WO2017073741A1 - Liquid detergent - Google Patents

Liquid detergent Download PDF

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Publication number
WO2017073741A1
WO2017073741A1 PCT/JP2016/082096 JP2016082096W WO2017073741A1 WO 2017073741 A1 WO2017073741 A1 WO 2017073741A1 JP 2016082096 W JP2016082096 W JP 2016082096W WO 2017073741 A1 WO2017073741 A1 WO 2017073741A1
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WO
WIPO (PCT)
Prior art keywords
component
mass
liquid
carbon atoms
liquid detergent
Prior art date
Application number
PCT/JP2016/082096
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French (fr)
Japanese (ja)
Inventor
貴広 林
貴行 黒川
将人 福井
Original Assignee
ライオン株式会社
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Application filed by ライオン株式会社 filed Critical ライオン株式会社
Priority to KR1020187003617A priority Critical patent/KR20180074657A/en
Priority to JP2017547895A priority patent/JP7357433B2/en
Publication of WO2017073741A1 publication Critical patent/WO2017073741A1/en

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Classifications

    • C—CHEMISTRY; METALLURGY
    • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D17/00—Detergent materials or soaps characterised by their shape or physical properties
    • C11D17/0008—Detergent materials or soaps characterised by their shape or physical properties aqueous liquid non soap compositions
    • 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
    • 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
    • C11D3/20—Organic compounds containing oxygen
    • 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
    • C11D3/20—Organic compounds containing oxygen
    • C11D3/2003—Alcohols; Phenols
    • C11D3/2065—Polyhydric alcohols
    • 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
    • C11D3/26—Organic compounds containing nitrogen
    • C11D3/30—Amines; Substituted amines ; Quaternized amines

Definitions

  • the present invention relates to a liquid cleaning agent.
  • This application claims priority based on Japanese Patent Application No. 2015-214548 filed in Japan on October 30, 2015, the contents of which are incorporated herein by reference.
  • Patent Document 1 discloses a detergent composition comprising an alkyl sulfate surfactant and an anionic surfactant system containing an alcohol ethoxy sulfate surfactant. Things are listed.
  • Patent Document 2 describes a detergent composition comprising a cleaning polymer having a specific amount of a hydrophilic main chain and at least one hydrophobic pendant group.
  • Patent Documents 1 and 2 are not satisfactory in terms of detergency against oily dirt.
  • the detergency against stains with stronger lipophilicity such as oil-based ink stains was not sufficient.
  • liquid stability is required so that the liquid detergent does not solidify or precipitate when stored in an environment of room temperature or low temperature (eg, 5 to 35 ° C.). It is done.
  • drum-type washing machines In a drum type washing machine, washing by tapping is usually performed. At this time, if there are too many bubbles, the bubbles may become a cushion and the cleaning effect by tapping may not be sufficiently obtained. For this reason, the liquid detergent may be required to have antifoaming properties.
  • the present invention has been made in view of the above circumstances, and an object of the present invention is to provide a liquid cleaning agent that excels in cleaning power against oily dirt.
  • a liquid detergent according to [1] wherein the mass ratio represented by the component (A) / the component (B) is 0.01 to 0.15.
  • the content of the component (A) is 0.1 to 5% by mass with respect to the total mass of the liquid detergent, and the content of the component (B) is based on the total mass of the liquid detergent.
  • the liquid detergent according to any one of [1] to [4], which is 15 to 70% by mass.
  • the mass ratio of the nonionic surfactant to the anionic surfactant is 0.1 to 20 in terms of a mass ratio represented by nonionic surfactant / anionic surfactant. 6]
  • the liquid cleaning agent in any one of.
  • the liquid cleaning agent of the present invention is superior in cleaning power against oily dirt.
  • the liquid detergent of the present invention is a composition containing a propylene oxide adduct of trihydric alcohol (component (A)) and a surfactant (component (B)).
  • the component (A) is a propylene oxide adduct of a trihydric alcohol.
  • the liquid cleaning agent of the present invention increases the cleaning power against oily dirt. Furthermore, foam suppression is enhanced. Oil-based ink stains are stains that penetrate fibers and are difficult to remove by washing.
  • the component (A) has a high affinity with oil-based ink stains and effectively acts on oil-based ink stains that have penetrated into the fibers. By containing the component (A), the liquid cleaning agent of the present invention increases the cleaning power against oil-based ink stains.
  • Examples of the trihydric alcohol include trihydric alcohols having 3 to 20 carbon atoms.
  • the trihydric alcohol having 3 to 20 carbon atoms is preferably an aliphatic trihydric alcohol having 3 to 20 carbon atoms.
  • the aliphatic group of the aliphatic trihydric alcohol may be interrupted by a nitrogen atom or the like.
  • Examples of the trihydric alcohol include glycerin, trimethylolethane, trimethylolpropane, trimethylolbutane, trimethyloloctane, trimethylolnonane, 2-methyl-1,2,3-propanetriol, 1,2,3-butane.
  • Triol 1,2,4-butanetriol, 2-methyl-2,3,4-butanetriol, 2-ethyl-1,2,3-butanetriol, 1,2,3-pentanetriol, 1,2, 4-pentanetriol, 2,3,4-pentanetriol, 1,2,6-hexanetriol, 2,3,4-hexanetriol, 4-propyl-3,4,5-heptanetriol, 2,4-dimethyl -2,3,4-pentanetriol, 3-methyl 1,3,5-pentanetriol, trialkanolamine And the like.
  • the trihydric alcohol glycerin and trimethylolpropane are preferable, and glycerin is more preferable.
  • the propylene oxide adduct of a trihydric alcohol preferably has a weight average molecular weight of 1500 to 6000, more preferably 2500 to 5500, still more preferably 3000 to 5000, and particularly preferably 3500 to 4500. . If a weight average molecular weight is more than the said lower limit, the detergency with respect to oily dirt will be improved more easily. If a weight average molecular weight is below the said upper limit, liquid stability (a liquid cleaning agent will not solidify or a precipitate will not arise) will become more easy to be improved.
  • the weight average molecular weight in this specification is a value calculated
  • a propylene oxide adduct of a trihydric alcohol a propylene oxide adduct of glycerin is preferable.
  • a propylene oxide adduct of glycerin a compound represented by the following general formula (I) is preferable.
  • PO is an oxypropylene group.
  • a, b, and c each independently represent the average number of PO repeats, and the compound represented by the formula (I) has a weight average molecular weight of 1500 to 6000.
  • a, b and c are preferably a number such that the weight average molecular weight of the compound represented by the formula (I) is 2500 to 5500, more preferably 3000 to 5000, and particularly preferably 3500 to 4500.
  • the total number of a, b and c (a + b + c) is preferably 20 to 120, more preferably 50 to 100, still more preferably 55 to 90, and particularly preferably 55 to 80.
  • the component (A) can be produced by addition polymerization of propylene oxide to a trihydric alcohol, and a propylene oxide adduct having a desired weight average molecular weight can be produced by adjusting the number of added moles of propylene oxide. .
  • the content of the component (A) in the liquid detergent is preferably from 0.1 to 5 mass%, more preferably from 0.5 to 3 mass%, more preferably from 0.6 to 2 based on the total mass of the liquid detergent. More preferred is mass%.
  • the content of the component (A) is equal to or higher than the lower limit, the detergency against oily dirt is more easily increased. Moreover, it becomes easy to improve foam suppression property.
  • the content of the component (A) is equal to or less than the upper limit, the liquid stability is more easily increased.
  • the component (B) is a surfactant.
  • the component (B) functions as a cleaning component.
  • distribution stability of (A) component is improved because the liquid cleaning agent of this invention contains (B) component.
  • a known surfactant can be used.
  • the component (B) include anionic surfactants, nonionic surfactants, cationic surfactants, amphoteric surfactants, and semipolar surfactants. From the viewpoint of cleaning performance, anionic surfactants and nonionic surfactants are preferred. Moreover, a nonionic surfactant is preferable from the point which the dispersion stability of (A) component is improved more.
  • Nonionic surfactant examples include the following (1) to (8).
  • polyoxyethylene alkyl (or alkenyl) ether and polyoxyethylene polyoxypropylene alkyl (or alkenyl) ether are preferable.
  • Examples of 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.
  • 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 EO repeats, 3 to 20
  • w represents an average number of PO repeats of 0 to 6
  • x represents the average number of repetitions of EO, 0 to 20
  • 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 numbers independently representing the average number of repetitions of EO.
  • s + u is preferably 6 to 20, more preferably 6 to 18, and still more preferably 11 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. 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 still more 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 (IV).
  • 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, still more preferably from 6 to 18, and particularly preferably from 11 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. 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.
  • Nonionic surfactant represented by formula (II) (hereinafter also referred to as “component (b1)”) and nonionic surfactant represented by formula (III) (hereinafter also referred to as “component (b2)”) .) Is preferably 20% by mass or more, 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, it becomes easy to obtain a liquid cleaning agent with less raw material odor of the surfactant.
  • the product contains, together with the component (b1), a component that does not contribute to detergency, for example, a fatty acid ester that is a raw material of the component (b1), or a formula (II)
  • a component that does not contribute to detergency for example, a fatty acid ester that is a raw material of the component (b1), or a formula (II)
  • 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 (b2) 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).
  • Pmax shows the addition mole number of EO of the ethylene oxide adduct most abundant in the whole 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, a method for producing the component (b1) or the component (b2).
  • the production method of the component (b1) is not particularly limited.
  • a method of addition-polymerizing ethylene oxide to a fatty acid alkyl ester using a surface-modified composite metal oxide catalyst JP 2000-144179 A.
  • the component (b2) 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.
  • a calcined product catalyst is mentioned.
  • the surface modification using the composite metal oxide catalyst it is preferable to use a composite metal oxide in combination with a metal hydroxide and / or a metal alkoxide.
  • 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. .
  • the nonionic surfactant a commercially available product may be used, or a nonionic surfactant manufactured by a known synthesis method may be used.
  • the component (b1) can be produced, for example, by a method in which ethylene oxide and / or propylene oxide is added to a fatty acid alkyl ester.
  • the component (b2) 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.
  • One nonionic surfactant may be used alone, or two or more nonionic surfactants may be used in combination.
  • the component (b1) is preferable, and a compound in which t in the formula (II) is 0 (that is, polyoxyethylene fatty acid alkyl ester) is more preferable, and R 3 in the formula (II) is methyl.
  • MEE Polyoxyethylene fatty acid methyl ester
  • the liquid detergent of the present invention has a regular composition (liquid detergent by making the surfactant concentration in the liquid detergent more than 40% by mass with respect to the total mass of the liquid detergent).
  • the concentration of the surfactant in the inside is about 25% by mass with respect to the total mass of the liquid detergent
  • the compatibility with ink stains is increased and the detergency is enhanced.
  • the detergency is improved in the application cleaning.
  • the ultra-concentrated composition when MEE is used as the nonionic surfactant, the liquid stability of the liquid detergent is more likely to be improved. Further, when the component (b1) and the component (b2) are used in combination as the nonionic surfactant, the detergency is further enhanced.
  • the mass ratio between the component (b1) and the component (b2) is 0.
  • a mass ratio represented by the component (b1) / component (b2) hereinafter also referred to as “b1 / b2 mass ratio”
  • 1 to 15 is preferable
  • 1 to 10 is more preferable
  • 3 to 8 is more preferable.
  • the b1 / b2 mass ratio is in the preferred range, the detergency against oily dirt is further enhanced.
  • the content of the component (b1) in the component (B) is preferably from 30% by weight to 90% by weight, more preferably from 40% by weight to 80% by weight, based on the total weight of the component (B), 50 More preferably, it is at least 70% by mass.
  • the content of the nonionic surfactant in the component (B) is preferably 30 to 90% by mass, more preferably 40 to 80% by mass, and further 45 to 70% by mass based on the total mass of the component (B). preferable.
  • component (B) When the content of the nonionic surfactant is within the above preferable range, a liquid detergent having excellent detergency against oily soil and excellent liquid stability can be easily obtained.
  • components other than the nonionic surfactant in component (B) include anionic surfactants, cationic surfactants, amphoteric surfactants, and semipolar surfactants, which will be described later. The total of these surfactants does not exceed 100% by mass with respect to the total mass of the component (B).
  • anionic surfactant examples include the following (1) to (12).
  • ⁇ -olefin sulfonate (AOS) having 10 to 20 carbon atoms.
  • Alkyl sulfate or alkenyl sulfate (AS) having 10 to 20 carbon atoms.
  • alkyl (or alkenyl) An alkyl (or alkenyl) phenyl ether sulfate having a linear or branched alkyl (or alkenyl) group having 10 to 20 carbon atoms added with an average of 3 to 30 moles per mole of ether.
  • Alkyl polyhydric alcohol ether sulfates such as alkyl glyceryl ether sulfonic acids having 10 to 20 carbon atoms.
  • 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 (V).
  • 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 has a linear or branched alkyl group having 10 to 20 carbon atoms and an average of 1 to 5 moles of alkylene oxide added to 1 mole of alkyl ether. preferable. The number of carbon atoms in the alkyl group is preferably 10 to 20, and more preferably 12 to 14.
  • a dodecyl group a tridecyl group, a tetradecyl group, etc. are mentioned. Of these, a dodecyl group is preferable.
  • the average number of EO repeats is preferably 1 to 5, and more preferably 1 to 3.
  • the average number of PO repeats is preferably 0 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.
  • anionic surfactant may be used alone, or two or more anionic surfactants may be used in combination.
  • the content of the anionic surfactant in the component (B) is preferably 5 to 70% by mass, more preferably 10 to 60% by mass, and further preferably 10 to 50% by mass with respect to the total mass of the component (B). 20 to 40% by mass is particularly preferable. If content of an anionic surfactant is more than the said lower limit, the detergency with respect to oily dirt will improve more easily. If content of an anionic surfactant is below the said upper limit, liquid stability will become easier to improve.
  • a nonionic surfactant and an anionic surfactant are preferably used in combination.
  • the mass ratio of the nonionic surfactant to the anionic surfactant (“mass ratio represented by nonionic surfactant / anionic surfactant”) is preferably from 0.1 to 20, and preferably from 0.3 to 9 Is more preferably 0.5 to 9, particularly preferably 1 to 8, and most preferably 1.5 to 4.
  • the mass ratio is in the above preferred range, the detergency is further enhanced.
  • the cleaning power against oil-based ink stains when the liquid cleaning agent of the present invention is used for coating and cleaning is further enhanced.
  • 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.
  • the content of the cationic surfactant in the component (B) is preferably 0 to 10% by mass and more preferably 0 to 5% by mass with respect to the total mass of the component (A). That the content of the cationic surfactant is 0% by mass means that no cationic surfactant is contained in the component (B).
  • 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 in the component (B) is preferably 0 to 10% by mass and more preferably 0 to 5% by mass with respect to the total mass of the component (B). That the content of the amphoteric surfactant is 0% by mass means that the amphoteric surfactant is not contained in the component (B).
  • the content of the component (B) in the liquid detergent is preferably 15% by mass or more and 70% by mass or less, more preferably 30% by mass or more and 60% by mass or less, and more preferably 35% by mass or more with respect to the total mass of the liquid detergent. 60 mass% or less is further more preferable, and 40 mass% or more and 60 mass% or less are especially preferable.
  • the content of the component (B) is equal to or higher than the lower limit, the detergency against oily dirt is further enhanced.
  • the cleaning power against oil-based ink stains when the liquid cleaning agent of the present invention is used for application cleaning is further enhanced.
  • the content of the component (B) is equal to or less than the upper limit, the liquid stability is easily improved.
  • the component (B) is preferably a combination of a non-soap surfactant (B-1) and a higher fatty acid or salt (B-2).
  • the component (B-2) is a higher fatty acid having 8 to 20 carbon atoms, preferably 12 to 14 carbon atoms or a salt thereof, and the carbon chain of the fatty acid may be linear or branched.
  • As the component (B-2), lauric acid (dodecanoic acid), tridecylic acid, and myristic acid (tetradecanoic acid) are preferable.
  • Component (B-2) may be one type or two types. Of these, coconut fatty acid containing lauric acid and myristic acid is preferable.
  • the content of the component (B-2) in the liquid detergent for clothing is preferably 1 to 5 mass%, more preferably 1.5 to 3.5 mass%, based on the total mass of the liquid detergent for clothing. More preferably, it is 1.75 to 2% by mass. If it is more than the said lower limit, the recontamination prevention effect will become easier to improve. If it is below the said upper limit, rinse property will become easy to improve more.
  • the liquid detergent of the present invention has a mass ratio between the component (A) and the component (B) [mass ratio represented by the component (A) / component (B), hereinafter also referred to as “A / B ratio”]. 0.01 to 0.15 is preferable, 0.01 to 0.06 is more preferable, and 0.015 to 0.05 is more preferable.
  • a / B ratio is equal to or higher than the lower limit, the detergency against oily dirt is further enhanced. Furthermore, foam suppression is further improved. Liquid stability is improved more as A / B ratio is below the said upper limit.
  • the liquid detergent of the present invention preferably further contains an alkylene oxide adduct (component (C)) of polyalkyleneamine. Since the liquid cleaning agent of the present invention further contains the component (C), the cleaning power against oily stains such as ink is improved.
  • the component (C) include the following component (c1) and component (c2).
  • the component (c1) is an alkylene oxide adduct of polyalkyleneimine.
  • the polyalkyleneimine as the component (c1) is represented by the following general formula (VI), for example. NH 2 —R 21 — (NA—R 21 ) n —NH 2 (VI)
  • each R 21 independently represents an alkylene group having 2 to 6 carbon atoms
  • A represents a hydrogen atom or another polyamine chain by branching
  • n is a number of 1 or more.
  • the polyalkyleneimine represented by the formula (VI) has a branched polyamine chain 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.
  • PEI polyethyleneimine
  • 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 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.
  • polyalkyleneimine those having 5 to 30 active hydrogens in one molecule are preferable, those having 7 to 25 are more preferable, and those having 10 to 20 are more preferable.
  • the component (c1) is obtained by adding alkylene oxide to polyalkyleneimine.
  • 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.
  • 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 (c1) include an ethylene oxide adduct of polyalkyleneimine, a propylene oxide adduct of polyalkyleneimine, an ethylene oxide-propylene oxide adduct of polyalkyleneimine, and the like.
  • 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 an active hydrogen atom of the polyalkyleneimine 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 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 (c1) 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 (c1) include compounds represented by the formula (Ic).
  • each R 22 is independently an alkylene group having 2 to 6 carbon atoms, and each m is 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.
  • 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.
  • the component (c2) is an alkylene oxide adduct of polyalkyleneamine represented by the following formula (VII). NH 2 (R 31 NH) 1 H (VII) 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.
  • 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.
  • the component is obtained by adding alkylene oxide to polyalkyleneamine. This reaction can be performed in the same manner as the component (c1).
  • 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.
  • Examples of the component (c2) include an ethylene oxide adduct of polyalkyleneamine, a propylene oxide adduct of polyalkyleneamine, and an ethylene oxide-propylene oxide adduct of polyalkyleneamine.
  • 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 one 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 (c2) is preferably 1000 to 80000, more preferably 2000 to 50000, still more preferably 5000 to 30000, and particularly preferably 10,000 to 20000.
  • the component (c1) is preferable.
  • an ethylene oxide adduct of polyethyleneimine represented by the formula (Ic) is particularly preferable.
  • the content of the component (C) is preferably 0.01 to 5% by mass, more preferably 0.05 to 3% by mass, and 0.1 to 2% by mass with respect to the total mass of the liquid detergent of the present invention. Is more preferable. If the component (C) is 0.01% by mass or more, the detergency against oily stains such as ink is improved, and if it is 5% by mass or less, the liquid stability is good.
  • the mass ratio (A / C) of component (A) / component (C) is preferably 0.1 to 4, more preferably 0.2 to 2.5, and 0.3 to 1.5 is more preferable.
  • the mass ratio of the component (A) / component (C) is in the above range, the detergency against oily stains such as ink is further improved.
  • the component (A) and the component (B) are essential components, and the remaining components are optional components such as the component (C), water, and a water-miscible organic solvent.
  • the content of component (A) is 0.1 to 5% by mass with respect to the total mass of the liquid detergent, and the content of component (B) is 15 to 5% with respect to the total mass of the liquid detergent.
  • the content of component (C) is 0.01 to 5 mass% with respect to the total mass of the liquid detergent
  • the water content is 10 with respect to the total mass of the liquid detergent.
  • content of an arbitrary component is 0 mass% with respect to the total mass of a liquid cleaning agent means that an arbitrary component is not contained in a liquid cleaning agent.
  • the liquid detergent of the present invention preferably contains water from the viewpoints of ease of handling during production, solubility in water when used, and the like.
  • the content of water in the liquid detergent is not particularly limited, but is preferably 10 to 90% by mass, more preferably 20 to 70% by mass, and further preferably 30 to 50% by mass with respect to the total mass of the liquid detergent. preferable.
  • the sum of (A) component, (B) component, (C) component and water does not exceed 100 mass% with respect to the total mass of the liquid detergent.
  • the liquid detergent of the present invention includes enzymes such as proteases (eg, alcalase and coronase), water miscible organic solvents such as ethanol, and monoethanolamine.
  • enzymes such as proteases (eg, alcalase and coronase), water miscible organic solvents such as ethanol, and monoethanolamine.
  • alkaline agents such as dibutylhydroxytoluene, preservatives such as sodium benzoate, enzyme stabilizers such as calcium chloride and sodium lactate, flavoring agents such as fragrances, coloring agents such as pigments, etc. May be.
  • the liquid cleaning agent of the present invention preferably contains a water-miscible organic solvent from the viewpoints of improving the coating cleaning performance, reducing the viscosity and improving the usability.
  • Water miscible organic solvents include alcohols such as ethanol, 1-propanol, 2-propanol, 1-butanol, glycols such as propylene glycol (PG), butylene glycol, hexylene glycol, diethylene glycol, triethylene glycol, tetra Polyethylenes such as ethylene glycol, polyethylene glycol having a weight average molecular weight of about 200 to 1000, dipropylene glycol, alkyl ethers such as diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, diethylene glycol monobutyl ether (butyl carbitol), diethylene glycol dimethyl ether, etc.
  • ethanol propylene glycol
  • polyethylene glycol having a weight average molecular weight of about 200 to 1000
  • diethylene glycol monobutyl ether butyl carbitol
  • One type of water-miscible organic solvent may be used alone, or two or more types may be used in combination.
  • the content of the water-miscible organic solvent is preferably 0.1 to 30% by mass with respect to the total mass of the liquid detergent, More preferred is 15% by mass.
  • the water-miscible organic solvent means an organic solvent that dissolves 50 g or more in 1 L of ion-exchanged water at 25 ° C.
  • the alkaline agent examples include monoethanolamine, diethanolamine, and triethanolamine.
  • the content of the alkali agent is preferably 0.1 to 6% by mass with respect to the total mass of the liquid detergent.
  • the total of component (A), component (B), component (C), water, and optional component does not exceed 100% by mass relative to the total mass of the liquid detergent.
  • the liquid detergent of the present invention preferably has a pH at 25 ° C. of 4 to 9, more preferably pH 6 to 9. When the pH is in such a range, the liquid stability of the liquid detergent can be maintained well.
  • the pH of the liquid detergent can be adjusted by blending a pH adjuster as necessary.
  • the pH adjuster is optional as long as the effects of the present invention are not impaired, but sulfuric acid, sodium hydroxide, potassium hydroxide, alkanolamine and the like are preferable.
  • the pH is a value measured at 25 ° C. according to JIS Z8802: 2011.
  • the liquid detergent of the present invention is produced by a conventionally known production method. For example, the method of adding the said (A) and (B) component to water which is a solvent, adding an arbitrary component as needed, and mixing this is mentioned.
  • the liquid cleaning agent of the present invention is used as a cleaning agent for various uses, but is excellent as a cleaning agent for oily soils, and is therefore suitable as a cleaning agent for objects to be cleaned to which oily soils adhere.
  • the liquid cleaning agent of the present invention is suitable as a liquid cleaning agent for textiles such as clothing, a liquid cleaning agent for hard surfaces such as window glass, and a liquid cleaning agent for kitchens such as tableware and cooking utensils.
  • the liquid cleaning agent of the present invention is excellent in cleaning power against oil-based ink stains, and is therefore suitable as a liquid cleaning agent for textiles such as clothing to which oil-based ink stains adhere, and a liquid cleaning agent for hard surfaces such as window glass. is there.
  • the liquid cleaning agent of the present invention is particularly suitable as a liquid cleaning agent for textiles because it has excellent cleaning power when coated and washed on textiles with oily ink stains.
  • a normal method of use can be mentioned.
  • the liquid detergent of the present invention is used for washing textile products, for example, a method of washing an object to be washed with a washing machine using a washing liquid obtained by adding 5 to 30 ml of a liquid detergent to 30 L of water, the washing liquid The method of immersing the item to be washed is mentioned.
  • the liquid cleaning agent may be applied directly to the article to be washed and left for a certain period of time, and then used in a normal washing method (application cleaning).
  • the liquid cleaning agent of the present invention When the liquid cleaning agent of the present invention is used for cleaning a hard surface, there is a method in which the liquid cleaning agent is applied to the hard surface to be cleaned by spraying or the like and then rubbed with a cleaning tool such as a sponge. .
  • a cleaning tool such as a sponge.
  • the liquid detergent of the present invention When the liquid detergent of the present invention is used for washing dishes, etc., a method for washing dishes with the liquid detergent contained in a sponge as a stock solution, preparing a diluted washing liquid by dissolving the liquid detergent in water And a method of rubbing with a sponge while immersing tableware or the like in the cleaning liquid.
  • the liquid cleaning agent of the present invention Since the liquid cleaning agent of the present invention is excellent in coating cleaning power against oily dirt, it is preferably used in coating cleaning. In particular, when application cleaning is performed on oil-based ink stains attached to the fibers, the component (A) is more likely to act on oil-based ink stains, and the de
  • the liquid cleaning agent of the present invention contains the component (A) and the component (B), it is excellent in cleaning power against oily stains such as oily ink stains. Furthermore, it is excellent in liquid stability and foam suppression.
  • A-1 polyoxypropylene glyceryl ether, Actol T-1500 (trade name), manufactured by Mitsui Chemicals, Inc., weight average molecular weight 1500.
  • A-2 polyoxypropylene glyceryl ether, Actol T-3000 (trade name), manufactured by Mitsui Chemicals, Inc., weight average molecular weight 3000.
  • A-3 polyoxypropylene glyceryl ether, Actol T-4000 (trade name), manufactured by Mitsui Chemicals, Inc., weight average molecular weight 4000.
  • A-4 Polyoxypropylene glyceryl ether, Actol T-5000 (trade name), manufactured by Mitsui Chemicals, Inc., weight average molecular weight 5000.
  • A′-1 polyoxypropylene ethylene glycol ether, Actol D-3000 (trade name), manufactured by Mitsui Chemicals, Inc., weight average molecular weight 3000.
  • A′-2 polyoxypropylene ethylene glycol ether, Actol D-4000 (trade name), manufactured by Mitsui Chemicals, Inc., weight average molecular weight 4000.
  • R 2 alkyl group having 11 carbon atoms and alkyl group having 13 carbon atoms
  • R 3 methyl group
  • Alumina-magnesium hydroxide (Kyoward 300 (trade name), manufactured by Kyowa Chemical Industry Co., Ltd.) having a composition of 2.5 MgO.Al 2 O 3 .wH 2 O was calcined at 600 ° C. for 1 hour in a nitrogen atmosphere.
  • a calcined alumina / magnesium hydroxide (unmodified) catalyst was obtained.
  • a 4 L 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 methyl laurate, and 70 g of methyl myristate. Catalyst reforming was performed.
  • MEE polyoxyethylene fatty acid methyl ester
  • R 2 alkyl group having 11 carbon atoms and alkyl group having 13 carbon atoms
  • R 3 methyl group
  • Softanol a secondary alcohol having 12 to 14 carbon atoms added with 7 mol of ethylene oxide, Softanol 70 (trade name), manufactured by Nippon Shokubai Co., Ltd.
  • B-4 Polyoxyethylene alkyl ether, which is obtained by adding 15 moles of ethylene oxide to a natural alcohol (primary alcohol) having 12 and 14 carbon atoms.
  • R 4 a linear alkyl group having 12 to 14 carbon atoms
  • [Synthesis example of B-4] CO-1214 (trade name, natural alcohols having 12 and 14 carbon atoms) manufactured by Procter & Gamble Co., and 244.4 g of a 30% by mass aqueous sodium hydroxide solution were charged into a pressure-resistant reaction vessel. The reaction vessel was purged with nitrogen. Next, after dehydrating for 30 minutes at a temperature of 100 ° C.
  • B-7 AEPS, monoethanolamine salt of polyoxyethylene polyoxypropane-1,2-diyl alkyl ether sulfate.
  • V linear alkyl group having 12 carbon atoms
  • 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 potassium hydroxide 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 by a falling film reactor using sulfur trioxide 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
  • B-8 LAS, linear alkylbenzene sulfonic acid, Rypon LH-200 (trade name), manufactured by Lion Corporation.
  • B-9 Coconut fatty acid, manufactured by NOF Corporation, trade name “coconut fatty acid”.
  • B-10 Alkyl chloride (12 carbon atoms) trimethylammonium, manufactured by Lion Akzo, trade name “ARCARD 12-37W”.
  • B-11 Amidoamine, manufactured by Toho Chemical Co., Ltd., trade name “Catinal MPAS-R”.
  • HP-20 Polyethyleneimine ethylene oxide adduct (trade name “Sokalan HP20” manufactured by BASF).
  • Coronase (enzyme), manufactured by Novozymes, trade name “Coronase 48L”.
  • MEA Monoethanolamine (alkaline agent), manufactured by Nippon Shokubai Co., Ltd., trade name “monoethanolamine”.
  • -BHT Dibutylhydroxytoluene (antioxidant), trade name “SUMILZER BHT-R”, manufactured by Sumitomo Chemical Co., Ltd. 3-Methoxy-3-methylbutanol (trade name “Solfit”, manufactured by Kuraray Co., Ltd.).
  • PEG1000 polyethylene glycol, weight average molecular weight 1000 (water-miscible organic solvent), manufactured by Lion Corporation, trade name “PEG # 1000-L60”.
  • PEG # 1000-L60 ⁇ Butyl carbitol, manufactured by Nippon Emulsifier Co., Ltd., trade name “butyl diglycol”.
  • PG Propylene glycol (water miscible organic solvent), manufactured by BASF.
  • -Ethanol water-miscible organic solvent
  • specific alcohol 95 degree synthesis trade name "specific alcohol 95 degree synthesis”.
  • -Sodium benzoate preservative
  • Toa Gosei Co., Ltd. trade name “Sodium benzoate”.
  • Examples 1 to 21, Comparative Examples 1 to 7 According to the compositions shown in Tables 1 to 4, the liquid cleaning agents of Examples 1 to 21 were obtained by adding (A), (B), (C) and optional components to water and mixing. Further, liquid detergents of Comparative Examples 1, 2, and 5 were obtained in the same manner as in Examples 1 to 21 except that the component (A) was not added. Liquid detergents of Comparative Examples 3, 4, 6, and 7 were obtained in the same manner as in Examples 1 to 21 except that the component (A ′) was used instead of the component (A). Tables 1 to 4 show the compositions (formulation components, content (mass%)) of the obtained liquid cleaning agents in the respective examples. In addition, unless otherwise indicated, mass% shows a pure part. In the table, when there is a blank blending component, the blending component is not blended. In the table, the A / B ratios of Comparative Examples 3, 4, 6, and 7 indicate mass ratios of the component (A ′) and the component (B).
  • a cotton cloth cut into 5 cm x 5 cm is used as an evaluation cloth, and an oil-based ballpoint pen (trade name “Clip-on-Slim oil-based ballpoint pen” manufactured by ZEBRA) is applied with an ink-stained cloth with oil-based ink stains attached. Produced. At this time, oil-based ink was applied to the center of the cotton cloth so as to form a circle having a diameter of 2 cm. This ink soiled cloth was washed by the following procedure. Apply 0.05 mL of the liquid cleaning agent in each example to the ink stain cloth so that the oil-based ink stain attached to the stain cloth becomes the center, and leave it for 3 minutes.
  • Washing rate (%) 100 ⁇ (K / S of ink dirt cloth before washing ⁇ K / S of ink dirt cloth after washing) / (K / S of ink dirt cloth before washing ⁇ Evaluation cloth) K / S) ⁇ 100.
  • K / S is a value obtained by the formula: (1-R / 100) 2 / (2R / 100)
  • R is an evaluation cloth, an ink dirt cloth before washing, or an ink dirt after washing. This is the reflectance (%) of the cloth. A cleaning rate of 30% or more was accepted.
  • a cleaning solution was prepared by dissolving 0.3 g of the liquid cleaning agent for clothing in 900 mL of 3 ° hard water at 25 ° C. 20 mL of this cleaning solution was put into an Epton tube having a capacity of 100 mL, shaken 20 times in 20 seconds, and allowed to stand for 3 minutes. The height of the subsequent foam (the length from the boundary between the foam and the cleaning liquid to the upper end surface of the foam) was measured. The measured bubble height (unit: mm) is shown in the table. As an evaluation of rinsing properties, the following ink stain cleaning power and re-staining prevention effect were evaluated.
  • the rinsing properties were evaluated in Examples 3, 15, 16 and 16 in order to confirm the effects of the presence or absence of the component (A), the presence or absence of the component (C), and the amount of the component (B) (B-9). Only Comparative Example 1 was performed. [Ink stain cleaning power] (Detergency with soil release effect by repeated washing treatment) Cotton cloth was put into a fully automatic electric washing machine (AW-80VC, manufactured by Toshiba Corporation), and the bath ratio was adjusted to 20 times. Thereto, 12 g of the liquid cleaning agent of each example was added, and a washing operation was performed in which washing, rinsing, and dehydration were sequentially performed in a standard course.
  • the washing time, rinsing, dehydration, and water volume were not adjusted at all and the standard settings of the washing machine were used.
  • the temperature of the tap water used was 15 ° C. This preliminary washing operation was repeated twice or five times. After finishing the pre-washing twice or five times, the cotton cloth was dried overnight by flat laying, and the cotton cloth after drying was cut into 5 ⁇ 5 cm to obtain a cotton cloth for evaluation.
  • An oil-based ballpoint pen (trade name “Clip-on-Slim oil-based ballpoint pen” manufactured by ZEBRA) was applied to the evaluation cloth to prepare an ink-stained cloth with oil-based ink stains attached thereto.
  • oil-based ink was applied to the center of the cotton cloth so as to form a circle having a diameter of 2 cm.
  • This ink soiled cloth was washed by the following procedure. Apply 0.05 mL of the liquid cleaning agent in each example to the ink stain cloth so that the oil-based ink stain attached to the stain cloth becomes the center, and leave it for 3 minutes. On the other hand, it was cleaned using a washing liquid in which 6 mL of the liquid cleaning agent of each example was dissolved.
  • Terg-O-Tometer manufactured by UNITED STATES TESTING
  • the above-mentioned ink stain cloth and the washing liquid are put into a cleaning tester, and the bath ratio is set to 30 times. Washed for minutes. Next, it was transferred to a two-tank washing machine (product number: CW-C30A1-H1 manufactured by Mitsubishi Electric Corporation), dehydrated for 1 minute, rinsed in 30 L of tap water (15 ° C., 4 ° DH) for 3 minutes, and air-dried. The reflectance was measured with a color difference meter (product name: SE200 type) manufactured by Nippon Denshoku Co., Ltd. for each of the evaluation cloth without ink stain, the ink dirt cloth before washing, and the ink dirt cloth after washing.
  • a color difference meter product name: SE200 type
  • the washing rate (%) was calculated by the following formula.
  • the cleaning rate (%) was calculated for 10 ink-stained cloths, and the average value was used to evaluate the cleaning power against ink stains based on the following criteria.
  • Washing rate (%) 100 ⁇ (K / S of ink dirt cloth before washing ⁇ K / S of ink dirt cloth after washing) / (K / S of ink dirt cloth before washing ⁇ Evaluation cloth) K / S) ⁇ 100.
  • K / S is a value obtained by the formula: (1-R / 100) 2 / (2R / 100)
  • R is an evaluation cloth, an ink dirt cloth before washing, or an ink dirt after washing. This is the reflectance (%) of the cloth.
  • Wet artificial contamination cloth Contamination cloth manufactured by Japan Association of Laundry Science (28.3% oleic acid, 15.6% triolein, 12.2% cholesterol oleate, 2.5% liquid paraffin, 2.5% squalene, cholesterol 20 sheets of fabric with 1.6% gelatin, 7.0% gelatin, 29.8% mud, and 0.5% carbon black (mass ratio).
  • Skin shirt A skin shirt (LL size, manufactured by DVD) cut into pieces (about 3 cm x 3 cm). In a Terg-o-meter (manufactured by UNITED STATES TESTING), 900 mL of 3 ° DH hard water at 25 ° C. was added, and 0.6 g of a liquid cleaning agent was added thereto, and then the article to be cleaned was added.
  • the liquid detergent (Comparative Example 5) that does not contain the component (A) and the liquid detergent (Comparative Examples 6 and 7) that contain the component (A ′) instead of the component (A) did not have sufficient foam suppression. . From the above results, it was confirmed that the liquid cleaning agent to which the present invention was applied was superior in cleaning power against oily dirt.
  • the liquid cleaning agent of the present invention is superior in cleaning power against oily dirt.

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Abstract

A liquid detergent which contains (A) a propylene oxide addition product of a trihydric alcohol and (B) a surfactant.

Description

液体洗浄剤Liquid cleaning agent
　本発明は、液体洗浄剤に関する。
本願は、２０１５年１０月３０日に、日本に出願された特願２０１５－２１４５４８号に基づき優先権を主張し、その内容をここに援用する。 The present invention relates to a liquid cleaning agent.
This application claims priority based on Japanese Patent Application No. 2015-214548 filed in Japan on October 30, 2015, the contents of which are incorporated herein by reference.
　従来、食べこぼし汚れ、泥汚れ、襟袖の皮脂汚れ、口紅汚れ等の落とし難い汚れに対する洗浄力に優れる洗浄剤が提案されている。
　例えば、口紅汚れ等の油性汚れに対する洗浄力に優れる洗浄剤として、特許文献１には、アルキルサルフェート系界面活性剤と、アルコールエトキシサルフェート系界面活性剤を含むアニオン性界面活性剤系を含む洗剤組成物が記載されている。特許文献２には、特定量の親水性主鎖と、少なくとも１つの疎水性ペンダント基を有する洗浄ポリマーを含む洗剤組成物が記載されている。 Conventionally, detergents have been proposed that have excellent detergency against hard-to-remove stains such as spilled dirt, mud stains, sebum stains on collar sleeves, and lipstick stains.
For example, as a detergent excellent in detergency against oily dirt such as lipstick dirt, Patent Document 1 discloses a detergent composition comprising an alkyl sulfate surfactant and an anionic surfactant system containing an alcohol ethoxy sulfate surfactant. Things are listed. Patent Document 2 describes a detergent composition comprising a cleaning polymer having a specific amount of a hydrophilic main chain and at least one hydrophobic pendant group.
特表２０１４－５３１５０６号公報Special table 2014-531506 gazette 特表２００８－５４０８１３号公報JP-T 2008-540813
　しかしながら、特許文献１，２の技術では、油性汚れに対する洗浄力が充分に満足できるものでなかった。特に、油性インク汚れ等の親油性がより強い汚れに対する洗浄力が充分でなかった。
　また、液体洗浄剤を提供するに際しては、常温や低温（例えば５～３５℃）の環境下で保管した際にも、液体洗浄剤が固化したり、沈殿物が生じたりしない液安定性が求められる。
　さらに、近年、衣料等の繊維製品を洗浄する際にドラム式洗濯機が使用される機会が増えてきた。ドラム式洗濯機では、通常、叩き洗いによる洗浄が行われる。この際、泡が多すぎると、泡がクッションとなり叩き洗いによる洗浄効果が充分に得られなくなる場合がある。そのため、液体洗浄剤には抑泡性が求められる場合がある。 However, the techniques of Patent Documents 1 and 2 are not satisfactory in terms of detergency against oily dirt. In particular, the detergency against stains with stronger lipophilicity such as oil-based ink stains was not sufficient.
In addition, when providing a liquid detergent, liquid stability is required so that the liquid detergent does not solidify or precipitate when stored in an environment of room temperature or low temperature (eg, 5 to 35 ° C.). It is done.
Furthermore, in recent years, there have been increased opportunities for drum-type washing machines to be used when washing textiles such as clothing. In a drum type washing machine, washing by tapping is usually performed. At this time, if there are too many bubbles, the bubbles may become a cushion and the cleaning effect by tapping may not be sufficiently obtained. For this reason, the liquid detergent may be required to have antifoaming properties.
　本発明は上記事情に鑑みてなされたものであり、油性汚れに対する洗浄力により優れる液体洗浄剤を目的とする。 The present invention has been made in view of the above circumstances, and an object of the present invention is to provide a liquid cleaning agent that excels in cleaning power against oily dirt.
　本発明者らは、鋭意検討した結果、以下の液体洗浄剤が、上記課題を解決できることを見出した。
　すなわち本発明は、以下の態様を有する。
　［１］３価アルコールのプロピレンオキシド付加物（Ａ）と、界面活性剤（Ｂ）を含有する液体洗浄剤。
　［２］前記（Ａ）成分／前記（Ｂ）成分で表される質量比が０．０１～０．１５である、［１］に記載の液体洗浄剤。
　［３］前記（Ａ）成分の重量平均分子量が１５００～６０００である、［１］又は［２］に記載の液体洗浄剤。
　［４］前記（Ａ）成分が、グリセリンのプロピレンオキシド付加物である、［１］～［３］のいずれかに記載の液体洗浄剤。
　［５］前記（Ａ）成分の含有量が、液体洗浄剤の総質量に対して０．１～５質量％であり、前記（Ｂ）成分の含有量が、液体洗浄剤の総質量に対して１５～７０質量％である、［１］～［４］のいずれかに記載の液体洗浄剤。
　［６］前記（Ｂ）成分が、ノニオン界面活性剤とアニオン界面活性剤を含有する、［１］～［５］のいずれかに記載の液体洗浄剤。
　［７］前記ノニオン界面活性剤と、前記アニオン界面活性剤との質量比が、ノニオン界面活性剤／アニオン界面活性剤で表される質量比で０．１～２０である、［１］～［６］のいずれかに記載の液体洗浄剤。
　［８］さらに、ポリアルキレンアミンのアルキレンオキシド付加体（Ｃ）を含有する、［１］～［７］のいずれかに記載の液体洗浄剤。
　［９］前記（Ｂ）成分が、非石鹸系界面活性剤、及び高級脂肪酸又は、その塩である、［１］～［８］のいずれかに記載の液体洗浄剤。 As a result of intensive studies, the present inventors have found that the following liquid cleaning agents can solve the above problems.
That is, this invention has the following aspects.
[1] A liquid detergent containing a propylene oxide adduct (A) of a trihydric alcohol and a surfactant (B).
[2] The liquid detergent according to [1], wherein the mass ratio represented by the component (A) / the component (B) is 0.01 to 0.15.
[3] The liquid detergent according to [1] or [2], wherein the component (A) has a weight average molecular weight of 1500 to 6000.
[4] The liquid detergent according to any one of [1] to [3], wherein the component (A) is a propylene oxide adduct of glycerin.
[5] The content of the component (A) is 0.1 to 5% by mass with respect to the total mass of the liquid detergent, and the content of the component (B) is based on the total mass of the liquid detergent. The liquid detergent according to any one of [1] to [4], which is 15 to 70% by mass.
[6] The liquid cleaning agent according to any one of [1] to [5], wherein the component (B) contains a nonionic surfactant and an anionic surfactant.
[7] The mass ratio of the nonionic surfactant to the anionic surfactant is 0.1 to 20 in terms of a mass ratio represented by nonionic surfactant / anionic surfactant. 6] The liquid cleaning agent in any one of.
[8] The liquid detergent according to any one of [1] to [7], further comprising an alkylene oxide adduct (C) of polyalkyleneamine.
[9] The liquid detergent according to any one of [1] to [8], wherein the component (B) is a non-soap surfactant and a higher fatty acid or a salt thereof.
　本発明の液体洗浄剤は、油性汚れに対する洗浄力により優れる。 The liquid cleaning agent of the present invention is superior in cleaning power against oily dirt.
　本発明の液体洗浄剤は、３価アルコールのプロピレンオキシド付加物（（Ａ）成分）と、界面活性剤（（Ｂ）成分）を含有する組成物である。 The liquid detergent of the present invention is a composition containing a propylene oxide adduct of trihydric alcohol (component (A)) and a surfactant (component (B)).
　＜（Ａ）成分＞
　（Ａ）成分は、３価アルコールのプロピレンオキシド付加物である。
　本発明の液体洗浄剤は、（Ａ）成分を含有することで、油性汚れに対する洗浄力が高められる。さらに、抑泡性が高められる。
　油性インク汚れは、繊維に浸透し洗浄によって除去するのが困難な汚れである。（Ａ）成分は、油性インク汚れとの親和性が高く、繊維に浸透した油性インク汚れに対して効果的に作用する。本発明の液体洗浄剤は、（Ａ）成分を含有することで、油性インク汚れに対する洗浄力が高められる。 <(A) component>
The component (A) is a propylene oxide adduct of a trihydric alcohol.
By containing the component (A), the liquid cleaning agent of the present invention increases the cleaning power against oily dirt. Furthermore, foam suppression is enhanced.
Oil-based ink stains are stains that penetrate fibers and are difficult to remove by washing. The component (A) has a high affinity with oil-based ink stains and effectively acts on oil-based ink stains that have penetrated into the fibers. By containing the component (A), the liquid cleaning agent of the present invention increases the cleaning power against oil-based ink stains.
　３価アルコールとしては、炭素数３～２０の３価アルコールが挙げられる。前記炭素数３～２０の３価アルコールとしては、炭素数３～２０の脂肪族３価アルコールが好ましい。前記脂肪族３価アルコールの脂肪族基は、窒素原子等で中断されてもよい。
　３価アルコールとしては、例えば、グリセリン、トリメチロールエタン、トリメチロールプロパン、トリメチロールブタン、トリメチロールオクタン、トリメチロールノナン、２－メチル－１，２，３－プロパントリオール、１，２，３－ブタントリオール、１，２，４－ブタントリオール、２－メチル－２，３，４－ブタントリオール、２－エチル－１，２，３－ブタントリオール、１，２，３－ペンタントリオール、１，２，４－ペンタントリオール、２，３，４－ペンタントリオール、１，２，６－ヘキサントリオール、２，３，４－ヘキサントリオール、４－プロピル－３，４，５－ヘプタントリオール、２，４－ジメチル－２，３，４－ペンタントリオール、３－メチル１，３，５－ペンタントリオール、トリアルカノールアミン等が挙げられる。
　３価アルコールとしては、グリセリン、トリメチロールプロパンが好ましく、グリセリンがより好ましい。 Examples of the trihydric alcohol include trihydric alcohols having 3 to 20 carbon atoms. The trihydric alcohol having 3 to 20 carbon atoms is preferably an aliphatic trihydric alcohol having 3 to 20 carbon atoms. The aliphatic group of the aliphatic trihydric alcohol may be interrupted by a nitrogen atom or the like.
Examples of the trihydric alcohol include glycerin, trimethylolethane, trimethylolpropane, trimethylolbutane, trimethyloloctane, trimethylolnonane, 2-methyl-1,2,3-propanetriol, 1,2,3-butane. Triol, 1,2,4-butanetriol, 2-methyl-2,3,4-butanetriol, 2-ethyl-1,2,3-butanetriol, 1,2,3-pentanetriol, 1,2, 4-pentanetriol, 2,3,4-pentanetriol, 1,2,6-hexanetriol, 2,3,4-hexanetriol, 4-propyl-3,4,5-heptanetriol, 2,4-dimethyl -2,3,4-pentanetriol, 3-methyl 1,3,5-pentanetriol, trialkanolamine And the like.
As the trihydric alcohol, glycerin and trimethylolpropane are preferable, and glycerin is more preferable.
　３価アルコールのプロピレンオキシド付加物としては、重量平均分子量が、１５００～６０００のものが好ましく、２５００～５５００のものがより好ましく、３０００～５０００のものがさらに好ましく、３５００～４５００のものが特に好ましい。
　重量平均分子量が前記下限値以上であれば、油性汚れに対する洗浄力がより高められやすくなる。重量平均分子量が前記上限値以下であれば、液安定性（液体洗浄剤が固化したり、沈殿物が生じたりしないこと）がより高められやすくなる。
　なお、本明細書における重量平均分子量は、ポリプロピレングリコール（重量平均分子量：８００、１２００、２０００、４０００）を標準としたＧＰＣ（ゲル浸透クロマトグラフィー）で得られる分子量分布より求められる値である。 The propylene oxide adduct of a trihydric alcohol preferably has a weight average molecular weight of 1500 to 6000, more preferably 2500 to 5500, still more preferably 3000 to 5000, and particularly preferably 3500 to 4500. .
If a weight average molecular weight is more than the said lower limit, the detergency with respect to oily dirt will be improved more easily. If a weight average molecular weight is below the said upper limit, liquid stability (a liquid cleaning agent will not solidify or a precipitate will not arise) will become more easy to be improved.
In addition, the weight average molecular weight in this specification is a value calculated | required from molecular weight distribution obtained by GPC (gel permeation chromatography) which used polypropylene glycol (weight average molecular weight: 800, 1200, 2000, 4000) as a standard.
　３価アルコールのプロピレンオキシド付加物としては、グリセリンのプロピレンオキシド付加物が好ましい。
　グリセリンのプロピレンオキシド付加物としては、下記一般式（Ｉ）で表される化合物が好ましい。 As a propylene oxide adduct of a trihydric alcohol, a propylene oxide adduct of glycerin is preferable.
As the propylene oxide adduct of glycerin, a compound represented by the following general formula (I) is preferable.
Figure JPOXMLDOC01-appb-C000001
Figure JPOXMLDOC01-appb-C000001
　式（Ｉ）中、ＰＯは、オキシプロピレン基である。ａ、ｂ、ｃは、それぞれ独立にＰＯの平均繰り返し数を表し、式（Ｉ）で表される化合物の重量平均分子量が１５００～６０００となる数である。ａ、ｂ、ｃは、式（Ｉ）で表される化合物の重量平均分子量が２５００～５５００となる数が好ましく、３０００～５０００となる数がより好ましく、３５００～４５００が特に好ましい。
　ａ、ｂ、ｃは、ａ、ｂ、ｃを合計した数（ａ＋ｂ＋ｃ）が、２０～１２０が好ましく、５０～１００がより好ましく、５５～９０がさらに好ましく、５５～８０が特に好ましい。 In the formula (I), PO is an oxypropylene group. a, b, and c each independently represent the average number of PO repeats, and the compound represented by the formula (I) has a weight average molecular weight of 1500 to 6000. a, b and c are preferably a number such that the weight average molecular weight of the compound represented by the formula (I) is 2500 to 5500, more preferably 3000 to 5000, and particularly preferably 3500 to 4500.
As for a, b and c, the total number of a, b and c (a + b + c) is preferably 20 to 120, more preferably 50 to 100, still more preferably 55 to 90, and particularly preferably 55 to 80.
　（Ａ）成分の製造方法は、３価アルコールにプロピレンオキシドを付加重合させる方法により製造でき、プロピレンオキシドの付加モル数を調節することにより、所望の重量平均分子量を有するプロピレンオキシド付加物を製造できる。 The component (A) can be produced by addition polymerization of propylene oxide to a trihydric alcohol, and a propylene oxide adduct having a desired weight average molecular weight can be produced by adjusting the number of added moles of propylene oxide. .
　（Ａ）成分は、１種が単独で用いられてもよいし、２種以上が組み合わされて用いられてもよい。
　液体洗浄剤中の（Ａ）成分の含有量は、液体洗浄剤の総質量に対して、０．１～５質量％が好ましく、０．５～３質量％がより好ましく、０．６～２質量％がさらに好ましい。（Ａ）成分の含有量が前記下限値以上であると、油性汚れに対する洗浄力がより高められやすくなる。また、抑泡性がより高められやすくなる。（Ａ）成分の含有量が前記上限値以下であると、液安定性がより高められやすくなる。 As 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) in the liquid detergent is preferably from 0.1 to 5 mass%, more preferably from 0.5 to 3 mass%, more preferably from 0.6 to 2 based on the total mass of the liquid detergent. More preferred is mass%. When the content of the component (A) is equal to or higher than the lower limit, the detergency against oily dirt is more easily increased. Moreover, it becomes easy to improve foam suppression property. When the content of the component (A) is equal to or less than the upper limit, the liquid stability is more easily increased.
　＜（Ｂ）成分＞
　（Ｂ）成分は、界面活性剤である。本発明の液体洗浄剤において、（Ｂ）成分は、洗浄成分として機能する。また、本発明の液体洗浄剤は、（Ｂ）成分を含有することで、（Ａ）成分の分散安定性が高められる。
　（Ｂ）成分としては、公知の界面活性剤を用いることができる。
　（Ｂ）成分としては、アニオン界面活性剤、ノニオン界面活性剤、カチオン界面活性剤、両性界面活性剤及び半極性界面活性剤が挙げられる。洗浄性能の点から、アニオン界面活性剤、ノニオン界面活性剤が好ましい。また、（Ａ）成分の分散安定性がより高められる点から、ノニオン界面活性剤が好ましい。 <(B) component>
The component (B) is a surfactant. In the liquid cleaning agent of the present invention, the component (B) functions as a cleaning component. Moreover, the dispersion | distribution stability of (A) component is improved because the liquid cleaning agent of this invention contains (B) component.
As the component (B), a known surfactant can be used.
Examples of the component (B) include anionic surfactants, nonionic surfactants, cationic surfactants, amphoteric surfactants, and semipolar surfactants. From the viewpoint of cleaning performance, anionic surfactants and nonionic surfactants are preferred. Moreover, a nonionic surfactant is preferable from the point which the dispersion stability of (A) component is improved more.
　［ノニオン界面活性剤］
　ノニオン界面活性剤としては、例えば以下の（１）～（８）が挙げられる。
　（１）炭素数６～２２、好ましくは８～１８の１価脂肪族アルコール１モルに対して、炭素数２～４のアルキレンオキシドを平均３～３０モル、好ましくは３～２０モル、さらに好ましくは５～２０モル付加した、ポリオキシアルキレンアルキル（又はアルケニル）エーテル。この中でも、ポリオキシエチレンアルキル（又はアルケニル）エーテル、ポリオキシエチレンポリオキシプロピレンアルキル（又はアルケニル）エーテルが好適である。ここで使用される１価脂肪族アルコールとしては、第１級アルコール、第２級アルコールが挙げられる。また、そのアルキル基は、分岐鎖を有していてもよい。脂肪族アルコールとしては、第１級アルコールが好ましい。
　（２）ポリオキシエチレンアルキル（又はアルケニル）フェニルエーテル。
　（３）炭素数６～２２の長鎖脂肪酸アルキルエステルのエステル結合間にアルキレンオキシドが付加した脂肪酸アルキルエステルアルコキシレート。
　（４）ポリオキシエチレンソルビタン脂肪酸（炭素数６～２２）エステル。
　（５）ポリオキシエチレンソルビット脂肪酸（炭素数６～２２）エステル。
　（６）ポリオキシエチレン脂肪酸（炭素数６～２２）エステル。
　（７）ポリオキシエチレン硬化ヒマシ油。
　（８）グリセリン脂肪酸（炭素数６～２２）エステル。 [Nonionic surfactant]
Examples of nonionic surfactants include the following (1) to (8).
(1) An average of 3 to 30 moles, preferably 3 to 20 moles, more preferably 3 to 20 moles of an alkylene oxide having 2 to 4 carbon atoms per mole of a monohydric aliphatic alcohol having 6 to 22 carbon atoms, preferably 8 to 18 carbon atoms. Is a polyoxyalkylene alkyl (or alkenyl) ether added in an amount of 5 to 20 mol. Among these, polyoxyethylene alkyl (or alkenyl) ether and polyoxyethylene polyoxypropylene alkyl (or alkenyl) ether are preferable. Examples of the monohydric aliphatic alcohol used here include primary alcohols and secondary alcohols. The alkyl group may have a branched chain. As the aliphatic alcohol, a primary alcohol is preferable.
(2) Polyoxyethylene alkyl (or alkenyl) phenyl ether.
(3) A fatty acid alkyl ester alkoxylate having an alkylene oxide added between ester bonds of a long-chain fatty acid alkyl ester having 6 to 22 carbon atoms.
(4) Polyoxyethylene sorbitan fatty acid (carbon number 6-22) ester.
(5) Polyoxyethylene sorbite fatty acid (carbon number 6-22) ester.
(6) Polyoxyethylene fatty acid (C6-C22) ester.
(7) Polyoxyethylene hydrogenated castor oil.
(8) Glycerin fatty acid (carbon number 6-22) ester.
　ノニオン界面活性剤としては、上記（１）又は（３）のものが好ましく、中でも、下記一般式（ＩＩ）又は（ＩＩＩ）で表されるものが好ましい。
　Ｒ２－Ｃ（＝Ｏ）Ｏ－［（ＥＯ）ｓ／（ＰＯ）ｔ］－（ＥＯ）ｕ－Ｒ３　・・・（ＩＩ）
　Ｒ４－Ｏ－［（ＥＯ）ｖ／（ＰＯ）ｗ］－（ＥＯ）ｘ－Ｈ　・・・（ＩＩＩ）
　（式（ＩＩ）中、Ｒ２は炭素数７～２２の炭化水素基であり、Ｒ３は炭素数１～６のアルキル基であり、ｓはＥＯの平均繰り返し数を表し、６～２０の数であり、ｔはＰＯの平均繰り返し数を表し、０～６の数であり、ｕはＥＯの平均繰り返し数を表し、０～２０の数であり、ＥＯはオキシエチレン基を表し、ＰＯはオキシプロピレン基を表す。
　式（ＩＩＩ）中、Ｒ４は炭素数６～２２の炭化水素であり、ｖはＥＯの平均繰り返し数を表し、３～２０の数であり、ｗはＰＯの平均繰り返し数を表し、０～６の数であり、ｘはＥＯの平均繰り返し数を表し、０～２０の数であり、ＥＯはオキシエチレン基を表し、ＰＯはオキシプロピレン基を表す。） As a nonionic surfactant, the thing of said (1) or (3) is preferable, and what is represented by the following general formula (II) or (III) is especially preferable.
R 2 —C (═O) O — [(EO) s / (PO) t ] — (EO) u —R 3 (II)
R 4 —O — [(EO) v / (PO) w ] — (EO) x —H (III)
(In the formula (II), 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, Wherein 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, is a number from 0 to 20, EO represents an oxyethylene group, PO is Represents an oxypropylene group.
In the formula (III), R 4 is a hydrocarbon having 6 to 22 carbon atoms, v represents an average number of EO repeats, 3 to 20, and w represents an average number of PO repeats of 0 to 6, x represents the average number of repetitions of EO, 0 to 20, EO represents an oxyethylene group, and PO represents an oxypropylene group. )
　式（ＩＩ）において、Ｒ２は、炭素数７～２２の炭化水素基である。Ｒ２の炭素数は、９～２１が好ましく、１１～２１がより好ましい。
　Ｒ２は、アルキル基、アルケニル基が好ましい。
　Ｒ２は直鎖又は分岐鎖のいずれであってもよい。
　洗浄力のさらなる向上を図る観点から、Ｒ２は、直鎖もしくは分岐鎖の炭素数７～２２のアルキル基、又は直鎖もしくは分岐鎖の炭素数７～２２のアルケニル基が好ましい。
　Ｒ３は、炭素数１～６のアルキル基であり、直鎖又は分岐鎖のいずれであってもよい。
なかでもメチル基及びエチル基が好ましい。
　式（ＩＩ）中、ｓ、ｕは、それぞれ独立にＥＯの平均繰り返し数を表す数である。
　ｓ＋ｕは６～２０であることが好ましく、６～１８がより好ましく、１１～１８がさらに好ましい。上記下限値以上であれば、液安定性がより向上しやすくなる。上記上限値以下であれば、洗浄力がより向上しやすくなる。
　式（ＩＩ）中、ｔは、ＰＯの平均繰り返し数を表す数である。
　ｔは０～６の数であり、０～３が好ましい。上記上限値以下であれば、液安定性がより向上しやすくなる。
　ｔが１以上である場合、［（ＥＯ）ｓ／（ＰＯ）ｔ］において、オキシエチレン基とオキシプロピレン基とは、ランダム状に結合してもよいし、ブロック状に結合してもよい。
　なお、本明細書において平均繰り返し数は、ガスクロマトグラフィー等によって測定することができる。 In the formula (II), 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.
In formula (II), s and u are numbers independently representing the average number of repetitions of EO.
s + u is preferably 6 to 20, more preferably 6 to 18, and still more preferably 11 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.
In formula (II), t is a number representing the average number of repetitions of PO.
t is a number from 0 to 6, preferably 0 to 3. If it is below the said upper limit, liquid stability will improve more easily.
When t is 1 or more, in [(EO) s / (PO) t ], the oxyethylene group and the oxypropylene group may be bonded in a random manner or in a block shape.
In the present specification, the average number of repetitions can be measured by gas chromatography or the like.
　式（ＩＩＩ）において、Ｒ４は、炭素数６～２２の炭化水素基である。
　式（ＩＩＩ）において、Ｒ４の炭素数は、洗浄力のさらなる向上を図る観点から、１０～２２が好ましく、１０～２０がより好ましく、１０～１８がさらに好ましい。
　Ｒ４は、直鎖又は分岐鎖であってもよい。
　好ましいＲ４－Ｏ－としては、下記一般式（ＩＶ）で表される基が挙げられる。
　（Ｒ１０１）（Ｒ１０２）ＣＨ－Ｏ－・・・（ＩＶ）
　（式（ＩＶ）中、Ｒ１０１及びＲ１０２は、それぞれ独立して水素原子、又は鎖状の炭化水素基を表し、Ｒ１０１とＲ１０２の合計の炭素数は５～２１である。）
　Ｒ１０１とＲ１０２との合計の炭素数は、９～２１が好ましく、９～１９より好ましく、９～１７がさらに好ましい。
　Ｒ１０１及びＲ１０２は直鎖又は分岐鎖であってもよい。
　Ｒ４としては、具体的には、炭素数１２～１４の第２級アルコール由来のアルキル基が好ましい。
　式（ＩＩＩ）中、ｖ及びｘは、それぞれ独立にＥＯの平均繰り返し数を表す数である。
　ｖ＋ｘは３～２０であることが好ましく、５～１８がより好ましく、６～１８がさらに好ましく、１１～１８が特に好ましい。上記下限値以上であれば、液安定性がより向上しやすくなる。上記上限値以下であれば、洗浄力がより向上しやすくなる。
　式（ＩＩＩ）中、ｗは、ＰＯの平均繰り返し数を表す数である。
　ｗは０～６の数であり、０～３が好ましい。上記上限値以下であれば、液安定性がより向上しやすくなる。
　ｗが１以上である場合、［（ＥＯ）ｖ／（ＰＯ）ｗ］において、オキシエチレン基とオキシプロピレン基とは、ランダム状に結合してもよいし、ブロック状に結合してもよい。
　式（ＩＩＩ）中のＥＯ又はＰＯの分布は、製造する際の反応方法によって変動する。例えば、一般的なアルカリ触媒である水酸化ナトリウムや水酸化カリウム等を用いて、エチレンオキシドやプロピレンオキシドを原料に付加した場合には、ｖ又はｗの分布は、比較的広くなる。特公平６－１５０３８号公報に記載のＡｌ３＋、Ｇａ３＋、Ｉｎ３＋、Ｔｌ３＋、Ｃｏ３＋、Ｓｃ３＋、Ｌａ３＋、Ｍｎ２＋等の金属イオンを添加した酸化マグネシウム等の特定のアルコキシル化触媒を用いてエチレンオキシドやプロピレンオキシドを原料に付加した場合には、ｖ又はｗの分布は、比較的狭くなる。 In the formula (III), R 4 is a hydrocarbon group having 6 to 22 carbon atoms.
In the formula (III), the carbon number of R 4 is preferably 10 to 22, more preferably 10 to 20, and still more 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 (IV).
(R 101 ) (R 102 ) CH—O— (IV)
(In Formula (IV), 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.
Specifically, R 4 is preferably an alkyl group derived from a secondary alcohol having 12 to 14 carbon atoms.
In formula (III), 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, still more preferably from 6 to 18, and particularly preferably from 11 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.
In formula (III), w is a number representing the average number of repetitions of PO.
w is a number from 0 to 6, preferably 0 to 3. If it is below the said upper limit, liquid stability will improve more easily.
When 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. When ethylene oxide or propylene oxide is added to the raw material, the distribution of v or w becomes relatively narrow.
　式（ＩＩ）で表されるノニオン界面活性剤（以下、「（ｂ１）成分」ともいう。）、及び式（ＩＩＩ）で表されるノニオン界面活性剤（以下、「（ｂ２）成分」ともいう。）は、ナロー率が２０質量％以上であることが好ましく、２５質量％以上であることがより好ましい。前記ナロー率が高いほど、良好な洗浄力が得られる。また、前記ナロー率が２０質量％以上、特に２５質量％以上であると、界面活性剤の原料臭気の少ない液体洗浄剤が得られやすくなる。
　（ｂ１）成分を常法により製造した場合、生成物中には、（ｂ１）成分とともに、洗浄力に寄与しない成分、例えば（ｂ１）成分の原料である脂肪酸エステルや、式（ＩＩ）で表されるノニオン界面活性剤のｓが１または２であるエチレンオキシド付加体が共存し、ナロー率を低下させる。そのためナロー率が高いと、共存する成分が充分に少なく、洗浄力の低下、原料臭気の問題が生じにくくなる。（ｂ２）成分の場合も同様である。
　前記ナロー率の上限値としては特に限定されないが、実質的には８０質量％以下であることが好ましい。
　前記ナロー率としては、液安定性と溶解性が向上するため、２０～５０質量％であることがより好ましく、２０～４０質量％がさらに好ましい。
　ここで、本明細書において「ナロー率」とは、ＥＯの付加モル数が異なるエチレンオキシド付加体の分布の割合を示し、下記の数式（Ｓ）で表される。 Nonionic surfactant represented by formula (II) (hereinafter also referred to as “component (b1)”) and nonionic surfactant represented by formula (III) (hereinafter also referred to as “component (b2)”) .) Is preferably 20% by mass or more, 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, it becomes easy to obtain a liquid cleaning agent with less raw material odor of the surfactant.
When the component (b1) is produced by a conventional method, the product contains, together with the component (b1), a component that does not contribute to detergency, for example, a fatty acid ester that is a raw material of the component (b1), or a formula (II) 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 same applies to the component (b2).
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.
Here, in this specification, 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).
Figure JPOXMLDOC01-appb-M000002
Figure JPOXMLDOC01-appb-M000002
　［式中、Ｐｍａｘは、全体のエチレンオキシド付加体中に最も多く存在するエチレンオキシド付加体のＥＯの付加モル数を示す。ｉはＥＯの付加モル数を示す。Ｙｉは全体のエチレンオキシド付加体中に存在する、ＥＯの付加モル数がｉであるエチレンオキシド付加体の割合（質量％）を示す。］ [In formula, Pmax shows the addition mole number of EO of the ethylene oxide adduct most abundant in the whole 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. ]
　前記ナロー率は、例えば（ｂ１）成分又は（ｂ２）成分の製造方法等によって制御することができる。（ｂ１）成分の製造方法としては、特に限定されるものではないが、例えば表面改質された複合金属酸化物触媒を用いて、脂肪酸アルキルエステルにエチレンオキシドを付加重合させる方法（特開２０００－１４４１７９号公報参照）により容易に製造することができる。（ｂ２）成分の製造方法としては、例えば表面改質された複合金属酸化物触媒を用いて、炭素数６～２２のアルコールにエチレンオキシドを付加重合させる方法により製造することができる。
　かかる方法に用いられる表面改質された複合金属酸化物触媒の好適なものとしては、具体的には、金属水酸化物等により表面改質された金属イオン（Ａｌ３＋、Ｇａ３＋、Ｉｎ３＋、Ｔｌ３＋、Ｃｏ３＋、Ｓｃ３＋、Ｌａ３＋、Ｍｎ２＋等）が添加された酸化マグネシウム等の複合金属酸化物触媒や金属水酸化物および／または金属アルコキシド等により表面改質されたハイドロタルサイトの焼成物触媒が挙げられる。
　前記複合金属酸化物触媒を用いた表面改質においては、複合金属酸化物と、金属水酸化物および／または金属アルコキシドとを併用することが好ましい。この場合、複合金属酸化物１００質量部に対して、金属水酸化物及び／または金属アルコキシドの割合を０．５～１０質量部とすることが好ましく、１～５質量部とすることがより好ましい。 The narrow rate can be controlled by, for example, a method for producing the component (b1) or the component (b2). The production method of the component (b1) is not particularly limited. For example, a method of addition-polymerizing ethylene oxide to a fatty acid alkyl ester using a surface-modified composite metal oxide catalyst (JP 2000-144179 A). Can be easily manufactured. The component (b2) 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.
Specific examples of 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. A calcined product catalyst is mentioned.
In the surface modification using the composite metal oxide catalyst, it is preferable to use a composite metal oxide in combination with a metal hydroxide and / or a metal alkoxide. In this case, 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. .
　ノニオン界面活性剤としては、市販品を用いてもよいし、公知の合成方法で製造したものを用いてもよい。公知の製造方法として、（ｂ１）成分は、例えば脂肪酸アルキルエステルにエチレンオキシド及び／又はプロピレンオキシドを付加重合させる方法により製造することができる。（ｂ２）成分は、例えば炭素数６～２２のアルコールにエチレンオキシド及び／又はプロピレンオキシドを付加重合させる方法により製造することができる。 As the nonionic surfactant, a commercially available product may be used, or a nonionic surfactant manufactured by a known synthesis method may be used. As a known production method, the component (b1) can be produced, for example, by a method in which ethylene oxide and / or propylene oxide is added to a fatty acid alkyl ester. The component (b2) 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.
　ノニオン界面活性剤は、１種が単独で用いられてもよいし、２種以上が組み合わされて用いられてもよい。
　ノニオン界面活性剤としては、（ｂ１）成分が好ましく、式（ＩＩ）中のｔが０である化合物（即ち、ポリオキシエチレン脂肪酸アルキルエステル）がさらに好ましく、式（ＩＩ）中のＲ３がメチル基であるポリオキシエチレン脂肪酸メチルエステル（以下「ＭＥＥ」と表記する。）が、洗浄力や液体洗浄剤の溶解性の向上の点から特に好ましい。
　また、本発明の液体洗浄剤は、超濃縮組成（液体洗浄剤中の界面活性剤濃度が、液体洗浄剤の総質量に対して４０質量％超）とすることにより、レギュラー組成（液体洗浄剤中の界面活性剤濃度が、液体洗浄剤の総質量に対して２５質量％程度）とした場合よりも、インク汚れとの相溶性が高まり洗浄力が高められる。特に、塗布洗浄において洗浄力が高められる。また、前記超濃縮組成において、ノニオン界面活性剤としてＭＥＥが用いられると、液体洗浄剤の液安定性がより高められやすくなる。さらに、ノニオン界面活性剤として、（ｂ１）成分と、（ｂ２）成分が併用されると、洗浄力がより高められる。
　（ｂ１）成分と、（ｂ２）成分との質量比としては、（ｂ１）成分／（ｂ２）成分で表される質量比（以下、「ｂ１／ｂ２質量比」ともいう。）として、０．１～１５が好ましく、１～１０がより好ましく、３～８がさらに好ましい。ｂ１／ｂ２質量比が前記好ましい範囲であると、油性汚れに対する洗浄力がより高められる。 One nonionic surfactant may be used alone, or two or more nonionic surfactants may be used in combination.
As the nonionic surfactant, the component (b1) is preferable, and a compound in which t in the formula (II) is 0 (that is, polyoxyethylene fatty acid alkyl ester) is more preferable, and R 3 in the formula (II) is methyl. Polyoxyethylene fatty acid methyl ester (hereinafter referred to as “MEE”), which is a group, is particularly preferable from the viewpoint of improvement in detergency and solubility of a liquid detergent.
In addition, the liquid detergent of the present invention has a regular composition (liquid detergent by making the surfactant concentration in the liquid detergent more than 40% by mass with respect to the total mass of the liquid detergent). Compared with the case where the concentration of the surfactant in the inside is about 25% by mass with respect to the total mass of the liquid detergent, the compatibility with ink stains is increased and the detergency is enhanced. In particular, the detergency is improved in the application cleaning. In addition, in the ultra-concentrated composition, when MEE is used as the nonionic surfactant, the liquid stability of the liquid detergent is more likely to be improved. Further, when the component (b1) and the component (b2) are used in combination as the nonionic surfactant, the detergency is further enhanced.
The mass ratio between the component (b1) and the component (b2) is 0. As a mass ratio represented by the component (b1) / component (b2) (hereinafter also referred to as “b1 / b2 mass ratio”), 1 to 15 is preferable, 1 to 10 is more preferable, and 3 to 8 is more preferable. When the b1 / b2 mass ratio is in the preferred range, the detergency against oily dirt is further enhanced.
　（Ｂ）成分中の（ｂ１）成分の含有量は、（Ｂ）成分の総質量に対して、３０質量％以上９０質量％以下が好ましく、４０質量％以上８０質量％以下がより好ましく、５０質量％以上７０質量％以下がさらに好ましい。（ｂ１）成分の含有量が前記好ましい範囲であると、油性汚れに対する洗浄力に優れ、かつ、液安定性に優れる液体洗浄剤が得られやすくなる。
　（Ｂ）成分中のノニオン界面活性剤の含有量は、（Ｂ）成分の総質量に対して、３０～９０質量％が好ましく、４０～８０質量％がより好ましく、４５～７０質量％がさらに好ましい。ノニオン界面活性剤の含有量が前記好ましい範囲であると、油性汚れに対する洗浄力に優れ、かつ、液安定性に優れる液体洗浄剤が得られやすくなる。
　なお、（Ｂ）成分中のノニオン界面活性剤以外の成分は、後述するアニオン界面活性剤、カチオン界面活性剤、両性界面活性剤及び半極性界面活性剤が挙げられる。
　これら、界面活性剤の合計は、（Ｂ）成分の総質量に対して１００質量％を超えない。 The content of the component (b1) in the component (B) is preferably from 30% by weight to 90% by weight, more preferably from 40% by weight to 80% by weight, based on the total weight of the component (B), 50 More preferably, it is at least 70% by mass. When the content of the component (b1) is within the above preferred range, a liquid cleaning agent having excellent detergency against oily dirt and excellent liquid stability can be easily obtained.
The content of the nonionic surfactant in the component (B) is preferably 30 to 90% by mass, more preferably 40 to 80% by mass, and further 45 to 70% by mass based on the total mass of the component (B). preferable. When the content of the nonionic surfactant is within the above preferable range, a liquid detergent having excellent detergency against oily soil and excellent liquid stability can be easily obtained.
Examples of components other than the nonionic surfactant in component (B) include anionic surfactants, cationic surfactants, amphoteric surfactants, and semipolar surfactants, which will be described later.
The total of these surfactants does not exceed 100% by mass with respect to the total mass of the component (B).
　［アニオン界面活性剤］
　アニオン界面活性剤としては、例えば以下の（１）～（１２）が挙げられる。
　（１）炭素数８～２０の飽和又は不飽和α－スルホ脂肪酸のメチル、エチルもしくはプロピルエステル塩。
　（２）炭素数８～１８のアルキル基を有する直鎖状又は分岐鎖状のアルキルベンゼンスルホン酸塩（ＬＡＳ又はＡＢＳ）。
　（３）炭素数１０～２０のアルカンスルホン酸塩。
　（４）炭素数１０～２０のα－オレフィンスルホン酸塩（ＡＯＳ）。
　（５）炭素数１０～２０のアルキル硫酸塩又はアルケニル硫酸塩（ＡＳ）。
　（６）炭素数２～４のアルキレンオキシドのいずれか、又はエチレンオキシド（ＥＯ）とプロピレンオキシド（ＰＯ）（モル比ＥＯ／ＰＯ＝０．１／９．９～９．９／０．１）を、アルキル（又はアルケニル）エーテル１モルに対して、平均０．５～１０モル付加した炭素数１０～２０の直鎖状又は分岐鎖状のアルキル（又はアルケニル）基を有するポリオキシアルキレンアルキル（又はアルケニル）エーテル硫酸塩（ＡＥＳ）。
　（７）炭素数２～４のアルキレンオキシドのいずれか、又はエチレンオキシドとプロピレンオキシド（モル比ＥＯ／ＰＯ＝０．１／９．９～９．９／０．１）を、アルキル（又はアルケニル）エーテル１モルに対して、平均３～３０モル付加した炭素数１０～２０の直鎖状又は分岐鎖状のアルキル（又はアルケニル）基を有するアルキル（又はアルケニル）フェニルエーテル硫酸塩。
　（８）炭素数２～４のアルキレンオキシドのいずれか、又はエチレンオキシドとプロピレンオキシド（モル比ＥＯ／ＰＯ＝０．１／９．９～９．９／０．１）を、アルキル（又はアルケニル）エーテル１モルに対して、平均０．５～１０モル付加した炭素数１０～２０の直鎖状又は分岐鎖状のアルキル（又はアルケニル）基を有するアルキル（又はアルケニル）エーテルカルボン酸塩。
　（９）炭素数１０～２０のアルキルグリセリルエーテルスルホン酸のようなアルキル多価アルコールエーテル硫酸塩。
　（１０）長鎖（炭素数８～２０の）モノアルキル、ジアルキル又はセスキアルキルリン酸塩。
　（１１）ポリオキシエチレンモノアルキル、ジアルキル又はセスキアルキルリン酸塩。
　（１２）高級脂肪酸又はその塩。平均炭素数が１０～２０（好ましくは炭素数１２～１８）の高級脂肪酸又はその塩。 [Anionic surfactant]
Examples of the anionic surfactant include the following (1) to (12).
(1) Methyl, ethyl or propyl ester salts of saturated or unsaturated α-sulfo fatty acids having 8 to 20 carbon atoms.
(2) Linear or branched alkylbenzene sulfonate (LAS or ABS) having an alkyl group having 8 to 18 carbon atoms.
(3) Alkanesulfonate having 10 to 20 carbon atoms.
(4) α-olefin sulfonate (AOS) having 10 to 20 carbon atoms.
(5) Alkyl sulfate or alkenyl sulfate (AS) having 10 to 20 carbon atoms.
(6) 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) In addition, polyoxyalkylene alkyl 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 per mole of alkyl (or alkenyl) ether (or Alkenyl) ether sulfate (AES).
(7) Any of alkylene oxides having 2 to 4 carbon atoms, or ethylene oxide and propylene oxide (molar ratio EO / PO = 0.1 / 9.9 to 9.9 / 0.1), alkyl (or alkenyl) An alkyl (or alkenyl) phenyl ether sulfate having a linear or branched alkyl (or alkenyl) group having 10 to 20 carbon atoms added with an average of 3 to 30 moles per mole of ether.
(8) Any of alkylene oxides having 2 to 4 carbon atoms, or ethylene oxide and propylene oxide (molar ratio EO / PO = 0.1 / 9.9 to 9.9 / 0.1), alkyl (or alkenyl) An alkyl (or alkenyl) ether carboxylate 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 per mole of ether.
(9) Alkyl polyhydric alcohol ether sulfates such as alkyl glyceryl ether sulfonic acids having 10 to 20 carbon atoms.
(10) Long chain (C8-20) monoalkyl, dialkyl or sesquialkyl phosphates.
(11) Polyoxyethylene monoalkyl, dialkyl or sesquialkyl phosphate.
(12) A higher fatty acid or a salt thereof. A higher fatty acid having an average carbon number of 10 to 20 (preferably having a carbon number of 12 to 18) or a salt thereof.
　上記で例示した以外のアニオン界面活性剤を用いてもよい。例えば、アルキルエーテルカルボン酸塩、ポリオキシアルキレンエーテルカルボン酸塩、アルキルアミドエーテルカルボン酸塩又はアルケニルアミドエーテルカルボン酸塩、アシルアミノカルボン酸塩等のカルボン酸型アニオン界面活性剤；アルキルリン酸エステル塩、ポリオキシアルキレンアルキルリン酸エステル塩、ポリオキシアルキレンアルキルフェニルリン酸エステル塩、グリセリン脂肪酸エステルモノリン酸エステル塩等のリン酸エステル型アニオン界面活性剤等が挙げられる。
　アニオン界面活性剤としては、上記（２）又は（６）のものが好ましい。 Anionic surfactants other than those exemplified above may be used. For example, carboxylic acid type anionic surfactants such as alkyl ether carboxylates, polyoxyalkylene ether carboxylates, alkylamide ether carboxylates or alkenylamide ether carboxylates, acylaminocarboxylates; alkyl phosphate ester salts And phosphoric acid ester type anionic surfactants such as polyoxyalkylene alkyl phosphoric acid ester salt, polyoxyalkylene alkyl phenyl phosphoric acid ester salt and glycerin fatty acid ester monophosphoric acid ester salt.
As the anionic surfactant, the above (2) or (6) is preferable.
　（６）のポリオキシアルキレンアルキルエーテル硫酸塩としては、具体的には一般式（Ｖ）で表される化合物であることが好ましい。
　Ｒ４０－Ｏ－［（ＥＯ）ｍ／（ＰＯ）ｎ］－ＳＯ３ －Ｍ＋・・・（Ｖ）
　［式（Ｖ）中、Ｒ４０は炭素数８～２０の直鎖もしくは分岐鎖のアルキル基である。ＥＯはオキシエチレン基を表し、ＰＯはオキシプロピレン基を表す。ｍは、ＥＯの平均繰り返し数を表し、１以上の数である。ｎは、ＰＯの平均繰り返し数を表し、０～６の数である。Ｍ＋は対カチオンである。ｎが０超の場合、［（ＰＯ）ｍ（ＥＯ）ｎ］におけるＰＯとＥＯは、ブロック状に配列しても、ランダム状に配列してもよい。また、ＰＯとＥＯは、ＰＯが「Ｒ４０－Ｏ－」に結合してもよいし、ＥＯが「Ｒ４０－Ｏ－」に結合してもよい。］
　ポリオキシアルキレンアルキルエーテル硫酸塩としては、炭素数１０～２０の直鎖もしくは分岐鎖のアルキル基を有し、アルキルエーテル１モルに対して、平均１～５モルのアルキレンオキシドが付加されたものが好ましい。
　アルキル基の炭素数としては、１０～２０が好ましく、１２～１４がより好ましい。具体的には、ドデシル基、トリデシル基、テトラデシル基等が挙げられる。なかでもドデシル基が好ましい。
　ＥＯの平均繰り返し数は、１～５であることが好ましく、１～３がより好ましい。
　ＰＯの平均繰り返し数は、０～３であることが好ましい。
　上記式（Ｖ）におけるｍ＝０、ｎ＝０の化合物は、式（Ｖ）で表されるポリオキシアルキレンアルキルエーテル硫酸塩の総質量に対して３５～５５質量％含有することが好ましい。 Specifically, the polyoxyalkylene alkyl ether sulfate (6) is preferably a compound represented by the general formula (V).
R 40 —O — [(EO) m / (PO) n ] —SO 3 − M + (V)
[In the formula (V), R 40 represents a linear or branched alkyl group having 8 to 20 carbon atoms. EO represents an oxyethylene group, and 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. When n is greater than 0, 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 has a linear or branched alkyl group having 10 to 20 carbon atoms and an average of 1 to 5 moles of alkylene oxide added to 1 mole of alkyl ether. preferable.
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. Of these, a dodecyl group is preferable.
The average number of EO repeats is preferably 1 to 5, and more preferably 1 to 3.
The average number of PO repeats is preferably 0 to 3.
The compound of m = 0 and n = 0 in the formula (V) is preferably contained in an amount of 35 to 55% by mass with respect to the total mass of the polyoxyalkylene alkyl ether sulfate represented by the formula (V).
　アニオン界面活性剤の塩の形態としては、ナトリウム塩、カリウム塩等のアルカリ金属塩；マグネシウム塩等のアルカリ土類金属塩；モノエタノールアミン塩、ジエタノールアミン塩等のアルカノールアミン塩；アンモニウム塩等が挙げられる。中でも、アルカリ金属塩が好ましい。 Examples of the salt form of the anionic surfactant include alkali metal salts such as sodium salts and potassium salts; alkaline earth metal salts such as magnesium salts; alkanolamine salts such as monoethanolamine salts and diethanolamine salts; ammonium salts and the like. It is done. Of these, alkali metal salts are preferred.
　アニオン界面活性剤の製造方法としては、例えば、ＬＡＳの場合、アルキルベンゼンを無水硫酸でスルホン化し、アルカリで中和する方法で製造することができる。例えば、ＡＥＳの場合、ポリオキシアルキレンアルキルエーテルに、無水硫酸を反応させるか、クロルスルホン酸を反応させてスルホン化し、アルカリで中和する方法により製造することができる。 As a method for producing an anionic surfactant, for example, in the case of LAS, alkylbenzene can be produced by sulfonating with sulfuric anhydride and neutralizing with alkali. For example, in the case of 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.
　アニオン界面活性剤は、１種が単独で用いられてもよいし、２種以上が組み合わされて用いられてもよい。
　（Ｂ）成分中のアニオン界面活性剤の含有量は、（Ｂ）成分の総質量に対し、５～７０質量％が好ましく、１０～６０質量％がより好ましく、１０～５０質量％がさらに好ましく、２０～４０質量％が特に好ましい。アニオン界面活性剤の含有量が前記下限値以上であれば、油性汚れに対する洗浄力がより向上しやすくなる。アニオン界面活性剤の含有量が前記上限値以下であれば液安定性がより向上しやすくなる。 One anionic surfactant may be used alone, or two or more anionic surfactants may be used in combination.
The content of the anionic surfactant in the component (B) is preferably 5 to 70% by mass, more preferably 10 to 60% by mass, and further preferably 10 to 50% by mass with respect to the total mass of the component (B). 20 to 40% by mass is particularly preferable. If content of an anionic surfactant is more than the said lower limit, the detergency with respect to oily dirt will improve more easily. If content of an anionic surfactant is below the said upper limit, liquid stability will become easier to improve.
　（Ｂ）成分としては、ノニオン界面活性剤と、アニオン界面活性剤が併用されることが好ましい。この場合、ノニオン界面活性剤と、アニオン界面活性剤との質量比（「ノニオン界面活性剤／アニオン界面活性剤で表される質量比）は、０．１～２０が好ましく、０．３～９がより好ましく、０．５～９がさらに好ましく、１～８が特に好ましく、１．５～４が最も好ましい。前記質量比が前記の好ましい範囲であると、洗浄力がより高められる。特に、本発明の液体洗浄剤を塗布洗浄に用いた際の油性インク汚れに対する洗浄力がより高められる。 As the component (B), a nonionic surfactant and an anionic surfactant are preferably used in combination. In this case, the mass ratio of the nonionic surfactant to the anionic surfactant (“mass ratio represented by nonionic surfactant / anionic surfactant”) is preferably from 0.1 to 20, and preferably from 0.3 to 9 Is more preferably 0.5 to 9, particularly preferably 1 to 8, and most preferably 1.5 to 4. When the mass ratio is in the above preferred range, the detergency is further enhanced. The cleaning power against oil-based ink stains when the liquid cleaning agent of the present invention is used for coating and cleaning is further enhanced.
　［カチオン界面活性剤］
　カチオン界面活性剤としては、例えばアルキルトリメチルアンモニウム塩、ジアルキルジメチルアンモニウム塩、アルキルベンジルジメチルアンモニウム塩、アルキルピリジニウム塩の陽イオン性界面活性剤等が挙げられる。これらの塩としては、ナトリウム、カリウムなどのアルカリ金属塩、マグネシウムなどのアルカリ土類金属塩、モノエタノールアミン、ジエタノールアミンなどのアルカノールアミン塩などが挙げられる。 [Cationic surfactant]
Examples of the cationic surfactant include an alkyltrimethylammonium salt, a dialkyldimethylammonium salt, an alkylbenzyldimethylammonium salt, and an alkylpyridinium salt cationic surfactant. Examples of 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.
　カチオン界面活性剤は、１種が単独で用いられてもよいし、２種以上が組み合わされて用いられてもよい。
　（Ｂ）成分中のカチオン界面活性剤の含有量は、（Ａ）成分の総質量に対し、０～１０質量％が好ましく、０～５質量％がより好ましい。カチオン界面活性剤の含有量が０質量％であるとは、（Ｂ）成分中にカチオン界面活性剤を含有しないということである。 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 in the component (B) is preferably 0 to 10% by mass and more preferably 0 to 5% by mass with respect to the total mass of the component (A). That the content of the cationic surfactant is 0% by mass means that no cationic surfactant is contained in the component (B).
　［両性界面活性剤］
　両性界面活性剤としては、例えばアルキルベタイン型、アルキルアミドベタイン型、イミダゾリン型、アルキルアミノスルホン型、アルキルアミノカルボン酸型、アルキルアミドカルボン酸型、アミドアミノ酸型、リン酸型両性界面活性剤等が挙げられる。
　両性界面活性剤は、１種が単独で用いられてもよいし、２種以上が組み合わされて用いられてもよい。
　（Ｂ）成分中の両性界面活性剤の含有量は、（Ｂ）成分の総質量に対し、０～１０質量％が好ましく、０～５質量％がより好ましい。両性界面活性剤の含有量が０質量％であるとは、（Ｂ）成分中に両性界面活性剤を含有しないということである。 [Amphoteric surfactant]
Examples of amphoteric surfactants 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 in the component (B) is preferably 0 to 10% by mass and more preferably 0 to 5% by mass with respect to the total mass of the component (B). That the content of the amphoteric surfactant is 0% by mass means that the amphoteric surfactant is not contained in the component (B).
　液体洗浄剤中の（Ｂ）成分の含有量は、液体洗浄剤の総質量に対し、１５質量％以上７０質量％以下が好ましく、３０質量％以上６０質量％以下がより好ましく、３５質量％以上６０質量％以下がさらに好ましく、４０質量％以上６０質量％以下が特に好ましい。（Ｂ）成分の含有量が前記下限値以上であると、油性汚れに対する洗浄力がより高められる。特に、本発明の液体洗浄剤を塗布洗浄に用いた際の油性インク汚れに対する洗浄力がより高められる。
　（Ｂ）成分の含有量が前記上限値以下であると、液安定性が高められやすくなる。 The content of the component (B) in the liquid detergent is preferably 15% by mass or more and 70% by mass or less, more preferably 30% by mass or more and 60% by mass or less, and more preferably 35% by mass or more with respect to the total mass of the liquid detergent. 60 mass% or less is further more preferable, and 40 mass% or more and 60 mass% or less are especially preferable. When the content of the component (B) is equal to or higher than the lower limit, the detergency against oily dirt is further enhanced. In particular, the cleaning power against oil-based ink stains when the liquid cleaning agent of the present invention is used for application cleaning is further enhanced.
When the content of the component (B) is equal to or less than the upper limit, the liquid stability is easily improved.
　（Ｂ）成分は、非石鹸系界面活性剤（Ｂ－１）と高級脂肪酸又はその塩（Ｂ－２）を併用することが好ましい。
（Ｂ－２）成分は、炭素数８～２０、好ましくは１２～１４の高級脂肪酸又はその塩であり、脂肪酸の炭素鎖は直鎖であってもよく分岐鎖であってもよい。
成分（Ｂ－２）としては、ラウリン酸（ドデカン酸）、トリデシル酸、ミリスチン酸（テトラデカン酸）が好ましい。
　成分（Ｂ－２）は、１種であってもよく２種であってもよい。なかでもラウリン酸と、ミリスチン酸とを含むヤシ脂肪酸が好ましい。
　衣料用液体洗浄剤中の成分（Ｂ－２）の含有量は、衣料用液体洗浄剤の総質量に対し、１～５質量％が好ましく、１．５～３．５質量％がより好ましく、１．７５～２質量％がさらに好ましい。
　上記下限値以上であれば、再汚染防止効果がより向上しやすくなる。上記上限値以下であれば、すすぎ性がより向上しやすくなる。 The component (B) is preferably a combination of a non-soap surfactant (B-1) and a higher fatty acid or salt (B-2).
The component (B-2) is a higher fatty acid having 8 to 20 carbon atoms, preferably 12 to 14 carbon atoms or a salt thereof, and the carbon chain of the fatty acid may be linear or branched.
As the component (B-2), lauric acid (dodecanoic acid), tridecylic acid, and myristic acid (tetradecanoic acid) are preferable.
Component (B-2) may be one type or two types. Of these, coconut fatty acid containing lauric acid and myristic acid is preferable.
The content of the component (B-2) in the liquid detergent for clothing is preferably 1 to 5 mass%, more preferably 1.5 to 3.5 mass%, based on the total mass of the liquid detergent for clothing. More preferably, it is 1.75 to 2% by mass.
If it is more than the said lower limit, the recontamination prevention effect will become easier to improve. If it is below the said upper limit, rinse property will become easy to improve more.
　本発明の液体洗浄剤は、（Ａ）成分と（Ｂ）成分との質量比［（Ａ）成分／（Ｂ）成分で表される質量比、以下、「Ａ／Ｂ比」ともいう］が、０．０１～０．１５が好ましく、０．０１～０．０６がより好ましく、０．０１５～０．０５がより好ましい。Ａ／Ｂ比が前記下限値以上であると、油性汚れに対する洗浄力がより高められる。さらに、抑泡性がより高められる。Ａ／Ｂ比が前記上限値以下であると、液安定性がより高められる。 The liquid detergent of the present invention has a mass ratio between the component (A) and the component (B) [mass ratio represented by the component (A) / component (B), hereinafter also referred to as “A / B ratio”]. 0.01 to 0.15 is preferable, 0.01 to 0.06 is more preferable, and 0.015 to 0.05 is more preferable. When the A / B ratio is equal to or higher than the lower limit, the detergency against oily dirt is further enhanced. Furthermore, foam suppression is further improved. Liquid stability is improved more as A / B ratio is below the said upper limit.
　＜（Ｃ）成分＞
　本発明の液体洗浄剤は、さらにポリアルキレンアミンのアルキレンオキシド付加体（（Ｃ）成分）を含有することが好ましい。本発明の液体洗浄剤は、さらに（Ｃ）成分を含有することで、インク等の油性汚れに対する洗浄力が向上する。
（Ｃ）成分としては、例えば、下記（ｃ１）成分、（ｃ２）成分が挙げられる。 <(C) component>
The liquid detergent of the present invention preferably further contains an alkylene oxide adduct (component (C)) of polyalkyleneamine. Since the liquid cleaning agent of the present invention further contains the component (C), the cleaning power against oily stains such as ink is improved.
Examples of the component (C) include the following component (c1) and component (c2).
［（ｃ１）成分］
　（ｃ１）成分は、ポリアルキレンイミンのアルキレンオキシド付加体である。
　（ｃ１）成分のポリアルキレンイミンは、例えば、下記一般式（ＶＩ）で表される。
　ＮＨ２－Ｒ２１－（ＮＡ－Ｒ２１）ｎ－ＮＨ２　・・・（ＶＩ）
　式（ＶＩ）中、Ｒ２１は、それぞれ独立して炭素数２～６のアルキレン基であり、Ａは、水素原子又は分岐による別のポリアミン鎖を示し、ｎは、１以上の数である。ただし、前記Ａがすべて水素原子であることはない。
　即ち、（ＶＩ）式で表されるポリアルキレンイミンは、構造中に分岐したポリアミン鎖を有する。 [(C1) component]
The component (c1) is an alkylene oxide adduct of polyalkyleneimine.
The polyalkyleneimine as the component (c1) is represented by the following general formula (VI), for example.
NH 2 —R 21 — (NA—R 21 ) n —NH 2 (VI)
In the formula (VI), each R 21 independently represents an alkylene group having 2 to 6 carbon atoms, A represents a hydrogen atom or another polyamine chain by branching, and n is a number of 1 or more. However, not all of the A are hydrogen atoms.
That is, the polyalkyleneimine represented by the formula (VI) has a branched polyamine chain in the structure.
　Ｒ２１は、炭素数２～６の直鎖アルキレン基又は炭素数３～６の分岐アルキレン基である。Ｒ２１は、炭素数２～４のアルキレン基が好ましく、炭素数２のアルキレン基がより好ましい。
　ポリアルキレンイミンは、炭素数２～６のアルキレンイミンの１種又は２種以上を常法により重合して得られる。炭素数２～６のアルキレンイミンとしては、エチレンイミン、プロピレンイミン、１，２－ブチレンイミン、２，３－ブチレンイミン、１，１－ジメチルエチレンイミン等が挙げられる。
　ポリアルキレンイミンとしては、ポリエチレンイミン（ＰＥＩ）、ポリプロピレンイミンが好ましく、ＰＥＩがより好ましい。ＰＥＩは、エチレンイミンを重合することによって得られ、その構造中に、１級、２級及び３級アミン窒素原子を含む分岐鎖構造を有している。 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.
As polyalkyleneimine, polyethyleneimine (PEI) and polypropyleneimine are preferable, and PEI is more preferable. PEI is obtained by polymerizing ethyleneimine and has a branched chain structure containing primary, secondary and tertiary amine nitrogen atoms in the structure.
　ポリアルキレンイミンの質量平均分子量は、２００～２０００が好ましく、３００～１５００がより好ましく、４００～１０００がさらに好ましく、５００～８００が特に好ましい。 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.
　ポリアルキレンイミンとしては、その１分子中に活性水素を５～３０個有するものが好ましく、７～２５個有するものがより好ましく、１０～２０個有するものがさらに好ましい。 As the polyalkyleneimine, those having 5 to 30 active hydrogens in one molecule are preferable, those having 7 to 25 are more preferable, and those having 10 to 20 are more preferable.
　（ｃ１）成分は、ポリアルキレンイミンにアルキレンオキシドを付加して得られる。この方法としては、例えば、水酸化ナトリウム、水酸化カリウム、ナトリウムメチラート等の塩基性触媒の存在下、出発物質であるポリアルキレンイミンに対して、１００～１８０℃でエチレンオキシド等のアルキレンオキシドを付加させる方法等が挙げられる。
　アルキレンオキシドとしては、炭素数２～４のアルキレンオキシドが挙げられる。前記アルキレンオキシドとしては、エチレンオキシド、プロピレンオキシド、ブチレンオキシドが挙げられ、エチレンオキシド及びプロピレンオキシドが好ましく、エチレンオキシドがより好ましい。 The component (c1) is obtained by adding alkylene oxide to polyalkyleneimine. As this method, for example, 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. And the like.
Examples of 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.
　（ｃ１）成分としては、ポリアルキレンイミンのエチレンオキシド付加体、ポリアルキレンイミンのプロピレンオキシド付加体、ポリアルキレンイミンのエチレンオキシド－プロピレンオキシド付加体等が挙げられる。なお、前記ポリアルキレンイミンのエチレンオキシド－プロピレンオキシド付加体は、ポリアルキレンイミンにエチレンオキシド及びプロピレンオキシドを付加したものであり、ポリアルキレンイミンに対するエチレンオキシドとプロピレンオキシドの付加順序や付加形態（ブロック状、ランダム状）は任意である。
　（ｃ１）成分としては、ポリアルキレンイミンのエチレンオキシド付加体、ポリアルキレンイミンのエチレンオキシド－プロピレンオキシド付加体が好ましく、ポリアルキレンイミンのエチレンオキシド付加体がより好ましい。 Examples of the component (c1) include an ethylene oxide adduct of polyalkyleneimine, a propylene oxide adduct of polyalkyleneimine, an ethylene oxide-propylene oxide adduct of polyalkyleneimine, and the like. 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.
As the component (c1), 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.
　（ｃ１）成分としては、原料であるポリアルキレンイミンが有する活性水素１原子に対し、平均５～４０個のアルキレンオキシドが付加されたものが好ましく、平均１０～３０個のアルキレンオキシドが付加されたものがより好ましい。即ち、原料であるポリアルキレンイミンが有する活性水素１モルあたりに、平均５～４０モルのアルキレンオキシドが付加されたものが好ましく、平均１０～３０モルのアルキレンオキシドが付加されたものがより好ましい。 As the component (c1), an average of 5 to 40 alkylene oxides are preferably added to an active hydrogen atom of the polyalkyleneimine 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 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.
　（ｃ１）成分の質量平均分子量は、１０００～８００００が好ましく、２０００～５００００がより好ましく、５０００～３００００がさらに好ましく、１００００～２００００が特に好ましい。
　なお、質量平均分子量は、溶媒としてＴＨＦ（テトラヒドロフラン）を用いてＧＰＣ（ゲルパーミネーションクロマトグラフィー）により測定した値を、ＰＥＧ（ポリエチレングリコール）における較正曲線に基づいて換算した値を示す。
　（ｃ１）成分としては、例えば、式（Ｉ－ｃ）で示される化合物が挙げられる。 The mass average molecular weight of the component (c1) is preferably 1000 to 80000, more preferably 2000 to 50000, still more preferably 5000 to 30000, and particularly preferably 10,000 to 20000.
In addition, 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 (c1) include compounds represented by the formula (Ic).
Figure JPOXMLDOC01-appb-C000003
Figure JPOXMLDOC01-appb-C000003
　式（Ｉ－ｃ）中、Ｒ２２は、それぞれ独立に炭素数２～６のアルキレン基であり、ｍは、それぞれ独立に１以上の数である。
　Ｒ２２は、炭素数２又は３のアルキレン基が好ましく、炭素数２のアルキレン基がより好ましい。ｍは、（Ｒ２２Ｏ）の平均繰り返し数であり、５～４０が好ましく、１０～３０がより好ましい。
　（ｃ１）成分としては、合成品が用いられてもよいし、市販品が用いられてもよい。
　市販品としては、例えばＢＡＳＦ社製の商品名「Ｓｏｋａｌａｎ　ＨＰ２０」等が挙げられる。 In the formula (Ic), each R 22 is independently an alkylene group having 2 to 6 carbon atoms, and each m is 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.
As the component (c1), a synthetic product may be used, or a commercially available product may be used.
As a commercial item, the brand name "Sokalan HP20" by BASF, etc. are mentioned, for example.
　［（ｃ２）成分］
　（ｃ２）成分は、下記式（ＶＩＩ）で表されるポリアルキレンアミンのアルキレンオキシド付加体である。
　ＮＨ２（Ｒ３１ＮＨ）ｌＨ　・・・（ＶＩＩ）
　式（ＩＩ）中、Ｒ３１は、炭素数２～６のアルキレン基であり、ｌは、１以上の数である。 [(C2) component]
The component (c2) is an alkylene oxide adduct of polyalkyleneamine represented by the following formula (VII).
NH 2 (R 31 NH) 1 H (VII)
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.
　Ｒ３１は、炭素数２～６の直鎖アルキレン基又は炭素数３～６の分岐アルキレン基である。Ｒ３１は、炭素数２～４のアルキレン基が好ましく、炭素数２のアルキレン基がより好ましい。
　ポリアルキレンアミンとしては、ポリエチレンアミンが好ましい。ポリエチレンアミンとしては、エチレンジアミン、ジエチレントリアミン、トリエチレンテトラミン、テトラエチレンペンタミン、ペンタエチレンヘキサミン等が挙げられる。なお、これらのポリエチレンアミンは、公知の製造方法、例えばアンモニア及びエチレンジクロリドを反応させることで得られる。 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.
As the polyalkyleneamine, 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.
　ポリアルキレンアミンの質量平均分子量は、６０～１８００が好ましく、６０～１０００がより好ましく、６０～８００がさらに好ましい。 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.
　ポリアルキレンアミンとしては、その１分子中に活性水素を６～３０個有するものが好ましく、７～２０個有するものがさらに好ましい。 As the polyalkyleneamine, those having 6 to 30 active hydrogens in one molecule are preferable, and those having 7 to 20 active hydrogens are more preferable.
　（ｃ２）成分は、ポリアルキレンアミンにアルキレンオキシドを付加して得られる。この反応は、（ｃ１）成分と同様に行える。アルキレンオキシドとしては、炭素数２～４のアルキレンオキシドが挙げられる。前記アルキレンオキシドとしては、エチレンオキシド、プロピレンオキシド、ブチレンオキシドが挙げられ、エチレンオキシド及びプロピレンオキシドが好ましく、エチレンオキシドがより好ましい。 (C2) The component is obtained by adding alkylene oxide to polyalkyleneamine. This reaction can be performed in the same manner as the component (c1). Examples of 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.
　（ｃ２）成分としては、ポリアルキレンアミンのエチレンオキシド付加体、ポリアルキレンアミンのプロピレンオキシド付加体、ポリアルキレンアミンのエチレンオキシド－プロピレンオキシド付加体等が挙げられる。
　ポリアルキレンアミンのアルキレンオキシド付加体としては、ポリアルキレンアミンのエチレンオキシド付加体、ポリアルキレンアミンのエチレンオキシド－プロピレンオキシド付加体が好ましく、ポリアルキレンアミンのエチレンオキシド付加体がより好ましい。 Examples of the component (c2) include an ethylene oxide adduct of polyalkyleneamine, a propylene oxide adduct of polyalkyleneamine, and an ethylene oxide-propylene oxide adduct of polyalkyleneamine.
As the 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.
　（ｃ２）成分としては、原料であるポリアルキレンアミンが有する活性水素１原子に対し、平均５～４０個のアルキレンオキシドが付加されたものが好ましく、平均１０～３０個のアルキレンオキシドが付加されたものがより好ましい。即ち、原料であるポリアルキレンアミンが有する活性水素１モルあたりに、平均５～４０モルのアルキレンオキシドが付加されたものが好ましく、平均１０～３０モルのアルキレンオキシドが付加されたものがより好ましい。 As the component (c2), an average of 5 to 40 alkylene oxides are preferably added to one 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.
　（ｃ２）成分の質量平均分子量は、１０００～８００００が好ましく、２０００～５００００がより好ましく、５０００～３００００がさらに好ましく、１００００～２００００が特に好ましい。 The mass average molecular weight of the component (c2) is preferably 1000 to 80000, more preferably 2000 to 50000, still more preferably 5000 to 30000, and particularly preferably 10,000 to 20000.
　（Ｃ）成分としては、（ｃ１）成分が好ましい。（ｃ１）成分の中でも、式（Ｉ－ｃ）で表されるポリエチレンイミンのエチレンオキシド付加体が特に好ましい。 As the component (C), the component (c1) is preferable. Among the components (c1), an ethylene oxide adduct of polyethyleneimine represented by the formula (Ic) is particularly preferable.
　本発明の液体洗浄剤の総質量に対して、（Ｃ）成分の含有量は、０．０１～５質量％が好ましく、０．０５～３質量％がより好ましく、０．１～２質量％がさらに好ましい。
　（Ｃ）成分が０．０１質量％以上あれば、インク等の油性汚れに対する洗浄力が向上し、５質量％以下であれば液安定性が良好である。 The content of the component (C) is preferably 0.01 to 5% by mass, more preferably 0.05 to 3% by mass, and 0.1 to 2% by mass with respect to the total mass of the liquid detergent of the present invention. Is more preferable.
If the component (C) is 0.01% by mass or more, the detergency against oily stains such as ink is improved, and if it is 5% by mass or less, the liquid stability is good.
　本発明の液体洗浄剤において、（Ａ）成分／（Ｃ）成分の質量比（Ａ／Ｃ）は、０．１～４が好ましく、０．２～２．５がより好ましく、０．３～１．５がさらに好ましい。
　（Ａ）成分／（Ｃ）成分の質量比が上記範囲にあることで、インク等の油性汚れに対する洗浄力がより一層向上する。 In the liquid detergent of the present invention, the mass ratio (A / C) of component (A) / component (C) is preferably 0.1 to 4, more preferably 0.2 to 2.5, and 0.3 to 1.5 is more preferable.
When the mass ratio of the component (A) / component (C) is in the above range, the detergency against oily stains such as ink is further improved.
　本発明の液体洗浄剤は、（Ａ）成分と（Ｂ）成分とを必須成分とし、残りの成分は、（Ｃ）成分、水、水混和性有機溶剤等の任意成分である。
　例えば、（Ａ）成分の含有量が、液体洗浄剤の総質量に対して０．１～５質量％であり、（Ｂ）成分の含有量が、液体洗浄剤の総質量に対して１５～７０質量％であり、（Ｃ）成分の含有量が、液体洗浄剤の総質量に対して０．０１～５質量％であり、水の含有量が、液体洗浄剤の総質量に対して１０～９０質量％であり、任意成分の含有量が、液体洗浄剤の総質量に対して０～３０質量％である液体洗浄剤が挙げられる。
　なお、任意成分の含有量が、液体洗浄剤の総質量に対して０質量％であるとは、液体洗浄剤中に任意成分を含有しないということである。 In the liquid detergent of the present invention, the component (A) and the component (B) are essential components, and the remaining components are optional components such as the component (C), water, and a water-miscible organic solvent.
For example, the content of component (A) is 0.1 to 5% by mass with respect to the total mass of the liquid detergent, and the content of component (B) is 15 to 5% with respect to the total mass of the liquid detergent. 70 mass%, the content of component (C) is 0.01 to 5 mass% with respect to the total mass of the liquid detergent, and the water content is 10 with respect to the total mass of the liquid detergent. And a liquid detergent having an optional component content of 0 to 30% by mass relative to the total mass of the liquid detergent.
In addition, content of an arbitrary component is 0 mass% with respect to the total mass of a liquid cleaning agent means that an arbitrary component is not contained in a liquid cleaning agent.
　＜水＞
　本発明の液体洗浄剤は、製造時のハンドリングのし易さ、使用する際の水への溶解性等の点から、水を含有することが好ましい。
　液体洗浄剤中の水の含有量は、特に限定されないが、液体洗浄剤の総質量に対して、１０～９０質量％が好ましく、２０～７０質量％がより好ましく、３０～５０質量％がさらに好ましい。
　（Ａ）成分、（Ｂ）成分、（Ｃ）成分及び水の合計は、液体洗浄剤の総質量に対して１００質量％を超えない。 <Water>
The liquid detergent of the present invention preferably contains water from the viewpoints of ease of handling during production, solubility in water when used, and the like.
The content of water in the liquid detergent is not particularly limited, but is preferably 10 to 90% by mass, more preferably 20 to 70% by mass, and further preferably 30 to 50% by mass with respect to the total mass of the liquid detergent. preferable.
The sum of (A) component, (B) component, (C) component and water does not exceed 100 mass% with respect to the total mass of the liquid detergent.
　＜任意成分＞
　本発明の液体洗浄剤は、上記（Ａ）成分、（Ｂ）成分及び（Ｃ）成分以外に、プロテアーゼ（例えばアルカラーゼ、コロナーゼ等）等の酵素、エタノール等の水混和性有機溶剤、モノエタノールアミン等のアルカリ剤、ジブチルヒドロキシトルエン等の酸化防止剤、安息香酸ナトリウム等の防腐剤、塩化カルシウム、乳酸ナトリウム等の酵素安定化剤、香料等の着香剤、色素等の着色剤等を含んでいてもよい。 <Optional component>
In addition to the components (A), (B) and (C), the liquid detergent of the present invention includes enzymes such as proteases (eg, alcalase and coronase), water miscible organic solvents such as ethanol, and monoethanolamine. Including alkaline agents such as dibutylhydroxytoluene, preservatives such as sodium benzoate, enzyme stabilizers such as calcium chloride and sodium lactate, flavoring agents such as fragrances, coloring agents such as pigments, etc. May be.
　本発明の液体洗浄剤は、塗布洗浄性能が向上される点、粘度を低下させ使用性が向上される点等から、水混和性有機溶剤を含有することが好ましい。
　水混和性有機溶剤としては、エタノール、１－プロパノール、２－プロパノール、１－ブタノール等のアルコール類、プロピレングリコール（ＰＧ）、ブチレングリコール、ヘキシレングリコール等のグリコール類、ジエチレングリコール、トリエチレングリコール、テトラエチレングリコール、重量平均分子量約２００～１０００のポリエチレングリコール、ジプロピレングリコール等のポリグリコール類、ジエチレングリコールモノメチルエーテル、ジエチレングリコールモノエチルエーテル、ジエチレングリコールモノブチルエーテル（ブチルカルビトール）、ジエチレングリコールジメチルエーテル等のアルキルエーテル類等が挙げられる。
　これらの中でも、臭気の少なさ、入手のしやすさ、液体洗浄剤の流動性の点等から、エタノール、プロピレングリコール、重量平均分子量約２００～１０００のポリエチレングリコール、ジエチレングリコールモノブチルエーテル（ブチルカルビトール）が好ましい。
　水混和性有機溶剤は、１種が単独で用いられてもよいし、２種以上が組み合わされて用いられてもよい。
　本発明の液体洗浄剤が水混和性有機溶剤を含有する場合、水混和性有機溶剤の含有量は、液体洗浄剤の総質量に対して、０．１～３０質量％が好ましく、０．１～１５質量％がより好ましい。
　なお、本発明において、水混和性有機溶剤とは、２５℃のイオン交換水１Ｌに５０ｇ以上溶解する有機溶剤をいう。 The liquid cleaning agent of the present invention preferably contains a water-miscible organic solvent from the viewpoints of improving the coating cleaning performance, reducing the viscosity and improving the usability.
Water miscible organic solvents include alcohols such as ethanol, 1-propanol, 2-propanol, 1-butanol, glycols such as propylene glycol (PG), butylene glycol, hexylene glycol, diethylene glycol, triethylene glycol, tetra Polyethylenes such as ethylene glycol, polyethylene glycol having a weight average molecular weight of about 200 to 1000, dipropylene glycol, alkyl ethers such as diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, diethylene glycol monobutyl ether (butyl carbitol), diethylene glycol dimethyl ether, etc. Can be mentioned.
Among these, ethanol, propylene glycol, polyethylene glycol having a weight average molecular weight of about 200 to 1000, diethylene glycol monobutyl ether (butyl carbitol) from the viewpoint of low odor, availability, and fluidity of the liquid detergent. Is preferred.
One type of water-miscible organic solvent may be used alone, or two or more types may be used in combination.
When the liquid detergent of the present invention contains a water-miscible organic solvent, the content of the water-miscible organic solvent is preferably 0.1 to 30% by mass with respect to the total mass of the liquid detergent, More preferred is 15% by mass.
In the present invention, the water-miscible organic solvent means an organic solvent that dissolves 50 g or more in 1 L of ion-exchanged water at 25 ° C.
　アルカリ剤として、モノエタノールアミン、ジエタノールアミン、トリエタノールアミン等が挙げられる。
　本発明の液体洗浄剤がアルカリ剤を含有する場合、アルカリ剤の含有量は、液体洗浄剤の総質量に対して、０．１～６質量％が好ましい。
　（Ａ）成分、（Ｂ）成分、（Ｃ）成分、水、及び任意成分の合計は、液体洗浄剤の総質量に対して１００質量％を超えない。 Examples of the alkaline agent include monoethanolamine, diethanolamine, and triethanolamine.
When the liquid detergent of the present invention contains an alkali agent, the content of the alkali agent is preferably 0.1 to 6% by mass with respect to the total mass of the liquid detergent.
The total of component (A), component (B), component (C), water, and optional component does not exceed 100% by mass relative to the total mass of the liquid detergent.
　＜ｐＨ＞
　本発明の液体洗浄剤は、２５℃におけるｐＨが４～９であることが好ましく、ｐＨ６～９であることがより好ましい。ｐＨがこのような範囲にあると液体洗浄剤の液安定性を良好に維持できる。
　液体洗浄剤のｐＨは、必要に応じて、ｐＨ調整剤を配合することにより調整できる。ｐＨ調整剤としては、本発明の効果を損なわない限りにおいて随意であるが、硫酸、水酸化ナトリウム、水酸化カリウム、アルカノールアミン等が好ましい。
　ｐＨは、ＪＩＳ　Ｚ８８０２：２０１１によって２５℃において測定した値である。 <PH>
The liquid detergent of the present invention preferably has a pH at 25 ° C. of 4 to 9, more preferably pH 6 to 9. When the pH is in such a range, the liquid stability of the liquid detergent can be maintained well.
The pH of the liquid detergent can be adjusted by blending a pH adjuster as necessary. The pH adjuster is optional as long as the effects of the present invention are not impaired, but sulfuric acid, sodium hydroxide, potassium hydroxide, alkanolamine and the like are preferable.
The pH is a value measured at 25 ° C. according to JIS Z8802: 2011.
　＜製造方法＞
　本発明の液体洗浄剤は、従来公知の製造方法により製造される。例えば、溶媒である水に、上記（Ａ）及び（Ｂ）成分を添加し、必要に応じて任意成分を加え、これを混合する方法が挙げられる。 <Manufacturing method>
The liquid detergent of the present invention is produced by a conventionally known production method. For example, the method of adding the said (A) and (B) component to water which is a solvent, adding an arbitrary component as needed, and mixing this is mentioned.
　＜用途＞
　本発明の液体洗浄剤は、各種用途の洗浄剤として用いられるが、油性汚れに対する洗浄力に優れることから、油性汚れが付着した被洗物の洗浄剤として好適である。本発明の液体洗浄剤は、衣料等の繊維製品用液体洗浄剤、窓ガラス等の硬表面用液体洗浄剤、食器、調理器具等の台所用液体洗浄剤等として好適である。なかでも、本発明の液体洗浄剤は、油性インク汚れに対する洗浄力に優れるため、油性インク汚れの付着した衣料等の繊維製品用液体洗浄剤、窓ガラス等の硬表面用液体洗浄剤として好適である。本発明の液体洗浄剤は、特に、油性インク汚れが付着した繊維製品に対して、塗布洗浄した際の洗浄力に優れるため、繊維製品用液体洗浄剤として好適である。 <Application>
The liquid cleaning agent of the present invention is used as a cleaning agent for various uses, but is excellent as a cleaning agent for oily soils, and is therefore suitable as a cleaning agent for objects to be cleaned to which oily soils adhere. The liquid cleaning agent of the present invention is suitable as a liquid cleaning agent for textiles such as clothing, a liquid cleaning agent for hard surfaces such as window glass, and a liquid cleaning agent for kitchens such as tableware and cooking utensils. Among them, the liquid cleaning agent of the present invention is excellent in cleaning power against oil-based ink stains, and is therefore suitable as a liquid cleaning agent for textiles such as clothing to which oil-based ink stains adhere, and a liquid cleaning agent for hard surfaces such as window glass. is there. The liquid cleaning agent of the present invention is particularly suitable as a liquid cleaning agent for textiles because it has excellent cleaning power when coated and washed on textiles with oily ink stains.
　＜使用方法＞
　本発明の液体洗浄剤の使用方法としては、通常の使用方法が挙げられる。本発明の液体洗浄剤を繊維製品の洗浄に使用する場合には、例えば、水３０Ｌに対し液体洗浄剤５～３０ｍＬを添加した洗浄液を用い、洗濯機で被洗物を洗浄する方法、前記洗浄液に被洗物を漬け置く方法等が挙げられる。また、液体洗浄剤を被洗物に直接塗布して一定時間放置し、その後、通常の洗濯を行う方法（塗布洗浄）で使用されてもよい。
　本発明の液体洗浄剤を硬表面の洗浄に使用する場合には、液体洗浄剤を洗浄対象である硬表面にスプレー等して塗布した後、スポンジ等の洗浄用具で擦り洗いする方法が挙げられる。
　本発明の液体洗浄剤を食器等の洗浄に用いる場合には、液体洗浄剤を原液のままスポンジに含ませて食器等を洗浄する方法、液体洗浄剤を水に溶解して希薄な洗浄液を調製し、この洗浄液に食器等を浸しつつスポンジで擦る方法等が挙げられる。
　本発明の液体洗浄剤は、油性汚れに対する塗布洗浄力に優れるため、塗布洗浄で用いられることが好ましい。特に、繊維に付着した油性インク汚れに対して塗布洗浄が行われると、（Ａ）成分が油性インク汚れに対してより作用しやすくなり油性インク汚れに対する洗浄力がより高められる。 <How to use>
As a method of using the liquid detergent of the present invention, a normal method of use can be mentioned. When the liquid detergent of the present invention is used for washing textile products, for example, a method of washing an object to be washed with a washing machine using a washing liquid obtained by adding 5 to 30 ml of a liquid detergent to 30 L of water, the washing liquid The method of immersing the item to be washed is mentioned. Alternatively, the liquid cleaning agent may be applied directly to the article to be washed and left for a certain period of time, and then used in a normal washing method (application cleaning).
When the liquid cleaning agent of the present invention is used for cleaning a hard surface, there is a method in which the liquid cleaning agent is applied to the hard surface to be cleaned by spraying or the like and then rubbed with a cleaning tool such as a sponge. .
When the liquid detergent of the present invention is used for washing dishes, etc., a method for washing dishes with the liquid detergent contained in a sponge as a stock solution, preparing a diluted washing liquid by dissolving the liquid detergent in water And a method of rubbing with a sponge while immersing tableware or the like in the cleaning liquid.
Since the liquid cleaning agent of the present invention is excellent in coating cleaning power against oily dirt, it is preferably used in coating cleaning. In particular, when application cleaning is performed on oil-based ink stains attached to the fibers, the component (A) is more likely to act on oil-based ink stains, and the detergency against oil-based ink stains is further enhanced.
　以上、説明したとおり、本発明の液体洗浄剤は、（Ａ）成分及び（Ｂ）成分を含有するため、油性インク汚れ等の油性汚れに対する洗浄力により優れる。さらに、液安定性、抑泡性に優れる。 As described above, since the liquid cleaning agent of the present invention contains the component (A) and the component (B), it is excellent in cleaning power against oily stains such as oily ink stains. Furthermore, it is excellent in liquid stability and foam suppression.
　以下に実施例を用いて本発明をさらに詳しく説明するが、本発明はこれら実施例に限定されるものではない。本実施例において「％」は特に断りがない限り「質量％」を示す。
　本実施例において使用した原料は下記の通りである。 Hereinafter, the present invention will be described in more detail using examples, but the present invention is not limited to these examples. In this example, “%” indicates “% by mass” unless otherwise specified.
The raw materials used in this example are as follows.
　＜（Ａ）成分＞
　・Ａ－１：ポリオキシプロピレングリセリルエーテル、アクトコールＴ－１５００（商品名）、三井化学株式会社製、重量平均分子量１５００。
　・Ａ－２：ポリオキシプロピレングリセリルエーテル、アクトコールＴ－３０００（商品名）、三井化学株式会社製、重量平均分子量３０００。
　・Ａ－３：ポリオキシプロピレングリセリルエーテル、アクトコールＴ－４０００（商品名）、三井化学株式会社製、重量平均分子量４０００。
　・Ａ－４：ポリオキシプロピレングリセリルエーテル、アクトコールＴ－５０００（商品名）、三井化学株式会社製、重量平均分子量５０００。 <(A) component>
A-1: polyoxypropylene glyceryl ether, Actol T-1500 (trade name), manufactured by Mitsui Chemicals, Inc., weight average molecular weight 1500.
A-2: polyoxypropylene glyceryl ether, Actol T-3000 (trade name), manufactured by Mitsui Chemicals, Inc., weight average molecular weight 3000.
A-3: polyoxypropylene glyceryl ether, Actol T-4000 (trade name), manufactured by Mitsui Chemicals, Inc., weight average molecular weight 4000.
A-4: Polyoxypropylene glyceryl ether, Actol T-5000 (trade name), manufactured by Mitsui Chemicals, Inc., weight average molecular weight 5000.
　＜（Ａ’）成分：（Ａ）成分の比較成分＞
　・Ａ’－１：ポリオキシプロピレンエチレングリコールエーテル、アクトコールＤ－３０００（商品名）、三井化学株式会社製、重量平均分子量３０００。
　・Ａ’－２：ポリオキシプロピレンエチレングリコールエーテル、アクトコールＤ－４０００（商品名）、三井化学株式会社製、重量平均分子量４０００。 <(A ′) Component: Comparative Component of (A) Component>
A′-1: polyoxypropylene ethylene glycol ether, Actol D-3000 (trade name), manufactured by Mitsui Chemicals, Inc., weight average molecular weight 3000.
A′-2: polyoxypropylene ethylene glycol ether, Actol D-4000 (trade name), manufactured by Mitsui Chemicals, Inc., weight average molecular weight 4000.
　＜（Ｂ）成分＞
　・Ｂ－１：ＭＥＥ（ポリオキシエチレン脂肪酸メチルエステル）、ヤシ脂肪酸メチル（質量比でラウリン酸メチル／ミリスチン酸メチル＝８／２の混合物）に対して、アルコキシル化触媒を用いて、１５モル相当のエチレンオキシドを付加したもの。上記一般式（ＩＩ）中、Ｒ２＝炭素数１１のアルキル基及び炭素数１３のアルキル基、Ｒ３＝メチル基、ｓ＝１５、ｔ＝０、ｕ＝０。下記合成方法により合成されたもの。
　［Ｂ－１の合成例］
　特開２０００－１４４１７９号公報に記載の合成方法に準じて合成した。
　組成が２．５ＭｇＯ・Ａｌ２Ｏ３・ｗＨ２Ｏである水酸化アルミナ・マグネシウム（キョーワード３００（商品名）、協和化学工業株式会社製）を６００℃で１時間、窒素雰囲気下で焼成して、焼成水酸化アルミナ・マグネシウム（未改質）触媒を得た。焼成水酸化アルミナ・マグネシウム（未改質）触媒２．２ｇと、０．５Ｎ水酸化カリウムエタノール溶液２．９ｍＬと、ラウリン酸メチル２８０ｇと、ミリスチン酸メチル７０ｇとを４Ｌオートクレーブに仕込み、オートクレーブ内で触媒の改質を行った。次いで、オートクレーブ内を窒素で置換した後、温度を１８０℃、圧力を０．３ＭＰａに維持しつつ、エチレンオキシド１０５２ｇを導入し、撹拌しながら反応させた。
　得られた反応液を８０℃に冷却し、水１５９ｇと、濾過助剤として活性白土及び珪藻土をそれぞれ５ｇとを添加し混合した後、触媒を濾別してＢ－１を得た。
　Ｂ－１のナロー率は３０質量％であった。 <(B) component>
B-1: Equivalent to 15 moles of MEE (polyoxyethylene fatty acid methyl ester), palm fatty acid methyl (mixture of methyl laurate / methyl myristate = 8/2 by mass ratio) using an alkoxylation catalyst To which ethylene oxide is added. In the general formula (II), R 2 = alkyl group having 11 carbon atoms and alkyl group having 13 carbon atoms, R 3 = methyl group, s = 15, t = 0, u = 0. Synthesized by the following synthesis method.
[Synthesis example of B-1]
Synthesis was performed according to the synthesis method described in JP-A No. 2000-144179.
Alumina-magnesium hydroxide (Kyoward 300 (trade name), manufactured by Kyowa Chemical Industry Co., Ltd.) having a composition of 2.5 MgO.Al 2 O 3 .wH 2 O was calcined at 600 ° C. for 1 hour in a nitrogen atmosphere. Thus, a calcined alumina / magnesium hydroxide (unmodified) catalyst was obtained. A 4 L 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 methyl laurate, and 70 g of methyl myristate. Catalyst reforming was performed. Next, after the inside of the autoclave was replaced with nitrogen, 1052 g of ethylene oxide was introduced and reacted while stirring while maintaining the temperature at 180 ° C. and the pressure at 0.3 MPa.
The obtained reaction liquid was cooled to 80 ° C., 159 g of water and 5 g of activated clay and diatomaceous earth as filter aids were added and mixed, and then the catalyst was filtered off to obtain B-1.
The narrow ratio of B-1 was 30% by mass.
　・Ｂ－２：ＭＥＥ（ポリオキシエチレン脂肪酸メチルエステル）、ヤシ脂肪酸メチル（質量比でラウリン酸メチル／ミリスチン酸メチル＝７４／２６の混合物）に対して、アルコキシル化触媒を用いて、１５モル相当のエチレンオキシドを付加したもの。上記一般式（ＩＩ）中、Ｒ２＝炭素数１１のアルキル基及び炭素数１３のアルキル基、Ｒ３＝メチル基、ｓ＝１５、ｔ＝０、ｕ＝０。下記合成方法により合成されたもの。
　［Ｂ－２の合成例］
　Ｂ－２を以下の合成方法に準じて合成した。
　５００ｍＬビーカーに、２－エチルヘキサノール（一級試薬、関東化学株式会社製）１３７ｇと、酢酸カルシウム一水和物（特級試薬、関東化学株式会社製）４１．７ｇを入れ、パドル攪拌翼により室温（２５℃）で混合して分散物を得た（分散工程）。前記分散物を攪拌しながら、滴下ロートによって、硫酸（特級試薬、関東化学株式会社製）２０．９ｇを１０分間かけて添加し混合した（混合工程）。混合工程では硫酸の添加で発熱するので、ビーカーを水浴して冷却し、反応温度を３０～５０℃に制御した。硫酸を添加した後、５０℃に保ちながら、さらに２時間攪拌し（触媒熟成工程）、アルコキシル化触媒を得た。
　オートクレーブに、上記アルコキシル化触媒１２．５ｇと、ラウリン酸メチル（パステルＭ１２、ライオンケミカル株式会社製）４６２ｇと、ミリスチン酸メチル（パステルＭ１４、ライオンケミカル株式会社製）１６６ｇとを入れ、攪拌した。攪拌しながら、オートクレーブ内を窒素置換し、１００℃に昇温し、１．３ｋＰａ以下の減圧条件で３０分間、脱水を行った。次いで、１６０℃に昇温し、０．１～０．５ＭＰａの条件で、エチレンオキシド１８７６ｇ（ラウリン酸メチルとミリスチン酸メチルとの合計の１５倍モル）を導入して攪拌した（付加反応工程）。さらに、付加反応温度で０．５時間攪拌した（熟成工程）後、８０℃に冷却し、反応粗製物（ポリオキシエチレン脂肪酸メチルエステル（ＭＥＥ）、ＥＯ平均付加モル数＝１５）２５１６ｇを得た。前記反応粗製物をろ過して触媒を除去したものをＢ－２とした。
　Ｂ－２のナロー率は３０質量％であった。 -B-2: MEE (polyoxyethylene fatty acid methyl ester), coconut fatty acid methyl (mixture of methyl laurate / methyl myristate = 74/26 by mass ratio) equivalent to 15 moles using an alkoxylation catalyst To which ethylene oxide is added. In the general formula (II), R 2 = alkyl group having 11 carbon atoms and alkyl group having 13 carbon atoms, R 3 = methyl group, s = 15, t = 0, u = 0. Synthesized by the following synthesis method.
[Synthesis example of B-2]
B-2 was synthesized according to the following synthesis method.
In a 500 mL beaker, 137 g of 2-ethylhexanol (primary reagent, manufactured by Kanto Chemical Co., Inc.) and 41.7 g of calcium acetate monohydrate (special grade reagent, manufactured by Kanto Chemical Co., Ltd.) were placed, and room temperature (25 (° C.) to obtain a dispersion (dispersing step). While stirring the dispersion, 20.9 g of sulfuric acid (special grade reagent, manufactured by Kanto Chemical Co., Inc.) was added and mixed for 10 minutes with a dropping funnel (mixing step). In the mixing step, heat was generated by the addition of sulfuric acid, so the beaker was cooled in a water bath and the reaction temperature was controlled at 30-50 ° C. After adding sulfuric acid, the mixture was further stirred for 2 hours while maintaining at 50 ° C. (catalyst aging step) to obtain an alkoxylation catalyst.
Into an autoclave, 12.5 g of the alkoxylation catalyst, 462 g of methyl laurate (Pastel M12, manufactured by Lion Chemical Co., Ltd.) and 166 g of methyl myristate (Pastel M14, manufactured by Lion Chemical Co., Ltd.) were added and stirred. While stirring, the inside of the autoclave was purged with nitrogen, heated to 100 ° C., and dehydrated under reduced pressure conditions of 1.3 kPa or less for 30 minutes. Next, the temperature was raised to 160 ° C., and 1876 g of ethylene oxide (15 times mol of the total of methyl laurate and methyl myristate) was introduced and stirred under the condition of 0.1 to 0.5 MPa (addition reaction step). Furthermore, after stirring for 0.5 hour at the addition reaction temperature (aging step), the reaction mixture was cooled to 80 ° C. to obtain 2516 g of a crude reaction product (polyoxyethylene fatty acid methyl ester (MEE), EO average addition mole number = 15). . B-2 was obtained by filtering the crude reaction product to remove the catalyst.
The narrow rate of B-2 was 30% by mass.
　・Ｂ－３：ソフタノール、炭素数１２～１４の第２級アルコールに、７モル相当のエチレンオキシドを付加したもの、ソフタノール７０（商品名）、株式会社日本触媒製。上記一般式（ＩＩＩ）中、Ｒ４＝炭素数１２～１４の分岐鎖のアルキル基、ｖ＝７、ｗ＝０、ｘ＝０。 B-3: Softanol, a secondary alcohol having 12 to 14 carbon atoms added with 7 mol of ethylene oxide, Softanol 70 (trade name), manufactured by Nippon Shokubai Co., Ltd. In the general formula (III), R 4 = a branched alkyl group having 12 to 14 carbon atoms, v = 7, w = 0, x = 0.
　・Ｂ－４：ポリオキシエチレンアルキルエーテル、炭素数１２及び１４の天然アルコール（第１級アルコール）に１５モル相当のエチレンオキシドを付加したもの。上記一般式（ＩＩＩ）中、Ｒ４＝炭素数１２～１４の直鎖のアルキル基、ｖ＝１５、ｗ＝０、ｘ＝０。
　［Ｂ－４の合成例］
　プロクター・アンド・ギャンブル社製のＣＯ－１２１４（商品名、炭素数１２及び１４の天然アルコール）２２４．４ｇと、３０質量％水酸化ナトリウム水溶液２．０ｇとを耐圧型反応容器内に仕込み、該反応容器内を窒素置換した。次に、温度１００℃、圧力２．０ｋＰａ以下で３０分間脱水した後、温度を１６０℃まで昇温した。次いで、反応液を撹拌しながら、エチレンオキシド（ガス状）７６０．６ｇを反応液中に徐々に加えた。この時、反応温度が１８０℃を超えないように添加速度を調節しながら、エチレンオキシドを吹き込み管で加えた。
　エチレンオキシドの添加終了後、温度１８０℃、圧力０．３ＭＰａ以下で３０分間熟成した後、温度１８０℃、圧力６．０ｋＰａ以下で１０分間、未反応のエチレンオキシドを留去した。
　次に、温度を１００℃以下まで冷却した後、反応物の１質量％水溶液のｐＨが約７になるように、７０質量％ｐ－トルエンスルホン酸を加えて中和し、Ｂ－４を得た。 B-4: Polyoxyethylene alkyl ether, which is obtained by adding 15 moles of ethylene oxide to a natural alcohol (primary alcohol) having 12 and 14 carbon atoms. In the above general formula (III), R 4 = a linear alkyl group having 12 to 14 carbon atoms, v = 15, w = 0, x = 0.
[Synthesis example of B-4]
CO-1214 (trade name, natural alcohols having 12 and 14 carbon atoms) manufactured by Procter & Gamble Co., and 244.4 g of a 30% by mass aqueous sodium hydroxide solution were charged into a pressure-resistant reaction vessel. 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. Next, while stirring the reaction solution, 760.6 g of ethylene oxide (gaseous) was gradually added to the reaction solution. At this time, ethylene oxide was added through the blowing tube while adjusting the addition rate so that the reaction temperature did not exceed 180 ° C.
After completion of the addition of ethylene oxide, aging was performed at a temperature of 180 ° C. and a pressure of 0.3 MPa or less for 30 minutes, and then unreacted ethylene oxide was distilled off at a temperature of 180 ° C. and a pressure of 6.0 kPa or less for 10 minutes.
Next, after cooling the temperature to 100 ° C. or lower, 70% by mass p-toluenesulfonic acid was added to neutralize so that the pH of the 1% by mass aqueous solution of the reaction was about 7, thereby obtaining B-4. It was.
　・Ｂ－５：ＥＰノニオン、天然アルコール（質量比で炭素数１２の第１級アルコール／炭素数１４の第１級アルコール＝７／３）に、８モルのエチレンオキシド、２モルのプロピレンオキシド、８モルのエチレンオキシドの順にブロック付加させて得られたノニオン界面活性剤。上記一般式（ＩＩＩ）中、Ｒ４＝炭素数１２～１４の直鎖のアルキル基、ｖ＝８、ｗ＝２、ｘ＝８。 B-5: EP nonion, natural alcohol (primary alcohol having 12 carbon atoms / primary alcohol having 14 carbon atoms = 7/3 by mass ratio), 8 mol ethylene oxide, 2 mol propylene oxide, 8 Nonionic surfactant obtained by block addition in the order of molar ethylene oxide. In the general formula (III), R 4 = a linear alkyl group having 12 to 14 carbon atoms, v = 8, w = 2, x = 8.
　・Ｂ－６：ＡＥＳ、ポリオキシアルキレンアルキルエーテル硫酸塩（ポリオキシエチレンラウリルエーテル硫酸ナトリウムとポリオキシエチレンミリスチルエーテル硫酸ナトリウムとの混合物、ＥＯの平均付加モル数１）、一般式（Ｖ）におけるＲ４０＝炭素数１２及び１４の直鎖のアルキル基、ｍ＝１．０、ｎ＝０、Ｍ＝ナトリウム、Ｂ－６全体に対するｍ＝０、ｎ＝０の化合物の割合＝４３質量％。
　［Ｂ－６の合成例］
　容量４Ｌのオートクレーブ中に、原料アルコールとしてＰ＆Ｇ社製の商品名ＣＯ１２７０アルコール（炭素数１２のアルコールと炭素数１４のアルコールとの質量比７５／２５の混合物）４００ｇと、反応用触媒として水酸化カリウム触媒０．８ｇとを仕込み、該オートクレーブ内を窒素で置換した後、攪拌しながら昇温した。続いて、温度を１８０℃、圧力を０．３ＭＰａ以下に維持しながらエチレンオキシド９１ｇを導入し、反応させることによりアルコールエトキシレートを得た。
　ガスクロマトグラフ質量分析計：Ｈｅｗｌｅｔｔ－Ｐａｃｋａｒｄ社製のＧＣ－５８９０と、検出器：水素炎イオン化型検出器（ＦＩＤ）と、カラム：Ｕｌｔｒａ－１（ＨＰ社製、Ｌ２５ｍ×φ０．２ｍｍ×Ｔ０．１１μｍ）とを用いて分析した結果、得られたアルコールエトキシレートは、エチレンオキシドの平均付加モル数が１．０であった。また、エチレンオキシドが付加していない化合物（最終的に一般式（Ｖ）においてｍ＝０、ｎ＝０の化合物となるもの）の量が、得られたアルコールエトキシレート全体に対して４３質量％であった。
　次に、上記で得たアルコールエトキシレート２３７ｇを、攪拌装置付の５００ｍＬフラスコに採り、窒素で置換した後、液体無水硫酸（サルファン）９６ｇを、反応温度４０℃に保ちながらゆっくりと滴下した。滴下終了後、１時間攪拌を続け（硫酸化反応）、ポリオキシエチレンアルキルエーテル硫酸を得た。次いで、これを水酸化ナトリウム水溶液で中和することによりＢ－６を得た。 B-6: AES, polyoxyalkylene alkyl ether sulfate (mixture of sodium polyoxyethylene lauryl ether sulfate and sodium polyoxyethylene myristyl ether sulfate, average addition mole number of EO 1), R in the general formula (V) 40 = straight chain alkyl group having 12 and 14 carbon atoms, m = 1.0, n = 0, M = sodium, m = 0 to the whole B-6, ratio of n = 0 compound = 43% by mass.
[Synthesis Example of B-6]
In an autoclave with a capacity of 4 L, 400 g of a trade name CO1270 alcohol (mixture of 75/25 mass ratio of 12-carbon alcohol and 14-carbon alcohol) manufactured by P & G as raw material alcohol and potassium hydroxide as a reaction catalyst After charging 0.8 g of the catalyst and replacing the inside of the autoclave with nitrogen, the temperature was raised with stirring. Subsequently, while maintaining the temperature at 180 ° C. and the pressure at 0.3 MPa or less, 91 g of ethylene oxide was introduced and reacted to obtain an alcohol ethoxylate.
Gas chromatograph mass spectrometer: GC-5890 manufactured by Hewlett-Packard, detector: flame ionization detector (FID), column: Ultra-1 (manufactured by HP, L25m × φ0.2mm × T0.11 μm As a result, the alcohol ethoxylate obtained had an average addition mole number of ethylene oxide of 1.0. In addition, the amount of the compound to which ethylene oxide is not added (the compound which finally becomes a compound of m = 0 and n = 0 in the general formula (V)) is 43% by mass with respect to the whole alcohol ethoxylate obtained. there were.
Next, 237 g of the alcohol ethoxylate obtained above was placed in a 500 mL flask equipped with a stirrer and replaced with nitrogen, and 96 g of liquid sulfuric anhydride (sulfane) was slowly added dropwise while maintaining the reaction temperature at 40 ° C. After completion of dropping, stirring was continued for 1 hour (sulfation reaction) to obtain polyoxyethylene alkyl ether sulfuric acid. Then, this was neutralized with an aqueous sodium hydroxide solution to obtain B-6.
　・Ｂ－７：ＡＥＰＳ、ポリオキシエチレンポリオキシプロパン－１，２－ジイルアルキルエーテル硫酸エステルのモノエタノールアミン塩。一般式（Ｖ）におけるＲ４０＝炭素数１２の直鎖のアルキル基、ｍ＝２．０、ｎ＝１．０、Ｍ＝モノエタノールアミン。
　［Ｂ－７の合成例］
　撹拌装置、温度制御装置及び自動導入装置を備えたオートクレーブ内に、炭素数１２の直鎖の第１級アルコール［東京化成工業株式会社製、商品名：１－ドデカノール（分子量１８６．３３）、純度＞９９％］６４０ｇと、水酸化カリウム１．０ｇと、を仕込み、１１０℃、１．３ｋＰａにて３０分間脱水を行った。脱水後、窒素置換を行い、１２０℃まで昇温した後、プロパン－１，２－ジイルオキシド１９９ｇを仕込んだ。次いで、１２０℃にて付加反応・熟成を行った後、１４５℃に昇温し、エチレンオキシド３０３ｇを仕込んだ。次いで、１４５℃にて付加反応・熟成を行った後、８０℃まで冷却し、４．０ｋＰａで未反応のエチレンオキシドを除去した。未反応のエチレンオキシドを除去した後、酢酸１．０ｇをオートクレーブ内に加え、８０℃で３０分間撹拌した後、抜き出しを行い、アルキル基がドデシル基、ＰＯの平均付加モル数が１．０、ＥＯの平均付加モル数が２．０であるアルコキシレートを得た。
　得られたアルコキシレートを、三酸化硫黄ガスを用いて下降薄膜式反応器により硫酸化した。得られた硫酸化物をモノエタノールアミンにて中和し、ポリオキシエチレンポリオキシプロパン－１，２－ジイルアルキルエーテル硫酸エステルのモノエタノールアミン塩（ＡＥＰＳ）を含む組成物を得た。 B-7: AEPS, monoethanolamine salt of polyoxyethylene polyoxypropane-1,2-diyl alkyl ether sulfate. R 40 in the general formula (V) = a linear alkyl group having 12 carbon atoms, m = 2.0, n = 1.0, M = monoethanolamine.
[Synthesis example of B-7]
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 potassium hydroxide 1.0 g were charged and dehydrated at 110 ° C. and 1.3 kPa for 30 minutes. After dehydration, nitrogen substitution was carried out, and after heating up to 120 ° C., 199 g of propane-1,2-diyl oxide was charged. Subsequently, after addition reaction and aging at 120 ° C., the temperature was raised to 145 ° C., and 303 g of ethylene oxide was charged. Subsequently, after addition reaction and aging at 145 ° C., the mixture was cooled to 80 ° C., and unreacted ethylene oxide was removed at 4.0 kPa. After removing unreacted ethylene oxide, 1.0 g of acetic acid was added to the autoclave, and the mixture was stirred at 80 ° C. for 30 minutes and then extracted. 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 by a falling film reactor using sulfur trioxide 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.
　・Ｂ－８：ＬＡＳ、直鎖アルキルベンゼンスルホン酸、ライポンＬＨ－２００（商品名）、ライオン株式会社製。
　・Ｂ－９：ヤシ脂肪酸、日油株式会社製、商品名「ヤシ脂肪酸」。
　・Ｂ－１０：塩化アルキル（炭素数１２）トリメチルアンモニウム、ライオンアクゾ社製、商品名「アーカード１２－３７Ｗ」。
　・Ｂ－１１：アミドアミン、東邦化学株式会社製、商品名「カチナールＭＰＡＳ－Ｒ」。 B-8: LAS, linear alkylbenzene sulfonic acid, Rypon LH-200 (trade name), manufactured by Lion Corporation.
B-9: Coconut fatty acid, manufactured by NOF Corporation, trade name “coconut fatty acid”.
B-10: Alkyl chloride (12 carbon atoms) trimethylammonium, manufactured by Lion Akzo, trade name “ARCARD 12-37W”.
B-11: Amidoamine, manufactured by Toho Chemical Co., Ltd., trade name “Catinal MPAS-R”.
　＜（Ｃ）成分＞
　・ＨＰ－２０：ポリエチレンイミンのエチレンオキシド付加体（ＢＡＳＦ社製、商品名「Ｓｏｋａｌａｎ　ＨＰ２０」）。 <(C) component>
HP-20: Polyethyleneimine ethylene oxide adduct (trade name “Sokalan HP20” manufactured by BASF).
　＜任意成分＞
　・コロナーゼ（酵素）、ノボザイムズ社製、商品名「Ｃｏｒｏｎａｓｅ４８Ｌ」。
　・アルカラーゼ（酵素）、ノボザイムズ社製、商品名「Ａｌｃａｌａｓｅ２．５Ｌ」。
　・ＭＥＡ：モノエタノールアミン（アルカリ剤）、株式会社日本触媒製、商品名「モノエタノールアミン」。
　・ＢＨＴ：ジブチルヒドロキシトルエン（酸化防止剤）、商品名「ＳＵＭＩＬＺＥＲ　ＢＨＴ－Ｒ」、住友化学株式会社製。
　・３－メトキシ－３－メチルブタノール（クラレ社製、商品名「ソルフィット」）。
　・ＰＥＧ１０００：ポリエチレングリコール、重量平均分子量１０００（水混和性有機溶剤）、ライオン株式会社製、商品名「ＰＥＧ＃１０００－Ｌ６０」。
　・ブチルカルビトール、日本乳化剤株式会社製、商品名「ブチルジグリコール」。
　・ＰＧ：プロピレングリコール（水混和性有機溶剤）、ＢＡＳＦ社製。
　・エタノール（水混和性有機溶剤）、日本アルコール販売株式会社製、商品名「特定アルコール９５度合成」。
　・安息香酸ナトリウム（防腐剤）、東亜合成株式会社製、商品名「安息香酸ナトリウム」。
　・塩化カルシウム（酵素安定化剤）、関東化学株式会社製、商品名「塩化カルシウム」。
　・乳酸ナトリウム（酵素安定化剤）、関東化学株式会社製、商品名「乳酸ナトリウム」。
　・香料（着香剤）、特開２００２－１４６３９９号公報の表１１～１８に記載の香料組成物Ａ。
　・色素（着色剤）、癸巳化成株式会社製、商品名「緑色３号」。
　・水（蒸留水）、関東化学株式会社製。 <Optional component>
Coronase (enzyme), manufactured by Novozymes, trade name “Coronase 48L”.
Alcalase (enzyme), manufactured by Novozymes, trade name “Alcalase 2.5L”.
MEA: Monoethanolamine (alkaline agent), manufactured by Nippon Shokubai Co., Ltd., trade name “monoethanolamine”.
-BHT: Dibutylhydroxytoluene (antioxidant), trade name “SUMILZER BHT-R”, manufactured by Sumitomo Chemical Co., Ltd.
3-Methoxy-3-methylbutanol (trade name “Solfit”, manufactured by Kuraray Co., Ltd.).
PEG1000: polyethylene glycol, weight average molecular weight 1000 (water-miscible organic solvent), manufactured by Lion Corporation, trade name “PEG # 1000-L60”.
・ Butyl carbitol, manufactured by Nippon Emulsifier Co., Ltd., trade name “butyl diglycol”.
PG: Propylene glycol (water miscible organic solvent), manufactured by BASF.
-Ethanol (water-miscible organic solvent), manufactured by Nippon Alcohol Sales Co., Ltd., trade name "specific alcohol 95 degree synthesis".
-Sodium benzoate (preservative), manufactured by Toa Gosei Co., Ltd., trade name “Sodium benzoate”.
・ Calcium chloride (enzyme stabilizer), manufactured by Kanto Chemical Co., Ltd., trade name “Calcium chloride”.
-Sodium lactate (enzyme stabilizer), manufactured by Kanto Chemical Co., Ltd., trade name “sodium lactate”.
Perfume (flavoring agent), perfume composition A described in Tables 11 to 18 of JP-A-2002-146399.
-Dye (colorant), manufactured by Sakai Kasei Co., Ltd., trade name "Green No. 3".
・ Water (distilled water), manufactured by Kanto Chemical Co., Inc.
　（実施例１～２１、比較例１～７）
　表１～４に示す組成に従い、水に、（Ａ）成分、（Ｂ）成分、（Ｃ）成分及び任意成分を添加し混合して、実施例１～２１の液体洗浄剤を得た。
　また、（Ａ）成分を添加しなかったこと以外は実施例１～２１と同様にして、比較例１，２，５の液体洗浄剤を得た。（Ａ）成分に代えて（Ａ’）成分を用いたこと以外は実施例１～２１と同様にして、比較例３，４，６，７の液体洗浄剤を得た。
　得られた各例の液体洗浄剤の組成（配合成分、含有量（質量％））を表１～４に示す。
尚、特に断りがない限り質量％は純分を示す。
　表中、空欄の配合成分がある場合、その配合成分は配合されていない。
　表中、比較例３，４，６，７のＡ／Ｂ比は、（Ａ’）成分と（Ｂ）成分との質量比を示す。 (Examples 1 to 21, Comparative Examples 1 to 7)
According to the compositions shown in Tables 1 to 4, the liquid cleaning agents of Examples 1 to 21 were obtained by adding (A), (B), (C) and optional components to water and mixing.
Further, liquid detergents of Comparative Examples 1, 2, and 5 were obtained in the same manner as in Examples 1 to 21 except that the component (A) was not added. Liquid detergents of Comparative Examples 3, 4, 6, and 7 were obtained in the same manner as in Examples 1 to 21 except that the component (A ′) was used instead of the component (A).
Tables 1 to 4 show the compositions (formulation components, content (mass%)) of the obtained liquid cleaning agents in the respective examples.
In addition, unless otherwise indicated, mass% shows a pure part.
In the table, when there is a blank blending component, the blending component is not blended.
In the table, the A / B ratios of Comparative Examples 3, 4, 6, and 7 indicate mass ratios of the component (A ′) and the component (B).
　実施例１～１６、比較例１～４の各例の液体洗浄剤について、洗浄力、液安定性、すすぎ性を以下のように評価した。
　評価結果を、表１～３に示す。 With respect to the liquid detergents of Examples 1 to 16 and Comparative Examples 1 to 4, the cleaning power, liquid stability, and rinsing properties were evaluated as follows.
The evaluation results are shown in Tables 1 to 3.
　＜洗浄力の評価＞
　５ｃｍ×５ｃｍにカットした綿布を評価用布とし、油性ボールペン（ＺＥＢＲＡ社製、商品名「Ｃｌｉｐ－ｏｎ－Ｓｌｉｍ油性ボールペン」）のインクを塗り付けて、油性インク汚れが付着したインク汚垢布を作製した。この際、綿布の中央に直径２ｃｍの円となるように油性インクを塗り付けた。
　このインク汚垢布を、以下の手順で洗浄した。
　各例の液体洗浄剤０．０５ｍＬを、汚垢布に付着させた油性インク汚れが中心となるように前記インク汚垢布に塗布し、３分間放置したのち、下記洗濯方法によって、水１５Ｌに対して各例の液体洗浄剤６ｍＬを溶解した洗濯液を使用して、洗浄した。
　洗浄試験器としてＴｅｒｇ－Ｏ－Ｔｏｍｅｔｅｒ（ＵＮＩＴＥＤ　ＳＴＡＴＥＳ　ＴＥＳＴＩＮＧ社製）を用いた。各例の液体洗浄剤を塗布し３分間放置した後の上記インク汚垢布１０枚と、前記洗濯液とを洗浄試験器に入れ、浴比３０倍に合わせて、１２０ｒｐｍ、１５℃で１０分間洗浄した。次に、二槽式洗濯機（三菱電機社製、品番：ＣＷ－Ｃ３０Ａ１－Ｈ１）に移し、１分間脱水後、水道水（１５℃、４゜ＤＨ）３０Ｌ中で３分間濯ぎ、風乾した。
　インク汚れを付けなかった評価用布、洗浄前のインク汚垢布及び洗浄後のインク汚垢布について、それぞれ反射率を日本電色社製の色差計（製品名：ＳＥ２００型）で測定し、洗浄率（％）を以下の式で算出した。インク汚垢布１０枚について洗浄率（％）を算出し、その平均値を用いて、インク汚れに対する洗浄力を評価した。
　洗浄率（％）＝１００×（洗浄前のインク汚垢布のＫ／Ｓ－洗浄後のインク汚垢布のＫ／Ｓ）／（洗浄前のインク汚垢布のＫ／Ｓ－評価用布のＫ／Ｓ）×１００。
　ただし、Ｋ／Ｓは式：（１－Ｒ／１００）２／（２Ｒ／１００）で求められる値であり、Ｒは、評価用布、洗浄前のインク汚垢布または洗浄後のインク汚垢布の反射率（％）である。
　洗浄率３０％以上を合格とした。 <Evaluation of cleaning power>
A cotton cloth cut into 5 cm x 5 cm is used as an evaluation cloth, and an oil-based ballpoint pen (trade name “Clip-on-Slim oil-based ballpoint pen” manufactured by ZEBRA) is applied with an ink-stained cloth with oil-based ink stains attached. Produced. At this time, oil-based ink was applied to the center of the cotton cloth so as to form a circle having a diameter of 2 cm.
This ink soiled cloth was washed by the following procedure.
Apply 0.05 mL of the liquid cleaning agent in each example to the ink stain cloth so that the oil-based ink stain attached to the stain cloth becomes the center, and leave it for 3 minutes. On the other hand, it was cleaned using a washing liquid in which 6 mL of the liquid cleaning agent of each example was dissolved.
As a cleaning tester, Terg-O-Tometer (manufactured by UNITED STATES TESTING) was used. After applying the liquid cleaning agent of each example and leaving it to stand for 3 minutes, 10 sheets of the ink stain cloth and the washing liquid are put into a cleaning tester, and the bath ratio is 30 times, at 120 rpm, 15 ° C. for 10 minutes. Washed. Next, it was transferred to a two-tank washing machine (product number: CW-C30A1-H1 manufactured by Mitsubishi Electric Corporation), dehydrated for 1 minute, rinsed in 30 L of tap water (15 ° C., 4 ° DH) for 3 minutes, and air-dried.
The reflectance was measured with a color difference meter (product name: SE200 type) manufactured by Nippon Denshoku Co., Ltd. for each of the evaluation cloth without ink stain, the ink dirt cloth before washing, and the ink dirt cloth after washing. The washing rate (%) was calculated by the following formula. The cleaning rate (%) was calculated for 10 ink-stained cloths, and the average value was used to evaluate the cleaning power against ink stains.
Washing rate (%) = 100 × (K / S of ink dirt cloth before washing−K / S of ink dirt cloth after washing) / (K / S of ink dirt cloth before washing−Evaluation cloth) K / S) × 100.
However, K / S is a value obtained by the formula: (1-R / 100) 2 / (2R / 100), and R is an evaluation cloth, an ink dirt cloth before washing, or an ink dirt after washing. This is the reflectance (%) of the cloth.
A cleaning rate of 30% or more was accepted.
　＜液安定性の評価＞
　透明のガラス瓶（広口規格びん、ＰＳ－ＮＯ．１１）に、各例の液体洗浄剤１００ｍＬを充填し、蓋を閉めて密封した。この状態で５℃又は２５℃の恒温槽内に７日間静置して保存した。
　かかる保存の後、液の外観を目視で観察し、下記評価基準に従って、液体洗浄剤の液安定性を評価した。
　（評価基準）
　○：ガラス瓶の底部に沈殿物質が認められず、液の流動性がある。
　△：ガラス瓶の底部に沈殿物質が認められるが、ガラス瓶を軽く振ると、その沈殿物質は消失（溶解）する。
　×：ガラス瓶の底部に沈殿物質が認められ、ガラス瓶を軽く振ってもその沈殿物質は消失しない、又は、液体洗浄剤の製造直後にゲル化もしくは白濁を生じる。
　かかる評価結果を、表１～３の液安定性（２５℃）、液安定性（５℃）の欄にそれぞれ示す。 <Evaluation of liquid stability>
A transparent glass bottle (wide-mouth bottle, PS-NO.11) was filled with 100 mL of the liquid cleaning agent of each example, and the lid was closed and sealed. In this state, it was stored in a constant temperature bath at 5 ° C. or 25 ° C. for 7 days.
After such storage, the appearance of the liquid was visually observed, and the liquid stability of the liquid detergent was evaluated according to the following evaluation criteria.
(Evaluation criteria)
○: Precipitated material is not observed at the bottom of the glass bottle, and the fluidity of the liquid is present.
Δ: 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 the precipitated substance does not disappear even if the glass bottle is shaken lightly, or gelation or cloudiness occurs immediately after the production of the liquid detergent.
The evaluation results are shown in the columns of liquid stability (25 ° C.) and liquid stability (5 ° C.) in Tables 1 to 3, respectively.
　＜すすぎ性の評価＞
　各衣料用液体洗浄剤０．３ｇを、２５℃の３°硬水９００ｍＬに溶解して洗浄液を調製した。この洗浄液２０ｍＬを１００ｍＬ容量のエプトン管に入れ、２０秒で２０回震とうして泡立てた後、３分静置した。その後の泡の高さ（泡と洗浄液との境界から、泡の上端面までの長さ）を測定した。測定した泡の高さ（単位：ｍｍ）を表中に示す。
　すすぎ性の評価として、以下のインク汚れ洗浄力、再汚染防止効果について評価した。なお、すすぎ性の評価は、（Ａ）成分の有無、（Ｃ）成分の有無、（Ｂ）成分（Ｂ－９）の量についての効果を確認するために、実施例３、１５、１６、比較例１についてのみ行った。
　［インク汚れ洗浄力］
　（繰り返し洗濯処理によってソイルリリース効果を加味した洗浄力）
　全自動電気洗濯機（ＡＷ－８０ＶＣ、株式会社東芝製）に、綿布を投入し、浴比２０倍に合わせた。そこに、各例の液体洗浄剤１２ｇを添加し、標準コースにて洗浄、すすぎ、脱水を順次行う洗濯操作を行った。洗浄時間、すすぎ、脱水、水量（３６Ｌに設定）に関しては、一切調整せず、洗濯機の標準設定を使用した。用いた水道水の温度は、１５℃であった。この事前の洗浄操作を２回又は５回繰り返した。２回又は５回の事前洗浄を終えた後、綿布を平干しにて一晩乾燥させ、乾燥後の綿布を５×５ｃｍにカットしたものを評価用綿布とした。
評価用布に、油性ボールペン（ＺＥＢＲＡ社製、商品名「Ｃｌｉｐ－ｏｎ－Ｓｌｉｍ油性ボールペン」）のインクを塗り付けて、油性インク汚れが付着したインク汚垢布を作製した。この際、綿布の中央に直径２ｃｍの円となるように油性インクを塗り付けた。
このインク汚垢布を、以下の手順で洗浄した。
　各例の液体洗浄剤０．０５ｍＬを、汚垢布に付着させた油性インク汚れが中心となるように前記インク汚垢布に塗布し、３分間放置したのち、下記洗濯方法によって、水１５Ｌに対して各例の液体洗浄剤６ｍＬを溶解した洗濯液を使用して、洗浄した。
　洗浄試験器としてＴｅｒｇ－Ｏ－Ｔｏｍｅｔｅｒ（ＵＮＩＴＥＤ　ＳＴＡＴＥＳ　ＴＥＳＴＩＮＧ社製）を用いた。各例の液体洗浄剤を塗布して３分間放置した後の上記インク汚垢布１０枚と、前記洗濯液とを洗浄試験器に入れ、浴比３０倍に合わせて、１２０ｒｐｍ、１５℃で１０分間洗浄した。次に、二槽式洗濯機（三菱電機社製、品番：ＣＷ－Ｃ３０Ａ１－Ｈ１）に移し、１分間脱水後、水道水（１５℃、４゜ＤＨ）３０Ｌ中で３分間濯ぎ、風乾した。
　インク汚れを付けなかった評価用布、洗浄前のインク汚垢布及び洗浄後のインク汚垢布について、それぞれ反射率を日本電色社製の色差計（製品名：ＳＥ２００型）で測定し、洗浄率（％）を以下の式で算出した。インク汚垢布１０枚について洗浄率（％）を算出し、その平均値を用いて、下記基準に基づいてインク汚れに対する洗浄力を評価した。
　洗浄率（％）＝１００×（洗浄前のインク汚垢布のＫ／Ｓ－洗浄後のインク汚垢布のＫ／Ｓ）／（洗浄前のインク汚垢布のＫ／Ｓ－評価用布のＫ／Ｓ）×１００。
ただし、Ｋ／Ｓは式：（１－Ｒ／１００）２／（２Ｒ／１００）で求められる値であり、Ｒは、評価用布、洗浄前のインク汚垢布または洗浄後のインク汚垢布の反射率（％）である。
　［再汚染防止効果の評価］
各例の液体洗浄剤を用いて、以下に示す洗浄工程、すすぎ工程、乾燥工程をこの順序で３回繰り返す洗濯処理を行った。
洗浄工程：被洗物として、下記の綿布、ポリエステル（ＰＥ）布、湿式人工汚染布及び肌シャツを用いた。
綿布：再汚染判定布として綿メリヤス（谷頭商店製）５ｃｍ×５ｃｍを５枚。
ポリエステル（ＰＥ）布：再汚染判定布としてポリエステルトロピカル（谷頭商店製）５ｃｍ×５ｃｍを５枚。
湿式人工汚染布：財団法人洗濯科学協会製の汚染布（オレイン酸２８．３％、トリオレイン１５．６％、コレステロールオレート１２．２％、流動パラフィン２．５％、スクアレン２．５％、コレステロール１．６％、ゼラチン７．０％、泥２９．８％、カーボンブラック０．５％（質量比）の組成の汚れが付着した布）を２０枚。
肌シャツ：肌シャツ（ＬＬサイズ、ＤＶＤ社製）を細かく（３ｃｍ×３ｃｍ程度）裁断したもの。
Ｔｅｒｇ－ｏ－ｔｏｍｅｔｅｒ（ＵＮＩＴＥＤ　ＳＴＡＴＥＳ　ＴＥＳＴＩＮＧ社製）内に、２５℃の３°ＤＨ硬水９００ｍＬを入れ、ここに液体洗浄剤０．６ｇを加え、次いで、前記被洗物を入れた。その後、３°ＤＨ硬水を加えて浴比を２０倍に調整し、１２０ｒｐｍ、２５℃で１０分間洗浄した。
すすぎ工程：
洗浄後の被洗物を、１分間脱水した後、２５℃の３°ＤＨ硬水９００ｍＬを入れ、１２０ｒｐｍ、２５℃で３分間すすいだ。この操作（脱水、すすぎ）を２回繰り返した。２回目には、２５℃の３°ＤＨ硬水９００ｍＬに、所定量の柔軟剤を添加してすすぎを行った。柔軟剤には、部屋干しソフラン（ライオン株式会社製）を用いた。
乾燥工程：
すすいだ被洗物を１分間脱水した後、再汚染判定布（綿布、ＰＥ布）のみを取り出し、濾紙に挟み、アイロンで乾燥した。
反射率計（分光式色差計ＳＥ２０００、日本電色工業株式会社製）を用い、洗濯処理前後の再汚染判定布の反射率（Ｚ値）を測定し、下式よりΔＺを求めた。
ΔＺ＝（洗濯処理前のＺ値）－（洗濯処理後のＺ値）
綿布、ＰＥ布のそれぞれの再汚染判定布におけるΔＺについて、５枚の平均値を求めた。そして、この平均値を指標とした下記判定基準に従い、液体洗浄剤による綿布、ＰＥ布への再汚染防止効果を評価した。下記判定基準において、◎及び○を合格とした。評価結果を表１～３に示す。
　＜綿布における判定基準＞
◎：△Ｚが５未満。
○：△Ｚが５以上７未満。
△：△Ｚが７以上９未満。
×：△Ｚが９以上。
＜ＰＥ布における判定基準＞
◎：△Ｚが３未満。
○：△Ｚが３以上４未満。
△：△Ｚが４以上５未満。
×：△Ｚが５以上。 <Rinse evaluation>
A cleaning solution was prepared by dissolving 0.3 g of the liquid cleaning agent for clothing in 900 mL of 3 ° hard water at 25 ° C. 20 mL of this cleaning solution was put into an Epton tube having a capacity of 100 mL, shaken 20 times in 20 seconds, and allowed to stand for 3 minutes. The height of the subsequent foam (the length from the boundary between the foam and the cleaning liquid to the upper end surface of the foam) was measured. The measured bubble height (unit: mm) is shown in the table.
As an evaluation of rinsing properties, the following ink stain cleaning power and re-staining prevention effect were evaluated. The rinsing properties were evaluated in Examples 3, 15, 16 and 16 in order to confirm the effects of the presence or absence of the component (A), the presence or absence of the component (C), and the amount of the component (B) (B-9). Only Comparative Example 1 was performed.
[Ink stain cleaning power]
(Detergency with soil release effect by repeated washing treatment)
Cotton cloth was put into a fully automatic electric washing machine (AW-80VC, manufactured by Toshiba Corporation), and the bath ratio was adjusted to 20 times. Thereto, 12 g of the liquid cleaning agent of each example was added, and a washing operation was performed in which washing, rinsing, and dehydration were sequentially performed in a standard course. The washing time, rinsing, dehydration, and water volume (set to 36 L) were not adjusted at all and the standard settings of the washing machine were used. The temperature of the tap water used was 15 ° C. This preliminary washing operation was repeated twice or five times. After finishing the pre-washing twice or five times, the cotton cloth was dried overnight by flat laying, and the cotton cloth after drying was cut into 5 × 5 cm to obtain a cotton cloth for evaluation.
An oil-based ballpoint pen (trade name “Clip-on-Slim oil-based ballpoint pen” manufactured by ZEBRA) was applied to the evaluation cloth to prepare an ink-stained cloth with oil-based ink stains attached thereto. At this time, oil-based ink was applied to the center of the cotton cloth so as to form a circle having a diameter of 2 cm.
This ink soiled cloth was washed by the following procedure.
Apply 0.05 mL of the liquid cleaning agent in each example to the ink stain cloth so that the oil-based ink stain attached to the stain cloth becomes the center, and leave it for 3 minutes. On the other hand, it was cleaned using a washing liquid in which 6 mL of the liquid cleaning agent of each example was dissolved.
As a cleaning tester, Terg-O-Tometer (manufactured by UNITED STATES TESTING) was used. After applying the liquid cleaning agent of each example and leaving it to stand for 3 minutes, the above-mentioned ink stain cloth and the washing liquid are put into a cleaning tester, and the bath ratio is set to 30 times. Washed for minutes. Next, it was transferred to a two-tank washing machine (product number: CW-C30A1-H1 manufactured by Mitsubishi Electric Corporation), dehydrated for 1 minute, rinsed in 30 L of tap water (15 ° C., 4 ° DH) for 3 minutes, and air-dried.
The reflectance was measured with a color difference meter (product name: SE200 type) manufactured by Nippon Denshoku Co., Ltd. for each of the evaluation cloth without ink stain, the ink dirt cloth before washing, and the ink dirt cloth after washing. The washing rate (%) was calculated by the following formula. The cleaning rate (%) was calculated for 10 ink-stained cloths, and the average value was used to evaluate the cleaning power against ink stains based on the following criteria.
Washing rate (%) = 100 × (K / S of ink dirt cloth before washing−K / S of ink dirt cloth after washing) / (K / S of ink dirt cloth before washing−Evaluation cloth) K / S) × 100.
However, K / S is a value obtained by the formula: (1-R / 100) 2 / (2R / 100), and R is an evaluation cloth, an ink dirt cloth before washing, or an ink dirt after washing. This is the reflectance (%) of the cloth.
[Evaluation of anti-recontamination effect]
Using the liquid cleaning agent of each example, a washing process in which the following cleaning process, rinsing process, and drying process were repeated three times in this order was performed.
Cleaning step: The following cotton cloth, polyester (PE) cloth, wet artificial contamination cloth and skin shirt were used as the objects to be cleaned.
Cotton cloth: Five cotton knitted fabrics (manufactured by Tanigami Shoten) 5 cm × 5 cm as re-contamination judgment cloths.
Polyester (PE) cloth: 5 sheets of polyester tropical (manufactured by Tanigami Shoten) 5 cm × 5 cm as re-contamination determination cloth.
Wet artificial contamination cloth: Contamination cloth manufactured by Japan Association of Laundry Science (28.3% oleic acid, 15.6% triolein, 12.2% cholesterol oleate, 2.5% liquid paraffin, 2.5% squalene, cholesterol 20 sheets of fabric with 1.6% gelatin, 7.0% gelatin, 29.8% mud, and 0.5% carbon black (mass ratio).
Skin shirt: A skin shirt (LL size, manufactured by DVD) cut into pieces (about 3 cm x 3 cm).
In a Terg-o-meter (manufactured by UNITED STATES TESTING), 900 mL of 3 ° DH hard water at 25 ° C. was added, and 0.6 g of a liquid cleaning agent was added thereto, and then the article to be cleaned was added. Thereafter, 3 ° DH hard water was added to adjust the bath ratio to 20 times, followed by washing at 120 rpm and 25 ° C. for 10 minutes.
Rinsing process:
The washed article after dehydration was dehydrated for 1 minute, and then 900 mL of 3 ° DH hard water at 25 ° C. was added and rinsed at 120 rpm, 25 ° C. for 3 minutes. This operation (dehydration, rinsing) was repeated twice. In the second time, a predetermined amount of a softening agent was added to 900 mL of 3 ° DH hard water at 25 ° C. and rinsed. As the softener, room-dried saffron (manufactured by Lion Corporation) was used.
Drying process:
After the rinsed object was dehydrated for 1 minute, only the recontamination determination cloth (cotton cloth, PE cloth) was taken out, sandwiched between filter papers, and dried with an iron.
Using a reflectance meter (spectral color difference meter SE2000, manufactured by Nippon Denshoku Industries Co., Ltd.), the reflectance (Z value) of the recontamination determination cloth before and after the washing treatment was measured, and ΔZ was determined from the following equation.
ΔZ = (Z value before washing process) − (Z value after washing process)
The average value of 5 sheets was obtained for ΔZ in the respective recontamination determination cloths of cotton cloth and PE cloth. Then, according to the following criteria using this average value as an index, the effect of preventing recontamination of the cotton fabric and PE fabric with the liquid detergent was evaluated. In the following criteria, ◎ and ○ were accepted. The evaluation results are shown in Tables 1 to 3.
<Criteria for cotton cloth>
A: ΔZ is less than 5.
○: ΔZ is 5 or more and less than 7.
Δ: ΔZ is 7 or more and less than 9.
X: ΔZ is 9 or more.
<Criteria for PE cloth>
A: ΔZ is less than 3.
○: ΔZ is 3 or more and less than 4.
Δ: ΔZ is 4 or more and less than 5.
X: ΔZ is 5 or more.
Figure JPOXMLDOC01-appb-T000004
Figure JPOXMLDOC01-appb-T000004
Figure JPOXMLDOC01-appb-T000005
Figure JPOXMLDOC01-appb-T000005
Figure JPOXMLDOC01-appb-T000006
Figure JPOXMLDOC01-appb-T000006
　実施例１７～２１、比較例５～７の各例の液体洗浄剤について、抑泡性を以下のように評価した。評価結果を、表４に示す。
　＜抑泡性の評価＞
　１００ｍＬのエプトン管に上記各例の液体洗浄剤の水溶液（濃度：０．１質量％）を２０ｍＬ入れて、これを２０秒で２０回震とうして泡立てた。３分間静置後、直ちに泡の高さ（泡と上記水溶液との境界から、泡の上端までの長さ）を測定した。測定した泡の高さ（単位：ｍｍ）を表中に示す。 With respect to the liquid detergents of Examples 17 to 21 and Comparative Examples 5 to 7, the antifoaming property was evaluated as follows. The evaluation results are shown in Table 4.
<Evaluation of foam suppression>
20 mL of an aqueous solution (concentration: 0.1% by mass) of the liquid detergent of each of the above examples was placed in a 100 mL Epton tube, and this was bubbled by shaking 20 times in 20 seconds. After standing for 3 minutes, the height of the foam (the length from the boundary between the foam and the aqueous solution to the top of the foam) was measured immediately. The measured bubble height (unit: mm) is shown in the table.
Figure JPOXMLDOC01-appb-T000007
Figure JPOXMLDOC01-appb-T000007
　表１～３に示す結果から、本発明を適用した実施例１～１６の液体洗浄剤は、油性汚れに対する洗浄力により優れることが確認できた。さらに、液安定性に優れることが確認できた。表４に示す結果から、本発明を適用した実施例１７～２１の液体洗浄剤は、抑泡性に優れることが確認できた。
　一方、（Ａ）成分を含まない液体洗浄剤（比較例１，２）、（Ａ）成分に代えて（Ａ’）成分を含む液体洗浄剤（比較例３，４）は、油性汚れに対する洗浄力が充分でなかった。（Ａ）成分に代えて（Ａ’－２）成分を含む液体洗浄剤（比較例４）は、低温における液安定性が充分でなかった。（Ａ）成分を含まない液体洗浄剤（比較例５）、（Ａ）成分に代えて（Ａ’）成分を含む液体洗浄剤（比較例６，７）は、抑泡性が充分でなかった。
　以上の結果から、本発明を適用した液体洗浄剤は、油性汚れに対する洗浄力により優れることが確認できた。 From the results shown in Tables 1 to 3, it was confirmed that the liquid detergents of Examples 1 to 16 to which the present invention was applied were superior in cleaning power against oily dirt. Furthermore, it was confirmed that the liquid stability was excellent. From the results shown in Table 4, it was confirmed that the liquid detergents of Examples 17 to 21 to which the present invention was applied were excellent in foam suppression.
On the other hand, liquid detergents (Comparative Examples 1 and 2) that do not contain the component (A), and liquid detergents (Comparative Examples 3 and 4) that contain the component (A ′) instead of the component (A) The power was not enough. The liquid detergent (Comparative Example 4) containing the component (A′-2) instead of the component (A) did not have sufficient liquid stability at low temperatures. The liquid detergent (Comparative Example 5) that does not contain the component (A) and the liquid detergent (Comparative Examples 6 and 7) that contain the component (A ′) instead of the component (A) did not have sufficient foam suppression. .
From the above results, it was confirmed that the liquid cleaning agent to which the present invention was applied was superior in cleaning power against oily dirt.
　本発明の液体洗浄剤は、油性汚れに対する洗浄力により優れる。 The liquid cleaning agent of the present invention is superior in cleaning power against oily dirt.

Claims (4)

  1. 　３価アルコールのプロピレンオキシド付加物（Ａ）と、界面活性剤（Ｂ）を含有する液体洗浄剤。 Liquid detergent containing propylene oxide adduct (A) of trihydric alcohol and surfactant (B).
  2. 　前記（Ａ）成分／前記（Ｂ）成分で表される質量比が０．０１～０．１５である、請求項１に記載の液体洗浄剤。 2. The liquid detergent according to claim 1, wherein the mass ratio represented by the component (A) / the component (B) is 0.01 to 0.15.
  3. 　さらに、ポリアルキレンアミンのアルキレンオキシド付加体（Ｃ）を含有する、請求項１または２に記載の液体洗浄剤。 The liquid detergent according to claim 1 or 2, further comprising an alkylene oxide adduct (C) of polyalkyleneamine.
  4. 　前記（Ｂ）成分が、非石鹸系界面活性剤、及び高級脂肪酸又は、その塩である、請求項１～３のいずれか一項に記載の液体洗浄剤。 The liquid cleaning agent according to any one of claims 1 to 3, wherein the component (B) is a non-soap surfactant and a higher fatty acid or a salt thereof.
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