WO2017142012A1 - Composition détergente - Google Patents

Composition détergente Download PDF

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Publication number
WO2017142012A1
WO2017142012A1 PCT/JP2017/005689 JP2017005689W WO2017142012A1 WO 2017142012 A1 WO2017142012 A1 WO 2017142012A1 JP 2017005689 W JP2017005689 W JP 2017005689W WO 2017142012 A1 WO2017142012 A1 WO 2017142012A1
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WO
WIPO (PCT)
Prior art keywords
component
mass
group
carbon atoms
cleaning composition
Prior art date
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Ceased
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PCT/JP2017/005689
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English (en)
Japanese (ja)
Inventor
貴行 黒川
将人 福井
貴広 林
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Lion Corp
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Lion Corp
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Filing date
Publication date
Application filed by Lion Corp filed Critical Lion Corp
Priority to SG11201806877XA priority Critical patent/SG11201806877XA/en
Priority to MYPI2018702816A priority patent/MY191406A/en
Priority to CN201780011861.1A priority patent/CN108699493B/zh
Priority to JP2018500187A priority patent/JP6591033B2/ja
Priority to KR1020187022155A priority patent/KR20180114019A/ko
Publication of WO2017142012A1 publication Critical patent/WO2017142012A1/fr
Anticipated expiration legal-status Critical
Ceased legal-status Critical Current

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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
    • C11D1/74—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
    • C11D3/00—Other compounding ingredients of detergent compositions covered in group C11D1/00
    • C11D3/16—Organic compounds
    • C11D3/37—Polymers
    • C11D3/3703—Macromolecular compounds obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds
    • C11D3/3723—Polyamines or polyalkyleneimines
    • 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
    • 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
    • C11D3/16—Organic compounds
    • C11D3/38—Products with no well-defined composition, e.g. natural products
    • C11D3/386—Preparations containing enzymes, e.g. protease or amylase
    • 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
    • C11D3/50—Perfumes

Definitions

  • the present invention relates to a cleaning composition.
  • This application claims priority based on Japanese Patent Application No. 2016-027293 filed in Japan on February 16, 2016, the contents of which are incorporated herein by reference.
  • Patent Document 1 discloses a perfume delivery system suitable for delivering a perfume to the surface using a composition containing polyethyleneimine and a perfume.
  • the present invention has been made in view of the above circumstances, and relates to a cleaning composition having a high residual fragrance. Furthermore, the present invention is also excellent in recontamination prevention performance (performance for preventing dirt from re-adhering to an object to be washed).
  • this invention has the following aspects.
  • the cleaning composition whose mass ratio represented by a component (B1) / component (B2) is 1.0 or more.
  • the component (B1) contains a fatty acid methyl ester ethoxylate
  • the detergent composition according to [1] wherein the content of the fatty acid methyl ester ethoxylate is 10% by mass or more based on the total mass of the component (B).
  • component (D) containing a polymer having at least one repeating unit (d1) selected from the group consisting of an alkylene terephthalate unit and an alkylene isophthalate unit and an oxyalkylene unit (d2) [1] or The cleaning composition according to [2].
  • component (E) at least one selected from carboxylic acids represented by the following general formula (VII) and salts thereof
  • component (F) an enzyme containing [1] to [3] The cleaning composition according to any one of the above.
  • R 1 is a divalent hydrocarbon group having 1 to 4 carbon atoms or an arylene group
  • X is —H, —OH, —CH 3 , or —COOH.
  • the cleaning composition of the present invention contains the following components (A) to (C).
  • Component (A) is an alkylene oxide adduct of polyalkyleneamine.
  • Examples of the component (A) include the following component (a1) and component (a2).
  • Component (a1) is an alkylene oxide adduct of polyalkyleneimine.
  • the polyalkyleneimine of component (a1) is represented by the following general formula (I), for example. NH 2 —R 21 — (NA—R 21 ) n —NH 2 (I)
  • R 21 each independently represents an alkylene group having 2 to 6 carbon atoms
  • A represents a hydrogen atom or another polyamine chain by branching
  • n is an integer of 1 or more.
  • the polyalkyleneimine represented by the formula (I) has a polyamine chain branched in the structure.
  • R 21 is a linear alkylene group having 2 to 6 carbon atoms or a branched alkylene group having 3 to 6 carbon atoms.
  • R 21 is preferably an alkylene group having 2 to 4 carbon atoms, more preferably an alkylene group having 2 carbon atoms.
  • the polyalkyleneimine can be obtained by polymerizing one or more 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.
  • polyethyleneimine (hereinafter also referred to as “PEI”) (in formula (I), R 21 represents an ethylene group), polypropyleneimine (in formula (I), R 21 represents a propylene group) Is preferred, and PEI is more preferred.
  • PEI is obtained by polymerizing ethyleneimine and has a branched chain structure containing primary, secondary and tertiary amine nitrogen atoms in the structure. n is an integer of 1 or more.
  • the mass 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.
  • active hydrogen means a highly reactive hydrogen atom, specifically, a hydrogen atom bonded to a nitrogen atom.
  • Component (a1) is obtained by adding an alkylene oxide to a polyalkyleneimine.
  • an alkylene oxide such as ethylene oxide is added to the starting polyalkyleneimine at 100 to 180 ° C. in the presence of a basic catalyst such as sodium hydroxide, potassium hydroxide or sodium methylate.
  • a basic catalyst such as sodium hydroxide, potassium hydroxide or sodium methylate.
  • the alkylene oxide include alkylene oxides having 2 to 4 carbon atoms.
  • Examples of the alkylene oxide include ethylene oxide, propylene oxide, and butylene oxide. Ethylene oxide and propylene oxide are preferable, and ethylene oxide is more preferable.
  • Examples of the component (a1) include polyalkyleneimine ethylene oxide adducts, polyalkyleneimine propylene oxide adducts, and polyalkyleneimine ethylene oxide-propylene oxide adducts.
  • the ethylene oxide-propylene oxide adduct of polyalkyleneimine is obtained by adding ethylene oxide and propylene oxide to polyalkyleneimine.
  • the addition order and addition form of ethylene oxide and propylene oxide with respect to polyalkyleneimine (block shape, random shape) ) 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.
  • an average of 5 to 40 alkylene oxides are preferably added to one active hydrogen atom of the starting polyalkyleneimine, and an average of 10 to 30 alkylene oxides are added. Those are more preferred. That is, an average of 5 to 40 moles of alkylene oxide is preferably added per mole of active hydrogen contained in the starting polyalkyleneimine, and an average of 10 to 30 moles of alkylene oxide is more preferable.
  • the mass average molecular weight of the component (a1) is preferably 1000 to 80000, more preferably 2000 to 50000, still more preferably 5000 to 30000, and particularly preferably 10,000 to 20000.
  • a mass average molecular weight shows the value which converted the value measured by GPC (gel permeation chromatography) using THF (tetrahydrofuran) as a solvent based on the calibration curve in PEG (polyethylene glycol).
  • Examples of the component (a1) include compounds represented by the formula (Ia).
  • R 22 is each independently an alkylene group having 2 to 6 carbon atoms, and m is each independently a number of 1 or more.
  • R 22 is preferably an alkylene group having 2 or 3 carbon atoms, and more preferably an alkylene group having 2 carbon atoms.
  • m is the average number of repetitions of (R 22 O), preferably 5 to 40, and more preferably 10 to 30.
  • in — (R 22 O) m —H, —R 22 O— may be bonded randomly or in a block form.
  • a synthetic product may be used, or a commercially available product may be used.
  • the brand name "Sokalan HP20" by BASF, etc. are mentioned, for example.
  • Component (a2) is an alkylene oxide adduct of a polyalkyleneamine represented by the following formula (II). NH 2 (R 31 NH) 1 H (II) In the formula (II), R 31 is an alkylene group having 2 to 6 carbon atoms, and l is a number of 1 or more.
  • R 31 is a linear alkylene group having 2 to 6 carbon atoms or a branched alkylene group having 3 to 6 carbon atoms.
  • R 31 is preferably an alkylene group having 2 to 4 carbon atoms, and more preferably an alkylene group having 2 carbon atoms.
  • polyethyleneamine is preferable. Examples of polyethyleneamine include ethylenediamine, diethylenetriamine, triethylenetetramine, tetraethylenepentamine, and pentaethylenehexamine. These polyethyleneamines can be obtained by a known production method, for example, by reacting ammonia and ethylene dichloride. l is a number of 1 or more.
  • the mass average molecular weight of the polyalkyleneamine is preferably 60 to 1800, more preferably 60 to 1000, and still more preferably 60 to 800.
  • polyalkyleneamine those having 6 to 30 active hydrogens in one molecule are preferable, and those having 7 to 20 active hydrogens are more preferable.
  • Component (a2) is obtained by adding alkylene oxide to polyalkyleneamine. This reaction can be carried out in the same manner as component (a1).
  • alkylene oxide include alkylene oxides having 2 to 4 carbon atoms.
  • alkylene oxide include ethylene oxide, propylene oxide, and butylene oxide. Ethylene oxide and propylene oxide are preferable, and ethylene oxide is more preferable.
  • component (a2) examples include polyalkyleneamine ethylene oxide adducts, polyalkyleneamine propylene oxide adducts, polyalkyleneamine ethylene oxide-propylene oxide adducts, and the like.
  • alkylene oxide adduct of polyalkylene amine an ethylene oxide adduct of polyalkylene amine and an ethylene oxide-propylene oxide adduct of polyalkylene amine are preferable, and an ethylene oxide adduct of polyalkylene amine is more preferable.
  • an average of 5 to 40 alkylene oxides are preferably added to an active hydrogen atom of the polyalkyleneamine as a raw material, and an average of 10 to 30 alkylene oxides are added. Those are more preferred. That is, an average of 5 to 40 moles of alkylene oxide is added per mole of active hydrogen of the polyalkyleneamine as a raw material, and an average of 10 to 30 moles of alkylene oxide is more preferable.
  • the mass average molecular weight of the component (a2) is preferably 1000 to 80000, more preferably 2000 to 50000, still more preferably 5000 to 30000, and particularly preferably 10,000 to 20000.
  • Component (A1) is preferred as component (A).
  • component (A) an ethylene oxide adduct of polyethyleneimine represented by the formula (Ia) is particularly preferable.
  • the component (A) one type may be used alone, or two or more types may be used in combination.
  • the content of the component (A) is preferably 0.01 to 5% by mass, preferably 0.05 to 3% by mass, and more preferably 0.1 to 2% by mass with respect to the total mass of the cleaning composition. If content of a component (A) is below the said upper limit, it will become easy to maintain the freedom degree of a mixing
  • Component (B) is a surfactant containing a nonionic surfactant (hereinafter also referred to as component (B1)) and an anionic surfactant (hereinafter also referred to as component (B2)).
  • component (B1) is a nonionic surfactant.
  • the component (B1) include the following (1) to (8). (1) An average of 3 to 30 moles, preferably 3 to 20 moles, more preferably 5 to 20 moles of an alkylene oxide having 2 to 4 carbon atoms to a monovalent aliphatic alcohol having 6 to 22 carbon atoms, preferably 8 to 18 carbon atoms. Added polyoxyalkylene alkyl (or alkenyl) ether.
  • polyoxyethylene alkyl (or alkenyl) ether and polyoxyethylene polyoxypropylene alkyl (or alkenyl) ether are preferable.
  • the monohydric aliphatic alcohol used here include primary alcohols and secondary alcohols.
  • the alkyl group may have a branched chain.
  • a primary alcohol is preferable.
  • Polyoxyethylene sorbitan fatty acid ester (5) Polyoxyethylene sorbite fatty acid ester. (6) Polyoxyethylene fatty acid ester. (7) Polyoxyethylene hydrogenated castor oil. (8) Glycerin fatty acid ester.
  • R 2 is a hydrocarbon group having 7 to 22 carbon atoms
  • R 3 is an alkyl group having 1 to 6 carbon atoms
  • s represents the average number of repeating EO
  • t represents the average number of repetitions of PO and is a number from 0 to 6
  • u represents the average number of repetitions of EO
  • PO is Represents an oxypropylene group.
  • R 4 is a hydrocarbon having 6 to 22 carbon atoms
  • v represents an average number of repetitions of EO
  • w represents an average number of repetitions of PO
  • x represents the average number of repetitions of EO
  • EO represents an oxyethylene group
  • PO represents an oxypropylene group.
  • R 2 is a hydrocarbon group having 7 to 22 carbon atoms.
  • the carbon number of R 2 is preferably 9 to 21, and more preferably 11 to 21.
  • R 2 is preferably an alkyl group or an alkenyl group.
  • R 2 may be linear or branched. From the viewpoint of further improving detergency, R 2 is preferably a linear or branched alkyl group having 7 to 22 carbon atoms, or a linear or branched chain alkenyl group having 7 to 22 carbon atoms.
  • R 3 is an alkyl group having 1 to 6 carbon atoms and may be linear or branched. Of these, a methyl group and an ethyl group are preferable.
  • s and u are each independently a number representing the average number of repetitions of EO.
  • s + u is preferably 6 to 20, more preferably 6 to 18, still more preferably 11 to 18, and particularly preferably 14 to 18. If it is more than the said lower limit, liquid stability will become easy to improve more. If it is below the said upper limit, cleaning power will improve more easily.
  • t is a number representing the average number of repetitions of PO. t is a number from 0 to 6, preferably 0 to 3, and more preferably 0. If it is below the said upper limit, liquid stability will improve more easily.
  • the oxyethylene group and the oxypropylene group may be bonded in a random manner or in a block shape.
  • the average number of repetitions can be measured by gas chromatography or the like.
  • R 4 is a hydrocarbon group having 6 to 22 carbon atoms.
  • the carbon number of R 4 is preferably 10 to 22, more preferably 10 to 20, and further preferably 10 to 18 from the viewpoint of further improving the detergency.
  • R 4 may be linear or branched.
  • Preferable R 4 —O— includes a group represented by the following general formula (V).
  • R 101 and R 102 each independently represent a hydrogen atom or a chain hydrocarbon group, and the total number of carbon atoms of R 101 and R 102 is 5 to 21.
  • the total number of carbon atoms of R 101 and R 102 is preferably 9 to 21, more preferably 9 to 19, and still more preferably 9 to 17.
  • R 101 and R 102 may be linear or branched.
  • R 4 is preferably an alkyl group derived from a secondary alcohol having 12 to 14 carbon atoms.
  • v and x are numbers independently representing the average number of repetitions of EO.
  • v + x is preferably from 3 to 20, more preferably from 5 to 18, even more preferably from 6 to 18, even more preferably from 11 to 18, and even more preferably from 14 to 18. If it is more than the said lower limit, liquid stability will become easy to improve more. If it is below the said upper limit, cleaning power will improve more easily.
  • w is a number representing the average number of repetitions of PO. w is a number from 0 to 6, preferably 0 to 3, and more preferably 0. If it is below the said upper limit, liquid stability will improve more easily.
  • w is 1 or more, in [(EO) v / (PO) w ], the oxyethylene group and the oxypropylene group may be bonded randomly or in a block form.
  • the distribution of EO or PO in the formula (III) 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 v or w 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.
  • ethylene oxide or propylene oxide is added to the raw material, the distribution of v or w becomes relatively narrow.
  • the nonionic surfactant represented by formula (III) (hereinafter also referred to as component (b11)) and the nonionic surfactant represented by formula (IV) (hereinafter also referred to as component (b12)) have a narrow rate. Is preferably 20% by mass or more, and more preferably 25% by mass or more. The higher the narrow rate, the better the cleaning power. Further, when the narrow ratio is 20% by mass or more, particularly 25% by mass or more, a detergent composition having a low raw material odor for the surfactant is easily obtained.
  • component (b11) When component (b11) is produced by a conventional method, in the product, together with component (b11), a component that does not contribute to detergency, for example, a fatty acid ester that is a raw material of component (b11), or a formula (III)
  • a component that does not contribute to detergency for example, a fatty acid ester that is a raw material of component (b11), or a formula (III)
  • the nonionic surfactant s with an ethylene oxide adduct having s of 1 or 2 coexists to reduce the narrow rate. For this reason, if the narrow ratio is high, the coexisting components are sufficiently small, and the problem of reduced cleaning power and raw material odor hardly occurs.
  • the component (b12) Although it does not specifically limit as an upper limit of the said narrow rate, It is preferable that it is 80 mass% or less substantially.
  • the narrow ratio is more preferably 20 to 50% by mass and further preferably 20 to 40% by mass in order to improve liquid stability and solubility.
  • the “narrow ratio” indicates a distribution ratio of ethylene oxide adducts having different EO addition mole numbers, and is represented by the following formula (S).
  • p max represents the number of moles of EO added to the ethylene oxide adduct most present in the entire ethylene oxide adduct.
  • i represents the number of moles of EO added.
  • Yi represents the ratio (% by mass) of the ethylene oxide adduct present in the entire ethylene oxide adduct, where the number of moles of EO added is i. ]
  • the narrow rate can be controlled by, for example, the production method of the component (b11) or the component (b12).
  • the production method of component (b11) is not particularly limited, but for example, a method in which ethylene oxide is addition-polymerized to a fatty acid alkyl ester using a surface-modified composite metal oxide catalyst (JP 2000-144179 A). Can be easily manufactured.
  • the component (b12) can be produced, for example, by a method in which ethylene oxide is addition-polymerized to an alcohol having 6 to 22 carbon atoms using a surface-modified composite metal oxide catalyst.
  • suitable surface-modified composite metal oxide catalysts used in such a method include metal ions (Al 3+ , Ga 3+ , In 3+ , Tl 3+ , Co 3+ , Sc 3+ , La 3+ , Mn 2+, etc.) are added to the composite metal oxide catalyst such as magnesium oxide and the hydrotalcite surface-modified with metal hydroxide and / or metal alkoxide.
  • metal ions Al 3+ , Ga 3+ , In 3+ , Tl 3+ , Co 3+ , Sc 3+ , La 3+ , Mn 2+, etc.
  • a calcined product catalyst is mentioned.
  • the proportion of the metal hydroxide and / or metal alkoxide is preferably 0.5 to 10 parts by mass, more preferably 1 to 5 parts by mass with respect to 100 parts by mass of the composite metal oxide.
  • a method for producing the component (b11) there is a method of adding an alkylene oxide 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 catalyst is disclosed in Japanese Patent No. 04977609, WO1993004030, WO2002028269, WO201220435, and the like, for example, alkaline earth metal salts of carboxylic acids and / or hydroxycarboxylic acids.
  • nonionic surfactant a commercially available product may be used, or a nonionic surfactant manufactured by a known synthesis method may be used.
  • component (b11) can be produced, for example, by a method of addition polymerization of ethylene oxide and / or propylene oxide to a fatty acid alkyl ester.
  • component (b12) can be produced, for example, by a method of addition polymerization of ethylene oxide and / or propylene oxide to an alcohol having 6 to 22 carbon atoms.
  • Component (B1) is preferably component (b11), more preferably a compound in which t in formula (III) is 0 (ie, a polyoxyethylene fatty acid alkyl ester), and R 3 in formula (III) is methyl.
  • the group is particularly preferably polyoxyethylene fatty acid methyl ester (fatty acid methyl ester ethoxylate) (hereinafter referred to as “MEE”).
  • MEE polyoxyethylene fatty acid methyl ester ethoxylate
  • the content of the fatty acid methyl ester ethoxylate is preferably 10% by mass or more, more preferably 15 to 90% by mass, and further preferably 20 to 80% by mass with respect to the total mass of the component (B).
  • the residual fragrance is easily enhanced.
  • the content of the fatty acid methyl ester ethoxylate is not less than the above lower limit, the residual fragrance property is easily improved and the recontamination preventing performance is easily improved.
  • the cleaning composition of the present invention is preferably used in combination of component (b11) and component (b12).
  • the mass ratio represented by component (b11) / component (b12) (hereinafter also referred to as b11 / b12 ratio) is preferably from 0.1 to 65, more preferably from 0.5 to 50.
  • the ratio b11 / b12 is within the above numerical range, the residual fragrance property is easily improved and the recontamination preventing performance is easily improved.
  • the content of the component (B1) is preferably 20 to 90% by mass, more preferably 25 to 80% by mass, and further preferably 30 to 70% by mass with respect to the total mass of the component (B).
  • the content of the component (B1) is equal to or less than the above upper limit value, it becomes easy to increase the residual fragrance.
  • the content of the component (B1) is equal to or higher than the lower limit, it becomes easy to improve the residual fragrance and to improve the recontamination preventing performance.
  • the content of the component (B1) is preferably 20 to 70% by mass, more preferably 20 to 60% by mass, further preferably 35 to 60% by mass, and more preferably 40 to 60% by mass with respect to the total mass of the cleaning composition. Is particularly preferred.
  • the content of the component (B1) is equal to or less than the above upper limit value, it becomes easy to increase the residual fragrance.
  • the content of the component (B1) is equal to or higher than the lower limit, it becomes easy to improve the residual fragrance and to improve the recontamination preventing performance.
  • the mass ratio represented by component (A) / component (B1) (hereinafter also referred to as A / B1 ratio) is preferably 0.001 to 1.0, more preferably 0.005 to 0.5, and More preferably, 01 to 0.25. If the A / B1 ratio is equal to or less than the above upper limit value, the residual fragrance property is easily improved and the recontamination preventing performance is easily improved. If A / B1 ratio is more than the said lower limit, it will become easy to improve a residual fragrance property.
  • Component (B2) is an anionic surfactant.
  • anionic surfactant include the following (1) to (12).
  • Alkanesulfonate having 10 to 20 carbon atoms.
  • ⁇ -olefin sulfonate (AOS) having 10 to 20 carbon atoms.
  • AS Alkyl sulfate or alkenyl sulfate
  • Any 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 (or alkenyl) group having 10 to 20 carbon atoms added with an average of 0.5 to 10 moles.
  • Alkyl polyhydric alcohol ether sulfates such as alkyl glyceryl ether sulfonic acids having 10 to 20 carbon atoms.
  • Polyoxyethylene monoalkyl, dialkyl or sesquialkyl phosphate (12) A higher fatty acid or a salt thereof.
  • Anionic surfactants other than those exemplified above 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
  • 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.
  • the anionic surfactant the above (2) or (6) is preferable.
  • the polyoxyalkylene alkyl ether sulfate (6) is preferably a compound represented by the general formula (VI).
  • R 40 represents a linear or branched alkyl group having 8 to 20 carbon atoms.
  • EO represents an oxyethylene group
  • PO represents an oxypropylene group.
  • m represents the average number of repetitions of EO and is a number of 1 or more.
  • n represents the average number of repetitions of PO and is a number from 0 to 6.
  • M + is a counter cation.
  • PO and EO in [(PO) m (EO) n ] may be arranged in blocks or randomly. Also, PO and EO may be bonded PO in the "R 40 -O-", EO may be attached to "R 40 -O-”.
  • the polyoxyalkylene alkyl ether sulfate those having a linear or branched alkyl group having 10 to 20 carbon atoms and having an average of 1 to 5 moles of alkylene oxide added are preferred.
  • the number of carbon atoms in the alkyl group is preferably 10 to 20, and more preferably 12 to 14. Specifically, a dodecyl group, a tridecyl group, a tetradecyl group, etc. are mentioned.
  • the average number of EO repeats is preferably 1 to 5, and more preferably 1 to 3.
  • 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.
  • alkylbenzene can be produced by sulfonating with sulfuric anhydride and neutralizing with alkali.
  • AES it can be produced by a method in which polyoxyalkylene alkyl ether is reacted with sulfuric anhydride or chlorsulfonic acid to be sulfonated and neutralized with an alkali.
  • the detergent composition of the present invention is preferably used in combination of AES, LAS and higher fatty acid or a salt thereof.
  • the component (B2) one type may be used alone, or two or more types may be used in combination.
  • the content of the component (B2) is preferably 2 to 50% by mass, more preferably 5 to 45% by mass, and still more preferably 10 to 40% by mass with respect to the total mass of the component (B). If content of a component (B2) is below the said upper limit, it will become easy to improve a residual fragrance property. If content of a component (B2) is more than the said lower limit, it will become easy to improve recontamination prevention performance, improving residual fragrance property.
  • the content of the component (B2) is preferably 1 to 40% by mass, more preferably 2 to 35% by mass, and still more preferably 5 to 30% by mass with respect to the total mass of the cleaning composition. If content of a component (B2) is below the said upper limit, it will become easy to improve a residual fragrance property. If content of a component (B2) is more than the said lower limit, it will become easy to improve recontamination prevention performance, improving residual fragrance property.
  • the mass ratio represented by component (A) / component (B2) (hereinafter also referred to as A / B2 ratio) is preferably 0.01 to 5, more preferably 0.05 to 2, and preferably 0.1 to 1. Further preferred. If A / B2 ratio is below the said upper limit, it will become easy to improve recontamination prevention performance, improving residual fragrance property. If A / B2 ratio is more than the said lower limit, it will become easy to improve a residual fragrance property.
  • the mass ratio (hereinafter also referred to as B1 / B2 ratio) represented by component (B1) / component (B2) is 1.0 or more, preferably more than 1.0, more preferably 1.5 or more, and 2 0.0 or more is particularly preferable. Further, the B1 / B2 ratio is preferably 30 or less, more preferably 15 or less, and even more preferably 10 or less. Specifically, the B1 / B2 ratio is preferably 1.0 to 30, more preferably more than 1.0 and 15 or less, and further preferably 1.5 to 10. If the B1 / B2 ratio is equal to or less than the above upper limit value, the recontamination prevention performance can be easily enhanced while enhancing the residual fragrance. If B1 / B2 ratio is more than the said lower limit, it will become easy to improve a residual fragrance property.
  • cationic surfactant examples include an alkyltrimethylammonium salt, a dialkyldimethylammonium salt, an alkylbenzyldimethylammonium salt, and an alkylpyridinium salt cationic surfactant.
  • these salts include alkali metal salts such as sodium and potassium, alkaline earth metal salts such as magnesium, and alkanolamine salts such as monoethanolamine and diethanolamine.
  • One type of cationic surfactant may be used alone, or two or more types may be used in combination.
  • the content of the cationic surfactant is preferably 0 to 10% by mass and more preferably 0 to 5% by mass with respect to the total mass of the cleaning composition.
  • amphoteric surfactant examples include alkylbetaine type, alkylamide betaine type, imidazoline type, alkylaminosulfone type, alkylaminocarboxylic acid type, alkylamidecarboxylic acid type, amide amino acid type, and phosphoric acid type amphoteric surfactant. Can be mentioned. One amphoteric surfactant may be used alone, or two or more amphoteric surfactants may be used in combination. The content of the amphoteric surfactant is preferably 0 to 10% by mass, more preferably 0 to 5% by mass, based on the total mass of the cleaning composition.
  • the content of component (B) is 15 to 70% by mass, and more preferably 20 to 65% by mass, based on the total mass of the cleaning composition.
  • the content of component (B) is less than or equal to the above upper limit value, it becomes easy to increase the residual fragrance.
  • the content of the component (B) is not less than the above lower limit value, it becomes easy to improve the recontamination preventing performance while enhancing the residual fragrance.
  • Ingredient (C) is a fragrance.
  • Ingredient (C) is a fragrance.
  • the “perfume” contains at least one perfume component, and a solvent (perfume solvent) is blended as necessary.
  • flavor component is suitably selected according to the desired fragrance, and a some fragrance
  • the fragrance component is not particularly limited, and fragrance components generally used for detergents, fiber finishes, hair cosmetics, and the like can be used. Specific examples of such fragrance components include phenols, alcohols, carboxylic acids, aldehydes, ethers, esters, hydrocarbons, ketones, lactones, musks, natural fragrances as shown below, for example. And animal flavors.
  • the carboxylic acids are not particularly limited and may be appropriately selected depending on the intended purpose. For example, geranilic acid, citronellic acid, phenylpropionic acid, cinnamic acid, 2-methyl-2-pentenoic acid, anthranilic acid, benzoic acid An acid, phenylacetic acid, etc. are mentioned.
  • the phenols are not particularly limited and can be appropriately selected according to the purpose.
  • the alcohols are not particularly limited and can be appropriately selected depending on the purpose.
  • the aldehydes are not particularly limited and may be appropriately selected depending on the intended purpose.
  • the ethers are not particularly limited and may be appropriately selected depending on the intended purpose. Examples thereof include cedula bar, glycalva, ⁇ -naphthol methyl ether, ⁇ -naphthol ethyl ether, herbooxide, and rose oxide.
  • the esters are not particularly limited and may be appropriately selected depending on the intended purpose. Examples thereof include cis-3-hexenyl acetate, cis-3-hexenyl propionate, cis-3-hexenyl salicylate, p-cresate.
  • the hydrocarbons are not particularly limited and may be appropriately selected depending on the intended purpose.
  • the ketones are not particularly limited and may be appropriately selected depending on the intended purpose.
  • Examples thereof include ⁇ -ionone, ⁇ -ionone, methyl- ⁇ -naphthyl ketone, ⁇ -damascon, ⁇ -damascon, and ⁇ -damascon.
  • the lactone is not particularly limited and may be appropriately selected depending on the intended purpose. Examples thereof include ⁇ -decalactone, ⁇ -undecalactone, ⁇ -nonalactone, ⁇ -dodecalactone, coumarin, ambroxan, and amblet. Examples thereof include lido, pentalide, habanolide, and traseolide.
  • the musk is not particularly limited and may be appropriately selected depending on the intended purpose.
  • cyclopentadecanolide ethylene brushate, galaxolide, musk ketone, tonalid, nitromusk, musk ambulette, musk civeten, muscone
  • Examples include ambretlide, cyclohexadecanolide, and galaxolide.
  • the natural perfume is not particularly limited and may be appropriately selected depending on the intended purpose.
  • perfume solvent examples include ethanol, acetin (triacetin), MMB acetate (3-methoxy-3-methylbutyl acetate), sucrose diacetate hexaisobutyrate, ethylene glycol dibutyrate, hexylene glycol, dibutyl sebacate, Deltyl extra (isopropyl myristate), methyl carbitol (diethylene glycol monomethyl ether), carbitol (diethylene glycol monoethyl ether), TEG (triethylene glycol), benzyl benzoate, propylene glycol, diethyl phthalate, tripropylene glycol, aboline (Dimethyl phthalate), deltyl prime (isopropyl palmitate), dipropylene glycol DPG-FC (dipropylene glycol) ), Farnesene, dioctyl adipate, tributyrin (glyceryl tributanoate), hydrolite-5 (1,2-pent
  • Component (C) preferably contains 30 to 75% by mass of a compound having at least one functional group selected from the group consisting of a hydroxyl group and a carboxyl group, based on the total mass of component (C). More preferably, it is contained in an amount of ⁇ 50 mass%.
  • the compound having at least one functional group selected from the group consisting of a hydroxyl group and a carboxyl group include carboxylic acids, phenols, alcohols and the like among the fragrance components described above.
  • the component (C) one type may be used alone, or two or more types may be used in combination.
  • the content of the component (C) is preferably 0.01 to 5% by mass, more preferably 0.05 to 3% by mass, and further preferably 0.1 to 2% by mass with respect to the total mass of the cleaning composition. preferable. When the content of the component (C) is within the numerical range, it becomes easy to increase the residual fragrance.
  • the mass ratio represented by component (A) / component (C) (hereinafter also referred to as A / C ratio) is preferably 0.01 to 100, and preferably 0.1 to 50.
  • a / C ratio is within the above numerical range, it becomes easy to enhance the residual fragrance.
  • the sum of components (A) to (C) does not exceed 100% by weight.
  • Component (D) is a polymer having at least one repeating unit (d1) and oxyalkylene unit (d2) selected from the group consisting of alkylene terephthalate units and alkylene isophthalate units.
  • the liquid cleaning agent of the present invention has an effect of easily removing dirt adhering to the object to be cleaned by combining the component (A) and the component (D) (soil release effect, hereinafter also referred to as “SR effect”).
  • SR effect oil release effect
  • “repeating unit” means a monomer unit constituting a polymer.
  • repeating unit (d1) As the alkylene terephthalate unit (hereinafter, this repeating unit is also referred to as "repeating unit (d11)"), the following general formula (D1-1) The repeating unit represented by these is mentioned.
  • R 41 represents a lower alkylene group.
  • the lower alkylene group for R 41 preferably has 1 to 5 carbon atoms, more preferably 1 to 4 carbon atoms, and still more preferably 2 to 4 carbon atoms.
  • Specific examples of the repeating unit (d11) include an ethylene terephthalate unit, an n-propylene terephthalate unit, an isopropylene terephthalate unit, an n-butylene terephthalate unit, an isobutylene terephthalate unit, a sec-butylene terephthalate unit, and a tert-butylene terephthalate unit. It is done. Of these, isopropylene terephthalate units are preferred.
  • the repeating unit (d11) one type may be used alone, or two or more types may be used in combination.
  • repeating unit (d1) the alkylene isophthalate unit (hereinafter, this repeating unit is also referred to as “repeating unit (d12)”) includes a repeating unit represented by the following general formula (D1-2). It is done.
  • R 42 represents a lower alkylene group.
  • the lower alkylene group for R 42 preferably has 1 to 5 carbon atoms, more preferably 1 to 4 carbon atoms, and still more preferably 2 to 4 carbon atoms.
  • Specific examples of the repeating unit (d12) include ethylene isophthalate units, n-propylene isophthalate units, isopropylene isophthalate units, n-butylene isophthalate units, sec-butylene isophthalate units, tert-butylene isophthalate units, and the like. Is mentioned. Of these, isopropylene isophthalate units are preferred.
  • the repeating unit (d12) one type may be used alone, or two or more types may be used in combination.
  • Component (D) may have only one type of repeating unit (d1), or may have two or more types. That is, the component (D) may have only the repeating unit (d11) as the repeating unit (d1) or only the repeating unit (d12) in one molecule. You may have both a unit (d11) and a repeating unit (d12). Moreover, you may have 2 or more types of repeating units (d11) and / or 2 or more types of repeating units (d12).
  • the repeating unit (d1) may be introduced as one unit in one molecule, or may be introduced as two or more units (that is, in a block form).
  • the number of repeating units (d1) of one molecule in component (D) is preferably 1 to 10, more preferably 1 to 6, and further preferably 1 to 4. When the number of repeating units (d1) is within the above preferred range, the cleaning effect is easily enhanced.
  • repeating unit (d2) examples include repeating units represented by the following general formula (D2-1).
  • R 43 represents a lower alkylene group.
  • the lower alkylene group for R 43 preferably has 1 to 4 carbon atoms, more preferably 2 to 4 carbon atoms, and still more preferably 2 or 3 carbon atoms.
  • Examples of the repeating unit (d2) include oxyethylene units, oxypropylene units, and oxybutylene units. Of these, oxyethylene units and oxypropylene units are preferred.
  • Component (D) may have only one type of repeating unit (d2), or may have two or more types. That is, the component (D) may have, for example, only an oxyethylene unit, only an oxypropylene unit, or only an oxyethylene unit as a repeating unit (d2) in one molecule. And an oxypropylene unit. In addition, the component (D) may have an oxyalkylene group (one having a repeating unit (d2) of 1) as a repeating unit (d2) in one molecule, and a polyoxyalkylene group (The number of repeating units (d2) is 2 or more) and may have both an oxyalkylene group and a polyoxyalkylene group.
  • the number of repeating units (d2) contained in one molecule in component (D) is 1 or more, preferably 1 to 100, more preferably 1 to 80, and still more preferably 1 to 50.
  • the number of repeating units (d2) is in the above-mentioned preferable range, the cleaning effect on oily soil is likely to be enhanced.
  • Component (D) may be a polymer in which the repeating unit (d1) and the repeating unit (d2) are polymerized in a block shape, or a polymer in which the repeating unit (d1) is polymerized in a random shape.
  • a polymer polymerized in a block shape is preferable.
  • the component (D) may have other repeating units.
  • the other repeating unit include a repeating unit derived from a polymerization initiator, a polymerization terminator and the like, a repeating unit derived from a monomer copolymerizable with the monomer that provides the repeating unit (d1) or the repeating unit (d2), and the like. It is done.
  • the component (D) has another repeating unit, the total of the repeating unit (d1) and the repeating unit (d2) is 80 mol% based on the total of all the repeating units constituting the component (D). Preferably, it is 90 mol% or more, and may be 100 mol%.
  • the sum of the repeating unit (d1) and the repeating unit (d2) is not less than the preferable lower limit value, the detergency is more likely to be increased.
  • Component (D) is preferably a water-soluble polymer from the standpoint of its own solubility and liquid stability when used as a liquid detergent.
  • water-soluble polymer as used herein means that 10 g of polymer is added to 1000 g of water in a 1 liter beaker at 40 ° C. and stirred for 12 hours (200 rpm) with a stirrer (thickness 8 mm, length 50 mm). The one that has been dissolved after.
  • the weight average molecular weight of component (D) is preferably 500 to 10,000. If a weight average molecular weight is in the said range, the solubility dispersibility to water will improve and it will become easy to raise SR effect and a recontamination prevention effect more. In addition, the low temperature stability of the liquid detergent is likely to be increased.
  • the lower limit of the weight average molecular weight is more preferably 800 or more, and even more preferably 1000 or more.
  • the upper limit of the weight average molecular weight is more preferably 9000 or less, and even more preferably 8000 or less.
  • the weight average molecular weight of the component (D) is more preferably 800 to 9000, further preferably 1000 to 8000.
  • the weight average molecular weight of a component (D) is the value which converted the value measured by GPC (gel permeation chromatography) using THF (tetrahydrofuran) as a solvent based on the calibration curve in PEG (polyethylene glycol). Show.
  • Component (D) is a synthesis method disclosed in various documents, textbooks, patent documents, etc., for example, Journal of Polymer Science, Vol. 3, pages 609 to 630 (1948); Journal of Polymer Science, No. 8. Volume 1 pages 22 (1951); can be produced by the method described in JP-A-61-218699.
  • component (D) include a polymer compound represented by the following general formula (D1), a polymer compound represented by the general formula (D2), or a mixture thereof. .
  • R 40 and R 50 are each independently a hydrogen atom or a methyl group, each preferably a methyl group, and more preferably a methyl group.
  • R 44 and R 47 are each a methyl group or a hydrogen atom, and each is preferably a methyl group.
  • R 45 , R 46 , R 48 and R 49 are each independently an alkylene group having 2 to 4 carbon atoms.
  • s1 and s2 are each 0 to 10, preferably 0.5 to 5, and more preferably 0.5 to 2.5.
  • t1, t2, u1 and u2 are each independently 1 to 100, preferably 1 to 80, more preferably 1 to 50, still more preferably 10 to 50, and particularly preferably 20 ⁇ 30.
  • component (D) When s1, s2, t1, t2, u1, and u2 are within the above preferred ranges, the blending effect of component (D) can be sufficiently exerted. Moreover, the solubility with respect to water improves more, and when it mix
  • the ratio [s1: (t1 + u1)] of s1 to (t1 + u1) is preferably 1: 5 to 1:20, more preferably 1: 8 to 1:18.
  • the ratio [s2: (t2 + u2)] of s2 and (t2 + u2) in (D2) is preferably in the same range as the ratio [s1: (t1 + u1)].
  • TexCare SRN-100 (Clariant, weight average molecular weight 2000-3000), trade name TexCare SRN-300 (Clariant, weight average molecular weight 7000), trade name Repel- Examples thereof include O-Tex Crystal (manufactured by Rhodia) and trade name Repel-O-Tex QC (manufactured by Rhodia).
  • TexCare SRN-100 is preferable because it is highly soluble in water and excellent in storage stability.
  • TexCare SRN-170 (manufactured by Clariant) commercially available as a 70% aqueous solution of the TexCare SRN-100.
  • the content of component (D) is preferably from 0.1 to 1.5% by mass, more preferably from 0.5 to 1% by mass, based on the total mass of the cleaning agent.
  • the content of the component (D) is equal to or greater than the lower limit, the SR effect is more easily enhanced. In addition, the effect of preventing recontamination can be further enhanced.
  • the content of the component (D) is not more than the above upper limit value, the blending stability into the liquid detergent is likely to be enhanced, and the low temperature stability is likely to be enhanced.
  • the total content of the component (A) and the component (D) in the liquid detergent is preferably 0.1 to 3.5% by mass, 0.6 More preferably, it is preferably -3.3 mass%, more preferably 1-3 mass%.
  • the total content of (A + D) in the liquid detergent is equal to or more than the lower limit value, the SR effect is more easily enhanced. In addition, the effect of preventing recontamination can be further enhanced.
  • the (A + D) total content in the liquid detergent is not more than the above upper limit value, the low temperature stability is more likely to be enhanced.
  • the mass ratio represented by the component (A) / component (D) [the mass ratio of the content of the component (A) to the content of the component (D), hereinafter also referred to as “A / D ratio”) is 0.5 To 4 are preferable, and 1 to 3 are more preferable.
  • a / D ratio is within the above-mentioned preferable range, the SR effect is more easily enhanced.
  • the EO average added mole number of the nonionic surfactant (B1) is 10 or more, the SR effect is further enhanced.
  • Component (E) is at least one selected from carboxylic acids represented by the following general formula (VII) and salts thereof.
  • X—R 1 —COOH (VII) In the formula (VII), R 1 is a divalent hydrocarbon group having 1 to 4 carbon atoms or an arylene group, and X is —H, —OH, —CH 3 , or —COOH.
  • the enzyme stability is enhanced by the combined use of the component (B) and the component (E).
  • R 1 is a divalent hydrocarbon group having 1 to 4 carbon atoms or an arylene group. These divalent hydrocarbon groups having 1 to 4 carbon atoms and arylene groups may or may not have a substituent. A hydroxy group etc. are mentioned as a substituent. Further, the divalent hydrocarbon group having 1 to 4 carbon atoms may be saturated or unsaturated, and may be linear, branched or cyclic. Good. Examples of such a divalent hydrocarbon group having 1 to 4 carbon atoms include a divalent group obtained by removing one hydrogen atom from an alkyl group having 1 to 4 carbon atoms, and one from an alkenyl group having 1 to 4 carbon atoms.
  • a divalent group obtained by removing one hydrogen atom from an alkynyl group having 1 to 4 carbon atoms examples include a phenylene group.
  • X is —H, —OH, —CH 3 , or —COOH.
  • Examples of the carboxylic acid represented by the formula (VII) include benzoic acid, acetic acid, propionic acid, butyric acid, hydroxybutyric acid, hydroxyisobutyric acid, lactic acid, adipic acid, maleic acid, fumaric acid, phthalic acid, isophthalic acid, terephthalic acid. , Malic acid, glutaric acid and the like.
  • Examples of the carboxylic acid salt include sodium salt, potassium salt, calcium salt, monoethanolamine salt, diethanolamine salt, triethanolamine salt and the like.
  • benzoic acid, lactic acid, or a salt thereof is preferable, and lactic acid or a salt thereof is more preferable because the enzyme stability is further improved.
  • a sodium salt is preferable from the point which external appearance stability is improved more.
  • sodium lactate is preferable because the enzyme stability and the appearance stability are further improved.
  • any one kind may be used alone, or two or more kinds may be used in combination.
  • the content of the component (E) is preferably 0.1 to 5% by mass, more preferably 0.1 to 3% by mass, and further preferably 0.2 to 2% by mass with respect to the total mass of the liquid detergent. .
  • Component (F) is an enzyme.
  • the liquid cleaning agent of the present invention contains the component (F), so that the cleaning power is further enhanced.
  • enzymes used for laundry detergent applications can be used, and examples thereof include protease, amylase, lipase, cellulase, mannanase and the like.
  • enzyme means an enzyme preparation.
  • proteases trade names Savinase 16L, Savinase Ultra 16L, Savinase Ultra 16XL, Everase 16L Type 2.5, Eraase Ultra 16L, Esperase 2.5L, Esperase 2.5L, Esperase 2.5L, Esperase L , Liquanase Ultra 2.5L, Liquanase Ultra 2.5XL, Coronase 48L, trade names available from Genencor, Inc., Purefect L, Purefect OX, Properase L, and the like.
  • amylases trade names available from Novozymes as amylase preparations are: Termamyl 300L, Termamyl Ultra 300L, Duramyl 300L, Stainzyme 12L, Steinzyme Plus 12L And trade name DB-250 available from Seikagaku Corporation.
  • lipase examples include trade names Lipex 100L and Lipolase 100L, which are available from Novozymes as lipase preparations.
  • cellulase include trade names Endolase 5000L, Celluzyme 0.4L, Carzyme 4500L and the like which are available from Novozymes as cellulase preparations.
  • mannanase include Mannaway 4L, which is a mannanase preparation available from Novozymes.
  • Component (F) preferably contains a protease.
  • proteases include, among others, trade names Savinase 16L, Savinase Ultra 16L, Savinase Ultra 16XL, Everase 16L, Everase Ultra 16L, Alcalase 2.5L, Alcalase 2.5L, Alcalase Ultra 2.5L, Alcalase Ultra 2.5L, Alcalase Ultra 2.5L Ultra 2.5XL and Coronase 48L are preferable, and Alcalase 2.5L, Everase 16L, Savinase 16L, and Coronase 48L are particularly preferable.
  • the component (F) any one kind may be used alone, or two or more kinds may be used in combination.
  • the content of the component (F) is preferably 0.01 to 3% by mass, more preferably 0.05 to 2% by mass, and more preferably 0.1 to 1.5% by mass with respect to the total mass of the liquid detergent. Further preferred.
  • the content of the component (D) is not less than the lower limit of the preferable range, the detergency is further increased.
  • the content of the component (D) is not more than the upper limit of the preferable range, the precipitation of the enzyme is suppressed and the appearance stability is further improved.
  • the compounding quantity of the enzyme in a liquid detergent is a compounding quantity as a formulation.
  • the blending amount is obtained by a general method, for example, by calculating back from the amount of raw material used or the amount of enzyme protein in the liquid detergent.
  • Mass ratio represented by said component (A) / component (E) [mass ratio of content of component (A) to content of component (E), hereinafter also referred to as “A / E ratio”. ] Is 0.1-20.
  • a / E ratio is less than 0.1 or more than 20, appearance stability is impaired.
  • the A / E ratio is preferably 0.3 to 10, more preferably 0.5 to 7, and further preferably 1 to 5.
  • the total content of component (A) and component (E) is preferably from 0.1 to 4% by mass, more preferably from 0.5 to 3% by mass, based on the total mass of the liquid detergent. 5 mass% is more preferable.
  • the total content of the component (A) and the component (E) is not less than the lower limit, it is easy to adjust the A / E ratio to a specific range of the present application, and a liquid detergent excellent in appearance stability is easily obtained. Moreover, it becomes easy to maintain the freedom degree of the mixing
  • the detergent composition of the present invention comprises an enzyme such as protease, a water-miscible organic solvent such as ethanol, an alkaline agent such as monoethanolamine, an antioxidant such as dibutylhydroxytoluene, a preservative such as sodium benzoate, calcium chloride Further, an enzyme stabilizer such as sodium lactate, a colorant such as a pigment, zeolite, a detergency builder and the like may be contained.
  • the component (A) is at least one selected from the group consisting of the compound represented by the general formula (I) and the compound represented by the general formula (II).
  • the component (B1) is at least one selected from the group consisting of the compound represented by the general formula (III) and the compound represented by the general formula (IV), and the component (C) is a phenol. , Alcohols, carboxylic acids, aldehydes, ethers, esters, hydrocarbons, ketones, lactones, musks, natural fragrances, and animal fragrances.
  • the mass ratio represented by (B1) / component (B2) is preferably 1.0 or more.
  • the component (A) is at least one selected from the group consisting of the compound represented by the general formula (I) and the compound represented by the general formula (II).
  • Component (B1), component (B1) contains fatty acid methyl ester ethoxylate
  • component (C) is phenols, alcohols, carboxylic acids, aldehydes, ethers, esters, hydrocarbons, ketones
  • It is at least one selected from the group consisting of lactones, musks, natural fragrances, and animal fragrances
  • the mass ratio represented by component (B1) / component (B2) is 1.0 or more. preferable.
  • the component (A) is at least one selected from the group consisting of the compound represented by the general formula (I) and the compound represented by the general formula (II).
  • Component (B1) contains fatty acid methyl ester ethoxylate
  • component (C) contains phenols, alcohols, carboxylic acids, aldehydes, ethers, esters, hydrocarbons, ketones, lactones, musk
  • the mass ratio represented by component (B1) / component (B2) is 1.0 or more
  • the content of the rate is preferably 10% by mass or more based on the total mass of the component (B).
  • the component (A) is at least one selected from the group consisting of the compound represented by the general formula (I) and the compound represented by the general formula (II).
  • the component (B1) is at least one selected from the group consisting of the compound represented by the general formula (III) and the compound represented by the general formula (IV), and the component (B2) is the above formula.
  • the component (A) is a compound represented by the above general formula (Ia)
  • the component (B1) is represented by the above general formula (III)
  • the above general formula A compound selected from the group consisting of compounds represented by formula (IV) is at least one selected from the group consisting of compounds represented by the above formula (VI) and component (B2) and an alkyl group having 8 to 18 carbon atoms.
  • component (C) is phenols, alcohols, carboxylic acids, aldehydes, ethers, esters, hydrocarbons, It is at least one selected from the group consisting of ketones, lactones, musks, natural fragrances, and animal fragrances, and the mass ratio represented by component (B1) / component (B2) is 1.0 or more. Ah It is preferable.
  • the component (A) is a compound represented by the above general formula (Ia)
  • the component (B1) is represented by the above general formula (III)
  • the above general formula A compound selected from the group consisting of compounds represented by formula (IV) is at least one selected from the group consisting of compounds represented by the above formula (VI) and component (B2) and an alkyl group having 8 to 18 carbon atoms.
  • component (C) is phenols, alcohols, carboxylic acids, aldehydes, ethers, esters, hydrocarbons, It is at least one selected from the group consisting of ketones, lactones, musks, natural fragrances, and animal fragrances, and the mass ratio represented by component (B1) / component (B2) is 1.0 to 30 so Ri is preferably a mass ratio represented by component (A) / component (B2) is 0.01 to 5.
  • the cleaning composition of the present invention is a liquid, it is produced by mixing the components (A) to (C) and optional components as required by a conventionally known method.
  • the cleaning composition of the present invention is granular, it can be produced by a conventionally known method, for example, a dry blend method in which each raw material is powder-mixed, a dry granulation method in which powder raw materials are mixed and fluidized to granulate, Agitation granulation method in which powder raw material is mixed and fluidized while spraying and granulating by liquid binder, extrusion granulation method in which raw material is kneaded and extruded with an extruder, raw material is kneaded and pulverized Examples thereof include a pulverization granulation method and a spray drying method in which a slurry containing raw materials is spray dried.
  • Examples of the method of using the cleaning composition of the present invention include a normal method of use.
  • a method of cleaning an object to be cleaned with a washing machine using a cleaning liquid in which 5 to 30 mL of the cleaning composition is added to 30 L of water Examples include a method of immersing an object to be washed in the cleaning liquid.
  • the cleaning composition may be applied directly to an object to be washed and left for a certain period of time, and then used in a normal washing method (application cleaning).
  • the cleaning composition of the present invention When the cleaning composition of the present invention is used for cleaning a hard surface, the cleaning composition is dissolved in water to prepare a cleaning solution, and applied to the hard surface to be cleaned by spraying or the like.
  • a method of scrubbing with a cleaning tool such as When the cleaning composition of the present invention is used for cleaning dishes, etc., a method of cleaning the dishes by including the cleaning composition in a sponge, a diluted cleaning solution is prepared by dissolving the cleaning composition in water And a method of rubbing with a sponge while immersing tableware or the like in the cleaning liquid.
  • Tables 6 to 7 show the composition (content (mass%)) of the cleaning composition in each example.
  • the blending component is not blended.
  • “balance” means the balance added so that the total amount of all the ingredients contained in the cleaning composition is 100% by mass.
  • the raw materials used in this example are as follows.
  • A-1 Polyethyleneimine ethylene oxide adduct, manufactured by BASF, trade name “Sokalan HP20”. In the above formula (Ia), compounds wherein R 22 is an ethylene group and m is 20.
  • A-2 Polyethyleneimine, manufactured by BASF, trade name “Lupazole P”, weight average molecular weight of about 75000, comparative product of component (A).
  • MEE Fatty acid methyl ester ethoxylate
  • Composition alumina hydroxide magnesium is 2.5MgO ⁇ Al 2 O 3 ⁇ zH 2 O ( Kyoward 300 (trade name), manufactured by Kyowa Chemical Industry Co., Ltd.) for 1 hour at 600 ° C., and calcined in a nitrogen atmosphere
  • 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.
  • MEE fatty acid methyl ester ethoxylate
  • Synthesized by the following synthesis method. (Synthesis of B1-2) 224.4 g of CO-1214 (trade name) manufactured by Procter & Gamble Co. and 2.0 g of 30% by mass NaOH aqueous solution were charged into a pressure-resistant reaction vessel, and the inside of the reaction vessel was purged 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.
  • B1-3 Alcohol ethoxylate (AE), natural alcohol with 7 mole equivalent of ethylene oxide added.
  • R 4 an alkyl group having 12 carbon atoms and an alkyl group having 14 carbon atoms
  • B1-5 A product obtained by adding 7 moles of ethylene oxide to a secondary alcohol having 12 carbon atoms and a secondary alcohol having 14 carbon atoms.
  • B2-3 monoethanolamine salt (AEPS) of polyoxyalkylene alkyl ether sulfate.
  • AEPS monoethanolamine salt
  • Synthesized by the following synthesis method. (Synthesis of B2-3) In an autoclave equipped with a stirrer, a temperature controller and an automatic introduction device, a linear primary alcohol having 12 carbon atoms [manufactured by Tokyo Chemical Industry Co., Ltd., trade name: 1-dodecanol (molecular weight 186.33), purity > 99%] 640 g and KOH 1.0 g were charged and dehydrated at 110 ° C.
  • the alkyl group was dodecyl group, the average added mole number of PO was 1.0, EO An alkoxylate having an average added mole number of 2.0 was obtained.
  • the resulting alkoxylate was sulfated in a falling film reactor using SO 3 gas.
  • the obtained sulfate was neutralized with monoethanolamine to obtain a composition containing a monoethanolamine salt (AEPS) of polyoxyethylene polyoxypropane-1,2-diylalkyl ether sulfate.
  • AEPS monoethanolamine salt
  • B2-4 Coconut fatty acid, trade name “Zushi fatty acid”, manufactured by NOF Corporation.
  • D-1 a polymer having a specific repeating unit (d1) and an oxyalkylene unit (d2). Made by Clariant, trade name “TexCare SRN-170”, weight average molecular weight 2000 to 3000, and a polymer compound represented by the above general formula (D1).
  • D-1 was added to 1000 g of water under the conditions of the above-mentioned “water-soluble polymer” (that is, in a 1 liter beaker at 40 ° C.) and stirred with a stirrer (thickness 8 mm, length 50 mm). ) And then dissolved after stirring (200 rpm) for 12 hours.
  • MEA Monoethanolamine (alkaline agent), manufactured by Nippon Shokubai Co., Ltd., trade name “monoethanolamine”.
  • BHT dibutylhydroxytoluene (antioxidant), manufactured by Sumitomo Chemical Co., Ltd., trade name “SUMILZER BHT-R”.
  • -Ethanol water-miscible organic solvent
  • -Sodium benzoate preservative
  • Toa Gosei Co., Ltd. trade name “Sodium benzoate”.
  • Examples 1 to 13, Comparative Examples 1 to 5 According to the compositions shown in Tables 6 to 7, the respective components were added to water and mixed to obtain cleaning compositions of Examples 1 to 13 and Comparative Examples 1 to 5.
  • the cleaning compositions of Examples 1 to 13 and Comparative Examples 1 to 5 were evaluated for recontamination prevention performance, residual fragrance property, and storage stability as follows.
  • -Skin shirt 150 skin shirts (LL size, manufactured by DVD) finely cut (about 3 cm x 3 cm).
  • 900 mL of 3 ° DH hard water at 25 ° C. is added, and 0.6 g of the detergent composition is added thereto, and then the washing object is added to adjust the bath ratio. It was adjusted to 20 times and washed 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 Soflan (manufactured by Lion Corporation) was used.
  • ⁇ Z is less than 5.
  • ⁇ : ⁇ Z is 5 or more and less than 7.
  • ⁇ : ⁇ Z is 7 or more and less than 9.
  • X: ⁇ Z is 9 or more.
  • ⁇ Precipitated material is observed at the bottom of the glass bottle, but when the glass bottle is shaken lightly, the precipitated material disappears (dissolves).
  • X A precipitated substance is observed at the bottom of the glass bottle, and even if the glass bottle is shaken lightly, the precipitated substance does not disappear, or gelation or white turbidity occurs immediately after the production of the cleaning composition.
  • the evaluation tet cotton cloth was dried overnight in a flat lay, and the evaluation tet cotton cloth after drying was cut into 5 ⁇ 5 cm to obtain an evaluation cloth.
  • the evaluation cloth was coated with 50 ⁇ L of fat (oleic acid, palmitic acid, myristic acid, lauric acid, triolein, tripalmitin, hexadecyl palmitate, squalene, carbon black), and dried for 24 hours.
  • a paste cloth was produced.
  • the dirt cloth was subjected to a cleaning test as follows. As a cleaning tester, Terg-O-meter (manufactured by UNITED STATES TESTING) was used.
  • the cleaning solution a solution prepared by adding 300 ⁇ L of the liquid cleaning agent of Comparative Example 4 to 900 mL of water and stirring for 30 seconds was used.
  • the cleaning tester was charged with 900 mL of the cleaning liquid, the five soiled cloths, and the cleaning knitted cloth, and was washed at 120 rpm and 15 ° C. for 20 minutes in accordance with the bath ratio of 20 times. Next, 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
  • 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 unsoiled cloth) ) ⁇ 100
  • K / S is (1-R / 100) 2 / (2R / 100) (R is the reflectance of the dirt cloth before washing, the reflectance of the dirt cloth after washing, or unstained Indicates the reflectance (%) of the cloth).
  • the average value of the cleaning rate of the five soiled cloths was determined, and the SR effects of the liquid cleaning agents of Examples 1 and 12 were evaluated according to the following evaluation criteria using this average value as an index. ⁇ and ⁇ were accepted.
  • Example 1 ⁇ Evaluation of enzyme stability (enzyme activity remaining rate)>
  • the liquid detergents of Example 1, Example 13, and Comparative Example 1 were manufactured and stored at 37 ° C. and 4 ° C. for 4 weeks, respectively.
  • the following protease activity was measured for a liquid detergent stored at 37 ° C. for 4 weeks (stored at 37 ° C.) and a liquid detergent stored at 4 ° C. for 4 weeks (stored at 4 ° C.).
  • 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 obtained liquid cleaning agent 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 the solution and stirred for 10 seconds with a vortex mixer.
  • TCA trichloroacetic acid
  • TCA which is an enzyme reaction terminator
  • 5 g of TCA which is an enzyme reaction terminator 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 B) at a wavelength of 275 nm of the filtrate was measured using UV-160.
  • the remaining rate of protease activity 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 product stored at 37 ° C. ⁇ Absorbance B of product stored at 37 ° C.) / (Absorbance of product stored at 4 ° C. A-4 Absorbance B of product stored at 4 ° C.) ⁇ 100
  • enzyme stability was evaluated based on the following criteria, and ⁇ , ⁇ , and ⁇ were accepted.
  • X Less than 60%.
  • Examples 1 to 13 to which the present invention was applied were excellent in recontamination prevention performance and excellent in residual fragrance properties.
  • the comparative example 1 which does not contain a component (A) was inferior to residual fragrance property.
  • Comparative Examples 2 and 5 in which the B1 / B2 ratio was outside the numerical range of the present invention were inferior in residual fragrance properties.
  • the comparative example 3 which does not contain a component (A) and whose B1 / B2 ratio is outside the numerical range of this invention was inferior to a residual scent property.
  • the comparative example 4 which used the polyethyleneimine instead of the component (A) was inferior in the recontamination prevention performance and the residual fragrance property.

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  • Chemical & Material Sciences (AREA)
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  • Engineering & Computer Science (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Oil, Petroleum & Natural Gas (AREA)
  • Wood Science & Technology (AREA)
  • Organic Chemistry (AREA)
  • Detergent Compositions (AREA)
  • Cosmetics (AREA)

Abstract

La présente invention concerne une composition détergente contenant (A) un adduit d'oxyde d'alkylène d'un polyalkylène amine, (B) un tensioactif contenant (B1) un tensioactif non ionique et (B2) un tensioactif anionique, et (C) un parfum, le rapport en masse exprimé par ingrédient (B1)/ingrédient (B2) étant de 1,0 ou plus.
PCT/JP2017/005689 2016-02-16 2017-02-16 Composition détergente Ceased WO2017142012A1 (fr)

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SG11201806877XA SG11201806877XA (en) 2016-02-16 2017-02-16 Detergent composition
MYPI2018702816A MY191406A (en) 2016-02-16 2017-02-16 Detergent composition
CN201780011861.1A CN108699493B (zh) 2016-02-16 2017-02-16 洗涤剂组合物
JP2018500187A JP6591033B2 (ja) 2016-02-16 2017-02-16 洗浄剤組成物
KR1020187022155A KR20180114019A (ko) 2016-02-16 2017-02-16 세정제 조성물

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JP2019189690A (ja) * 2018-04-19 2019-10-31 ライオン株式会社 衣料用液体洗浄剤
JP2020050839A (ja) * 2018-09-28 2020-04-02 ライオン株式会社 繊維製品用液体洗浄剤組成物
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