WO2017051776A1 - Composition d'agent de nettoyage liquide - Google Patents

Composition d'agent de nettoyage liquide 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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Prior art keywords
component
group
carbon atoms
liquid detergent
detergent composition
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PCT/JP2016/077444
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English (en)
Japanese (ja)
Inventor
圭輔 森
真嘉 大石
神藤　宏明
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ライオン株式会社
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Priority to JP2017541540A priority Critical patent/JP6770964B2/ja
Publication of WO2017051776A1 publication Critical patent/WO2017051776A1/fr

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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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  • Oil, Petroleum & Natural Gas (AREA)
  • Wood Science & Technology (AREA)
  • Organic Chemistry (AREA)
  • Detergent Compositions (AREA)

Abstract

La présente invention concerne la préparation d'une composition liquide d'agent de nettoyage capable de faire preuve d'une capacité de nettoyage élevée, d'une excellente stabilité à l'état liquide, et d'une efficacité élevée pour prévenir la redéposition de salissure, tout en étant capable de conférer d'excellentes propriétés antimicrobiennes à un objet de nettoyage et présentant d'excellents effets de suppression des odeurs au séchage en intérieur. La présente invention décrit une composition liquide d'agent de nettoyage contenant comme composant (A) un tensioactif non ionique incluant au moins une espèce sélectionnée parmi un groupe spécifique de composés, comme composant (B) au moins une espèce sélectionnée dans le groupe constitué d'un tensioactif anionique et d'un sel d'un tensioactif anionique, et comme composant (C) un agent antimicrobien ayant une structure phénolique.
PCT/JP2016/077444 2015-09-24 2016-09-16 Composition d'agent de nettoyage liquide WO2017051776A1 (fr)

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JP2018188542A (ja) * 2017-05-01 2018-11-29 ライオン株式会社 液体洗浄剤組成物
JP2018188641A (ja) * 2017-05-09 2018-11-29 ライオン株式会社 衣料用液体洗浄剤組成物
JP2018188600A (ja) * 2017-05-11 2018-11-29 ライオン株式会社 液体洗浄剤
JP2018203923A (ja) * 2017-06-07 2018-12-27 ライオン株式会社 液体洗浄剤
JP2019073568A (ja) * 2017-10-12 2019-05-16 ライオン株式会社 液体洗浄剤組成物
JP2019073688A (ja) * 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 抗菌洗濯洗剤組成物
JP2020033473A (ja) * 2018-08-30 2020-03-05 ライオン株式会社 バイオフィルム抑制剤組成物
JP2020041074A (ja) * 2018-09-12 2020-03-19 ライオン株式会社 衣料用液体洗浄剤組成物
JP2020105278A (ja) * 2018-12-26 2020-07-09 ライオン株式会社 繊維製品用の液体洗浄剤組成物
CN111778113A (zh) * 2020-07-10 2020-10-16 纳爱斯浙江科技有限公司 一种抗微生物洗涤剂组合物
CN112227071A (zh) * 2020-09-22 2021-01-15 纳爱斯浙江科技有限公司 一种抗微生物柔顺剂组合物
WO2021106851A1 (fr) * 2019-11-25 2021-06-03 花王株式会社 Composition de détergent liquide pour produits textiles

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JP2018188542A (ja) * 2017-05-01 2018-11-29 ライオン株式会社 液体洗浄剤組成物
JP7190823B2 (ja) 2017-05-09 2022-12-16 ライオン株式会社 衣料用液体洗浄剤組成物
JP2018188641A (ja) * 2017-05-09 2018-11-29 ライオン株式会社 衣料用液体洗浄剤組成物
JP2018188600A (ja) * 2017-05-11 2018-11-29 ライオン株式会社 液体洗浄剤
JP2018203923A (ja) * 2017-06-07 2018-12-27 ライオン株式会社 液体洗浄剤
JP2019073568A (ja) * 2017-10-12 2019-05-16 ライオン株式会社 液体洗浄剤組成物
JP2019073688A (ja) * 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 抗菌洗濯洗剤組成物
JP2020033473A (ja) * 2018-08-30 2020-03-05 ライオン株式会社 バイオフィルム抑制剤組成物
JP2020041074A (ja) * 2018-09-12 2020-03-19 ライオン株式会社 衣料用液体洗浄剤組成物
JP2020105278A (ja) * 2018-12-26 2020-07-09 ライオン株式会社 繊維製品用の液体洗浄剤組成物
JP7203596B2 (ja) 2018-12-26 2023-01-13 ライオン株式会社 繊維製品用の液体洗浄剤組成物
WO2021106851A1 (fr) * 2019-11-25 2021-06-03 花王株式会社 Composition de détergent liquide pour produits textiles
CN111778113B (zh) * 2020-07-10 2021-07-16 纳爱斯浙江科技有限公司 一种抗微生物洗涤剂组合物
WO2022007491A1 (fr) * 2020-07-10 2022-01-13 纳爱斯浙江科技有限公司 Composition détergente antimicrobienne
CN111778113A (zh) * 2020-07-10 2020-10-16 纳爱斯浙江科技有限公司 一种抗微生物洗涤剂组合物
CN112227071A (zh) * 2020-09-22 2021-01-15 纳爱斯浙江科技有限公司 一种抗微生物柔顺剂组合物
CN112227071B (zh) * 2020-09-22 2022-12-06 纳爱斯浙江科技有限公司 一种抗微生物柔顺剂组合物

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