し、ボルテックスミキサーで１０秒間撹拌し、０．４５μｍフィルターで除去してろ液を回収した。その後、前記ろ液の波長２７５ｎｍの吸光度（吸光度β）を、ＵＶ－１６０を用いて測定した。 (Enzyme stability)
<Measurement of protease activity>
Milk casein (Casein, Bovine Milk, Carbohydrate and Fatty Acid Free / Calbiochem (registered trademark)) is dissolved in 1N sodium hydroxide (1 mol / L sodium hydroxide solution (1N), manufactured by Kanto Chemical Co., Inc.), and the pH is adjusted to 10. 5 was diluted with 0.05M boric acid (boric acid (special grade), manufactured by Kanto Chemical Co., Ltd.) aqueous solution so that the concentration of milk casein was 0.6% to obtain a protease substrate.
A solution obtained by diluting 1 g of the liquid detergent composition obtained in each example 25 times with calcium chloride (calcium chloride (special grade), manufactured by Kanto Chemical Co., Inc.) 3 ° DH hard water was used as a sample solution.
5 g of the protease substrate was added to 1 g of the sample solution, and the mixture was stirred for 10 seconds with a vortex mixer, and then allowed to stand at 37 ° C. for 30 minutes to proceed the enzyme reaction. Thereafter, 5 g of a 0.44M aqueous solution of TCA (trichloroacetic acid (special grade), manufactured by Kanto Chemical Co., Inc.), an enzyme reaction terminator, was added to this solution and stirred for 10 seconds with a vortex mixer. Thereafter, this solution was allowed to stand at 20 ° C. for 30 minutes, the unreacted substrate that precipitated was removed with a 0.45 μm filter, and the filtrate was recovered.
The absorbance (absorbance α) at a wavelength of 275 nm of the collected filtrate was measured using an ultraviolet-visible spectrophotometer UV-160 manufactured by Shimadzu Corporation. The greater the absorbance α, the greater the amount of tyrosine (produced by the protease degrading the protease substrate) present in the filtrate.
In order to remove the influence of absorption other than the target component, 5 g of TCA as an enzyme reaction stopper was separately added to 1 g of each sample solution, stirred for 10 seconds with a vortex mixer, then 5 g of protease substrate was added, and 10 times with a vortex mixer. Stir for 2 seconds and remove with a 0.45 μm filter to collect the filtrate. Thereafter, the absorbance (absorbance β) at a wavelength of 275 nm of the filtrate was measured using UV-160.
　＜プロテアーゼ活性の保存安定性の評価＞
　製造後、３５℃で４週間保存した液体洗浄剤組成物（３５℃保存品）および４℃で４週間保存した液体洗浄剤組成物（４℃保存品）について上記プロテアーゼ活性の測定を行った。それらの測定結果から、下記式により、プロテアーゼ活性残存率（％）を求めた。
　なお、下式に代入した各試料の２７５ｎｍにおける吸光度の値は、気泡等の散乱光を吸光度から除外するため、同時に測定した６００ｎｍの吸光度値を除し用いた。
　プロテアーゼ活性残存率＝（３５℃保存品の吸光度α－３５℃保存品の吸光度β）／（４℃保存品の吸光度α－４℃保存品の吸光度β）×１００
　求めたプロテアーゼ活性残存率（％）から、プロテアーゼ活性の保存安定性を以下の評価基準で評価した。
　　◎：８０％以上。
　　○：７０％以上８０％未満。
　　△：６０％以上７０％未満。
　　×：６０％未満。
　かかる評価結果を、酵素安定性（安定性）の欄にそれぞれ示す。評価基準は、残存率（％）が６０％以上のものを合格、６０％未満のものを不合格とした。 <Evaluation of storage stability of protease activity>
After the production, the protease activity was measured for a liquid detergent composition stored at 35 ° C. for 4 weeks (stored at 35 ° C.) and a liquid detergent composition stored at 4 ° C. for 4 weeks (stored at 4 ° C.). From these measurement results, the protease activity remaining rate (%) was determined by the following formula.
The absorbance value at 275 nm of each sample assigned to the following formula was used by dividing the absorbance value at 600 nm measured at the same time in order to exclude scattered light such as bubbles from the absorbance.
Protease activity remaining rate = (absorbance of 35 ° C. stored product α−absorbance β of 35 ° C. stored product) / (absorbance of 4 ° C. stored product α-4 ° C. stored product β) × 100
From the obtained protease activity remaining rate (%), the storage stability of protease activity was evaluated according to the following evaluation criteria.
A: 80% or more.
○: 70% or more and less than 80%.
Δ: 60% or more and less than 70%.
X: Less than 60%.
The evaluation results are shown in the column of enzyme stability (stability). As evaluation criteria, those with a residual rate (%) of 60% or more were accepted, and those with less than 60% were rejected.
（再汚染防止効果）
　各例で作成した液体洗浄剤組成物を用いて、以下に示す洗浄工程、すすぎ工程、乾燥工程をこの順序で３回繰り返す洗濯処理を行った。
　＜洗浄工程＞
　被洗物として、下記の綿布、ポリエステル（ＰＥ）布、湿式人工汚染布及び肌シャツを用いた。
・綿布：再汚染判定布として綿メリヤス（谷頭商店製）５ｃｍ×５ｃｍを５枚。
・ポリエステル（ＰＥ）布：再汚染判定布としてポリエステルトロピカル（谷頭商店製）５ｃｍ×５ｃｍを５枚。
・湿式人工汚染布：財団法人洗濯科学協会製の汚染布（オレイン酸２８．３％、トリオレイン１５．６％、コレステロールオレート１２．２％、流動パラフィン２．５％、スクアレン２．５％、コレステロール１．６％、ゼラチン７．０％、泥２９．８％、カーボンブラック０．５％（質量比）の組成の汚れが付着した布）を２０枚。
・肌シャツ：肌シャツ（ＬＬサイズ、ＤＶＤ社製）を細かく（３ｃｍ×３ｃｍ程度）裁断したもの。
　Ｔｅｒｇ－ｏ－ｔｏｍｅｔｅｒ（ＵＮＩＴＥＤ　ＳＴＡＴＥＳ　ＴＥＳＴＩＮＧ社製）内に、２５℃の３°ＤＨ硬水９００ｍＬを入れ、ここに液体洗浄剤組成物０．６ｇを加え、次いで、前記被洗物を入れた。その後、３°ＤＨ硬水を加えて浴比を２０倍に調整し、１２０ｒｐｍ、２５℃で１０分間洗浄した。
　＜すすぎ工程＞
　洗浄後の被洗物を、１分間脱水した後、２５℃の３°ＤＨ硬水９００ｍＬを入れ、１２０ｒｐｍ、２５℃で３分間すすいだ。この操作（脱水、すすぎ）を２回繰り返した。２回目には、２５℃の３°ＤＨ硬水９００ｍＬに、所定量の柔軟剤を添加してすすぎを行った。柔軟剤には、部屋干しソフラン（ライオン株式会社製）を用いた。
　＜乾燥工程＞
　すすいだ被洗物を１分間脱水した後、再汚染判定布（綿布、ＰＥ布）のみを取り出し、濾紙に挟み、アイロンで乾燥した。 (Re-contamination prevention effect)
Using the liquid detergent composition prepared in each example, a washing process in which the following washing process, rinsing process, and drying process were repeated three times in this order was performed.
<Washing process>
The following cotton cloth, polyester (PE) cloth, wet artificial contamination cloth and skin shirt were used as the objects to be washed.
-Cotton cloth: Five cotton knitted fabrics (manufactured by Tanigami Shoten) 5 cm x 5 cm as re-contamination determination cloth.
-Polyester (PE) cloth: Polyester tropical (manufactured by Tanigami Shoten) 5 cm x 5 cm as re-contamination determination cloth.
-Wet artificial contamination cloth: Contamination cloth manufactured by Japan Association for Laundry Science (28.3% oleic acid, 15.6% triolein, 12.2% cholesterol oleate, 2.5% liquid paraffin, 2.5% squalene, 20 sheets of soil with a composition of 1.6% cholesterol, 7.0% gelatin, 29.8% mud, and 0.5% carbon mass (mass ratio).
-Skin shirt: A skin shirt (LL size, manufactured by DVD) cut into pieces (about 3 cm x 3 cm).
In a Terg-o-meter (manufactured by UNITED STATES TESTING), 900 mL of 3 ° DH hard water at 25 ° C. was added, and 0.6 g of a liquid detergent composition was added thereto, and then the article to be washed was added. Thereafter, 3 ° DH hard water was added to adjust the bath ratio to 20 times, followed by washing at 120 rpm and 25 ° C. for 10 minutes.
<Rinsing process>
The washed article after dehydration was dehydrated for 1 minute, and then 900 mL of 3 ° DH hard water at 25 ° C. was added and rinsed at 120 rpm, 25 ° C. for 3 minutes. This operation (dehydration, rinsing) was repeated twice. In the second time, a predetermined amount of a softening agent was added to 900 mL of 3 ° DH hard water at 25 ° C. and rinsed. As the softener, room-dried saffron (manufactured by Lion Corporation) was used.
<Drying process>
After the rinsed object was dehydrated for 1 minute, only the recontamination determination cloth (cotton cloth, PE cloth) was taken out, sandwiched between filter papers, and dried with an iron.
　反射率計（分光式色差計ＳＥ２０００、日本電色工業株式会社製）を用い、洗濯処理前後の再汚染判定布の反射率（Ｚ値）を測定し、下式より△Ｚを求めた。
　　△Ｚ＝（洗濯処理前のＺ値）－（洗濯処理後のＺ値）
　綿布、ＰＥ布のそれぞれの再汚染判定布における△Ｚについて、５枚の平均値を求めた。そして、この平均値を指標とした下記判定基準に従い、液体洗浄剤組成物による綿布、ＰＥ布への再汚染防止効果を以下の判定基準で評価した。
　綿布における判定基準
　　◎：△Ｚが５未満。
　　○：△Ｚが５以上７未満。
　　△：△Ｚが７以上９未満。
　　×：△Ｚが９以上。
　ＰＥ布における判定基準
　　◎：△Ｚが３未満。
　　○：△Ｚが３以上４未満。
　　△：△Ｚが４以上５未満。
　　×：△Ｚが５以上。 Using a reflectance meter (spectral color difference meter SE2000, manufactured by Nippon Denshoku Industries Co., Ltd.), the reflectance (Z value) of the recontamination determination cloth before and after the washing treatment was measured, and ΔZ was determined from the following equation.
ΔZ = (Z value before washing process) − (Z value after washing process)
The average value of 5 sheets was obtained for ΔZ in the respective recontamination determination cloths of cotton cloth and PE cloth. Then, according to the following criteria using this average value as an index, the effect of preventing the re-contamination of the cotton fabric and PE fabric with the liquid detergent composition was evaluated according to the following criteria.
Criteria for cotton cloth A: ΔZ is less than 5.
○: ΔZ is 5 or more and less than 7.
Δ: ΔZ is 7 or more and less than 9.
X: ΔZ is 9 or more.
Criteria for PE cloth A: ΔZ is less than 3.
○: ΔZ is 3 or more and less than 4.
Δ: ΔZ is 4 or more and less than 5.
X: ΔZ is 5 or more.
（液安定性の評価）
　透明のガラス瓶（広口規格びん、ＰＳ－ＮＯ．１１）に、液体洗浄剤組成物１００ｍＬを充填し、蓋を閉めて密封した。この状態で５℃（又は２５℃）の恒温槽内に７日間静置して保存した。
　かかる保存の後、液の外観を目視で観察し、下記評価基準に従って、液体洗浄剤組成物の液安定性を評価した。この評価結果が◎、○であるものを合格とした。
　評価基準
　　◎：ガラス瓶の底部に５℃でも沈殿物質が認められず、液の流動性がある。
　　○：ガラス瓶の底部に５℃では沈殿物質が認められず、一部にゲル化が認められるが、２５℃で３時間静置するとゲル化した部分は見られず、液全体が流動するようになる。
　　△：ガラス瓶の底部に２５℃では沈殿物質が認められるが、ガラス瓶を軽く振ると、その沈殿物質は消失（溶解）する。
　　×：ガラス瓶の底部に２５℃でも沈殿物質が認められ、ガラス瓶を軽く振ってもその沈殿物質は消失しない、又は、液体洗浄剤の製造直後にゲル化もしくは白濁した。 (Evaluation of liquid stability)
A transparent glass bottle (wide-mouth bottle, PS-NO.11) was filled with 100 mL of the liquid detergent composition, and the lid was closed and sealed. In this state, it was left to stand for 7 days in a 5 ° C. (or 25 ° C.) thermostat.
After such storage, the appearance of the liquid was visually observed, and the liquid stability of the liquid detergent composition was evaluated according to the following evaluation criteria. The evaluation results of “A” and “B” were regarded as acceptable.
Evaluation criteria A: No precipitate is observed even at 5 ° C. at the bottom of the glass bottle, and the liquid is fluid.
○: No precipitate was observed at 5 ° C at the bottom of the glass bottle and some gelation was observed, but when left at 25 ° C for 3 hours, no gelled portion was seen and the entire liquid flowed. Become.
Δ: Precipitated substance is observed at 25 ° C. at the bottom of the glass bottle, but when the glass bottle is shaken lightly, the precipitated substance disappears (dissolves).
X: Precipitated substances were observed even at 25 ° C. at the bottom of the glass bottle, and even if the glass bottle was shaken lightly, the precipitated substances did not disappear, or gelled or became cloudy immediately after the production of the liquid detergent.
（抗菌性）
　（１）洗浄処理方法
　全自動電気洗濯機（Ｈａｉｅｒ社製、製品名「ＪＷ－Ｚ２３Ａ」）に、約４００ｇの被洗布を投入した［浴比（洗濯水量／被洗布総質量）３０倍］。被洗布としては、５ｃｍ×５ｃｍの大きさに切り分けた綿市販のテトロン（登録商標）／綿ブロード混紡品（ポリエステル５０％／綿５０％）（以下、テト綿という。）約３０ｇと、綿肌シャツ（Ｂ．Ｖ．Ｄ．社製）とを合わせたものを用いた。
　次に、前記全自動電気洗濯機に、各例の液体洗浄剤組成物をそれぞれ３３３ｐｐｍ加え、標準コースで洗浄、すすぎ、脱水を順次行う洗浄操作を行った。その際、洗浄時間、すすぎ、脱水、水量（低水位に設定、水量約１２Ｌ）に関しては一切調整せず、洗濯機の標準コース設定をそのまま使用した。
　洗濯終了後、テト綿を取り出し、この取り出したテト綿を２５℃、相対湿度６５％ＲＨの恒温恒湿室に放置して乾燥させた。乾燥後、該テト綿を試験布として抗菌性の評価に用いた。また、未処理布として、前記洗濯操作を施していないテト綿を用いた。 (Antibacterial)
(1) Washing method Approximately 400 g of cloth to be washed was put into a fully automatic electric washing machine (product name “JW-Z23A” manufactured by Haier) [bath ratio (amount of washing water / total mass of cloth to be washed)] 30 times ]. As the cloth to be washed, about 30 g of cotton commercially available Tetron (registered trademark) / cotton broad blend (50% polyester / 50% cotton) (hereinafter referred to as tet cotton) cut into 5 cm × 5 cm sizes, and cotton A combination with a skin shirt (manufactured by BVD) was used.
Next, 333 ppm of the liquid detergent composition of each example was added to the fully automatic electric washing machine, and washing operations were sequentially performed for washing, rinsing and dehydration using a standard course. At that time, the standard course setting of the washing machine was used as it was without any adjustment regarding the washing time, rinsing, dehydration, and the amount of water (set to a low water level, about 12 L of water).
After washing, the tet cotton was taken out, and the tet cotton taken out was left to dry in a constant temperature and humidity room at 25 ° C. and a relative humidity of 65% RH. After drying, the Tet cotton was used as a test cloth for antibacterial evaluation. Moreover, the Tet cotton which has not performed the said washing operation was used as an untreated cloth.
　（２）黄色ブドウ球菌に対する抗菌性の評価
　本評価に用いた器具、水等は、予めオートクレーブにより滅菌処理を施した。また、本評価では、菌として黄色ブドウ球菌（Ｓｔａｐｈｙｌｏｃｏｃｃｕｓ　ａｕｒｅｕｓ）を用いた。
　ＪＩＳ　Ｌ１９０２に準じて培養を行った黄色ブドウ球菌を用い、ニュートリエント培地を２０倍に希釈し、菌数が１±０．３×１０５個／ｍＬとなるように、黄色ブドウ球菌母液を調製した。
　前記試験布（５ｃｍ×５ｃｍ）の４箇所に、前記黄色ブドウ球菌母液０．１ｍＬずつを接種し、３７℃の恒温槽にて１８時間培養して、試験布上で増殖又は静菌した。
　その後、抽出液（ＪＩＳ　Ｌ１９０２に記載の洗い出し用生理食塩水）にて試験布から菌を抽出し、その抽出液を生理食塩水によって１０倍に希釈した。得られた希釈液を１０倍に希釈する操作をさらに４回繰り返し、１００，０００倍の希釈液を得た。なお、「洗い出し用生理食塩水」とは、精製水１，０００ｍＬと塩化ナトリウム８．５ｇとをフラスコに入れて充分に溶解させ、さらに非イオン界面活性剤としてポリオキシエチレンソルビタンモノオレート（関東化学株式会社製、商品名「ポリソルベート８０、Ｔｗｅｅｎ８０」）２ｇを加えて溶解させた後、高圧蒸気殺菌（オートクレーブ処理）したものである。
　次いで、ＳＣＤＬＰ寒天培地（日本製薬株式会社製）上に、得られた１００，０００倍の希釈液から１ｍＬを採取し、予めオートクレーブにより滅菌処理して４８℃に保温したＳＣＤＬＰ寒天培地１５ｍＬをシャーレ上で混釈し、３７℃の恒温槽内で１～２日間培養した。培養後、コロニー数をカウントし、生菌数を求めた。
　未処理布についても試験布と同様の操作を行って生菌数を測定し、これらの測定値を用いて抗菌活性値（Ａ）を下記式より算出した。
　　抗菌活性値＝ｌｏｇ１０（未処理布の生菌数／試験布の生菌数） (2) Evaluation of antibacterial activity against Staphylococcus aureus The instruments, water, and the like used in this evaluation were sterilized in advance by an autoclave. In this evaluation, Staphylococcus aureus was used as the bacterium.
Using Staphylococcus aureus cultured according to JIS L1902, the Nutrient medium is diluted 20 times, and the Staphylococcus aureus mother solution is prepared so that the number of bacteria becomes 1 ± 0.3 × 10 5 cells / mL did.
Four portions of the test cloth (5 cm × 5 cm) were inoculated with 0.1 mL of the Staphylococcus aureus mother liquor, cultured in a thermostatic bath at 37 ° C. for 18 hours, and grown or bacteriostatic on the test cloth.
Thereafter, bacteria were extracted from the test cloth with an extract (washing saline described in JIS L1902), and the extract was diluted 10-fold with saline. The operation of diluting the obtained diluted solution 10 times was further repeated 4 times to obtain a 100,000 times diluted solution. In addition, “washing-out physiological saline” means that 1,000 mL of purified water and 8.5 g of sodium chloride are sufficiently dissolved in a flask, and polyoxyethylene sorbitan monooleate (Kanto Chemical Co., Ltd.) as a nonionic surfactant. 2 g of a trade name “Polysorbate 80, Tween 80”) manufactured by Co., Ltd. was added and dissolved, followed by high-pressure steam sterilization (autoclave treatment).
Next, 1 mL of the obtained 100,000-fold diluted solution was collected on an SCDLP agar medium (manufactured by Nippon Pharmaceutical Co., Ltd.), and 15 mL of SCDLP agar medium previously sterilized by autoclaving and kept at 48 ° C. was placed on a petri dish. And cultured in a constant temperature bath at 37 ° C. for 1-2 days. After culture, the number of colonies was counted to determine the number of viable bacteria.
For the untreated cloth, the number of viable bacteria was measured by the same operation as that of the test cloth, and the antibacterial activity value (A) was calculated from the following formula using these measured values.
Antibacterial activity value = log 10 (viable bacterial count of untreated cloth / viable bacterial count of test cloth)
　次いで、液体洗浄剤の代わりに、評価比較用液体洗浄剤を用いた以外は、（１）、（２）と同様の操作を行い、試験布及び未処理布について生菌数を測定して抗菌活性値（Ｂ）を算出した。
　算出した抗菌活性値（Ａ）と抗菌活性値（Ｂ）より、抗菌活性値の差｛抗菌活性値（Ａ）－抗菌活性値（Ｂ）｝を求め、下記の評価基準により抗菌性の評価を行った。△、×を不合格とした。
　評価基準
　　◎：抗菌活性値の差が２．５以上であった。
　　○：抗菌活性値の差が２．０以上～２．５未満であった。
　　△：抗菌活性値の差が１．０以上～２．０未満であった。
　　×：抗菌活性値の差が１．０未満であった。 Next, the same procedure as in (1) and (2) was performed, except that a liquid cleaning agent for evaluation and comparison was used instead of the liquid cleaning agent, and the number of viable bacteria was measured for the test cloth and the untreated cloth. Activity value (B) was calculated.
From the calculated antibacterial activity value (A) and antibacterial activity value (B), the difference between the antibacterial activity values {antibacterial activity value (A)-antibacterial activity value (B)} is obtained, and the antibacterial properties are evaluated according to the following evaluation criteria. went. △ and X were rejected.
Evaluation criteria A: Difference in antibacterial activity value was 2.5 or more.
A: The difference in antibacterial activity value was 2.0 or more and less than 2.5.
Δ: The difference in antibacterial activity value was 1.0 or more and less than 2.0.
X: The difference in antibacterial activity value was less than 1.0.
（部屋干し臭発生の抑制効果）
　混紡Ｔシャツ（綿６０％、ポリエステル４０％）に対し、市販合成洗剤トップ（ライオン株式会社製）を用いて、洗剤使用量を２５ｇ／水道水３０Ｌとして洗濯処理（ＪＷ－Ｚ２３Ａ型、ハイアール社製、水温２０℃、１０分間）を行った。
　次いで、混紡Ｔシャツを２０～４０代男性１０人に１２時間着用させた後、各例の液体洗浄剤組成物を用いて、洗濯機（ＪＷ－Ｚ２３Ａ型、ハイアール社製）の通常コースで洗濯処理（水温約２０℃、硬度約３゜ＤＨの水道水を注水、浴比２０倍）を行った。その際、液体洗浄剤組成物の洗濯機への投入量を１０ｍＬ／水道水３０Ｌとして洗濯処理を行った。なお、新品の綿１００％の肌シャツ（ＢＶＤ製）を、全自動洗濯機（パナソニック株式会社製、ＮＡ－Ｆ７０ＳＤ１）のおまかせコースで５回洗濯処理（水温約２０℃、硬度約３゜ＤＨの水道水を注水）したものを、浴比合わせの衣料として用いた。
　前記混紡Ｔシャツの洗濯処理が終了した後、室温（約２３℃）、相対湿度９０％ＲＨの室内に干して５時間乾燥（部屋干し）を行った。その後、６名の専門パネラーがそれぞれ５時間乾燥（部屋干し）後の混紡Ｔシャツの臭いを嗅ぐという官能評価を行った。該官能評価は、下記の評価基準に基づいて点数化することにより行った。具体的には、専門パネラーが、部屋干し後の混紡Ｔシャツのそれぞれの臭いを嗅ぎ、下記評価基準における６段階の臭気強度表示に従って評価した。そして、混紡Ｔシャツの平均点を算出し、この平均点を指標として、部屋干し臭発生の抑制効果について評価した。かかる平均点が３．０点以下のものを合格とした。
　官能評価の評価基準（臭気強度表示）
　　０点：異臭が全くしない。
　　１点：異臭がやっと感知できる程度に感じられる。
　　２点：異臭が弱く感じられる。
　　３点：異臭がやや強く感じられる。
　　４点：異臭が強く感じられる。
　　５点：異臭が強烈に感じられる。 (Suppressing the effects of drying room odor)
Washing treatment (JW-Z23A type, made by Haier Co., Ltd.) using a blended T-shirt (60% cotton, 40% polyester) with a commercially available detergent top (manufactured by Lion Corporation) and a detergent usage of 25g / 30L of tap water , Water temperature 20 ° C., 10 minutes).
Next, 10 males in their 20s to 40s wear a blended T-shirt for 12 hours, and then wash them in the normal course of a washing machine (JW-Z23A, manufactured by Haier) using the liquid detergent composition of each example. The treatment (water temperature of about 20 ° C. and hardness of about 3 ° DH was poured into the water, bath ratio 20 times). At that time, the washing treatment was performed by setting the amount of the liquid detergent composition to the washing machine as 10 mL / 30 L of tap water. A new 100% cotton skin shirt (manufactured by BVD) was washed 5 times with a fully automatic washing machine (NA-F70SD1 manufactured by Panasonic Corporation) with a water temperature of about 20 ° C and a hardness of about 3 ° DH. What was injected with tap water was used as clothing for bath ratio matching.
After the washing treatment of the blended T-shirt was completed, the blended T-shirt was dried in a room at room temperature (about 23 ° C.) and a relative humidity of 90% RH and dried (room dried) for 5 hours. After that, 6 expert panelists performed sensory evaluation to smell the blended T-shirts after drying (drying in the room) for 5 hours. The sensory evaluation was performed by scoring based on the following evaluation criteria. Specifically, a specialized panelist sniffs the odor of each of the blended T-shirts after the room was dried, and evaluated according to the 6-level odor intensity display in the following evaluation criteria. Then, the average score of the blended T-shirt was calculated, and the effect of suppressing the occurrence of room drying odor was evaluated using this average score as an index. Those having an average score of 3.0 or less were regarded as acceptable.
Sensory evaluation criteria (odor intensity display)
0 point: There is no off-flavor.
1 point: A strange odor can be perceived at last.
2 points: The off-flavor is felt weak.
3 points: A strange odor is felt slightly stronger.
4 points: Strong odor is felt.
5 points: A strange odor is felt intensely.
　各例の評価結果を表１～４に示す。 The evaluation results for each example are shown in Tables 1 to 4.
Figure JPOXMLDOC01-appb-T000009
Figure JPOXMLDOC01-appb-T000009
Figure JPOXMLDOC01-appb-T000010
Figure JPOXMLDOC01-appb-T000010
Figure JPOXMLDOC01-appb-T000011
Figure JPOXMLDOC01-appb-T000011
Figure JPOXMLDOC01-appb-T000012
Figure JPOXMLDOC01-appb-T000012
　表１～４に示すように、（Ａ）～（Ｃ）成分を含む実施例１～２８では、高い洗浄力、優れた液安定性、及び高い再汚染防止効果が得られたうえ、被洗物に優れた抗菌性が付与され、部屋干し臭発生の十分に抑制された。また、実施例１、７、２０～２３では、十分な酵素安定性も得られた。
　一方、（Ｃ）成分を含まない比較例１、２では、十分な抗菌性が得られなかった。
　（Ｂ）成分を含まない比較例３では、十分な洗浄力が得られず、再汚染防止効果も低かった。 As shown in Tables 1 to 4, in Examples 1 to 28 containing the components (A) to (C), a high detergency, excellent liquid stability, and a high anti-recontamination effect were obtained, and to-be-washed Excellent antibacterial properties were imparted to the objects, and the occurrence of room-dried odor was sufficiently suppressed. In Examples 1, 7, and 20 to 23, sufficient enzyme stability was also obtained.
On the other hand, in Comparative Examples 1 and 2 not including the component (C), sufficient antibacterial properties were not obtained.
In Comparative Example 3 containing no component (B), sufficient detergency was not obtained and the effect of preventing recontamination was low.

Claims (6)

  1. 　（Ａ）成分：下式（Ｉ）で表される化合物、及び下式（ＩＩ）で表される化合物からなる群から選ばれる少なくとも１種を含むノニオン界面活性剤と、（Ｂ）成分：アニオン界面活性剤からなる群から選ばれる少なくとも１種と、（Ｃ）成分：フェノール構造を有する抗菌剤と、を含有する、液体洗浄剤組成物。
    　Ｒ１－Ｃ（＝Ｏ）Ｏ－［（ＥＯ）ｓ／（ＰＯ）ｔ］－（ＥＯ）ｕ－Ｒ２　・・・（Ｉ）
    　Ｒ３－Ｏ－［（ＥＯ）ｖ／（ＰＯ）ｗ］－（ＥＯ）ｘ－Ｈ　・・・（ＩＩ）
    （ただし、式中、ＥＯはエチレンオキシ基であり、ＰＯはプロピレンオキシ基である。Ｒ１は炭素数７～２２の炭化水素基であり、Ｒ２はメチル基又はエチル基であり、Ｒ３は炭素数７～２２の炭化水素基である。ｓ、ｖ、ｕ、ｘはＥＯの平均繰り返し数であり、ｔ、ｗはＰＯの平均繰り返し数である。ｓは６～２０の数であり、ｔは０～６の数であり、ｕは０～２０の数である。ｖは８～２０の数であり、ｗは０～６の数であり、ｘは０～２０の数である。）     (A) component: a nonionic surfactant containing at least one selected from the group consisting of a compound represented by the following formula (I) and a compound represented by the following formula (II); and (B) component: an anion A liquid detergent composition comprising at least one selected from the group consisting of surfactants and (C) component: an antibacterial agent having a phenol structure.
    R 1 —C (═O) O — [(EO) s / (PO) t ] — (EO) u —R 2 (I)
    R 3 —O — [(EO) v / (PO) w ] — (EO) x —H (II)
    (In the formula, EO is an ethyleneoxy group, PO is a propyleneoxy group, R 1 is a hydrocarbon group having 7 to 22 carbon atoms, R 2 is a methyl group or an ethyl group, and R 3 Is a hydrocarbon group having 7 to 22 carbon atoms, s, v, u and x are the average number of repetitions of EO, t and w are the average number of repetitions of PO, and s is a number of 6 to 20 , T is a number from 0 to 6, u is a number from 0 to 20, v is a number from 8 to 20, w is a number from 0 to 6, and x is a number from 0 to 20. .)
  2. 　前記（Ａ）成分と前記（Ｂ）成分との（Ａ）／（Ｂ）比（質量比）が１以上である、請求項１に記載の液体洗浄剤組成物。 The liquid detergent composition according to claim 1, wherein the (A) / (B) ratio (mass ratio) between the component (A) and the component (B) is 1 or more.
  3. 　前記（Ｂ）成分と前記（Ｃ）成分との（Ｂ）／（Ｃ）比（質量比）が３以上である、請求項１又は２に記載の液体洗浄剤組成物。 The liquid detergent composition according to claim 1 or 2, wherein a (B) / (C) ratio (mass ratio) of the component (B) and the component (C) is 3 or more.
  4. 　さらに、（Ｄ）成分：アルキレンテレフタレート単位及びアルキレンイソフタレート単位のいずれか一方もしくは両方と、オキシアルキレン単位及びポリオキシアルキレン単位のいずれか一方もしくは両方とを有する水溶性ポリマーを、０．１～５質量％含有する、請求項１～３のいずれか一項に記載の液体洗浄剤組成物。 Further, a component (D): a water-soluble polymer having either one or both of an alkylene terephthalate unit and an alkylene isophthalate unit, and one or both of an oxyalkylene unit and a polyoxyalkylene unit, The liquid detergent composition according to any one of claims 1 to 3, which is contained by mass%.
  5. 　さらに、（Ｅ）成分：ポリアルキレンオキシド鎖を含むアルキレンアミン構造単位を有するポリアルキレンアミンアルキレンオキシド系共重合体を、０．１～５質量％含有する、請求項１～４のいずれか一項に記載の液体洗浄剤組成物。 The component (E) further comprises 0.1 to 5% by mass of a polyalkyleneamine alkylene oxide copolymer having an alkyleneamine structural unit containing a polyalkyleneoxide chain. A liquid detergent composition as described in 1. above.
  6. 　さらに、（Ｆ）成分：カチオン界面活性剤からなる群から選ばれる少なくとも１種を含有する、請求項１～５のいずれか一項に記載の液体洗浄剤組成物。 The liquid detergent composition according to any one of claims 1 to 5, further comprising at least one selected from the group consisting of component (F): a cationic surfactant.
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Cited By (12)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2018188542A (en) * 2017-05-01 2018-11-29 ライオン株式会社 Liquid detergent composition
JP2018188600A (en) * 2017-05-11 2018-11-29 ライオン株式会社 Liquid detergent
JP2018188641A (en) * 2017-05-09 2018-11-29 ライオン株式会社 Liquid detergent composition for garment
JP2018203923A (en) * 2017-06-07 2018-12-27 ライオン株式会社 Liquid detergent
JP2019073688A (en) * 2017-10-12 2019-05-16 ザ プロクター アンド ギャンブル カンパニー Anti-microbial laundry detergent composition
JP2019073568A (en) * 2017-10-12 2019-05-16 ライオン株式会社 Liquid detergent composition
JP2020033473A (en) * 2018-08-30 2020-03-05 ライオン株式会社 Biofilm inhibitor composition
JP2020041074A (en) * 2018-09-12 2020-03-19 ライオン株式会社 Liquid detergent composition for clothing
JP2020105278A (en) * 2018-12-26 2020-07-09 ライオン株式会社 Liquid detergent composition for fiber product
CN111778113A (en) * 2020-07-10 2020-10-16 纳爱斯浙江科技有限公司 Antimicrobial detergent composition
CN112227071A (en) * 2020-09-22 2021-01-15 纳爱斯浙江科技有限公司 Antimicrobial softener composition
WO2021106851A1 (en) * 2019-11-25 2021-06-03 花王株式会社 Liquid detergent composition for textile products

Citations (8)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2004515642A (en) * 2000-12-14 2004-05-27 チバ スペシャルティ ケミカルズ ホールディング インコーポレーテッド Surfactant composition
JP2007530499A (en) * 2004-03-23 2007-11-01 チバ　スペシャルティ　ケミカルズ　ホールディング　インコーポレーテッド Disinfectant composition
JP2009532592A (en) * 2006-04-06 2009-09-10 ヘンケル・アクチェンゲゼルシャフト・ウント・コムパニー・コマンディットゲゼルシャフト・アウフ・アクチェン Solid fabric and / or skin care composition
JP2011190368A (en) * 2010-03-15 2011-09-29 Lion Corp Liquid detergent composition for clothes
JP2012188515A (en) * 2011-03-09 2012-10-04 Lion Corp Liquid bleaching agent
JP2013116970A (en) * 2011-12-02 2013-06-13 Lion Corp Liquid bleaching composition for clothing
WO2015030940A1 (en) * 2013-08-26 2015-03-05 The Procter & Gamble Company Compositions comprising alkoxylated polyalkyleneimines having low melting points
WO2016159368A1 (en) * 2015-04-03 2016-10-06 ライオン株式会社 Liquid detergent for fiber product

Family Cites Families (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP5577090B2 (en) * 2009-02-12 2014-08-20 ライオン株式会社 Liquid detergent composition

Patent Citations (8)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2004515642A (en) * 2000-12-14 2004-05-27 チバ スペシャルティ ケミカルズ ホールディング インコーポレーテッド Surfactant composition
JP2007530499A (en) * 2004-03-23 2007-11-01 チバ　スペシャルティ　ケミカルズ　ホールディング　インコーポレーテッド Disinfectant composition
JP2009532592A (en) * 2006-04-06 2009-09-10 ヘンケル・アクチェンゲゼルシャフト・ウント・コムパニー・コマンディットゲゼルシャフト・アウフ・アクチェン Solid fabric and / or skin care composition
JP2011190368A (en) * 2010-03-15 2011-09-29 Lion Corp Liquid detergent composition for clothes
JP2012188515A (en) * 2011-03-09 2012-10-04 Lion Corp Liquid bleaching agent
JP2013116970A (en) * 2011-12-02 2013-06-13 Lion Corp Liquid bleaching composition for clothing
WO2015030940A1 (en) * 2013-08-26 2015-03-05 The Procter & Gamble Company Compositions comprising alkoxylated polyalkyleneimines having low melting points
WO2016159368A1 (en) * 2015-04-03 2016-10-06 ライオン株式会社 Liquid detergent for fiber product

Cited By (17)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2018188542A (en) * 2017-05-01 2018-11-29 ライオン株式会社 Liquid detergent composition
JP7190823B2 (en) 2017-05-09 2022-12-16 ライオン株式会社 Liquid detergent composition for clothes
JP2018188641A (en) * 2017-05-09 2018-11-29 ライオン株式会社 Liquid detergent composition for garment
JP2018188600A (en) * 2017-05-11 2018-11-29 ライオン株式会社 Liquid detergent
JP2018203923A (en) * 2017-06-07 2018-12-27 ライオン株式会社 Liquid detergent
JP2019073688A (en) * 2017-10-12 2019-05-16 ザ プロクター アンド ギャンブル カンパニー Anti-microbial laundry detergent composition
JP2019073568A (en) * 2017-10-12 2019-05-16 ライオン株式会社 Liquid detergent composition
JP2020033473A (en) * 2018-08-30 2020-03-05 ライオン株式会社 Biofilm inhibitor composition
JP2020041074A (en) * 2018-09-12 2020-03-19 ライオン株式会社 Liquid detergent composition for clothing
JP2020105278A (en) * 2018-12-26 2020-07-09 ライオン株式会社 Liquid detergent composition for fiber product
JP7203596B2 (en) 2018-12-26 2023-01-13 ライオン株式会社 Liquid detergent composition for textiles
WO2021106851A1 (en) * 2019-11-25 2021-06-03 花王株式会社 Liquid detergent composition for textile products
CN111778113B (en) * 2020-07-10 2021-07-16 纳爱斯浙江科技有限公司 Antimicrobial detergent composition
WO2022007491A1 (en) * 2020-07-10 2022-01-13 纳爱斯浙江科技有限公司 Antimicrobial detergent composition
CN111778113A (en) * 2020-07-10 2020-10-16 纳爱斯浙江科技有限公司 Antimicrobial detergent composition
CN112227071A (en) * 2020-09-22 2021-01-15 纳爱斯浙江科技有限公司 Antimicrobial softener composition
CN112227071B (en) * 2020-09-22 2022-12-06 纳爱斯浙江科技有限公司 Antimicrobial softener composition

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