WO2013054635A1 - Composition for dishwashing liquid for cleaning hands - Google Patents

Composition for dishwashing liquid for cleaning hands Download PDF

Info

Publication number
WO2013054635A1
WO2013054635A1 PCT/JP2012/073562 JP2012073562W WO2013054635A1 WO 2013054635 A1 WO2013054635 A1 WO 2013054635A1 JP 2012073562 W JP2012073562 W JP 2012073562W WO 2013054635 A1 WO2013054635 A1 WO 2013054635A1
Authority
WO
WIPO (PCT)
Prior art keywords
mass
component
less
composition
carbon atoms
Prior art date
Application number
PCT/JP2012/073562
Other languages
French (fr)
Japanese (ja)
Inventor
小西祥博
渡辺義幸
鈴木圭吾
Original Assignee
花王株式会社
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by 花王株式会社 filed Critical 花王株式会社
Priority to CN201280050578.7A priority Critical patent/CN103890156B/en
Priority to IN1969DEN2014 priority patent/IN2014DN01969A/en
Publication of WO2013054635A1 publication Critical patent/WO2013054635A1/en

Links

Images

Classifications

    • CCHEMISTRY; METALLURGY
    • C11ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11DDETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D3/00Other compounding ingredients of detergent compositions covered in group C11D1/00
    • C11D3/16Organic compounds
    • C11D3/18Hydrocarbons
    • CCHEMISTRY; METALLURGY
    • C11ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11DDETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D1/00Detergent compositions based essentially on surface-active compounds; Use of these compounds as a detergent
    • C11D1/88Ampholytes; Electroneutral compounds
    • C11D1/94Mixtures with anionic, cationic or non-ionic compounds
    • CCHEMISTRY; METALLURGY
    • C11ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11DDETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D1/00Detergent compositions based essentially on surface-active compounds; Use of these compounds as a detergent
    • C11D1/02Anionic compounds
    • C11D1/12Sulfonic acids or sulfuric acid esters; Salts thereof
    • CCHEMISTRY; METALLURGY
    • C11ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11DDETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D1/00Detergent compositions based essentially on surface-active compounds; Use of these compounds as a detergent
    • C11D1/02Anionic compounds
    • C11D1/12Sulfonic acids or sulfuric acid esters; Salts thereof
    • C11D1/123Sulfonic acids or sulfuric acid esters; Salts thereof derived from carboxylic acids, e.g. sulfosuccinates
    • CCHEMISTRY; METALLURGY
    • C11ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11DDETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D1/00Detergent compositions based essentially on surface-active compounds; Use of these compounds as a detergent
    • C11D1/88Ampholytes; Electroneutral compounds
    • C11D1/92Sulfobetaines ; Sulfitobetaines

Definitions

  • the present invention relates to a dishwashing composition for hand washing.
  • ⁇ Dishwashing agents for hand washing are required to have abundant foaming during washing and persistence of foam during washing.
  • This foamability / foam persistence is a very important physical property that has a correlation with the persistence of washing, and until now, the development of a detergent having excellent foamability / foam persistence has been mainly performed.
  • JP-A-62-215699 discloses a technique of a detergent suitable for dishwashing containing sulfosuccinate, having high foamability and excellent detergency.
  • JP 2008-507611 discloses a technique of a dishwashing composition containing a dialkyl sulfosuccinate and an amine oxide, and it is described in detail that a fatty acid can be contained as a builder.
  • JP-A-3-207799 describes that a fatty acid can be used as a foam inhibitor in a liquid detergent composition that can use a sulfosuccinic acid diester salt and an ethylene oxide condensate of a fatty alcohol as an anionic surfactant.
  • JP-A-3-33197 discloses a liquid or gel detergent composition that can use a dialkyl ester sulfosuccinate as an anionic surfactant, and further describes that it can contain betaine and / or an amine oxide. ing. JP 2008-506727 describes a hypoallergenic cleansing composition that contains a sulfosuccinic acid monoester salt and provides an excellent moisturizing and conditioning effect on the hair and skin.
  • Japanese Patent Application Laid-Open No. 2011-231310 distributed on November 17, 2011 discloses a dishwashing detergent composition for hand washing containing a sulfosuccinic acid di- or monoalkyl ester or a salt thereof, an anionic surfactant and a fatty acid or a salt thereof. Yes.
  • the present invention provides (a) a sulfosuccinic acid alkyl ester represented by the following general formula (1) or a salt thereof (hereinafter referred to as (a) component), (b) a hydrocarbon group having 8 to 21 carbon atoms, An anionic surfactant having a sulfate ester base or a sulfonate group (excluding (a)) [hereinafter referred to as component (b)] 5 to 35% by mass, and (c) a sulfobetaine type surfactant [ Hereinafter, it is related to the dishwashing composition for hand-washing containing (c) component].
  • R 1 and R 2 are each an alkyl group having 5 to 18 carbon atoms or a hydrogen atom, and at least one of R 1 and R 2 is an alkyl group having 5 to 18 carbon atoms. That is, the case where R 1 and R 2 are hydrogen atoms at the same time is excluded.
  • a 1 and A 2 are each independently an alkylene group having 2 to 4 carbon atoms, and x and y are average added mole numbers, and are each independently 0 to 6.
  • M 1 is a cation.
  • the present invention also relates to a tableware cleaning method in which tableware is washed by hand with a cleaning liquid using the dishwashing composition for handwashing of the present invention, and then rinsed with water.
  • Japanese Patent Application Laid-Open No. Sho 62-215699 Japanese Translation of PCT International Publication No. 2008-507611, Japanese Patent Application Laid-Open No. Hei 3-207799, and Japanese Patent Application Laid-Open No. 2008-506727 do not consider any bubble disappearance at the time of rinsing.
  • the fatty acid as an antifoaming agent which is listed as “Foaming Inhibitor” in JP-A-3-207799, is intended to make it low in foaming properties during cleaning. There is no suggestion of a relationship between the continuous formation of water and the technology of instant defoaming during rinsing.
  • JP-A-3-33197 there is no specific example using a sulfosuccinic acid alkyl ester, and there is an example using a carbobetaine type surfactant as a betaine, but a sulfobetaine type surfactant is used. No specific examples were given or suggested.
  • the present invention provides a dishwashing agent for hand washing that exhibits abundant foaming at the time of washing and the persistence of the foam at the time of washing, but the foam disappears instantaneously at the time of rinsing and the rinsing with a small amount of water is completed.
  • the component (a) of the present invention is a sulfosuccinic acid alkyl ester represented by the following general formula (1) or a salt thereof, preferably a sulfosuccinic acid di- or monoalkyl ester or a salt thereof.
  • R 1 and R 2 each have 5 to 18 carbon atoms, preferably 6 to 14 carbon atoms, more preferably 7 to 10 carbon atoms, 5 or more carbon atoms, preferably 6 or more carbon atoms, and further 7 or more carbon atoms, and It is an alkyl group or hydrogen atom having 18 or less, preferably 14 or less, and further 10 or less, and at least one of R 1 and R 2 is an alkyl group having 5 to 18 carbon atoms and 5 to 18 carbon atoms. That is, the case where R 1 and R 2 are hydrogen atoms at the same time is excluded.
  • a 1 and A 2 are each independently an alkylene group having 2 to 4 carbon atoms, preferably 2 to 3 carbon atoms, and 2 or more carbon atoms, and preferably 4 or less, preferably 3 or less, and x and y are the average number of moles added.
  • M 1 is a cation, preferably an inorganic or organic cation.
  • R 1 and R 2 in the general formula (1) may be the same or different, and the foamability at the time of washing and the foam at the time of rinsing
  • the number of carbons is 5 to 18, preferably 6 to 14, more preferably 7 to 10
  • the number of carbons is 5 or more, preferably 6 or more, further 7 or more, and 18 or less, preferably 14 or less.
  • it is an alkyl group of 10 or less, preferably an alkyl group having a branched structure.
  • one of R 1 and R 2 in the general formula (1) is a foaming property during washing and a foam disappearance property during rinsing.
  • the number of carbon atoms is 5 to 18, preferably 6 to 14, more preferably 7 to 10
  • the number of carbon atoms is 5 or more, preferably 6 or more, further 7 or more, and 18 or less, preferably 14 or less, further 10
  • the following are alkyl groups, and the other is a hydrogen atom.
  • R 1 and R 2 each have 5 to 18 carbon atoms, preferably 6 to 14 carbon atoms, more preferably 7 to 7 carbon atoms from the viewpoint of foaming properties during washing and foam disappearance properties during rinsing. 10 or more, preferably 6 or more, more preferably 7 or more, and 18 or less, preferably 14 or less, and further 10 or less, that is, the component (a) is a dialkyl ester of sulfosuccinic acid. Or it is preferable that it is the salt from a foaming power and a foam extinction viewpoint.
  • a 1 and A 2 are each independently 2 to 4, preferably 2 to 3, preferably 2 or more, and 4 or less, preferably 4 or less carbon atoms from the viewpoint of foaming properties during washing and foam disappearance properties during rinsing. Is an alkylene group of 3 or less.
  • x and y are the average number of moles added, and are each 0 to 6, preferably 0 to 3, more preferably 0 to 2, from the viewpoints of foamability during washing and foam extinction during rinsing. More preferably, it is 0 to 1, more than 0, and 6 or less, preferably 3 or less, further 2 or less, further 1 or less, and more preferably 0.
  • R 1 and R 2 are specifically hexyl, octyl, nonyl, decyl, dodecyl, tridecyl, 2-ethylhexyl, n-octyl, sec- An octyl group, an isopentyl group, an isononyl group, an isodecyl group, and a cyclohexyl group, and more preferably a group selected from an n-octyl group, a sec-octyl group, a decyl group, an isodecyl group, and a 2-ethylhexyl group. 2-ethylhexyl group is more preferable.
  • M 1 examples include inorganic cations selected from hydrogen ions, sodium ions, potassium ions, magnesium ions, and ammonium ions, organic cations selected from monoethanol ammonium ions, diethanol ammonium ions, and triethanol ammonium ions. Preferably, it is a cation selected from sodium ion, potassium ion, magnesium ion, and ammonium ion.
  • the preparation method of the compound in which R 1 and R 2 are the same is not particularly limited, but for example, US Pat. No. 2,028,091
  • a method for preparing an asymmetric compound having different R 1 and R 2 for example, it can be produced with reference to JP-A-58-24555.
  • PALEX OT-P a compound in which R 1 and R 2 are both 2-ethylhexyl groups
  • PELEX TR in which R 1 and R 2 are both tridecyl groups
  • LusitA-BO a compound in which R 1 and R 2 are both 2-ethylhexyl groups
  • aerosol AY-100 both R 1 and R 2 are amyl groups
  • the component (b) of the present invention is an anionic surfactant (except for the component (a)) having a hydrocarbon group having 8 to 21 carbon atoms and a sulfate ester group or a sulfonic acid group.
  • Such an anionic surfactant is known to be very excellent in foaming properties. More specifically, it has 8 to 18 carbon atoms, preferably 8 to 15 carbon atoms, and more than 8 carbon atoms.
  • an alkyl sulfate ester salt having an alkyl group of 18 or less, preferably 15 or less, an alkyl having 8 to 18 carbon atoms, preferably 8 to 15 carbon atoms, and having 8 or more carbon atoms, 18 or less, and further 15 or less alkyl.
  • the average added mole number of the oxyalkylene group having 2 to 3 carbon atoms is 0.1 to 6, preferably 0.3 to 3, more preferably 0.4 to 1.5, and more than 0.1 Further, 0.3 or more, further 0.4 or more, and 6 or less, further 3 or less, and further 1.5 or less polyoxyalkylene alkyl ether sulfate salt, alkylbenzene sulfone having an alkyl group having 8 to 15 carbon atoms Acid salt, Anionic surfactant selected from an alkane sulfonic acid salts having 8 to 15 carbon atoms in the beauty are preferred.
  • the salt an inorganic salt selected from sodium salts, potassium salts, magnesium salts, and ammonium salts, and organic amine salts selected from monoethanolamine salts, diethanolamine salts, and triethanolamine salts are preferable.
  • the compound represented by the following general formula (2) is preferable from the viewpoints of foamability at the time of washing, foam persistence, and foam extinction at the time of rinsing.
  • R 3 is an alkyl group having 8 to 18 carbon atoms, preferably 8 to 15 carbon atoms, and having 8 or more carbon atoms and 18 or less, and further 15 or less
  • R 4 is an ethylene group and / or A propylene group
  • n is an average number of moles added and is a number from 0 to 6, preferably from 0.1 to 2, more preferably from 0.3 to 1, and from 0 to 0.1 The number is further 0.3 or more, 6 or less, 2 or less, and 1 or less.
  • M 2 is a cation, preferably an inorganic or organic cation.
  • n is preferably 1.5 or less, more preferably 1 or less, and more preferably 0.3 or more, and even more preferably 0.5 or more. Further, n is preferably a number of 1.5 or less, more preferably 1 or less, and further 0.8 or less when R 4 is a propylene group, and 0.1 or more, further 0.3 or more, and further 0.4. The above number is preferred. When R 4 is an ethylene group or a propylene group, n can be selected from these ranges.
  • R 3 is preferably a compound containing an alkyl group having a branched structure.
  • the compound of the general formula (2) preferably has a branching ratio [ratio of the total number of moles of the compound having a branched alkyl group to the total number of moles of the compound of the general formula (2)]. 15 to 100 mol%, more preferably 40 to 100 mol%, still more preferably 70 to 100 mol%, 15 mol% or more, further 40 mol% or more, further 70 mol% or more, and 100 mol% or less Is preferred.
  • M 2 in the general formula (2) is an organic cation selected from an inorganic cation selected from sodium ion, potassium ion, magnesium ion and ammonium ion, monoethanolammonium ion, diethanolammonium ion and triethanolammonium ion.
  • they are sodium ion, potassium ion, and magnesium ion.
  • the method for preparing the compound of the general formula (2) is not particularly limited. For example, after a predetermined amount of ethylene oxide and / or propylene oxide is added to the fatty alcohol represented by R 3 —OH depending on the purpose. It is produced by sulfate formation with a sulfating agent selected from sulfur trioxide (liquid or gas), sulfur trioxide-containing gas, fuming sulfuric acid and chlorosulfonic acid, and neutralization with a predetermined alkali agent.
  • EO ethylene oxide
  • PO propylene oxide
  • an alkali hydroxide such as NaOH or KOH can be used.
  • a catalyst mainly composed of magnesium oxide described in JP-A-8-323200 can be used.
  • the former can obtain a polyoxyethylene alkyl ether having a relatively wide addition mole number distribution, and the latter is relatively narrow.
  • a compound having an addition mole number distribution can be obtained.
  • JP-A-10-158384 it is also possible to control the addition mole number distribution by using an alkali catalyst and a metal oxide catalyst in combination.
  • R 3 n are suitable in the case of 0 to obtain a compound containing an alkyl group having a branched structure in the general formula (2)
  • the alcohol represented by the raw material R 3 -OH carbon atoms from 8 to Alcohol obtained by hydroformylating 14 1-alkene (contains 15 to 70 mol% of an alkyl group having a methyl group branched at the ⁇ -position with respect to the OH group) and an aldehyde having 4 to 8 carbon atoms were condensed.
  • a gel-form alcohol obtained by reduction (containing 100 mol% of a structure in which an alkyl group having 3 to 6 carbon atoms is branched at the ⁇ -position relative to the OH group) and a dimer of isobutene are hydroformylated.
  • the obtained 3,5,5-trimethylhexanol and isobutene trimer are hydroformylated to obtain a multi-branched tridecanol (branching rate is 100 mol%), petroleum and coal.
  • Synthetic alcohol (branch index of about 20 to 100 mole% of the alkyl group) can be exemplified.
  • the component (b) is a compound represented by the general formula (2), wherein R 4 is a propylene group, n is 0.1 to 1.5, further 0.3 to 1, Compounds having a number of 0.4 to 0.8, 0.1 or more, further 0.3 or more, further 0.4 or more, 1.5 or less, further 1 or less, and further 0.8 or less are the most. preferable.
  • the sulfobetaine type surfactant as the component (c) is used as the surfactant having a foam increasing effect.
  • the sulfobetaine type surfactant improves the foamability / foam persistence at the time of washing, but does not impair the instant foam disappearance at the time of rinsing.
  • sulfobetaine surfactant examples include N-alkyl-N, N-dimethyl-N-sulfopropylammonium sulfobetaine having an alkyl group having 10 to 18 carbon atoms, N-alkyl-N, N-dimethyl-N- ( 2-hydroxysulfopropyl) ammonium sulfobetaine, N-alkanoylaminopropyl-N, N-dimethyl-N-sulfopropylammonium sulfobetaine having an alkanoyl group of 10 to 18 carbon atoms, N-alkanoylaminopropyl-N, N- Dimethyl-N- (2-hydroxysulfopropyl) ammonium sulfobetaine is preferred.
  • the dishwashing composition for hand-washing of the present invention is a relatively cleansing agent by combining the component (b) and the component (c) having foamability / foam persistence with the component (a) under specific conditions. In washing water with high concentration, it shows very high foaming and long-lasting foam. By adding rinsing water after washing, the foam disappears instantly and rinsing with a small amount of water can be completed. .
  • the component (a) is 1% by mass or more, preferably 2% by mass or more, more preferably 3% by mass or more, from the viewpoint of foaming power, foam disappearance and economy.
  • it is contained in an amount of 30% by mass or less, more preferably 25% by mass or less, further preferably 20% by mass or less, and still more preferably 15% by mass or less, for example, 1 to 30% by mass, further 3 to 25% by mass, 3 to 20% by mass, and further 3 to 15% by mass.
  • the dishwashing composition for hand-washing of this invention is 5 mass% or more, Preferably it is 7 mass% or more, More preferably, 9 mass from the viewpoint of foaming power, foam extinction property, and economical efficiency. % Or more, 35% by mass or less, preferably 20% by mass or less, more preferably 15% by mass or less, for example, 5 to 35% by mass, further 7 to 20% by mass, and further 9 to 15% by mass.
  • requiring mass%, mass ratio, etc. in this invention is the quantity as Na salt.
  • the dishwashing agent composition for hand-washing of this invention is 1 mass% or more from the viewpoint of foaming power, foam extinction property, and economical efficiency, More preferably, it is 2 mass% or more, More preferably, it is 3 More than 20% by mass, more preferably not more than 20% by mass, more preferably not more than 14% by mass, still more preferably not more than 12% by mass, for example, 1 to 20% by mass, further 2 to 14% by mass, further 3 to 12% by mass To do.
  • the dishwashing composition for hand-washing of the present invention preferably contains 1 to 30% by mass, more preferably 3 to 25% by mass of component (a) from the viewpoints of foaming power, foam disappearance and economy.
  • the component (b) is contained in an amount of 5 to 35% by mass, preferably 7 to 20% by mass, more preferably 9 to 15% by mass.
  • requiring mass%, mass ratio, etc. in this invention is the quantity as Na salt.
  • the content of the component (c) is preferably 1 to 20% by mass, more preferably 2 to 14% by mass, and further preferably 3 to 12% by mass in the composition.
  • the mass ratio of the component (a) / the component (b) is preferably 0.03 to 2.5, more preferably from the viewpoint of foaming power and foam extinction. Is 0.15 to 2, more preferably 0.2 to 1.5, even more preferably 0.25 to 1, and preferably 0.03 or more, more preferably 0.15 or more, further 0.2 or more, and further 0.25 or more, and preferably 2.5 or less, further 2 or less, further 1.5 or less, and further 1 or less.
  • the mass ratio of component (b) / component (c) is preferably 0.3 to 6, more preferably 0.5 to 5, still more preferably 1 to 4, still more preferably 1.5 to 3, , Preferably 0.3 or more, further 0.5 or more, further 1 or more, further 1.5 or more, and preferably 6 or less, further 5 or less, further 4 or less, further 3 or less.
  • the mass ratio of the component (c) is preferably 0.1 to 5, more preferably 0.3 to 2.6, still more preferably 0.6 to 2.3, still more preferably 0.6 to 1.8, Further, it is preferably 0.1 or more, further 0.3 or more, further 0.6 or more, and preferably 5 or less, further 2.6 or less, further 2.3 or less, and further 1.8 or less.
  • the mass ratio of (c) component / [(a) component + (b) component] is preferably 0.02 to 2, more preferably 0.1 to 2. 1.5, more preferably 0.15 to 1, still more preferably 0.15 to 0.5, preferably 0.02 or more, further 0.1 or more, further 0.15 or more, and preferably It is preferably 2 or less, further 1.5 or less, further 1 or less, and further 0.5 or less from the viewpoint of improvement in foamability / foam persistence during washing and foam extinction during rinsing.
  • the total mass of the component (a), the component (b), and the component (c) with respect to the total surfactant content in the composition is 50 to 100% by mass, more preferably 60 to 100% by mass, and further 80 to 100% by mass, further 90-100% by mass, 50% by mass or more, further 60% by mass or more, further 80% by mass or more, further 90% by mass or more, and 100% by mass or less And from the viewpoint of foam extinction.
  • the dishwashing composition for hand washing of the present invention has a magnesium-containing inorganic compound and / or an alkylenediamine compound (the alkylene group has a carbon number as component (d) for the purpose of enhancing the emulsifying power against oil stains and enhancing the cleaning power.
  • 2-6 preferably containing a magnesium-containing inorganic compound.
  • These compounds interact relatively weakly with at least two molecules of the effect necessary for the present invention, ie, component (a), component (b), and other anionic surfactants optionally contained to form a complex. And has a common effect / action mechanism as a compound that improves the surface activity such as emulsifying power.
  • magnesium-containing inorganic compound examples include magnesium chloride such as magnesium chloride, magnesium salts such as magnesium sulfate and magnesium nitrate, magnesium hydroxide, magnesium oxide, and the like, more preferably a compound selected from magnesium chloride and magnesium sulfate. Even more preferred is magnesium chloride.
  • magnesium chloride such as magnesium chloride
  • magnesium salts such as magnesium sulfate and magnesium nitrate
  • magnesium hydroxide magnesium oxide
  • magnesium oxide magnesium oxide
  • magnesium chloride Even more preferred is magnesium chloride.
  • alkylene diamine compound ethylene diamine, propylene diamine, hexylene diamine and cyclohexane diamine are preferable, but cyclohexane diamine is more preferable.
  • the content of the component (d) in the composition is 0.5 to 20% by mass, further 0.5 to 15% by mass, further 0.5 to 10% by mass, 0.5% by mass or more, 0.5 mass% or more and 20 mass% or less, 15 mass% or less, Furthermore 10 mass% or less are preferable.
  • these (d) components may contain crystal water, content shown here is the mass except crystal water.
  • an inorganic compound other than the component (d) may be used in combination with the component (d).
  • inorganic compounds include sodium chloride, potassium chloride, sodium iodide, potassium iodide, sodium sulfate, potassium sulfate, alum and the like.
  • the behavior of bubbles during washing and rinsing is very important.
  • a surfactant having a foam increasing effect is used in consideration of foaming property / sustainability of foaming at the time of washing.
  • the surfactant having the effect of increasing the foam has a great influence on the foam disappearance at the time of rinsing.
  • the component (e) attention should be paid to the handling of a surfactant selected from amine oxide surfactants, carbobetaine surfactants and alkanolamide surfactants.
  • carbobetaine surfactants include N-alkanoylaminopropyl-N, N-dimethyl-N-carboxymethylammonium betaine and N-alkyl-N, N-dimethyl-N-carboxymethylammonium betaine.
  • alkanolamide surfactant include amidated products of alkanolamines such as monoethanolamine, diethanolamine, and methylmonoethanolamine with fatty acids such as lauric acid and myristic acid.
  • the behavior of foam is very important. Care must be taken in using the component (e) which gives the composition a foam-enhancing effect, and the content of the component (e) in the composition is preferably 5% by mass or less, more preferably 3% by mass or less, further preferably 2% by mass or less, still more preferably 1% by mass or less, still more preferably 0.5% by mass or less, and most preferably not contained. is there.
  • the hand dishwashing detergent composition of the present invention may contain a fatty acid having 10 to 18 carbon atoms or a salt thereof as the component (f) for the purpose of improving rinsing properties.
  • a fatty acid having 10 to 18 carbon atoms or a salt thereof for the purpose of improving rinsing properties.
  • Specific examples include decanoic acid, lauric acid, myristic acid, palmitic acid, palmitoleic acid, stearic acid, oleic acid, linoleic acid, linolenic acid, and salts thereof.
  • mixed fatty acids such as an insulator composition fatty acid.
  • Fatty acid salts include inorganic salts selected from sodium, potassium, magnesium, and ammonium salts, and organic amine salts such as monoethanolamine, diethanolamine, and triethanolamine, preferably sodium and potassium.
  • the component (f) is more preferably lauric acid, myristic acid, palmitic acid or a salt thereof, still more preferably lauric acid, myristic acid or a salt thereof, most preferably myristic acid or a salt thereof. is there. Therefore, from the viewpoint of foaming ability and foam extinction, the component (f) preferably contains myristic acid or a salt thereof, and the proportion of myristic acid or a salt thereof in the component (f) is 20 to 100% by mass, 50 to 100% by mass, further 80 to 100% by mass, 20% by mass or more, further 50% by mass or more, further 80% by mass or more, and 100% by mass or less, and more preferably 100% by mass are preferable.
  • the content of the component (f) is preferably 3% by mass or less, further 2% by mass or less, further 1% by mass or less, further 0.5% by mass or less, and further preferably 0.3% by mass or less in the composition. Mass% is also preferred.
  • the dishwashing composition for hand-washing of the present invention is instantly free of moisture when rinsed and can be rinsed with a small amount of water, and as a component (g), alkyl glyceryl ether (the carbon number of the alkyl group is 6). -18, preferably 8-12, and preferably 6 or more, more preferably 8 or more, and 18 or less, more preferably 12 or less.
  • the compound of the following general formula (3) is suitable.
  • R 5 O— (Gly) r —H (3)
  • R 5 represents an alkyl group having 6 to 18 carbon atoms
  • Gly represents a residue obtained by removing two hydrogen atoms from glycerin
  • r represents a number of 1 to 4 in terms of the average number of moles added.
  • R 5 has 6 to 18 carbon atoms, preferably 7 to 12, more preferably 8 to 10 carbon atoms, 6 or more, further 7 or more, further 8 or more, and 18 or less
  • the alkyl group is 12 or less, and further 10 or less, and linear alkyl groups such as hexyl group, heptyl group, octyl group, nonyl group, and decyl group can be used. Therefore, a compound having a branched structure is preferable, and a specific alkyl group having a branched structure of R 5 is more preferably a group selected from 2-ethylhexyl group, sec-octyl group, isononyl group and isodecyl group.
  • the structure represented by Gly is a structure represented by —CH 2 CH (OH) CH 2 — in which the 1- and 3-position hydroxy groups of glycerin are bonded, or the 1- and 2-position hydroxy groups of glycerin are bonded.
  • This is a structure represented by —CH (CH 2 OH) CH 2 —, which varies depending on the catalyst and reaction conditions.
  • an alkyl alcohol represented by R 5 —OH is used as an alcohol having 6 to 10 carbon atoms
  • an epoxy compound such as epihalohydrin or glycidol is reacted with an acid catalyst such as BF 3
  • an acid catalyst such as BF 3
  • the method of manufacturing by making it react using an aluminum catalyst can be used.
  • the resulting 2-ethylhexyl monoglyceryl ether is a mixture that can contain a plurality of products as described in JP-A-2001-49291.
  • the content of the component (g) in the composition is 0.5 to 20% by mass, further 1 to 15% by mass, further 1.5 to 10% by mass, 0.5% by mass or more, and further 1% by mass. % Or more, further 1.5 mass% or more, 20 mass% or less, further 15 mass% or less, and further preferably 10 mass% or less.
  • the dishwashing composition for hand washing of the present invention is a nonionic surfactant [(g in the range which does not impair the rinsing property for the purpose of improving storage stability, foaming property at the time of washing, and washing performance. ) Except those corresponding to the component] [hereinafter referred to as the component (h)] may be used.
  • nonionic surface activity such as polyoxyalkylene sorbitan fatty acid ester, polyoxyalkylene fatty acid ester, polyoxyalkylene alkyl ether, polyoxyalkylene alkyl phenyl ether, sucrose fatty acid ester, sorbitan fatty acid ester, alkyl glycoside
  • an agent can be mentioned. Of these, polyoxyalkylene alkyl ethers and / or alkyl glycosides are preferred.
  • the content of the component (h) is preferably 1 to 20% by mass, more preferably 1.5 to 15% by mass, further preferably 2 to 10% by mass, and preferably 1% by mass or more in the composition. Further, it is 1.5% by mass or more, further 2% by mass or more, and preferably 20% by mass or less, further 15% by mass or less, and further 10% by mass or less.
  • the hand dishwashing detergent composition of the present invention preferably contains a hydrotrope [hereinafter referred to as component (i)] for the purpose of improving storage stability.
  • a hydrotrope hereinafter referred to as component (i)
  • toluenesulfonic acid, xylenesulfonic acid, cumenesulfonic acid or a sodium, potassium or magnesium salt thereof is preferable, and p-toluenesulfonic acid or a salt thereof is more preferable.
  • the content of the component (i) is 0.5 to 20% by mass, more preferably 1 to 15% by mass, further preferably 1.5 to 10% by mass, 0.5% by mass or more, and further 1% by mass. As mentioned above, it is 1.5 mass% or more and 20 mass% or less, 15 mass% or less, and also 10 mass% or less.
  • the dishwashing composition for hand washing of the present invention can contain a solvent (hereinafter referred to as component (j)) for the purpose of improving storage stability and adjusting viscosity.
  • a solvent hereinafter referred to as component (j)
  • the solvent include ethanol, isopropyl alcohol, ethylene glycol, propylene glycol, diethylene glycol, dipropylene glycol, glycerin, isoprene glycol, propylene glycol monomethyl ether, propylene glycol monoethyl ether, 3-methyl-3-methoxybutanol,
  • a water-soluble organic solvent selected from phenoxyethanol, phenyl glycol, phenoxyisopropanol, butyl diglycol (diethylene glycol monobutyl ether), dibutylene glycol, and benzyl alcohol is preferred.
  • the water-soluble organic solvent refers to a solvent having an octanol / water partition coefficient (LogPow) of 3.5 or less.
  • the content of the component (j) is preferably 1.5 to 30% by mass, more preferably 2 to 20% by mass, further preferably 3 to 15% by mass, and preferably 1.5% by mass in the composition.
  • the content is further 2% by mass or more, further 3% by mass or more, and preferably 30% by mass or less, further 20% by mass or less, and further 15% by mass or less.
  • the dishwashing detergent composition for hand-washing of the present invention includes a polymer for preventing gelation (hereinafter referred to as component (k)), for example, a gelation-preventing polymer described in JP-A-11-513067, It is preferable to blend polyalkylene glycol from the viewpoint of viscosity control and storage stability.
  • component (k) a polymer for preventing gelation
  • Specific examples of the polyalkylene glycol as a polymer for preventing gelation include polypropylene glycol having a weight average molecular weight of 200 to 3,000 determined by gel permeation chromatography using polyethylene glycol as a standard, and Examples thereof include polyethylene glycol having a weight average molecular weight of 200 to 3,000.
  • the content of the component (k) in the composition is preferably 0.05 to 10% by mass, more preferably 0.1 to 5% by mass, still more preferably 0.5 to 3% by mass, and preferably 0%. 0.05% by mass or more, further 0.1% by mass or more, further 0.5% by mass or more, and preferably 10% by mass or less, further 5% by mass or less, and further 3% by mass or less.
  • the hand dishwashing detergent composition of the present invention is preferably in the form of a liquid composition in which the above components are dissolved / dispersed / emulsified in water, and more preferably an aqueous solution.
  • a liquid composition in which the above components are dissolved / dispersed / emulsified in water, and more preferably an aqueous solution.
  • water to be used deionized water, distilled water, or hypochlorous acid sterilized water in which about 0.5 to 10 ppm of hypochlorous acid is dissolved can be used.
  • the pH of the dishwashing detergent composition for hand washing of the present invention at 25 ° C. is preferably 4 to 9, more preferably 4.5 to 7, and more preferably 5 to 6. From the viewpoint of low temperature stability, it is preferably 4 or more, more preferably 4.5 or more, more preferably 5 or more. On the other hand, from the viewpoint of detergency, it is preferably 10 or less, more preferably 9 or less, more preferably 8 or less, and more preferably 7 or less.
  • Such adjustment to pH is carried out by inorganic acid selected from sulfuric acid, hydrochloric acid and phosphoric acid, organic acid selected from citric acid, malic acid, maleic acid, fumaric acid and succinic acid, sodium hydroxide, potassium hydroxide, water It is carried out using an inorganic alkaline agent such as magnesium oxide, sodium carbonate or potassium carbonate.
  • inorganic acid selected from sulfuric acid, hydrochloric acid and phosphoric acid
  • organic acid selected from citric acid, malic acid, maleic acid, fumaric acid and succinic acid
  • sodium hydroxide sodium carbonate or potassium carbonate
  • an inorganic alkaline agent such as magnesium oxide, sodium carbonate or potassium carbonate.
  • the composition has a buffering ability from the viewpoint of foamability / foam persistence, and it is preferable to use the organic acid, preferably citric acid, and an inorganic alkaline agent in combination.
  • the organic acid may be added to the composition in the form of sodium salt or potassium salt.
  • component (d)
  • the viscosity at 20 ° C. of the dishwashing composition for hand washing of the present invention is preferably 5 to 15,000 mPa ⁇ s, more preferably 5 to 8,000 mPa ⁇ s, still more preferably 5 to 2,000 mPa ⁇ s, and further Preferably 5 to 500 mPa ⁇ s, more preferably 10 to 300 mPa ⁇ s, more preferably 5 mPa ⁇ s or more, further 10 mPa ⁇ s or more, and preferably 15,000 mPa ⁇ s or less, and further 8,000 mPa ⁇ s.
  • the viscosity can be adjusted by the component (i), the component (j), the component (k), and the like.
  • the dishwashing composition for hand washing of the present invention can contain components such as fragrances, dyes and pigments.
  • the dishwashing composition for handwashing of the present invention is used for handwashing dishes.
  • the cleaning liquid used for hand-washing is obtained using the dishwashing detergent composition for hand-washing of the present invention, and a stock solution of the composition or a diluted solution containing water is used.
  • the tableware is washed with water after washing the tableware with a flexible material to which a cleaning liquid using the dishwashing composition for hand-washing of the present invention is attached, and washing with tableware.
  • a method is mentioned.
  • the composition of the present invention is adhered to a flexible material such as a sponge containing water to hold the cleaning liquid, and the foam is rubbed by hand several times to rub the dishes.
  • the total concentration of the component (a), the component (b), and the component (c) in the cleaning liquid retained by the flexible material is preferably 1,000 to 30,000 ppm, more preferably 1,000 to 20,000 ppm. More preferably, it is 2,000 to 10,000 ppm, preferably 1,000 ppm or more, more preferably 2,000 ppm or more, and preferably 30,000 ppm or less, further 20,000 ppm or less, further 10,000 ppm or less.
  • water is added to perform rinsing.
  • the foam disappears sufficiently with 3.3 to 133 parts by mass of rinsing water with respect to 1 part by mass of the composition diluted to the washing concentration.
  • the amount of the rinsing water is about 2/3 to 1/10 when the conventional detergent composition for hand washing is used.
  • 1 part by mass of the composition indicates the concentration of the pure composition, and the above description regarding the amount of rinsing water is the washing of dishes for hand washing used in the preparation of the cleaning liquid regardless of the diluted concentration. It is shown that the foam disappears sufficiently when 3.3 to 133 parts by mass of rinsing water with respect to 1 part by mass of the pure composition is used.
  • the tableware is immersed in a washing solution obtained by diluting the dishwashing composition for hand washing of the present invention with water, and then the dishes are washed by hand using a flexible material such as a sponge. Then, the washing
  • the time for immersing the tableware is preferably 1 minute or more, more preferably 3 minutes or more, further preferably 5 minutes or more, still more preferably 10 minutes or more, most preferably 30 minutes or more, from the viewpoint of improving the cleanability. It is preferably 24 hours or less, more preferably 12 hours or less, still more preferably 6 hours or less, still more preferably 3 hours or less, and most preferably 1 hour or less.
  • the total concentration of component (a), component (b), and component (c) in the cleaning liquid in which the tableware is immersed is preferably 100 ppm or more, more preferably 200 ppm or more, and preferably 3,000 ppm or less, further 2,000 ppm or less. Further, it is preferably 1,000 ppm or less from the viewpoint of high foamability and foam persistence.
  • water is added to perform rinsing. For example, in the present invention, 3.3 to 133 parts by mass of rinsing water is sufficiently foamed with respect to 1 part by mass of the dishwashing composition for hand washing used for the preparation of the washing liquid. Disappears and rinsing can be completed quickly.
  • Embodiments of the present invention are exemplified below.
  • ⁇ 1> (a) A sulfosuccinic acid alkyl ester represented by the following general formula (1) or a salt thereof, preferably a sulfosuccinic acid dialkyl ester or a salt thereof, (b) a hydrocarbon group having 8 to 21 carbon atoms and sulfuric acid An anionic surfactant having an ester base or a sulfonate group (excluding (a)), 5 to 35% by mass, preferably 7 to 20% by mass, more preferably 9 to 15% by mass, and (c) sulfone A dishwashing composition for hand washing containing a betaine-type surfactant.
  • R 1 and R 2 are each an alkyl group having 5 to 18 carbon atoms, preferably 6 to 14 carbon atoms, more preferably 7 to 10 carbon atoms, preferably a branched alkyl group or a hydrogen atom, preferably 2 -Ethylhexyl group, and at least one of R 1 and R 2 is an alkyl group having 5 to 18 carbon atoms. That is, the case where R 1 and R 2 are hydrogen atoms at the same time is excluded.
  • a 1 and A 2 are each independently an alkylene group having 2 to 4 carbon atoms, preferably 2 to 3 carbon atoms, x and y are average added mole numbers, and are each independently 0 to 6, preferably 0 to 3, more preferably 0 to 2, more preferably 0 to 1, more preferably 0.
  • M 1 is a cation, preferably an organic or organic cation.
  • the tableware for hand-washing according to ⁇ 1> further comprising (d) a magnesium-containing inorganic compound and / or an alkylenediamine (the alkylene group has 2 to 6 carbon atoms), preferably a compound selected from magnesium chloride and magnesium sulfate. Cleaning composition.
  • ⁇ 4> (b) is an alkyl sulfate ester salt having an alkyl group having 8 to 18 carbon atoms, and an average addition mole number of an oxyalkylene group having 2 to 3 carbon atoms having an alkyl group having 8 to 18 carbon atoms is 0 1.
  • Polyoxyalkylene alkyl ether sulfates having 1 to 6, further 0.3 to 3, and further 0.4 to 1.5, alkylbenzene sulfonates having an alkyl group having 8 to 15 carbon atoms, and 10 carbon atoms
  • the dishwashing detergent composition for hand washing according to any one of ⁇ 1> to ⁇ 3>, which is an anionic surfactant selected from 15 alkane sulfonates.
  • the dishwashing detergent composition for hand washing according to any one of ⁇ 1> to ⁇ 4>, wherein the component (b) is a compound of the following general formula (2).
  • R 3 is an alkyl group having 8 to 18 carbon atoms, preferably 8 to 15 carbon atoms
  • R 4 is an ethylene group and / or a propylene group
  • n is an average addition mole number of 0 to 6 It is the following number, preferably 0.1 or more and 2 or less.
  • M 2 is a cation, preferably an inorganic or organic cation.
  • the total mass of (a), (b), and (c) with respect to the total surfactant content in the composition is 50 to 100 mass%, further 60 to 100 mass%, and further 80 to 100 mass%.
  • a fatty acid having 10 to 18 carbon atoms or a salt thereof in the composition is 3% by mass or less, further 2% by mass or less, further 1% by mass or less, and further 0.5% by mass or less.
  • the dishwashing composition for hand washing according to any one of ⁇ 1> to ⁇ 7>, wherein the component (a) is a sulfosuccinic acid dialkyl ester or a salt thereof.
  • Component (a) is 1% by mass or more, preferably 2% by mass or more, more preferably 3% by mass or more, and 30% by mass or less, more preferably 25% by mass or less, and further preferably 20% by mass or less. More preferably, the dishwashing composition for hand washing according to any one of ⁇ 1> to ⁇ 8>, which is contained in an amount of 15% by mass or less.
  • Component (b) is contained in an amount of 5% by mass or more, preferably 7% by mass or more, more preferably 9% by mass or more, and 35% by mass or less, preferably 20% by mass or less, more preferably 15% by mass or less.
  • Component (b) is contained in an amount of 5% by mass or more, preferably 7% by mass or more, more preferably 9% by mass or more, and 35% by mass or less, preferably 20% by mass or less, more preferably 15% by mass or less.
  • the component (c) is 1% by mass or more, more preferably 2% by mass or more, further preferably 3% by mass or more, 20% by mass or less, more preferably 14% by mass or less, and further preferably 12% by mass.
  • the mass ratio of (a) component / (b) component is 0.03 or more, preferably 0.15 or more, more preferably 0.2 or more, still more preferably 0.25 or more, and 2.5 or less.
  • the dishwashing composition for hand washing according to any one of ⁇ 1> to ⁇ 11>, preferably 2 or less, more preferably 1.5 or less, and even more preferably 1 or less.
  • the mass ratio of component (b) / component (c) is 0.3 or more, more preferably 0.5 or more, still more preferably 1 or more, still more preferably 1.5 or more, and 6 or less.
  • the dishwashing composition for hand washing according to any one of ⁇ 1> to ⁇ 12>, preferably 5 or less, more preferably 4 or less, and even more preferably 3 or less.
  • the mass ratio of (a) component / (c) component is 0.1 or more, preferably 0.3 or more, more preferably 0.6 or more, and 5 or less, preferably 3 or less, more preferably 2
  • the mass ratio of (c) component / [(a) component + (b) component] is 0.02 or more, more preferably 0.1 or more, still more preferably 0.15 or more, or 2 or less.
  • the pH at 25 ° C. is 4 or more, more preferably 4.5 or more, more preferably 5 or more, and 9 or less, more preferably 7 or less, more preferably 6 or less, ⁇ 1>
  • the viscosity at 20 ° C. is 5 mPa ⁇ s or more, more preferably 10 mPa ⁇ s or more, 15,000 mPa ⁇ s or less, more preferably 8,000 mPa ⁇ s or less, and still more preferably 2,000 mPa ⁇ s or less. More preferably, the dishwashing composition for hand washing according to any one of ⁇ 1> to ⁇ 16>, which is more preferably 500 mPa ⁇ s or less, and most preferably 300 mPa ⁇ s or less.
  • alkyl glyceryl ether (the alkyl group has 6 to 18, preferably 8 to 12 carbon atoms) in the composition is 0.5% by mass or more, and further 1% by mass or more.
  • Composition is 0.5% by mass or more, and further 1% by mass or more.
  • a hydrotrope agent is 0.5% by mass or more, more preferably 1% by mass or more, still more preferably 1.5% by mass or more, and 20% by mass in the composition.
  • a solvent is added to the composition in an amount of 1.5% by mass or more, more preferably 2% by mass or more, still more preferably 3% by mass or more, and more preferably 30% by mass or less.
  • component (k) one or two types selected from polymers, preferably polypropylene glycol having a weight average molecular weight of 200 to 3,000, and polyethylene glycol having a weight average molecular weight of 200 to 3,000.
  • the above polymer in the composition is 0.05% by mass or more, more preferably 0.1% by mass or more, further preferably 0.5% by mass or more, and 10% by mass or less, more preferably 5% by mass.
  • the hand dishwashing detergent composition according to any one of ⁇ 1> to ⁇ 20>, further preferably 3% by mass or less.
  • ⁇ 22> A method for washing dishes, wherein the dishes are washed with a washing solution using the dishwashing composition for washing hands according to any one of ⁇ 1> to ⁇ 21>, and then rinsed with water.
  • a tableware cleaning method to be performed wherein the total concentration of the component (a), the component (b), and the component (c) in the cleaning liquid retained by the flexible material is preferably 1,000 ppm or more, and 3,000 ppm or more, and preferably 30,000 ppm or less, further 20,000 ppm or less, and further 10,000 ppm or less, and from 3.3 parts by weight of water to 1 part by weight of the dishwashing composition for hand washing used in the preparation of the cleaning liquid.
  • cleaning method of the tableware which performs a rinse using 133 mass parts.
  • a method for washing tableware in which rinsing is performed using water, and the time for immersing the tableware is preferably 1 minute or more, more preferably 3 minutes or more, still more preferably 5 minutes or more, and even more preferably 10 minutes or more. Most preferably 30 minutes or longer, and preferably 24 hours or shorter, more preferably 12 hours or shorter, still more preferably 6 hours or shorter, even more preferably 3 hours or shorter, most preferably 1 hour or shorter.
  • the total concentration of the component (a), the component (b), and the component (c) in the cleaning solution for immersing the liquid is preferably 100 ppm or more, more preferably 200 ppm or more, and preferably 3,000 ppm or less, and further 2 000ppm or less, still more 1,000ppm or less, perform rinsing with water from 3.3 to 133 parts by weight with respect to 1 part by weight hand dishwashing detergent composition used to prepare the cleaning solution, tableware cleaning method.
  • Table 1 and the following blending components were used to prepare the hand-washing dishwashing composition of Table 1, and the following evaluations were made. The results are shown in Table 1. In addition, all the mass% of the mixing
  • A-1 Sodium di-2-ethylhexyl sulfosuccinate (Kanto Chemical Co., Inc.)
  • A-2 dipolyoxyethylene-2-ethylhexyl sodium sulfosuccinate: the one obtained by esterification reaction of sulfosuccinic acid and polyoxyethylene-2-ethylhexyl ether was used.
  • Polyoxyethylene-2-ethylhexyl ether was obtained by adding 1 mol of ethylene oxide to 1 mol of 2-ethylhexanol.
  • B-1 sodium lauryl sulfate b-2: 1 mol of EO is added to 1 mol of natural alcohol having an alkyl chain of 12 carbons, then sulfated with sulfur trioxide, and pH is adjusted with an aqueous sodium hydroxide solution.
  • B-3 1 mol of a natural alcohol having 12 carbon atoms added with an average of 0.6 mol of PO, then sulfated with sulfur trioxide and diluted with an aqueous sodium hydroxide solution simultaneously with pH adjustment (10 The pH of the mass% aqueous solution is 11)
  • B-4 linear / branched mixed alcohol [Isalchem 123 (containing 12 alkyl groups and 13 alkyl groups, branching rate: 94 mol%) manufactured by Sasol, sulfuric acid with sulfur trioxide Compound neutralized with sodium hydroxide (average molecular weight: 295)
  • C-1 N-lauryl-N, N-dimethyl-N- (2-hydroxysulfopropyl) ammonium sulfobetaine (manufactured by Kao Corporation: Amphitol 20HD)
  • C′-1 N-lauroylaminopropyl-N, N-dimethyl-N-carboxymethylammonium betaine (manufactured by Kao Corporation: Amphital 20AB)
  • D-1 MgCl 2 .6H 2 O (magnesium chloride hexahydrate), hexahydrate was used for blending, but the numerical values in Table 1 are shown in blending amounts excluding crystallization water.
  • E-1 N-lauryl-N, N-dimethylamine oxide (manufactured by Kao Corporation: Amphitol 20N)
  • the dishwashing composition of Table 1 was diluted to 3.5% by mass with 3.5 ° DH hard water and filled into a pump former container described in FIG. 1 of JP-A-2008-260852.
  • a single mesh having a mesh size of 200 / inch was attached to the foam discharge mechanism.
  • 3 g of foam was produced in a 500 ml graduated cylinder by continuously pushing out the pump head at the top of the container for 3 pushes. Note that the speed of pushing out was 1 second per push.
  • the volume was recorded from the scale of the graduated cylinder and used as the initial amount of foam. Foaming property was evaluated by this initial foam amount.
  • FIG. 1 shows how hard water is added to the graduated cylinder.
  • 1 is a graduated cylinder
  • 2 is foam
  • 3 is a hard water introduction means (manufactured by hand)
  • 4 is an opening of the introduction means
  • FIG. 2 is a perforation of the opening 4 of the hard water introduction means 3.
  • a method for producing a handmade water fountain as means for introducing hard water is as follows. First, from the bottom of a 250 ml polypropylene wide-mouthed bottle (manufactured by ASONE: I-boy wide-mouthed bottle) to the main body part having a height of about one third was excised. Next, as shown in FIG.
  • a polyethylene perforated plate having 13 holes with a diameter of 2 mm at 9 mm intervals was prepared for a thin circular polyethylene plate with a diameter of 4 cm.
  • the polyethylene perforated plate was fixed as the opening 4 to the lid opening (diameter 4 cm) at the top of the excised wide-mouth bottle to produce hard water introducing means 3 (handmade watering device).
  • the hard water introducing means 3 manufactured by hand

Landscapes

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

Abstract

The present invention is a composition for a dishwashing liquid for cleaning hands, containing: (a) a specified sulfosuccinate di- or monoalkyl ester or salt of the same; (b) a hydrocarbon base with a carbon number from 8 to 21, and 5 to 35 mass percent of an anion surfactant having a sulfate base or a sulfonate base (excluding (a)): and (c) a sulfobetaine-type surfactant.

Description

手洗い用食器洗浄剤組成物Dishwashing composition for hand washing
 本発明は、手洗い用食器洗浄剤組成物に関する。
背景技術
The present invention relates to a dishwashing composition for hand washing.
Background art
 手洗い用食器洗浄剤には、洗浄時に豊かな泡立ちと洗浄時の泡の持続性が求められる。この起泡性/泡持続性は洗浄持続性との相関がある非常に重要な物性であり、これまで起泡性/泡持続性に優れる洗浄剤の開発が主に行われてきた。 ¡Dishwashing agents for hand washing are required to have abundant foaming during washing and persistence of foam during washing. This foamability / foam persistence is a very important physical property that has a correlation with the persistence of washing, and until now, the development of a detergent having excellent foamability / foam persistence has been mainly performed.
 特開昭62-215699には、スルホスクシネートを含有し、起泡性が高く洗浄力に優れた食器洗浄用に好適な洗浄剤の技術が開示されている。また、特表2008-507611にはジアルキルスルホスクシネートとアミンオキシド類を含有する食器洗浄剤組成物の技術が開示され、ビルダーとして脂肪酸を含有し得ることが詳細な説明に記載されている。 特開平3-207799には、陰イオン界面活性剤としてスルホコハク酸ジエステル塩と脂肪アルコールのエチレンオキシド縮合物を使用し得る液体洗剤組成物の起泡抑制剤として脂肪酸を使用できることが記載されている。特開平3-33197には、陰イオン界面活性剤としてスルホコハク酸ジアルキルエステル塩を使用し得る液状又はゲル状の洗剤組成物が開示され、更にベタイン及び/又はアミンオキシドを含有し得ることが記載されている。特表2008-506727には、スルホコハク酸モノエステル塩を含有し、頭髪および皮膚に優れた湿潤効果およびコンデショニング効果を与える低刺激性クレンジング組成物が記載されている。 JP-A-62-215699 discloses a technique of a detergent suitable for dishwashing containing sulfosuccinate, having high foamability and excellent detergency. JP 2008-507611 discloses a technique of a dishwashing composition containing a dialkyl sulfosuccinate and an amine oxide, and it is described in detail that a fatty acid can be contained as a builder. JP-A-3-207799 describes that a fatty acid can be used as a foam inhibitor in a liquid detergent composition that can use a sulfosuccinic acid diester salt and an ethylene oxide condensate of a fatty alcohol as an anionic surfactant. JP-A-3-33197 discloses a liquid or gel detergent composition that can use a dialkyl ester sulfosuccinate as an anionic surfactant, and further describes that it can contain betaine and / or an amine oxide. ing. JP 2008-506727 describes a hypoallergenic cleansing composition that contains a sulfosuccinic acid monoester salt and provides an excellent moisturizing and conditioning effect on the hair and skin.
 2011年11月17日頒布された特開2011-231310はスルホコハク酸ジ又はモノアルキルエステル又はその塩、陰イオン界面活性剤と脂肪酸又はその塩を含有する手洗い用食器洗浄剤組成物を開示している。 Japanese Patent Application Laid-Open No. 2011-231310 distributed on November 17, 2011 discloses a dishwashing detergent composition for hand washing containing a sulfosuccinic acid di- or monoalkyl ester or a salt thereof, an anionic surfactant and a fatty acid or a salt thereof. Yes.
発明の要約
 本発明は、(a)下記一般式(1)で表されるスルホコハク酸アルキルエステル又はその塩〔以下、(a)成分という〕、(b)炭素数8~21の炭化水素基と、硫酸エステル塩基又はスルホン酸塩基とを有する陰イオン界面活性剤〔但し(a)を除く〕〔以下、(b)成分という〕5~35質量%、及び(c)スルホベタイン型界面活性剤〔以下、(c)成分という〕を含有する手洗い用食器洗浄剤組成物に関する。
SUMMARY OF THE INVENTION The present invention provides (a) a sulfosuccinic acid alkyl ester represented by the following general formula (1) or a salt thereof (hereinafter referred to as (a) component), (b) a hydrocarbon group having 8 to 21 carbon atoms, An anionic surfactant having a sulfate ester base or a sulfonate group (excluding (a)) [hereinafter referred to as component (b)] 5 to 35% by mass, and (c) a sulfobetaine type surfactant [ Hereinafter, it is related to the dishwashing composition for hand-washing containing (c) component].
Figure JPOXMLDOC01-appb-C000002
Figure JPOXMLDOC01-appb-C000002
〔式中、R1、R2は、それぞれ、炭素数5~18のアルキル基又は水素原子であり、R1、R2の少なくとも一方は炭素数5~18のアルキル基である。即ち、R1とR2が同時に水素原子である場合を除く。A1、A2はそれぞれ独立に炭素数2~4のアルキレン基、x、yは平均付加モル数でありそれぞれ独立に0~6である。M1は陽イオンである。〕 [Wherein, R 1 and R 2 are each an alkyl group having 5 to 18 carbon atoms or a hydrogen atom, and at least one of R 1 and R 2 is an alkyl group having 5 to 18 carbon atoms. That is, the case where R 1 and R 2 are hydrogen atoms at the same time is excluded. A 1 and A 2 are each independently an alkylene group having 2 to 4 carbon atoms, and x and y are average added mole numbers, and are each independently 0 to 6. M 1 is a cation. ]
 また、本発明は、上記本発明の手洗い用食器洗浄剤組成物を用いた洗浄液で食器を手洗い洗浄し、その後、水を用いてすすぎを行う、食器の洗浄方法に関する。 The present invention also relates to a tableware cleaning method in which tableware is washed by hand with a cleaning liquid using the dishwashing composition for handwashing of the present invention, and then rinsed with water.
発明の詳細な説明
 近年、環境負荷軽減、水資源有効利用の目的から、手洗い洗浄に用いる水の量を低減することが好ましく、食器洗浄剤で洗浄後のすすぎ水は極力低減することが望まれる。しかしながら、一般に起泡性/泡持続性に優れる洗浄剤は、すすぎを完了するためには多量の水を必要とする。従って、洗浄時には豊かな泡立ちと泡の持続性を示すが、すすぎ時には瞬時に泡が消え、少量の水ですすぎが完了する手洗い用食器洗浄剤が強く求められる。
DETAILED DESCRIPTION OF THE INVENTION In recent years, it has been preferable to reduce the amount of water used for hand washing and washing, and it is desirable to reduce the rinse water after washing with a dishwashing agent as much as possible for the purpose of reducing environmental impact and effectively using water resources. . However, detergents that are generally excellent in foamability / foam persistence require a large amount of water to complete rinsing. Accordingly, there is a strong demand for a dishwashing detergent for hand washing that exhibits abundant foaming and foam persistence during washing, but disappears instantly during rinsing and is rinsed with a small amount of water.
 この点、特開昭62-215699、特表2008-507611、特開平3-207799や特表2008-506727では、すすぎ時の泡消えに関してはなんら考慮されていない。また、特開平3-207799に「起泡抑制剤」として挙げられているような消泡剤としての脂肪酸は、洗浄時において低泡性にすることを目的としており、洗浄時には非常に豊かな泡を持続的に形成することと、すすぎ時には瞬時に消泡する技術との関連を示唆するものではない。更に、特開平3-33197では、スルホコハク酸アルキルエステルを用いた具体的な例がないのみならず、ベタインとしてカルボベタイン型界面活性剤を用いた例はあるものの、スルホベタイン型界面活性剤を用いた具体的な例については記載も示唆もなされていない。 In this respect, Japanese Patent Application Laid-Open No. Sho 62-215699, Japanese Translation of PCT International Publication No. 2008-507611, Japanese Patent Application Laid-Open No. Hei 3-207799, and Japanese Patent Application Laid-Open No. 2008-506727 do not consider any bubble disappearance at the time of rinsing. Further, the fatty acid as an antifoaming agent, which is listed as “Foaming Inhibitor” in JP-A-3-207799, is intended to make it low in foaming properties during cleaning. There is no suggestion of a relationship between the continuous formation of water and the technology of instant defoaming during rinsing. Furthermore, in JP-A-3-33197, there is no specific example using a sulfosuccinic acid alkyl ester, and there is an example using a carbobetaine type surfactant as a betaine, but a sulfobetaine type surfactant is used. No specific examples were given or suggested.
 従って本発明は、洗浄時には豊かな泡立ちと洗浄時の泡の持続性を示すが、すすぎ時には瞬時に泡が消え、少量の水ですすぎが完了する手洗い用食器洗浄剤を提供する。 Accordingly, the present invention provides a dishwashing agent for hand washing that exhibits abundant foaming at the time of washing and the persistence of the foam at the time of washing, but the foam disappears instantaneously at the time of rinsing and the rinsing with a small amount of water is completed.
は実施例で行った泡消え性の評価方法を示す概略図である。These are the schematic diagrams which show the foam extinction evaluation method performed in the Example. は実施例の泡消え性の評価で用いた硬水の導入手段(ジョウロ)の穿孔状態を示す概略図である。These are the schematic diagrams which show the piercing | piercing state of the introduction means (joro) of the hard water used by the foam extinction evaluation of the Example.
<(a)成分>
 本発明の(a)成分は、下記一般式(1)で表されるスルホコハク酸アルキルエステル又はその塩、好ましくはスルホコハク酸ジ若しくはモノアルキルエステル又はその塩である。
<(A) component>
The component (a) of the present invention is a sulfosuccinic acid alkyl ester represented by the following general formula (1) or a salt thereof, preferably a sulfosuccinic acid di- or monoalkyl ester or a salt thereof.
Figure JPOXMLDOC01-appb-C000003
Figure JPOXMLDOC01-appb-C000003
〔式中、R1、R2は、それぞれ、炭素数5~18、好ましくは6~14、より好ましくは7~10、また、炭素数5以上、好ましくは6以上、更に7以上、そして、18以下、好ましくは14以下、更に10以下のアルキル基又は水素原子であり、R1、R2の少なくとも一方は炭素数5~18、また、炭素数5以上、18以下のアルキル基である。即ち、R1とR2が同時に水素原子である場合を除く。A1、A2はそれぞれ独立に炭素数2~4、好ましくは2~3、また、炭素数2以上、そして、4以下、好ましくは3以下のアルキレン基、x、yは平均付加モル数であり、それぞれ独立に0~6、更に0~3、更に0~2、更に0~1、また、0以上、そして、6以下、更に2以下、更に1以下、更に0である。M1は陽イオン、好ましくは無機又は有機の陽イオンである。〕 [Wherein R 1 and R 2 each have 5 to 18 carbon atoms, preferably 6 to 14 carbon atoms, more preferably 7 to 10 carbon atoms, 5 or more carbon atoms, preferably 6 or more carbon atoms, and further 7 or more carbon atoms, and It is an alkyl group or hydrogen atom having 18 or less, preferably 14 or less, and further 10 or less, and at least one of R 1 and R 2 is an alkyl group having 5 to 18 carbon atoms and 5 to 18 carbon atoms. That is, the case where R 1 and R 2 are hydrogen atoms at the same time is excluded. A 1 and A 2 are each independently an alkylene group having 2 to 4 carbon atoms, preferably 2 to 3 carbon atoms, and 2 or more carbon atoms, and preferably 4 or less, preferably 3 or less, and x and y are the average number of moles added. Each independently 0 to 6, further 0 to 3, further 0 to 2, further 0 to 1, or more than 0, and 6 or less, further 2 or less, further 1 or less, and further 0. M 1 is a cation, preferably an inorganic or organic cation. ]
 (a)成分が、スルホコハク酸ジアルキルエステル又はその塩である場合、一般式(1)中のR1、R2は、同一あるいは異なっていても良く、洗浄時の起泡性及びすすぎ時の泡消え性の観点から、炭素数5~18、好ましくは6~14、より好ましくは7~10、また、炭素数5以上、好ましくは6以上、更に7以上、そして、18以下、好ましくは14以下、更に10以下のアルキル基であり、好ましくは分岐構造を有するアルキル基である。5以上の炭素数で良好なすすぎ時の泡消え性が得られ、18以下の炭素数で良好な洗浄時の起泡性が得られる。 In the case where the component (a) is a sulfosuccinic acid dialkyl ester or a salt thereof, R 1 and R 2 in the general formula (1) may be the same or different, and the foamability at the time of washing and the foam at the time of rinsing From the viewpoint of extinction, the number of carbons is 5 to 18, preferably 6 to 14, more preferably 7 to 10, and the number of carbons is 5 or more, preferably 6 or more, further 7 or more, and 18 or less, preferably 14 or less. Further, it is an alkyl group of 10 or less, preferably an alkyl group having a branched structure. When the number of carbons is 5 or more, good foam disappearance at rinsing is obtained, and when the number of carbons is 18 or less, good foaming at washing is obtained.
 また、(a)成分が、スルホコハク酸モノアルキルエステル又はその塩である場合、一般式(1)中のR1、R2の一方は、洗浄時の起泡性及びすすぎ時の泡消え性の観点から、炭素数5~18、好ましくは6~14、より好ましくは7~10、また、炭素数5以上、好ましくは6以上、更に7以上、そして、18以下、好ましくは14以下、更に10以下のアルキル基であり、他方は水素原子である。 In addition, when the component (a) is a sulfosuccinic acid monoalkyl ester or a salt thereof, one of R 1 and R 2 in the general formula (1) is a foaming property during washing and a foam disappearance property during rinsing. From the viewpoint, the number of carbon atoms is 5 to 18, preferably 6 to 14, more preferably 7 to 10, and the number of carbon atoms is 5 or more, preferably 6 or more, further 7 or more, and 18 or less, preferably 14 or less, further 10 The following are alkyl groups, and the other is a hydrogen atom.
 一般式(1)中のR1、R2は、洗浄時の起泡性及びすすぎ時の泡消え性の観点から、それぞれ、炭素数5~18、好ましくは6~14、より好ましくは7~10、また、炭素数5以上、好ましくは6以上、更に7以上、そして、18以下、好ましくは14以下、更に10以下のアルキル基であること、すなわち、(a)成分が、スルホコハク酸ジアルキルエステル又はその塩であることが、起泡力、泡消え性の観点から好ましい。A1、A2は洗浄時の起泡性及びすすぎ時の泡消え性の観点からそれぞれ独立に炭素数2~4、好ましくは2~3、また、炭素数2以上、そして、4以下、好ましくは3以下のアルキレン基である。x、yは平均付加モル数であり、洗浄時の起泡性及びすすぎ時の泡消え性の観点から、それぞれ0~6であり、好ましくは0~3、より好ましくは0~2であり、より好ましくは0~1、また、0以上、そして、6以下、好ましくは3以下、更に2以下、更に1以下であり、更に好ましくは0である。 In the general formula (1), R 1 and R 2 each have 5 to 18 carbon atoms, preferably 6 to 14 carbon atoms, more preferably 7 to 7 carbon atoms from the viewpoint of foaming properties during washing and foam disappearance properties during rinsing. 10 or more, preferably 6 or more, more preferably 7 or more, and 18 or less, preferably 14 or less, and further 10 or less, that is, the component (a) is a dialkyl ester of sulfosuccinic acid. Or it is preferable that it is the salt from a foaming power and a foam extinction viewpoint. A 1 and A 2 are each independently 2 to 4, preferably 2 to 3, preferably 2 or more, and 4 or less, preferably 4 or less carbon atoms from the viewpoint of foaming properties during washing and foam disappearance properties during rinsing. Is an alkylene group of 3 or less. x and y are the average number of moles added, and are each 0 to 6, preferably 0 to 3, more preferably 0 to 2, from the viewpoints of foamability during washing and foam extinction during rinsing. More preferably, it is 0 to 1, more than 0, and 6 or less, preferably 3 or less, further 2 or less, further 1 or less, and more preferably 0.
 一般式(1)中、R1、R2は、それぞれ、具体的にはヘキシル基、オクチル基、ノニル基、デシル基、ドデシル基、トリデシル基、2-エチルヘキシル基、n-オクチル基、sec-オクチル基、イソペンチル基、イソノニル基、イソデシル基、シクロヘキシル基であり、n-オクチル基、sec-オクチル基、デシル基、イソデシル基、及び2-エチルヘキシル基から選ばれる基であることがより好適であり、2-エチルヘキシル基が更に好適である。M1としては、水素イオン、ナトリウムイオン、カリウムイオン、マグネシウムイオン、アンモニウムイオンから選ばれる無機陽イオン、モノエタノールアンモニウムイオン、ジエタノールアンモニウムイオン、トリエタノールアンモニウムイオンから選ばれる有機陽イオンが挙げられるが、好ましくはナトリウムイオン、カリウムイオン、マグネシウムイオン、及びアンモニウムイオンから選ばれる陽イオンである。 In the general formula (1), R 1 and R 2 are specifically hexyl, octyl, nonyl, decyl, dodecyl, tridecyl, 2-ethylhexyl, n-octyl, sec- An octyl group, an isopentyl group, an isononyl group, an isodecyl group, and a cyclohexyl group, and more preferably a group selected from an n-octyl group, a sec-octyl group, a decyl group, an isodecyl group, and a 2-ethylhexyl group. 2-ethylhexyl group is more preferable. Examples of M 1 include inorganic cations selected from hydrogen ions, sodium ions, potassium ions, magnesium ions, and ammonium ions, organic cations selected from monoethanol ammonium ions, diethanol ammonium ions, and triethanol ammonium ions. Preferably, it is a cation selected from sodium ion, potassium ion, magnesium ion, and ammonium ion.
 (a)成分が、スルホコハク酸ジアルキルエステル又はその塩である場合、R1、R2が同一の化合物の調製方法としては、特に限定されるものではないが、例えば米国特許公報2,028,091に記載の方法を参考にして製造することができ、また、R1、R2が異なる非対称の化合物の調製方法としては、例えば特開昭58-24555を参考にして製造することができる。市販の化合物を用いる場合には、花王(株)製ペレックスOT-P(R1、R2が共に2-エチルヘキシル基である化合物)、同ペレックスTR(R1、R2が共にトリデシル基である化合物)、BASF社製LuensitA-BO(R1、R2が共に2-エチルヘキシル基である化合物)、三井サイテック株式会社から入手可能であったエアロゾルAY-100(R1、R2が共にアミル基である化合物)、同エアロゾルA-196(R1、R2が共にシクロヘキシル基である化合物)などを用いることができる。 When the component (a) is a sulfoalkyl succinate dialkyl ester or a salt thereof, the preparation method of the compound in which R 1 and R 2 are the same is not particularly limited, but for example, US Pat. No. 2,028,091 In addition, as a method for preparing an asymmetric compound having different R 1 and R 2 , for example, it can be produced with reference to JP-A-58-24555. In the case of using a commercially available compound, PALEX OT-P (a compound in which R 1 and R 2 are both 2-ethylhexyl groups) manufactured by Kao Corporation, and PELEX TR (in which R 1 and R 2 are both tridecyl groups) Compound), LusitA-BO (a compound in which R 1 and R 2 are both 2-ethylhexyl groups) manufactured by BASF, and aerosol AY-100 (both R 1 and R 2 are amyl groups) available from Mitsui Cytec Co., Ltd. And the same aerosol A-196 (a compound in which R 1 and R 2 are both cyclohexyl groups).
<(b)成分>
 本発明の(b)成分は、炭素数8~21の炭化水素基と、硫酸エステル基又はスルホン酸基を有する陰イオン界面活性剤〔但し(a)成分を除く〕である。このような陰イオン界面活性剤は非常に起泡性に優れることが知られており、より具体的には、炭素数8~18、好ましくは炭素数8~15、また、炭素数8以上、そして、18以下、好ましくは15以下のアルキル基を有するアルキル硫酸エステル塩、炭素数8~18、好ましくは炭素数8~15、また、炭素数8以上、そして、18以下、更に15以下のアルキル基を有し炭素数2~3のオキシアルキレン基の平均付加モル数が0.1~6、好ましくは0.3~3、より好ましくは0.4~1.5、また、0.1以上、更に0.3以上、更に0.4以上、そして、6以下、更に3以下、更に1.5以下であるポリオキシアルキレンアルキルエーテル硫酸エステル塩、炭素数8~15のアルキル基を有するアルキルベンゼンスルホン酸塩、並びに炭素数8~15のアルカンスルホン酸塩から選ばれる陰イオン界面活性剤が好適である。塩としてはナトリウム塩、カリウム塩、マグネシウム塩、アンモニウム塩から選ばれる無機塩、モノエタノールアミン塩、ジエタノールアミン塩、トリエタノールアミン塩から選ばれる有機アミン塩が好適である。
<(B) component>
The component (b) of the present invention is an anionic surfactant (except for the component (a)) having a hydrocarbon group having 8 to 21 carbon atoms and a sulfate ester group or a sulfonic acid group. Such an anionic surfactant is known to be very excellent in foaming properties. More specifically, it has 8 to 18 carbon atoms, preferably 8 to 15 carbon atoms, and more than 8 carbon atoms. And an alkyl sulfate ester salt having an alkyl group of 18 or less, preferably 15 or less, an alkyl having 8 to 18 carbon atoms, preferably 8 to 15 carbon atoms, and having 8 or more carbon atoms, 18 or less, and further 15 or less alkyl. The average added mole number of the oxyalkylene group having 2 to 3 carbon atoms is 0.1 to 6, preferably 0.3 to 3, more preferably 0.4 to 1.5, and more than 0.1 Further, 0.3 or more, further 0.4 or more, and 6 or less, further 3 or less, and further 1.5 or less polyoxyalkylene alkyl ether sulfate salt, alkylbenzene sulfone having an alkyl group having 8 to 15 carbon atoms Acid salt, Anionic surfactant selected from an alkane sulfonic acid salts having 8 to 15 carbon atoms in the beauty are preferred. As the salt, an inorganic salt selected from sodium salts, potassium salts, magnesium salts, and ammonium salts, and organic amine salts selected from monoethanolamine salts, diethanolamine salts, and triethanolamine salts are preferable.
 (b)成分としては、下記一般式(2)の化合物が洗浄時の起泡性や泡持続性及びすすぎ時の泡消え性の点から好適である。
   R3-O-(R4O)n-SO32    (2)
〔式中、R3は、炭素数8~18、好ましくは8~15、また、炭素数8以上、そして、18以下、更に15以下のアルキル基であり、R4は、エチレン基及び/又はプロピレン基であり、nは平均付加モル数であり0以上6以下の数、好ましくは0.1以上2以下の数、より好ましくは0.3以上1以下、また、0以上、更に0.1以上、更に0.3以上、そして、6以下、更に2以下、更に1以下の数である。M2は陽イオン、好ましくは無機又は有機の陽イオンである。〕
As the component (b), the compound represented by the following general formula (2) is preferable from the viewpoints of foamability at the time of washing, foam persistence, and foam extinction at the time of rinsing.
R 3 —O— (R 4 O) n —SO 3 M 2 (2)
[Wherein R 3 is an alkyl group having 8 to 18 carbon atoms, preferably 8 to 15 carbon atoms, and having 8 or more carbon atoms and 18 or less, and further 15 or less, and R 4 is an ethylene group and / or A propylene group, n is an average number of moles added and is a number from 0 to 6, preferably from 0.1 to 2, more preferably from 0.3 to 1, and from 0 to 0.1 The number is further 0.3 or more, 6 or less, 2 or less, and 1 or less. M 2 is a cation, preferably an inorganic or organic cation. ]
 nは、R4がエチレン基の場合には1.5以下、更に1以下の数が好ましく、また、0.3以上、更に0.5以上の数がより好ましい。また、nは、R4がプロピレン基の場合には1.5以下、更に1以下、更に0.8以下の数が好ましく、また、0.1以上、更に0.3以上、更に0.4以上の数が好ましい。また、R4がエチレン基及びプロピレン基の場合には、nはこれらの範囲からそれぞれ選択できる。 When R 4 is an ethylene group, n is preferably 1.5 or less, more preferably 1 or less, and more preferably 0.3 or more, and even more preferably 0.5 or more. Further, n is preferably a number of 1.5 or less, more preferably 1 or less, and further 0.8 or less when R 4 is a propylene group, and 0.1 or more, further 0.3 or more, and further 0.4. The above number is preferred. When R 4 is an ethylene group or a propylene group, n can be selected from these ranges.
 一般式(2)において、nが0の場合には、R3が分岐構造を有するアルキル基を含む化合物が好ましい。nが0である場合、一般式(2)の化合物は、分岐率〔一般式(2)の化合物の総モル数に対して分岐鎖アルキル基を有する化合物の総モル数の割合〕が好ましくは15~100モル%、より好ましくは40~100モル%、更に好ましくは70~100モル%、また15モル%以上、更に40モル%以上、更に70モル%以上、そして、100モル%以下の化合物が好適である。 In the general formula (2), when n is 0, R 3 is preferably a compound containing an alkyl group having a branched structure. When n is 0, the compound of the general formula (2) preferably has a branching ratio [ratio of the total number of moles of the compound having a branched alkyl group to the total number of moles of the compound of the general formula (2)]. 15 to 100 mol%, more preferably 40 to 100 mol%, still more preferably 70 to 100 mol%, 15 mol% or more, further 40 mol% or more, further 70 mol% or more, and 100 mol% or less Is preferred.
 一般式(2)中のM2はナトリウムイオン、カリウムイオン、マグネシウムイオン、アンモニウムイオンから選ばれる無機陽イオン、モノエタノールアンモニウムイオン、ジエタノールアンモニウムイオン、トリエタノールアンモニウムイオンから選ばれる有機陽イオンであるが、好ましくはナトリウムイオン、カリウムイオン、マグネシウムイオンである。 M 2 in the general formula (2) is an organic cation selected from an inorganic cation selected from sodium ion, potassium ion, magnesium ion and ammonium ion, monoethanolammonium ion, diethanolammonium ion and triethanolammonium ion. Preferably, they are sodium ion, potassium ion, and magnesium ion.
 一般式(2)の化合物の調製方法としては、特に限定されるものではないが、例えばR3-OHで示される脂肪アルコールに目的に応じてエチレンオキシド及び/又はプロピレンオキシドを所定量付加させた後、三酸化硫黄(液体又は気体)、三酸化硫黄含有ガス、発煙硫酸、クロルスルホン酸から選ばれる硫酸化剤で硫酸エステル化し、所定のアルカリ剤で中和して製造される。エチレンオキシド(以下、EOと表記する)及び/又はプロピレンオキシド(以下、POと表記する)の付加反応は触媒が必要でありNaOH、KOHなどの水酸化アルカリを用いることができる。また、特開平8-323200に記載の酸化マグネシウムを主成分とする触媒を用いることができ、前者は付加モル数分布が比較的広いポリオキシエチレンアルキルエーテルを得ることができ、後者は比較的狭い付加モル数分布を有する化合物を得ることができる。また、特開平10-158384に開示されているようにアルカリ触媒と金属酸化物触媒を併用することにより付加モル数分布を制御することも可能である。 The method for preparing the compound of the general formula (2) is not particularly limited. For example, after a predetermined amount of ethylene oxide and / or propylene oxide is added to the fatty alcohol represented by R 3 —OH depending on the purpose. It is produced by sulfate formation with a sulfating agent selected from sulfur trioxide (liquid or gas), sulfur trioxide-containing gas, fuming sulfuric acid and chlorosulfonic acid, and neutralization with a predetermined alkali agent. The addition reaction of ethylene oxide (hereinafter referred to as EO) and / or propylene oxide (hereinafter referred to as PO) requires a catalyst, and an alkali hydroxide such as NaOH or KOH can be used. Further, a catalyst mainly composed of magnesium oxide described in JP-A-8-323200 can be used. The former can obtain a polyoxyethylene alkyl ether having a relatively wide addition mole number distribution, and the latter is relatively narrow. A compound having an addition mole number distribution can be obtained. Further, as disclosed in JP-A-10-158384, it is also possible to control the addition mole number distribution by using an alkali catalyst and a metal oxide catalyst in combination.
 一般式(2)においてnが0の場合に好適であるR3が分岐構造を有するアルキル基を含む化合物を得る場合には、原料であるR3-OHで示されるアルコールとして、炭素数8~14の1-アルケンをヒドロホルミル化して得られたアルコール(OH基に対してβ位にメチル基が分岐したアルキル基が15~70モル%含まれる)、炭素数4~8のアルデヒドを縮合させた後、還元して得られるゲルベ型アルコール(OH基に対してβ位に炭素数3~6のアルキル基が分岐した構造のものが100モル%含まれる)、イソブテンの2量体をヒドロホルミル化して得られる3,5,5-トリメチルヘキサノール、イソブテンの3量体をヒドロホルミル化して得られる多分岐トリデカノール(分岐率は100モル%である)、石油、石炭を原料とした合成アルコール(分岐率が約20~100モル%のアルキル基である)を挙げることができる。 When R 3 n are suitable in the case of 0 to obtain a compound containing an alkyl group having a branched structure in the general formula (2), as the alcohol represented by the raw material R 3 -OH, carbon atoms from 8 to Alcohol obtained by hydroformylating 14 1-alkene (contains 15 to 70 mol% of an alkyl group having a methyl group branched at the β-position with respect to the OH group) and an aldehyde having 4 to 8 carbon atoms were condensed. Thereafter, a gel-form alcohol obtained by reduction (containing 100 mol% of a structure in which an alkyl group having 3 to 6 carbon atoms is branched at the β-position relative to the OH group) and a dimer of isobutene are hydroformylated. The obtained 3,5,5-trimethylhexanol and isobutene trimer are hydroformylated to obtain a multi-branched tridecanol (branching rate is 100 mol%), petroleum and coal. Synthetic alcohol (branch index of about 20 to 100 mole% of the alkyl group) can be exemplified.
 本発明では、(b)成分として、一般式(2)で表される化合物であって、R4がプロピレン基であり、nが0.1~1.5、更に0.3~1、更に0.4~0.8、また、0.1以上、更に0.3以上、更に0.4以上、そして、1.5以下、更に1以下、更に0.8以下の数である化合物が最も好ましい。 In the present invention, the component (b) is a compound represented by the general formula (2), wherein R 4 is a propylene group, n is 0.1 to 1.5, further 0.3 to 1, Compounds having a number of 0.4 to 0.8, 0.1 or more, further 0.3 or more, further 0.4 or more, 1.5 or less, further 1 or less, and further 0.8 or less are the most. preferable.
<(c)成分>
 本発明では、増泡効果のある界面活性剤として、(c)成分のスルホベタイン型界面活性剤を用いる。スルホベタイン型界面活性剤は洗浄時の起泡性/泡持続性を改善するが、すすぎ時の瞬時の泡消え性を損なうことがない。スルホベタイン型界面活性剤としては、アルキル基の炭素数が10~18のN-アルキル-N,N-ジメチル-N-スルホプロピルアンモニウムスルホベタイン、N-アルキル-N,N-ジメチル-N-(2-ヒドロキシスルホプロピル)アンモニウムスルホベタイン、アルカノイル基の炭素数が10~18のN-アルカノイルアミノプロピル-N,N-ジメチル-N-スルホプロピルアンモニウムスルホベタイン、N-アルカノイルアミノプロピル-N,N-ジメチル-N-(2-ヒドロキシスルホプロピル)アンモニウムスルホベタインが好適である。
<(C) component>
In the present invention, the sulfobetaine type surfactant as the component (c) is used as the surfactant having a foam increasing effect. The sulfobetaine type surfactant improves the foamability / foam persistence at the time of washing, but does not impair the instant foam disappearance at the time of rinsing. Examples of the sulfobetaine surfactant include N-alkyl-N, N-dimethyl-N-sulfopropylammonium sulfobetaine having an alkyl group having 10 to 18 carbon atoms, N-alkyl-N, N-dimethyl-N- ( 2-hydroxysulfopropyl) ammonium sulfobetaine, N-alkanoylaminopropyl-N, N-dimethyl-N-sulfopropylammonium sulfobetaine having an alkanoyl group of 10 to 18 carbon atoms, N-alkanoylaminopropyl-N, N- Dimethyl-N- (2-hydroxysulfopropyl) ammonium sulfobetaine is preferred.
<手洗い用食器洗浄剤組成物>
 本発明の手洗い用食器洗浄剤組成物は、起泡性/泡持続性を有する(b)成分及び(c)成分と、(a)成分とを特定条件で併用することにより、比較的洗浄剤の濃度が高い洗浄水においては非常に高い起泡性と泡持続性を示すが、洗浄終了後にすすぎ水を添加することにより、瞬時に泡が消え、少量の水ですすぎを完了させることができる。この理由は必ずしも定かではないが、すすぎ時の界面活性剤濃度が低い環境下では、各分子の分子運動性が泡膜に及ぼす影響が大きくなると考えられるところ、カチオン基の位置が他のベタイン(例えば、カルボベタインなど)と異なる(c)成分と、(a)成分のアニオン基が相互作用した場合、非常に大きな分子運動性をもつコンプレックスが形成されることにより、瞬時に泡を消すことができるものと考えられる。
<Dishwashing composition for hand washing>
The dishwashing composition for hand-washing of the present invention is a relatively cleansing agent by combining the component (b) and the component (c) having foamability / foam persistence with the component (a) under specific conditions. In washing water with high concentration, it shows very high foaming and long-lasting foam. By adding rinsing water after washing, the foam disappears instantly and rinsing with a small amount of water can be completed. . The reason for this is not necessarily clear, but in an environment where the surfactant concentration at the time of rinsing is low, it is considered that the influence of molecular mobility of each molecule on the bubble membrane increases, and the position of the cation group is another betaine ( For example, when the component (c), which is different from carbobetaine, etc., and the anion group of the component (a) interact with each other, a foam having a very large molecular mobility is formed, so that bubbles can be extinguished instantaneously. It is considered possible.
 本発明の手洗い用食器洗浄剤組成物は、起泡力、泡消え性及び経済性の観点から、(a)成分を1質量%以上、好ましくは2質量%以上、より好ましくは3質量%以上、また、30質量%以下、より好ましくは25質量%以下、更に好ましくは20質量%以下、より更に好ましくは15質量%以下含有し、例えば1~30質量%、更に3~25質量%、更に3~20質量%、更に3~15質量%含有する。 In the dishwashing composition for hand washing of the present invention, the component (a) is 1% by mass or more, preferably 2% by mass or more, more preferably 3% by mass or more, from the viewpoint of foaming power, foam disappearance and economy. In addition, it is contained in an amount of 30% by mass or less, more preferably 25% by mass or less, further preferably 20% by mass or less, and still more preferably 15% by mass or less, for example, 1 to 30% by mass, further 3 to 25% by mass, 3 to 20% by mass, and further 3 to 15% by mass.
 また、本発明の手洗い用食器洗浄剤組成物は、起泡力、泡消え性及び経済性の観点から、(b)成分を5質量%以上、好ましくは7質量%以上、より好ましくは9質量%以上、また、35質量%以下、好ましくは20質量%以下、より好ましくは15質量%以下含有し、例えば5~35質量%、更に7~20質量%、更に9~15質量%含有する。なお、本発明において質量%や質量比等を求めるための(b)成分の量は、Na塩としての量である。 Moreover, the dishwashing composition for hand-washing of this invention is 5 mass% or more, Preferably it is 7 mass% or more, More preferably, 9 mass from the viewpoint of foaming power, foam extinction property, and economical efficiency. % Or more, 35% by mass or less, preferably 20% by mass or less, more preferably 15% by mass or less, for example, 5 to 35% by mass, further 7 to 20% by mass, and further 9 to 15% by mass. In addition, the quantity of (b) component for calculating | requiring mass%, mass ratio, etc. in this invention is the quantity as Na salt.
 また、本発明の手洗い用食器洗浄剤組成物は、起泡力、泡消え性及び経済性の観点から、(c)成分を1質量%以上、より好ましくは2質量%以上、更に好ましくは3質量%以上、また、20質量%以下、より好ましくは14質量%以下、更に好ましくは12質量%以下含有し、例えば1~20質量%、更に2~14質量%、更に3~12質量%含有する。 Moreover, the dishwashing agent composition for hand-washing of this invention is 1 mass% or more from the viewpoint of foaming power, foam extinction property, and economical efficiency, More preferably, it is 2 mass% or more, More preferably, it is 3 More than 20% by mass, more preferably not more than 20% by mass, more preferably not more than 14% by mass, still more preferably not more than 12% by mass, for example, 1 to 20% by mass, further 2 to 14% by mass, further 3 to 12% by mass To do.
 本発明の手洗い用食器洗浄剤組成物は、起泡力、泡消え性及び経済性の観点から、(a)成分を好ましくは1~30質量%、より好ましくは3~25質量%含有する。また、(b)成分を5~35質量%、好ましくは7~20質量%、より好ましくは9~15質量%含有する。なお、本発明において質量%や質量比等を求めるための(b)成分の量は、Na塩としての量である。また、(c)成分の含有量は、組成物中に好ましくは1~20質量%、より好ましくは2~14質量%、更に好ましくは3~12質量%である。 The dishwashing composition for hand-washing of the present invention preferably contains 1 to 30% by mass, more preferably 3 to 25% by mass of component (a) from the viewpoints of foaming power, foam disappearance and economy. The component (b) is contained in an amount of 5 to 35% by mass, preferably 7 to 20% by mass, more preferably 9 to 15% by mass. In addition, the quantity of (b) component for calculating | requiring mass%, mass ratio, etc. in this invention is the quantity as Na salt. Further, the content of the component (c) is preferably 1 to 20% by mass, more preferably 2 to 14% by mass, and further preferably 3 to 12% by mass in the composition.
 また、本発明の手洗い用食器洗浄剤組成物では、起泡力及び泡消え性の観点から、(a)成分/(b)成分の質量比が好ましくは0.03~2.5、より好ましくは0.15~2、更に好ましくは0.2~1.5、より更に好ましくは0.25~1、また、好ましくは0.03以上、更に0.15以上、更に0.2以上、更に0.25以上、そして、好ましくは2.5以下、更に2以下、更に1.5以下、更に1以下である。また、(b)成分/(c)成分の質量比が好ましくは0.3~6、より好ましくは0.5~5、更に好ましくは1~4、より更に好ましくは1.5~3、また、好ましくは0.3以上、更に0.5以上、更に1以上、更に1.5以上、そして、好ましくは6以下、更に5以下、更に4以下、更に3以下であり、(a)成分/(c)成分の質量比が好ましくは0.1~5、より好ましくは0.3~2.6、更に好ましくは0.6~2.3、より更に好ましくは0.6~1.8、また、好ましくは0.1以上、更に0.3以上、更に0.6以上、そして、好ましくは5以下、更に2.6以下、更に2.3以下、更に1.8以下である。 In the dishwashing composition for hand washing of the present invention, the mass ratio of the component (a) / the component (b) is preferably 0.03 to 2.5, more preferably from the viewpoint of foaming power and foam extinction. Is 0.15 to 2, more preferably 0.2 to 1.5, even more preferably 0.25 to 1, and preferably 0.03 or more, more preferably 0.15 or more, further 0.2 or more, and further 0.25 or more, and preferably 2.5 or less, further 2 or less, further 1.5 or less, and further 1 or less. The mass ratio of component (b) / component (c) is preferably 0.3 to 6, more preferably 0.5 to 5, still more preferably 1 to 4, still more preferably 1.5 to 3, , Preferably 0.3 or more, further 0.5 or more, further 1 or more, further 1.5 or more, and preferably 6 or less, further 5 or less, further 4 or less, further 3 or less. The mass ratio of the component (c) is preferably 0.1 to 5, more preferably 0.3 to 2.6, still more preferably 0.6 to 2.3, still more preferably 0.6 to 1.8, Further, it is preferably 0.1 or more, further 0.3 or more, further 0.6 or more, and preferably 5 or less, further 2.6 or less, further 2.3 or less, and further 1.8 or less.
 また、本発明の手洗い用食器洗浄剤組成物では、(c)成分/〔(a)成分+(b)成分〕の質量比は、好ましくは0.02~2、より好ましくは0.1~1.5、更に好ましくは0.15~1、より更に好ましくは0.15~0.5、また、好ましくは0.02以上、更に0.1以上、更に0.15以上、そして、好ましくは2以下、更に1.5以下、更に1以下、更に0.5以下であることが、洗浄時の起泡性/泡持続性の改善とすすぎ時の泡消え性の点から好ましい。 In the dishwashing composition for hand washing of the present invention, the mass ratio of (c) component / [(a) component + (b) component] is preferably 0.02 to 2, more preferably 0.1 to 2. 1.5, more preferably 0.15 to 1, still more preferably 0.15 to 0.5, preferably 0.02 or more, further 0.1 or more, further 0.15 or more, and preferably It is preferably 2 or less, further 1.5 or less, further 1 or less, and further 0.5 or less from the viewpoint of improvement in foamability / foam persistence during washing and foam extinction during rinsing.
 本発明では組成物中の全界面活性剤の含有量に対する(a)成分、(b)成分、及び(c)成分の合計質量が50~100質量%、更に60~100質量%、更に80~100質量%、より更に90~100質量%、また、50質量%以上、更に60質量%以上、更に80質量%以上、更に90質量%以上、そして、100質量%以下であることが起泡力及び泡消え性の観点から好ましい。  In the present invention, the total mass of the component (a), the component (b), and the component (c) with respect to the total surfactant content in the composition is 50 to 100% by mass, more preferably 60 to 100% by mass, and further 80 to 100% by mass, further 90-100% by mass, 50% by mass or more, further 60% by mass or more, further 80% by mass or more, further 90% by mass or more, and 100% by mass or less And from the viewpoint of foam extinction.
 本発明の手洗い用食器洗浄剤組成物は、油汚れに対する乳化力を高め、洗浄力を増強する目的から、(d)成分として、含マグネシウム無機化合物及び/又はアルキレンジアミン化合物(アルキレン基は炭素数2~6)、好ましくは含マグネシウム無機化合物を含有することが好ましい。これらの化合物は、本発明に必要な効果、すなわち(a)成分、(b)成分、及び所望により含有される他の陰イオン界面活性剤の少なくとも2分子と比較的弱く相互作用しコンプレックスを形成させ、乳化力などの界面活性能を向上させる化合物として共通の効果/作用機構を有するものである。 The dishwashing composition for hand washing of the present invention has a magnesium-containing inorganic compound and / or an alkylenediamine compound (the alkylene group has a carbon number as component (d) for the purpose of enhancing the emulsifying power against oil stains and enhancing the cleaning power. 2-6), preferably containing a magnesium-containing inorganic compound. These compounds interact relatively weakly with at least two molecules of the effect necessary for the present invention, ie, component (a), component (b), and other anionic surfactants optionally contained to form a complex. And has a common effect / action mechanism as a compound that improves the surface activity such as emulsifying power.
 含マグネシウム無機化合物としては、塩化マグネシウム等のマグネシウム塩化物、硫酸マグネシウム、硝酸マグネシウム等のマグネシウム塩、水酸化マグネシウム、酸化マグネシウム等が挙げられるが、塩化マグネシウム及び硫酸マグネシウムから選ばれる化合物がより好ましく、塩化マグネシウムが更により好ましい。また、アルキレンジアミン化合物としては、エチレンジアミン、プロピレンジアミン、へキシレンジアミン、シクロヘキサンジアミンが好適であるが、シクロヘキサンジアミンがより好ましい。 Examples of the magnesium-containing inorganic compound include magnesium chloride such as magnesium chloride, magnesium salts such as magnesium sulfate and magnesium nitrate, magnesium hydroxide, magnesium oxide, and the like, more preferably a compound selected from magnesium chloride and magnesium sulfate. Even more preferred is magnesium chloride. As the alkylene diamine compound, ethylene diamine, propylene diamine, hexylene diamine and cyclohexane diamine are preferable, but cyclohexane diamine is more preferable.
 (d)成分の含有量は、組成物中、0.5~20質量%、更に0.5~15質量%、より更に0.5~10質量%、また、0.5質量%以上、更に0.5質量%以上、そして、20質量%以下、更に15質量%以下、更に10質量%以下が好ましい。なお、これら(d)成分は結晶水を含む場合があるが、ここで示す含有量は、結晶水を除いた質量である。 The content of the component (d) in the composition is 0.5 to 20% by mass, further 0.5 to 15% by mass, further 0.5 to 10% by mass, 0.5% by mass or more, 0.5 mass% or more and 20 mass% or less, 15 mass% or less, Furthermore 10 mass% or less are preferable. In addition, although these (d) components may contain crystal water, content shown here is the mass except crystal water.
 本発明の手洗い用食器洗浄剤組成物は、(d)成分の補助として(d)成分以外の無機化合物を併用してもよい。無機化合物としては、塩化ナトリウム、塩化カリウム、ヨウ化ナトリウム、ヨウ化カリウム、硫酸ナトリウム、硫酸カリウム、ミョウバン等が挙げられる。 In the dishwashing composition for hand washing of the present invention, an inorganic compound other than the component (d) may be used in combination with the component (d). Examples of inorganic compounds include sodium chloride, potassium chloride, sodium iodide, potassium iodide, sodium sulfate, potassium sulfate, alum and the like.
 本発明においては洗浄時及びすすぎ時の泡の挙動が非常に重要である。手洗い用食器洗浄剤組成物の一般的な研究においては、洗浄時の起泡性/泡持続性を考慮して増泡効果のある界面活性剤を併用することが行われているが、本発明においてはこのような増泡効果のある界面活性剤はすすぎ時の泡消え性に大きな影響を及ぼすため、使用する場合注意が必要である。本発明では特に(e)成分として、アミンオキシド型界面活性剤、カルボベタイン型界面活性剤及びアルカノールアミド型界面活性剤から選ばれる界面活性剤の取り扱いに注意を要する。 In the present invention, the behavior of bubbles during washing and rinsing is very important. In a general study of a dishwashing composition for hand washing, a surfactant having a foam increasing effect is used in consideration of foaming property / sustainability of foaming at the time of washing. In such a case, the surfactant having the effect of increasing the foam has a great influence on the foam disappearance at the time of rinsing. In the present invention, as the component (e), attention should be paid to the handling of a surfactant selected from amine oxide surfactants, carbobetaine surfactants and alkanolamide surfactants.
 アミンオキシド型界面活性剤としてはN-アルカノイルアミノプロピル-N,N-ジメチルアミンオキシド(アルカノイルとしてはラウロイル又はミリスチロイル)、N-アルキル-N,N-ジメチルアミンオキシド(アルキル基としてはラウリル基又はミリスチル基)を挙げることができる。また、カルボベタイン型界面活性剤としてはN-アルカノイルアミノプロピル-N,N-ジメチル-N-カルボキシメチルアンモニウムベタイン、N-アルキル-N,N-ジメチル-N-カルボキシメチルアンモニウムベタインを挙げることができる。さらに、アルカノールアミド型界面活性剤としてはモノエタノールアミン、ジエタノールアミン、メチルモノエタノールアミンなどのアルカノールアミンとラウリン酸、ミリスチン酸などの脂肪酸とのアミド化物を挙げることができる。 As amine oxide type surfactants, N-alkanoylaminopropyl-N, N-dimethylamine oxide (lauroyl or myristyroyl as alkanoyl), N-alkyl-N, N-dimethylamine oxide (lauryl group or myristyl as alkyl group) Group). Examples of carbobetaine surfactants include N-alkanoylaminopropyl-N, N-dimethyl-N-carboxymethylammonium betaine and N-alkyl-N, N-dimethyl-N-carboxymethylammonium betaine. . Furthermore, examples of the alkanolamide surfactant include amidated products of alkanolamines such as monoethanolamine, diethanolamine, and methylmonoethanolamine with fatty acids such as lauric acid and myristic acid.
 本発明においては泡の挙動が非常に重要であり、組成物に増泡効果を与える(e)成分の使用には注意を要し、組成物中の(e)成分の含有量が、好ましくは5質量%以下、より好ましくは3質量%以下、更に好ましくは2質量%以下、より更に好ましくは1質量%以下であり、より更に好ましくは0.5質量%以下、最も好ましくは含有しないことである。 In the present invention, the behavior of foam is very important. Care must be taken in using the component (e) which gives the composition a foam-enhancing effect, and the content of the component (e) in the composition is preferably 5% by mass or less, more preferably 3% by mass or less, further preferably 2% by mass or less, still more preferably 1% by mass or less, still more preferably 0.5% by mass or less, and most preferably not contained. is there.
 本発明の手洗い用食器洗浄剤組成物は、すすぎ性改善の目的から、(f)成分として、炭素数10~18の脂肪酸又はその塩を含有しても良い。具体的にはデカン酸、ラウリン酸、ミリスチン酸、パルミチン酸、パルミトレイン酸、ステアリン酸、オレイン酸、リノール酸、リノレイン酸及びこれらの塩を挙げることができる。また、椰子組成脂肪酸などの混合脂肪酸を用いることも可能である。脂肪酸の塩としては、ナトリウム塩、カリウム塩、マグネシウム塩、アンモニウム塩から選ばれる無機塩、モノエタノールアミン塩、ジエタノールアミン塩、トリエタノールアミン塩などの有機アミン塩であるが、好ましくはナトリウム塩、カリウム塩、マグネシウム塩、より好ましくはナトリウム塩、カリウム塩が挙げられる。(f)成分としては、より好ましくはラウリン酸、ミリスチン酸、パルミチン酸又はこれらの塩であり、より更に好ましくはラウリン酸、ミリスチン酸又はこれらの塩であり、最も好ましくはミリスチン酸又はその塩である。従って、起泡力及び泡消え性の観点からは(f)成分がミリスチン酸又はその塩を含むことが好ましく、(f)成分中、ミリスチン酸又はその塩の割合は20~100質量%、更に50~100質量%、更に80~100質量%、また、20質量%以上、更に50質量%以上、更に80質量%以上、そして、100質量%以下、より更に100質量%が好ましい。 The hand dishwashing detergent composition of the present invention may contain a fatty acid having 10 to 18 carbon atoms or a salt thereof as the component (f) for the purpose of improving rinsing properties. Specific examples include decanoic acid, lauric acid, myristic acid, palmitic acid, palmitoleic acid, stearic acid, oleic acid, linoleic acid, linolenic acid, and salts thereof. Moreover, it is also possible to use mixed fatty acids, such as an insulator composition fatty acid. Fatty acid salts include inorganic salts selected from sodium, potassium, magnesium, and ammonium salts, and organic amine salts such as monoethanolamine, diethanolamine, and triethanolamine, preferably sodium and potassium. Salts, magnesium salts, more preferably sodium salts and potassium salts. The component (f) is more preferably lauric acid, myristic acid, palmitic acid or a salt thereof, still more preferably lauric acid, myristic acid or a salt thereof, most preferably myristic acid or a salt thereof. is there. Therefore, from the viewpoint of foaming ability and foam extinction, the component (f) preferably contains myristic acid or a salt thereof, and the proportion of myristic acid or a salt thereof in the component (f) is 20 to 100% by mass, 50 to 100% by mass, further 80 to 100% by mass, 20% by mass or more, further 50% by mass or more, further 80% by mass or more, and 100% by mass or less, and more preferably 100% by mass are preferable.
 (f)成分の含有量は、組成物中、3質量%以下、更に2質量%以下、更に1質量%以下、更に0.5質量%以下、より更に0.3質量%以下が好ましく、0質量%も好ましい。 The content of the component (f) is preferably 3% by mass or less, further 2% by mass or less, further 1% by mass or less, further 0.5% by mass or less, and further preferably 0.3% by mass or less in the composition. Mass% is also preferred.
 本発明の手洗い用食器洗浄剤組成物は、すすぎ時には瞬時にぬるつきがなくなり、少量の水ですすぎを完了できるという観点から、(g)成分として、アルキルグリセリルエーテル(アルキル基の炭素数は6~18、好ましくは8~12、また、炭素数6以上、更に8以上、そして、18以下、更に12以下)を含有することが好ましい。具体的には下記一般式(3)の化合物が好適である。
   R5-O-(Gly)r-H    (3)
〔式中、R5は炭素数6~18のアルキル基を示し、Glyはグリセリンから2つの水素原子を除いた残基を示し、rは平均付加モル数で1~4の数を示す。〕
The dishwashing composition for hand-washing of the present invention is instantly free of moisture when rinsed and can be rinsed with a small amount of water, and as a component (g), alkyl glyceryl ether (the carbon number of the alkyl group is 6). -18, preferably 8-12, and preferably 6 or more, more preferably 8 or more, and 18 or less, more preferably 12 or less. Specifically, the compound of the following general formula (3) is suitable.
R 5 —O— (Gly) r —H (3)
[Wherein R 5 represents an alkyl group having 6 to 18 carbon atoms, Gly represents a residue obtained by removing two hydrogen atoms from glycerin, and r represents a number of 1 to 4 in terms of the average number of moles added. ]
 一般式(3)において、R5は炭素数6~18、好ましくは7~12、より好ましくは8~10、また、炭素数6以上、更に7以上、更に8以上、そして、18以下、更に12以下、更に10以下のアルキル基であり、ヘキシル基、ヘプチル基、オクチル基、ノニル基、デシル基などの直鎖アルキル基を用いることができるが、本発明ではすすぎ時のぬるつき低減の観点から、分岐構造を有する化合物が好適であり、R5の分岐構造を有する具体的なアルキル基として、2-エチルヘキシル基、sec-オクチル基、イソノニル基及びイソデシル基から選ばれる基がより好ましく、2-エチルヘキシル基又はイソデシル基が更に好ましく、2-エチルヘキシル基がより更に好ましい。一般式(3)において、rは1~3が好ましく、1~2がより好ましく、r=1の化合物が更に好ましい。より更に好ましい化合物は、R5が2-エチルヘキシル基で、かつ、r=1の化合物である。 In the general formula (3), R 5 has 6 to 18 carbon atoms, preferably 7 to 12, more preferably 8 to 10 carbon atoms, 6 or more, further 7 or more, further 8 or more, and 18 or less, The alkyl group is 12 or less, and further 10 or less, and linear alkyl groups such as hexyl group, heptyl group, octyl group, nonyl group, and decyl group can be used. Therefore, a compound having a branched structure is preferable, and a specific alkyl group having a branched structure of R 5 is more preferably a group selected from 2-ethylhexyl group, sec-octyl group, isononyl group and isodecyl group. -Ethylhexyl group or isodecyl group is more preferable, and 2-ethylhexyl group is still more preferable. In the general formula (3), r is preferably 1 to 3, more preferably 1 to 2, and still more preferably a compound with r = 1. Even more preferred compounds are those in which R 5 is a 2-ethylhexyl group and r = 1.
 Glyで示される構造はグリセリンの1位と3位のヒドロキシ基が結合している-CH2CH(OH)CH2-で示される構造か、又はグリセリンの1位と2位のヒドロキシ基が結合している-CH(CH2OH)CH2-で示される構造であり、触媒や反応条件によって異なる。 The structure represented by Gly is a structure represented by —CH 2 CH (OH) CH 2 — in which the 1- and 3-position hydroxy groups of glycerin are bonded, or the 1- and 2-position hydroxy groups of glycerin are bonded. This is a structure represented by —CH (CH 2 OH) CH 2 —, which varies depending on the catalyst and reaction conditions.
 一般式(3)の化合物を得るには、例えば炭素数6~10のアルコールとしてR5-OHで示されるアルキルアルコールを用い、エピハロヒドリンやグリシドールなどのエポキシ化合物とを、BF3などの酸触媒、あるいはアルミニウム触媒を用いて反応させて製造する方法を用いることができる。 In order to obtain the compound of the general formula (3), for example, an alkyl alcohol represented by R 5 —OH is used as an alcohol having 6 to 10 carbon atoms, an epoxy compound such as epihalohydrin or glycidol is reacted with an acid catalyst such as BF 3 , Or the method of manufacturing by making it react using an aluminum catalyst can be used.
 例えば、2-エチルヘキサノールを用いた場合、得られる2-エチルヘキシルモノグリセリルエーテルは、特開2001-49291に記載されているように複数の生成物を含み得る混合物である。(g)成分の含有量は、組成物中、0.5~20質量%、更に1~15質量%、より更に1.5~10質量%、また、0.5質量%以上、更に1質量%以上、更に1.5質量%以上、そして、20質量%以下、更に15質量%以下、更に10質量%以下が好ましい。 For example, when 2-ethylhexanol is used, the resulting 2-ethylhexyl monoglyceryl ether is a mixture that can contain a plurality of products as described in JP-A-2001-49291. The content of the component (g) in the composition is 0.5 to 20% by mass, further 1 to 15% by mass, further 1.5 to 10% by mass, 0.5% by mass or more, and further 1% by mass. % Or more, further 1.5 mass% or more, 20 mass% or less, further 15 mass% or less, and further preferably 10 mass% or less.
 本発明の手洗い用食器洗浄剤組成物は、貯蔵安定性や、洗浄時の増泡性、洗浄性能を向上することを目的として、すすぎ性を損ねない範囲内で非イオン界面活性剤〔(g)成分に該当するものを除く〕〔以下(h)成分という〕を使用してもよい。(h)成分としては、ポリオキシアルキレンソルビタン脂肪酸エステル、ポリオキシアルキレン脂肪酸エステル、ポリオキシアルキレンアルキルエーテル、ポリオキシアルキレンアルキルフェニルエーテル、ショ糖脂肪酸エステル、ソルビタン脂肪酸エステル、アルキルグリコシド等の非イオン界面活性剤を挙げることができる。中でも、ポリオキシアルキレンアルキルエーテル及び/又はアルキルグリコシドが好適である。 The dishwashing composition for hand washing of the present invention is a nonionic surfactant [(g in the range which does not impair the rinsing property for the purpose of improving storage stability, foaming property at the time of washing, and washing performance. ) Except those corresponding to the component] [hereinafter referred to as the component (h)] may be used. (H) As a component, nonionic surface activity such as polyoxyalkylene sorbitan fatty acid ester, polyoxyalkylene fatty acid ester, polyoxyalkylene alkyl ether, polyoxyalkylene alkyl phenyl ether, sucrose fatty acid ester, sorbitan fatty acid ester, alkyl glycoside An agent can be mentioned. Of these, polyoxyalkylene alkyl ethers and / or alkyl glycosides are preferred.
 (h)成分の含有量は、組成物中に好ましくは1~20質量%、より好ましくは1.5~15質量%、更に好ましくは2~10質量%、また、好ましくは1質量%以上、更に1.5質量%以上、更に2質量%以上、そして、好ましくは20質量%以下、更に15質量%以下、更に10質量%以下である。 The content of the component (h) is preferably 1 to 20% by mass, more preferably 1.5 to 15% by mass, further preferably 2 to 10% by mass, and preferably 1% by mass or more in the composition. Further, it is 1.5% by mass or more, further 2% by mass or more, and preferably 20% by mass or less, further 15% by mass or less, and further 10% by mass or less.
 本発明の手洗い用食器洗浄剤組成物は、貯蔵安定性を向上させる目的でハイドロトロープ剤〔以下、(i)成分という〕を含有することが好ましい。ハイドロトロープ剤としては、トルエンスルホン酸、キシレンスルホン酸、クメンスルホン酸又はこれらのナトリウム、カリウムあるいはマグネシウム塩が良好であり、p-トルエンスルホン酸又はその塩がより良好である。(i)成分の含有量は、0.5~20質量%、より好ましくは1~15質量%、更に好ましくは1.5~10質量%、また、0.5質量%以上、更に1質量%以上、更に1.5質量%以上、そして、20質量%以下、更に15質量%以下、更に10質量%以下である。 The hand dishwashing detergent composition of the present invention preferably contains a hydrotrope [hereinafter referred to as component (i)] for the purpose of improving storage stability. As the hydrotrope, toluenesulfonic acid, xylenesulfonic acid, cumenesulfonic acid or a sodium, potassium or magnesium salt thereof is preferable, and p-toluenesulfonic acid or a salt thereof is more preferable. The content of the component (i) is 0.5 to 20% by mass, more preferably 1 to 15% by mass, further preferably 1.5 to 10% by mass, 0.5% by mass or more, and further 1% by mass. As mentioned above, it is 1.5 mass% or more and 20 mass% or less, 15 mass% or less, and also 10 mass% or less.
 本発明の手洗い用食器洗浄剤組成物は、貯蔵安定性の改善や粘度調節の目的で、溶剤〔以下、(j)成分という〕を含有することができる。溶剤の具体的例としては、エタノール、イソプロピルアルコール、エチレングリコール、プロピレングリコール、ジエチレングリコール、ジプロピレングリコール、グリセリン、イソプレングリコール、プロピレングリコールモノメチルエーテル、プロピレングリコールモノエチルエーテル、3-メチル-3-メトキシブタノール、フェノキシエタノール、フェニルグリコール、フェノキシイソプロパノール、ブチルジグリコール(ジエチレングリコールモノブチルエーテル)、ジブチレンジグリコール、ベンジルアルコールから選ばれる水溶性有機溶媒が好ましい。なかでも、ブチルジグリコール、エタノール、及びプロピレングリコールから選ばれる1種以上の水溶性有機溶剤が好ましく、ブチルジグリコール、及びプロピレングリコールから選ばれる1種以上の水溶性有機溶剤が更に好ましい。ここで、水溶性有機溶剤とは、オクタノール/水分配係数(LogPow)が3.5以下の溶剤を指すものとする。(j)成分の含有量は、組成物中に好ましくは1.5~30質量%、より好ましくは2~20質量%、更に好ましくは3~15質量%、また、好ましくは1.5質量%以上、更に2質量%以上、更に3質量%以上、そして、好ましくは30質量%以下、更に20質量%以下、更に15質量%以下である。 The dishwashing composition for hand washing of the present invention can contain a solvent (hereinafter referred to as component (j)) for the purpose of improving storage stability and adjusting viscosity. Specific examples of the solvent include ethanol, isopropyl alcohol, ethylene glycol, propylene glycol, diethylene glycol, dipropylene glycol, glycerin, isoprene glycol, propylene glycol monomethyl ether, propylene glycol monoethyl ether, 3-methyl-3-methoxybutanol, A water-soluble organic solvent selected from phenoxyethanol, phenyl glycol, phenoxyisopropanol, butyl diglycol (diethylene glycol monobutyl ether), dibutylene glycol, and benzyl alcohol is preferred. Among these, one or more water-soluble organic solvents selected from butyl diglycol, ethanol, and propylene glycol are preferable, and one or more water-soluble organic solvents selected from butyl diglycol and propylene glycol are more preferable. Here, the water-soluble organic solvent refers to a solvent having an octanol / water partition coefficient (LogPow) of 3.5 or less. The content of the component (j) is preferably 1.5 to 30% by mass, more preferably 2 to 20% by mass, further preferably 3 to 15% by mass, and preferably 1.5% by mass in the composition. In addition, the content is further 2% by mass or more, further 3% by mass or more, and preferably 30% by mass or less, further 20% by mass or less, and further 15% by mass or less.
 本発明の手洗い用食器洗浄剤組成物には、ゲル化防止のための重合体〔以下、(k)成分という〕、例えば特表平11-513067に記載されているゲル化防止重合体、とりわけポリアルキレングリコールを配合することが粘度調節及び貯蔵安定性の点から好ましい。ゲル化防止のための重合体としてのポリアルキレングリコールの具体例としては、ポリエチレングリコールを標準としたときのゲルパーミエーションクロマトグラフィーによって求められた重量平均分子量が200~3,000のポリプロピレングリコール、及び重量平均分子量が200~3,000のポリエチレングリコールを挙げることができる。(k)成分の含有量は、組成物中に好ましくは0.05~10質量%、より好ましくは0.1~5質量%、更に好ましくは0.5~3質量%、また、好ましくは0.05質量%以上、更に0.1質量%以上、更に0.5質量%以上、そして、好ましくは10質量%以下、更に5質量%以下、更に3質量%以下である。 The dishwashing detergent composition for hand-washing of the present invention includes a polymer for preventing gelation (hereinafter referred to as component (k)), for example, a gelation-preventing polymer described in JP-A-11-513067, It is preferable to blend polyalkylene glycol from the viewpoint of viscosity control and storage stability. Specific examples of the polyalkylene glycol as a polymer for preventing gelation include polypropylene glycol having a weight average molecular weight of 200 to 3,000 determined by gel permeation chromatography using polyethylene glycol as a standard, and Examples thereof include polyethylene glycol having a weight average molecular weight of 200 to 3,000. The content of the component (k) in the composition is preferably 0.05 to 10% by mass, more preferably 0.1 to 5% by mass, still more preferably 0.5 to 3% by mass, and preferably 0%. 0.05% by mass or more, further 0.1% by mass or more, further 0.5% by mass or more, and preferably 10% by mass or less, further 5% by mass or less, and further 3% by mass or less.
 本発明の手洗い用食器洗浄剤組成物は、上記成分を水に溶解/分散/乳化させた液体組成物の形態が好ましく、水溶液がより好ましい。用いる水は脱イオン水や蒸留水、或いは次亜塩素酸を0.5~10ppm程度溶解させた次亜塩素酸滅菌水などを使用することができる。 The hand dishwashing detergent composition of the present invention is preferably in the form of a liquid composition in which the above components are dissolved / dispersed / emulsified in water, and more preferably an aqueous solution. As the water to be used, deionized water, distilled water, or hypochlorous acid sterilized water in which about 0.5 to 10 ppm of hypochlorous acid is dissolved can be used.
 本発明の手洗い用食器洗浄剤組成物の25℃におけるpHは、好ましくは4~9、より好ましくは4.5~7、より好ましくは5~6である。低温安定性の観点から、好ましくは4以上、より好ましくは4.5以上、より好ましくは5以上である。一方、洗浄力の観点から、好ましくは10以下、より好ましくは9以下、より好ましくは8以下、より好ましくは7以下である。このようなpHへの調整は、硫酸、塩酸、リン酸から選ばれる無機酸、クエン酸、りんご酸、マレイン酸、フマール酸、コハク酸から選ばれる有機酸、水酸化ナトリウム、水酸化カリウム、水酸化マグネシウム、炭酸ナトリウム、炭酸カリウムなどの無機アルカリ剤を用いて行われる。本発明では、組成物に緩衝能を持たせることが起泡性/泡持続性の点から好ましく、上記有機酸、好ましくはクエン酸と、無機アルカリ剤とを併用することが好適である。有機酸はナトリウム塩やカリウム塩の形態で組成物に配合しても差し支えない。なお、pH調整のために用いた化合物のうち、水酸化マグネシウム等、(d)成分に該当するものは、(d)成分として取り扱うものとする。 The pH of the dishwashing detergent composition for hand washing of the present invention at 25 ° C. is preferably 4 to 9, more preferably 4.5 to 7, and more preferably 5 to 6. From the viewpoint of low temperature stability, it is preferably 4 or more, more preferably 4.5 or more, more preferably 5 or more. On the other hand, from the viewpoint of detergency, it is preferably 10 or less, more preferably 9 or less, more preferably 8 or less, and more preferably 7 or less. Such adjustment to pH is carried out by inorganic acid selected from sulfuric acid, hydrochloric acid and phosphoric acid, organic acid selected from citric acid, malic acid, maleic acid, fumaric acid and succinic acid, sodium hydroxide, potassium hydroxide, water It is carried out using an inorganic alkaline agent such as magnesium oxide, sodium carbonate or potassium carbonate. In the present invention, it is preferable that the composition has a buffering ability from the viewpoint of foamability / foam persistence, and it is preferable to use the organic acid, preferably citric acid, and an inorganic alkaline agent in combination. The organic acid may be added to the composition in the form of sodium salt or potassium salt. Of the compounds used for pH adjustment, those corresponding to component (d), such as magnesium hydroxide, are handled as component (d).
 本発明の手洗い用食器洗浄剤組成物の20℃における粘度は、好ましくは5~15,000mPa・s、より好ましくは5~8,000mPa・s、更に好ましくは5~2,000mPa・s、更に好ましくは5~500mPa・s、より更に好ましくは10~300mPa・s、また、好ましくは5mPa・s以上、更に10mPa・s以上、そして、好ましくは15,000mPa・s以下、更に8,000mPa・s以下、更に2,000mPa・s以下、更に500mPa・s以下、更に300mPa・s以下である。粘度は(i)成分、(j)成分、(k)成分などで調整することができる。 The viscosity at 20 ° C. of the dishwashing composition for hand washing of the present invention is preferably 5 to 15,000 mPa · s, more preferably 5 to 8,000 mPa · s, still more preferably 5 to 2,000 mPa · s, and further Preferably 5 to 500 mPa · s, more preferably 10 to 300 mPa · s, more preferably 5 mPa · s or more, further 10 mPa · s or more, and preferably 15,000 mPa · s or less, and further 8,000 mPa · s. Hereinafter, it is further 2,000 mPa · s or less, further 500 mPa · s or less, and further 300 mPa · s or less. The viscosity can be adjusted by the component (i), the component (j), the component (k), and the like.
 本発明の手洗い用食器洗浄剤組成物は、香料、染料、顔料などの成分を含有することができる。 The dishwashing composition for hand washing of the present invention can contain components such as fragrances, dyes and pigments.
<手洗い洗浄方法>
 本発明の手洗い用食器洗浄剤組成物は、食器の手洗い洗浄に用いられる。手洗い洗浄に用いられる洗浄液は、本発明の手洗い用食器洗浄剤組成物を用いて得られたものであり、組成物の原液又は水を含む希釈液が用いられる。具体的な手洗い洗浄方法としては、本発明の手洗い用食器洗浄剤組成物を用いた洗浄液を付着させた可撓性材料で食器を手洗い洗浄した後、水を用いてすすぎを行う、食器の洗浄方法が挙げられる。例えば、水を含んだスポンジなどの可撓性材料に本発明の組成物を付着させ洗浄液を保持させて、手で数回揉みながら泡立てて、食器をこすり洗いする。可撓性材料が保持する洗浄液中の(a)成分、(b)成分、及び(c)成分の合計濃度は、好ましくは1,000~30,000ppm、より好ましくは1,000~20,000ppm、更に好ましくは2,000~10,000ppm、また、好ましくは1,000ppm以上、更に2,000ppm以上、そして、好ましくは30,000ppm以下、更に20,000ppm以下、更に10,000ppm以下であることが、高い起泡性と泡持続性の点から好ましい。洗浄終了後には水を加えてすすぎを行うが、例えば、本発明では洗浄濃度に希釈された組成物1質量部に対してすすぎ水3.3~133質量部で十分泡が消え、すすぎを速やかに完了することができる。このすすぎ水の量は、従来の手洗い用洗浄剤組成物を用いた場合の2/3~1/10程度である。なお、ここでの組成物1質量部とは、組成物純分の濃度を示し、前記のすすぎ水の量に関する記述は、希釈された濃度に関わらず、洗浄液の調製に用いた手洗い用食器洗浄剤組成物純分1質量部に対するすすぎ水が3.3~133質量部で十分泡が消えることを示している。
<Hand-washing method>
The dishwashing composition for handwashing of the present invention is used for handwashing dishes. The cleaning liquid used for hand-washing is obtained using the dishwashing detergent composition for hand-washing of the present invention, and a stock solution of the composition or a diluted solution containing water is used. As a specific hand-washing method, the tableware is washed with water after washing the tableware with a flexible material to which a cleaning liquid using the dishwashing composition for hand-washing of the present invention is attached, and washing with tableware. A method is mentioned. For example, the composition of the present invention is adhered to a flexible material such as a sponge containing water to hold the cleaning liquid, and the foam is rubbed by hand several times to rub the dishes. The total concentration of the component (a), the component (b), and the component (c) in the cleaning liquid retained by the flexible material is preferably 1,000 to 30,000 ppm, more preferably 1,000 to 20,000 ppm. More preferably, it is 2,000 to 10,000 ppm, preferably 1,000 ppm or more, more preferably 2,000 ppm or more, and preferably 30,000 ppm or less, further 20,000 ppm or less, further 10,000 ppm or less. However, it is preferable from the viewpoint of high foamability and foam persistence. After completion of washing, water is added to perform rinsing. For example, in the present invention, the foam disappears sufficiently with 3.3 to 133 parts by mass of rinsing water with respect to 1 part by mass of the composition diluted to the washing concentration. Can be completed. The amount of the rinsing water is about 2/3 to 1/10 when the conventional detergent composition for hand washing is used. Here, 1 part by mass of the composition indicates the concentration of the pure composition, and the above description regarding the amount of rinsing water is the washing of dishes for hand washing used in the preparation of the cleaning liquid regardless of the diluted concentration. It is shown that the foam disappears sufficiently when 3.3 to 133 parts by mass of rinsing water with respect to 1 part by mass of the pure composition is used.
 また、別の具体的な手洗い洗浄方法としては、本発明の手洗い用食器洗浄剤組成物を水で希釈した洗浄液に食器を浸漬した後に、スポンジなどの可撓性材料を用いて食器を手洗い洗浄し、その後、水を用いてすすぎを行う、食器の洗浄方法が挙げられる。食器を浸漬する時間は、洗浄性向上の観点から1分以上が好ましく、3分以上がより好ましく、5分以上が更に好ましく、10分以上がより更に好ましく、30分以上が最も好ましく、また、24時間以下が好ましく、12時間以下がより好ましく、6時間以下が更に好ましく、3時間以下がより更に好ましく、1時間以下が最も好ましい。食器を浸漬する洗浄液中の(a)成分、(b)成分、及び(c)成分の合計濃度は、好ましくは100ppm以上、更に200ppm以上、そして、好ましくは3,000ppm以下、更に2,000ppm以下、更に1,000ppm以下であることが、高い起泡性と泡持続性の点から好ましい。洗浄終了後には水を加えてすすぎを行うが、例えば、本発明では、洗浄液の調製に用いた手洗い用食器洗浄剤組成物1質量部に対してすすぎ水3.3~133質量部で十分泡が消え、すすぎを速やかに完了することができる。 Further, as another specific hand-washing washing method, the tableware is immersed in a washing solution obtained by diluting the dishwashing composition for hand washing of the present invention with water, and then the dishes are washed by hand using a flexible material such as a sponge. Then, the washing | cleaning method of the tableware which performs rinsing using water is mentioned. The time for immersing the tableware is preferably 1 minute or more, more preferably 3 minutes or more, further preferably 5 minutes or more, still more preferably 10 minutes or more, most preferably 30 minutes or more, from the viewpoint of improving the cleanability. It is preferably 24 hours or less, more preferably 12 hours or less, still more preferably 6 hours or less, still more preferably 3 hours or less, and most preferably 1 hour or less. The total concentration of component (a), component (b), and component (c) in the cleaning liquid in which the tableware is immersed is preferably 100 ppm or more, more preferably 200 ppm or more, and preferably 3,000 ppm or less, further 2,000 ppm or less. Further, it is preferably 1,000 ppm or less from the viewpoint of high foamability and foam persistence. After completion of washing, water is added to perform rinsing. For example, in the present invention, 3.3 to 133 parts by mass of rinsing water is sufficiently foamed with respect to 1 part by mass of the dishwashing composition for hand washing used for the preparation of the washing liquid. Disappears and rinsing can be completed quickly.
 本発明の態様を以下に例示する。
<1> (a)下記一般式(1)で表されるスルホコハク酸アルキルエステル又はその塩、好ましくは、スルホコハク酸ジアルキルエステルまたはその塩、(b)炭素数8~21の炭化水素基と、硫酸エステル塩基又はスルホン酸塩基とを有する陰イオン界面活性剤〔但し(a)を除く〕5~35質量%、好ましくは7~20質量%、より好ましくは9~15質量%、及び(c)スルホベタイン型界面活性剤を含有する手洗い用食器洗浄剤組成物。
Embodiments of the present invention are exemplified below.
<1> (a) A sulfosuccinic acid alkyl ester represented by the following general formula (1) or a salt thereof, preferably a sulfosuccinic acid dialkyl ester or a salt thereof, (b) a hydrocarbon group having 8 to 21 carbon atoms and sulfuric acid An anionic surfactant having an ester base or a sulfonate group (excluding (a)), 5 to 35% by mass, preferably 7 to 20% by mass, more preferably 9 to 15% by mass, and (c) sulfone A dishwashing composition for hand washing containing a betaine-type surfactant.
Figure JPOXMLDOC01-appb-C000004
Figure JPOXMLDOC01-appb-C000004
〔式中、R1、R2は、それぞれ、炭素数5~18、好ましくは6~14、より好ましくは7~10のアルキル基、好ましくは分岐構造を有するアルキル基又は水素原子、好ましくは2-エチルヘキシル基であり、R1、R2の少なくとも一方は炭素数5~18のアルキル基である。即ち、R1とR2が同時に水素原子である場合を除く。A1、A2はそれぞれ独立に炭素数2~4、好ましくは2~3のアルキレン基、x、yは平均付加モル数でありそれぞれ独立に0~6、好ましくは0~3、より好ましくは0~2、より好ましくは0~1、より好ましくは0である。M1は陽イオン、好ましくは有機又は有機の陽イオンである。〕 [Wherein R 1 and R 2 are each an alkyl group having 5 to 18 carbon atoms, preferably 6 to 14 carbon atoms, more preferably 7 to 10 carbon atoms, preferably a branched alkyl group or a hydrogen atom, preferably 2 -Ethylhexyl group, and at least one of R 1 and R 2 is an alkyl group having 5 to 18 carbon atoms. That is, the case where R 1 and R 2 are hydrogen atoms at the same time is excluded. A 1 and A 2 are each independently an alkylene group having 2 to 4 carbon atoms, preferably 2 to 3 carbon atoms, x and y are average added mole numbers, and are each independently 0 to 6, preferably 0 to 3, more preferably 0 to 2, more preferably 0 to 1, more preferably 0. M 1 is a cation, preferably an organic or organic cation. ]
<2> 更に、(d)含マグネシウム無機化合物及び/又はアルキレンジアミン(アルキレン基は炭素数2~6)、好ましくは塩化マグネシウム及び硫酸マグネシウムから選ばれる化合物を含有する<1>記載の手洗い用食器洗浄剤組成物。 <2> The tableware for hand-washing according to <1>, further comprising (d) a magnesium-containing inorganic compound and / or an alkylenediamine (the alkylene group has 2 to 6 carbon atoms), preferably a compound selected from magnesium chloride and magnesium sulfate. Cleaning composition.
<3> (e)アミンオキシド型界面活性剤、カルボベタイン型界面活性剤及びアルカノールアミド型界面活性剤から選ばれる界面活性剤の含有量が、組成物中5質量%以下、好ましくは3質量%以下、より好ましくは2質量%以下、より好ましくは1質量%以下、より好ましくは0.5質量%以下、より好ましくは0質量%以下である、<1>又は<2>記載の手洗い用食器洗浄剤組成物。 <3> (e) Content of surfactant selected from amine oxide type surfactant, carbobetaine type surfactant and alkanolamide type surfactant is 5% by mass or less, preferably 3% by mass in the composition. Or less, more preferably 2% by mass or less, more preferably 1% by mass or less, more preferably 0.5% by mass or less, and more preferably 0% by mass or less, the tableware for hand washing according to <1> or <2> Cleaning composition.
<4> (b)が、炭素数8~18のアルキル基を有するアルキル硫酸エステル塩、炭素数8~18のアルキル基を有し炭素数2~3のオキシアルキレン基の平均付加モル数が0.1~6、更に0.3~3、更に0.4~1.5であるポリオキシアルキレンアルキルエーテル硫酸エステル塩、炭素数8~15のアルキル基を有するアルキルベンゼンスルホン酸塩、並びに炭素数10~15のアルカンスルホン酸塩から選ばれる陰イオン界面活性剤である、<1>~<3>の何れか1項記載の手洗い用食器洗浄剤組成物。 <4> (b) is an alkyl sulfate ester salt having an alkyl group having 8 to 18 carbon atoms, and an average addition mole number of an oxyalkylene group having 2 to 3 carbon atoms having an alkyl group having 8 to 18 carbon atoms is 0 1. Polyoxyalkylene alkyl ether sulfates having 1 to 6, further 0.3 to 3, and further 0.4 to 1.5, alkylbenzene sulfonates having an alkyl group having 8 to 15 carbon atoms, and 10 carbon atoms The dishwashing detergent composition for hand washing according to any one of <1> to <3>, which is an anionic surfactant selected from 15 alkane sulfonates.
<5> (b)成分が下記一般式(2)の化合物である、<1>~<4>の何れか1項記載の手洗い用食器洗浄剤組成物。
   R3-O-(R4O)n-SO32    (2)
〔式中、R3は、炭素数8~18、好ましくは8~15のアルキル基であり、R4は、エチレン基及び/又はプロピレン基であり、nは平均付加モル数であり0以上6以下の数、好ましくは0.1以上2以下の数である。M2は陽イオン、好ましくは無機又は有機の陽イオンである。〕
<5> The dishwashing detergent composition for hand washing according to any one of <1> to <4>, wherein the component (b) is a compound of the following general formula (2).
R 3 —O— (R 4 O) n —SO 3 M 2 (2)
[Wherein R 3 is an alkyl group having 8 to 18 carbon atoms, preferably 8 to 15 carbon atoms, R 4 is an ethylene group and / or a propylene group, and n is an average addition mole number of 0 to 6 It is the following number, preferably 0.1 or more and 2 or less. M 2 is a cation, preferably an inorganic or organic cation. ]
<6> 組成物中の全界面活性剤の含有量に対する(a)、(b)、及び(c)の合計質量が50~100質量%、更に60~100質量%、更に80~100質量%、更に90~100質量%である<1>~<5>の何れか1項記載の手洗い用食器洗浄剤組成物。 <6> The total mass of (a), (b), and (c) with respect to the total surfactant content in the composition is 50 to 100 mass%, further 60 to 100 mass%, and further 80 to 100 mass%. Furthermore, the dishwashing detergent composition for hand washing according to any one of <1> to <5>, which is 90 to 100% by mass.
<7> 更に、(f)炭素数10~18の脂肪酸又はその塩を、組成物中、3質量%以下、更に2質量%以下、更に1質量%以下、更に0.5質量%以下、より更に0質量%含有する<1>~<6>の何れか1項記載の手洗い用食器洗浄剤組成物。 <7> Further, (f) a fatty acid having 10 to 18 carbon atoms or a salt thereof in the composition is 3% by mass or less, further 2% by mass or less, further 1% by mass or less, and further 0.5% by mass or less. The dishwashing composition for hand washing according to any one of <1> to <6>, further comprising 0% by mass.
<8> (a)成分がスルホコハク酸ジアルキルエステル又はその塩である<1>~<7>の何れか1項記載の手洗い用食器洗浄剤組成物。 <8> The dishwashing composition for hand washing according to any one of <1> to <7>, wherein the component (a) is a sulfosuccinic acid dialkyl ester or a salt thereof.
<9> (a)成分を1質量%以上、好ましくは2質量%以上、より好ましくは3質量%以上、また、30質量%以下、より好ましくは25質量%以下、更に好ましくは20質量%以下、より更に好ましくは15質量%以下含有する、<1>~<8>の何れか1項記載の手洗い用食器洗浄剤組成物。 <9> Component (a) is 1% by mass or more, preferably 2% by mass or more, more preferably 3% by mass or more, and 30% by mass or less, more preferably 25% by mass or less, and further preferably 20% by mass or less. More preferably, the dishwashing composition for hand washing according to any one of <1> to <8>, which is contained in an amount of 15% by mass or less.
<10> (b)成分を5質量%以上、好ましくは7質量%以上、より好ましくは9質量%以上、また、35質量%以下、好ましくは20質量%以下、より好ましくは15質量%以下含有する、<1>~<9>の何れか1項記載の手洗い用食器洗浄剤組成物。 <10> Component (b) is contained in an amount of 5% by mass or more, preferably 7% by mass or more, more preferably 9% by mass or more, and 35% by mass or less, preferably 20% by mass or less, more preferably 15% by mass or less. <10> The dishwashing composition for hand washing according to any one of <1> to <9>.
<11> (c)成分を1質量%以上、より好ましくは2質量%以上、更に好ましくは3質量%以上、また、20質量%以下、より好ましくは14質量%以下、更に好ましくは12質量%以下含有する、<1>~<10>の何れか1項記載の手洗い用食器洗浄剤組成物。 <11> The component (c) is 1% by mass or more, more preferably 2% by mass or more, further preferably 3% by mass or more, 20% by mass or less, more preferably 14% by mass or less, and further preferably 12% by mass. The dishwashing composition for hand washing according to any one of <1> to <10>, which is contained below.
<12> (a)成分/(b)成分の質量比が0.03以上、好ましくは0.15以上、より好ましくは0.2以上、更に好ましくは0.25以上、また、2.5以下、好ましくは2以下、より好ましくは1.5以下、更に好ましくは1以下である、<1>~<11>の何れか1項記載の手洗い用食器洗浄剤組成物。 <12> The mass ratio of (a) component / (b) component is 0.03 or more, preferably 0.15 or more, more preferably 0.2 or more, still more preferably 0.25 or more, and 2.5 or less. The dishwashing composition for hand washing according to any one of <1> to <11>, preferably 2 or less, more preferably 1.5 or less, and even more preferably 1 or less.
<13> (b)成分/(c)成分の質量比が0.3以上、より好ましくは0.5以上、更に好ましくは1以上、より更に好ましくは1.5以上、また、6以下、より好ましくは5以下、更に好ましくは4以下、より更に好ましくは3以下である、<1>~<12>の何れか1項記載の手洗い用食器洗浄剤組成物。 <13> The mass ratio of component (b) / component (c) is 0.3 or more, more preferably 0.5 or more, still more preferably 1 or more, still more preferably 1.5 or more, and 6 or less. The dishwashing composition for hand washing according to any one of <1> to <12>, preferably 5 or less, more preferably 4 or less, and even more preferably 3 or less.
<14> (a)成分/(c)成分の質量比が0.1以上、好ましくは0.3以上、より好ましくは0.6以上、また、5以下、好ましくは3以下、より好ましくは2.6以下、更に好ましくは2.3以下、より更に好ましくは1.8以下である、<1>~<13>の何れか1項記載の手洗い用食器洗浄剤組成物。 <14> The mass ratio of (a) component / (c) component is 0.1 or more, preferably 0.3 or more, more preferably 0.6 or more, and 5 or less, preferably 3 or less, more preferably 2 The dishwashing composition for hand washing according to any one of <1> to <13>, which is .6 or less, more preferably 2.3 or less, and even more preferably 1.8 or less.
<15> (c)成分/〔(a)成分+(b)成分〕の質量比が0.02以上、より好ましくは0.1以上、更に好ましくは0.15以上、また、2以下、より好ましくは1.5以下、更に好ましくは1以下、より更に好ましくは0.5以下である、<1>~<14>の何れか1項記載の手洗い用食器洗浄剤組成物。 <15> The mass ratio of (c) component / [(a) component + (b) component] is 0.02 or more, more preferably 0.1 or more, still more preferably 0.15 or more, or 2 or less. The dishwashing composition for hand washing according to any one of <1> to <14>, which is preferably 1.5 or less, more preferably 1 or less, and still more preferably 0.5 or less.
<16> 25℃におけるpHが、4以上、より好ましくは4.5以上、より好ましくは5以上であり、また、9以下、より好ましくは7以下、より好ましくは6以下である、<1>~<15>の何れか1項記載の手洗い用食器洗浄剤組成物。 <16> The pH at 25 ° C. is 4 or more, more preferably 4.5 or more, more preferably 5 or more, and 9 or less, more preferably 7 or less, more preferably 6 or less, <1> The dishwashing composition for hand washing according to any one of to <15>.
<17> 20℃における粘度が、5mPa・s以上、より好ましくは10mPa・s以上、また、15,000mPa・s以下、より好ましくは8,000mPa・s以下、更に好ましくは2,000mPa・s以下、より更に好ましくは500mPa・s以下、最も好ましくは300mPa・s以下である、<1>~<16>の何れか1項記載の手洗い用食器洗浄剤組成物。 <17> The viscosity at 20 ° C. is 5 mPa · s or more, more preferably 10 mPa · s or more, 15,000 mPa · s or less, more preferably 8,000 mPa · s or less, and still more preferably 2,000 mPa · s or less. More preferably, the dishwashing composition for hand washing according to any one of <1> to <16>, which is more preferably 500 mPa · s or less, and most preferably 300 mPa · s or less.
<18> 更に、(g)成分として、アルキルグリセリルエーテル(アルキル基の炭素数は6~18、好ましくは8~12)を、組成物中、0.5質量%以上、更に1質量%以上、より更に1.5質量%以上、また、20質量%以下、更に15質量%以下、より更に10質量%以下含有する、<1>~<17>の何れか1項記載の手洗い用食器洗浄剤組成物。 <18> Further, as component (g), alkyl glyceryl ether (the alkyl group has 6 to 18, preferably 8 to 12 carbon atoms) in the composition is 0.5% by mass or more, and further 1% by mass or more. The dishwashing agent for hand-washing according to any one of <1> to <17>, further comprising 1.5% by mass or more, 20% by mass or less, further 15% by mass or less, and further 10% by mass or less. Composition.
<19> 更に、(i)成分として、ハイドロトロープ剤を、組成物中に0.5質量%以上、より好ましくは1質量%以上、更に好ましくは1.5質量%以上、また、20質量%以下、より好ましくは15質量%以下、更に好ましくは10質量%以下含有する、<1>~<18>の何れか1項記載の手洗い用食器洗浄剤組成物。 <19> Further, as component (i), a hydrotrope agent is 0.5% by mass or more, more preferably 1% by mass or more, still more preferably 1.5% by mass or more, and 20% by mass in the composition. The hand dishwashing detergent composition according to any one of <1> to <18>, which is more preferably contained in an amount of 15% by mass or less, and still more preferably 10% by mass or less.
<20> 更に、(j)成分として、溶剤を、組成物中に1.5質量%以上、より好ましくは2質量%以上、更に好ましくは3質量%以上、また、30質量%以下、より好ましくは20質量%以下、更に好ましくは15質量%以下含有する、<1>~<19>の何れか1項記載の手洗い用食器洗浄剤組成物。 <20> Further, as the component (j), a solvent is added to the composition in an amount of 1.5% by mass or more, more preferably 2% by mass or more, still more preferably 3% by mass or more, and more preferably 30% by mass or less. The dishwashing composition for hand washing according to any one of <1> to <19>, which contains 20% by mass or less, more preferably 15% by mass or less.
<21> 更に、(k)成分として、重合体、好ましくは重量平均分子量が200~3,000のポリプロピレングリコール、及び重量平均分子量が200~3,000のポリエチレングリコールから選ばれる1種又は2種以上の重合体を、組成物中に0.05質量%以上、より好ましくは0.1質量%以上、更に好ましくは0.5質量%以上、また、10質量%以下、より好ましくは5質量%以下、更に好ましくは3質量%以下含有する、<1>~<20>の何れか1項記載の手洗い用食器洗浄剤組成物。 <21> Further, as the component (k), one or two types selected from polymers, preferably polypropylene glycol having a weight average molecular weight of 200 to 3,000, and polyethylene glycol having a weight average molecular weight of 200 to 3,000. The above polymer in the composition is 0.05% by mass or more, more preferably 0.1% by mass or more, further preferably 0.5% by mass or more, and 10% by mass or less, more preferably 5% by mass. The hand dishwashing detergent composition according to any one of <1> to <20>, further preferably 3% by mass or less.
<22> <1>~<21>の何れか1項記載の手洗い用食器洗浄剤組成物を用いた洗浄液で食器を手洗い洗浄し、その後、水を用いてすすぎを行う、食器の洗浄方法。 <22> A method for washing dishes, wherein the dishes are washed with a washing solution using the dishwashing composition for washing hands according to any one of <1> to <21>, and then rinsed with water.
<23> <1>~<21>の何れか1項記載の手洗い用食器洗浄剤組成物を用いた洗浄液を付着させた可撓性材料で食器を手洗い洗浄した後、水を用いてすすぎを行う、食器の洗浄方法。 <23> After washing and washing the dishes with a flexible material to which a washing liquid using the dishwashing composition for washing according to any one of <1> to <21> is attached, rinse with water. How to wash the dishes.
<24> <1>~<21>の何れか1項記載の手洗い用食器洗浄剤組成物を用いた洗浄液を付着させた可撓性材料で食器を手洗い洗浄した後、水を用いてすすぎを行う、食器の洗浄方法であって、可撓性材料が保持する洗浄液中の(a)成分、(b)成分、及び(c)成分の合計濃度が、好ましくは1,000ppm以上、更に2,000ppm以上、そして、好ましくは30,000ppm以下、更に20,000ppm以下、更に10,000ppm以下であり、洗浄液の調製に用いた手洗い用食器洗浄剤組成物1質量部に対して水3.3~133質量部を用いてすすぎを行う、食器の洗浄方法。 <24> After washing and washing the tableware with a flexible material to which a washing liquid using the dishwashing composition for washing according to any one of <1> to <21> is attached, rinse with water. A tableware cleaning method to be performed, wherein the total concentration of the component (a), the component (b), and the component (c) in the cleaning liquid retained by the flexible material is preferably 1,000 ppm or more, and 3,000 ppm or more, and preferably 30,000 ppm or less, further 20,000 ppm or less, and further 10,000 ppm or less, and from 3.3 parts by weight of water to 1 part by weight of the dishwashing composition for hand washing used in the preparation of the cleaning liquid. The washing | cleaning method of the tableware which performs a rinse using 133 mass parts.
<25> <1>~<21>の何れか1項記載の手洗い用食器洗浄剤組成物を水で希釈した洗浄液に食器を浸漬し、手洗い洗浄した後、水を用いてすすぎを行う、食器の洗浄方法。 <25> Tableware in which the dishwashing composition for handwashing according to any one of <1> to <21> is immersed in a cleaning solution diluted with water, washed by hand and then rinsed with water. Cleaning method.
<26> <1>~<21>の何れか1項記載の手洗い用食器洗浄剤組成物を水で希釈した洗浄液に食器を浸漬した後に、可撓性材料を用いて食器をこすり洗いし、水を用いてすすぎを行う、食器の洗浄方法であって、食器を浸漬する時間が、好ましくは1分以上、より好ましくは3分以上、更に好ましくは5分以上、より更に好ましくは10分以上、最も好ましくは30分以上であり、また、好ましくは24時間以下、より好ましくは12時間以下、更に好ましくは6時間以下、より更に好ましくは3時間以下、最も好ましくは1時間以下であり、食器を浸漬する洗浄液中の(a)成分、(b)成分、及び(c)成分の合計濃度が、好ましくは100ppm以上、更に200ppm以上、そして、好ましくは3,000ppm以下、更に2,000ppm以下、更に1,000ppm以下であり、洗浄液の調製に用いた手洗い用食器洗浄剤組成物1質量部に対して水3.3~133質量部を用いてすすぎを行う、食器の洗浄方法。 <26> After immersing tableware in a cleaning solution obtained by diluting the dishwashing composition for hand washing according to any one of <1> to <21> with water, the tableware is rubbed with a flexible material, A method for washing tableware in which rinsing is performed using water, and the time for immersing the tableware is preferably 1 minute or more, more preferably 3 minutes or more, still more preferably 5 minutes or more, and even more preferably 10 minutes or more. Most preferably 30 minutes or longer, and preferably 24 hours or shorter, more preferably 12 hours or shorter, still more preferably 6 hours or shorter, even more preferably 3 hours or shorter, most preferably 1 hour or shorter. The total concentration of the component (a), the component (b), and the component (c) in the cleaning solution for immersing the liquid is preferably 100 ppm or more, more preferably 200 ppm or more, and preferably 3,000 ppm or less, and further 2 000ppm or less, still more 1,000ppm or less, perform rinsing with water from 3.3 to 133 parts by weight with respect to 1 part by weight hand dishwashing detergent composition used to prepare the cleaning solution, tableware cleaning method.
<27> <1>~<21>の何れか1項記載の手洗い用食器洗浄剤組成物の、洗浄液で食器を手洗い洗浄し、その後、水を用いてすすぎを行う、食器の洗浄における使用。 <27> Use of the dishwashing detergent composition for handwashing according to any one of <1> to <21> in washing dishes, wherein the dishes are washed with a washing solution and then rinsed with water.
実施例
  次の実施例は本発明の実施について述べる。実施例は本発明の例示について述べるものであり、本発明を限定するためではない。
 表1及び下記の配合成分を用いて表1の手洗い用食器洗浄剤組成物を調製し、下記の各評価を行った。結果を表1に示す。なお、表1中の配合成分の質量%は、全て有効分に基づく数値である。
Examples The following examples describe the practice of the present invention. The examples are illustrative of the invention and are not intended to limit the invention.
Table 1 and the following blending components were used to prepare the hand-washing dishwashing composition of Table 1, and the following evaluations were made. The results are shown in Table 1. In addition, all the mass% of the mixing | blending component in Table 1 is a numerical value based on an effective part.
<配合成分>
・a-1:スルホコハク酸ジ-2-エチルヘキシルナトリウム試薬〔関東化学(株)〕
・a-2:スルホコハク酸ジポリオキシエチレン-2-エチルヘキシルナトリウム:スルホコハク酸とポリオキシエキレン-2-エチルヘキシルエーテルのエステル化反応で得られたものを用いた。ポリオキシエキレン-2-エチルヘキシルエーテルは、2-エチルヘキサノール1モルに対して、エチレンオキシドを1モル付加して得られた。
・b-1:ラウリル硫酸ナトリウム
・b-2:アルキル鎖が炭素数12の天然アルコール1モルに、EOを平均1モル付加したのち、三酸化イオウにより硫酸化し、水酸化ナトリウム水溶液でpH調整と同時に希釈したもの(10質量%水溶液のpHは11)
・b-3:アルキル鎖が炭素数12の天然アルコール1モルに、POを平均0.6モル付加したのち、三酸化イオウにより硫酸化し、水酸化ナトリウム水溶液でpH調整と同時に希釈したもの(10質量%水溶液のpHは11)
・b-4:直鎖/分岐鎖混合アルコール〔サソール社製Isalchem123(炭素数12のアルキル基及び炭素数13のアルキル基を含有し、分岐率は94モル%)〕を、3酸化イオウで硫酸化し水酸化ナトリウムで中和した化合物(平均分子量:295)
<Compounding ingredients>
A-1: Sodium di-2-ethylhexyl sulfosuccinate (Kanto Chemical Co., Inc.)
A-2: dipolyoxyethylene-2-ethylhexyl sodium sulfosuccinate: the one obtained by esterification reaction of sulfosuccinic acid and polyoxyethylene-2-ethylhexyl ether was used. Polyoxyethylene-2-ethylhexyl ether was obtained by adding 1 mol of ethylene oxide to 1 mol of 2-ethylhexanol.
B-1: sodium lauryl sulfate b-2: 1 mol of EO is added to 1 mol of natural alcohol having an alkyl chain of 12 carbons, then sulfated with sulfur trioxide, and pH is adjusted with an aqueous sodium hydroxide solution. Diluted at the same time (pH of 10% by weight aqueous solution is 11)
B-3: 1 mol of a natural alcohol having 12 carbon atoms added with an average of 0.6 mol of PO, then sulfated with sulfur trioxide and diluted with an aqueous sodium hydroxide solution simultaneously with pH adjustment (10 The pH of the mass% aqueous solution is 11)
B-4: linear / branched mixed alcohol [Isalchem 123 (containing 12 alkyl groups and 13 alkyl groups, branching rate: 94 mol%) manufactured by Sasol, sulfuric acid with sulfur trioxide Compound neutralized with sodium hydroxide (average molecular weight: 295)
・c-1:N-ラウリル-N,N-ジメチル-N-(2-ヒドロキシスルホプロピル)アンモニウムスルホベタイン(花王(株)製:アンヒトール20HD)
・c’-1:N-ラウロイルアミノプロピル-N,N-ジメチル-N-カルボキシメチルアンモニウムベタイン(花王(株)製:アンヒトール20AB)
・d-1:MgCl2・6H2O(塩化マグネシウム6水塩)、配合には6水塩を用いたが、表1中の数値は、結晶水を除いた配合量で示した。
・e-1:N-ラウリル-N,N-ジメチルアミンオキシド(花王(株)製:アンヒトール20N)
C-1: N-lauryl-N, N-dimethyl-N- (2-hydroxysulfopropyl) ammonium sulfobetaine (manufactured by Kao Corporation: Amphitol 20HD)
C′-1: N-lauroylaminopropyl-N, N-dimethyl-N-carboxymethylammonium betaine (manufactured by Kao Corporation: Amphital 20AB)
D-1: MgCl 2 .6H 2 O (magnesium chloride hexahydrate), hexahydrate was used for blending, but the numerical values in Table 1 are shown in blending amounts excluding crystallization water.
E-1: N-lauryl-N, N-dimethylamine oxide (manufactured by Kao Corporation: Amphitol 20N)
<起泡力(初期泡量)及び泡消え性>
 表1の食器洗浄剤組成物を3.5°DH硬水で3.2質量%に希釈し、特開2008-260852の図1記載のポンプフォーマー容器に充填した。ここで、泡吐出機構には、メッシュサイズ200/インチのメッシュが1枚装着されていた。次いで、容器上部のポンプヘッド部を3プッシュ連続して押し切ることにより、3gの泡を500mlのメスシリンダーの中に作製した。なお、押し切るスピードは、1プッシュあたり1秒のスピードで行なった。このとき、メスシリンダーの目盛りからその容量を記録し、初期泡量とした。起泡性はこの初期泡量で評価した。
<Foaming power (initial foam amount) and foam disappearance>
The dishwashing composition of Table 1 was diluted to 3.5% by mass with 3.5 ° DH hard water and filled into a pump former container described in FIG. 1 of JP-A-2008-260852. Here, a single mesh having a mesh size of 200 / inch was attached to the foam discharge mechanism. Next, 3 g of foam was produced in a 500 ml graduated cylinder by continuously pushing out the pump head at the top of the container for 3 pushes. Note that the speed of pushing out was 1 second per push. At this time, the volume was recorded from the scale of the graduated cylinder and used as the initial amount of foam. Foaming property was evaluated by this initial foam amount.
 次に、メスシリンダーの上部に設置した硬水の導入手段(手製のジョウロ)を通して3.5°DH硬水を泡に100ml添加し10秒間放置した。この操作を、添加した硬水の合計が300mlになるまで繰り返した。最後の水を添加し、10秒間放置した後の泡量を測定した。尚、泡消え性については、硬水300ml添加において、次式で示す泡量変化率から求め、300ml添加までに70%以上になれば希釈(すすぎ)による速やかな泡消えが達成できるものと判断した。
 泡量変化率(%)=[1-(硬水300ml添加後の泡量/初期の泡量)]×100
Next, 100 ml of 3.5 ° DH hard water was added to the foam through a means for introducing hard water (manufactured by hand) installed at the top of the graduated cylinder and left for 10 seconds. This operation was repeated until the total amount of hard water added reached 300 ml. The final amount of water was added and the amount of foam after standing for 10 seconds was measured. In addition, about 300-ml hard water addition, it calculated | required from the foam amount change rate shown by following Formula, and if it became 70% or more by 300 ml addition, it was judged that rapid foam disappearance by dilution (rinsing) could be achieved. .
Foam amount change rate (%) = [1− (foam amount after adding 300 ml of hard water / initial foam amount)] × 100
 硬水をメスシリンダーに添加するときの様子を図1に示す。図1中、1はメスシリンダー、2は泡、3は硬水の導入手段(手製のジョウロ)、4は該導入手段の開口部であり、図2は硬水の導入手段3の開口部4の穿孔状態を示す概略図である。硬水の導入手段である手製のジョウロの作製方法は、以下の通りである。先ず、250mlのポリプロピレン製広口びん(アズワン製:アイボーイ広口びん)の底部から高さ約3分の1の本体部分迄を切除した。次いで、直径4cmの薄い円状のポリエチレン製板に対して、図2に示すように、9mm間隔で13個の直径2mmの穴を開けたポリエチレン製多孔板を用意した。最後に、切除した広口びん上部のフタ開口部(直径4cm)に対して、上記のポリエチレン製多孔板を開口部4として固定して硬水の導入手段3(手製のジョウロ)を作製した。このようにして作製した硬水の導入手段3(手製のジョウロ)を、図1のように、倒置状態に保ちながら、メスシリンダー1の開口部にはめ込んだ。硬水は広口びんの切除側から投入した。 Fig. 1 shows how hard water is added to the graduated cylinder. In FIG. 1, 1 is a graduated cylinder, 2 is foam, 3 is a hard water introduction means (manufactured by hand), 4 is an opening of the introduction means, and FIG. 2 is a perforation of the opening 4 of the hard water introduction means 3. It is the schematic which shows a state. A method for producing a handmade water fountain as means for introducing hard water is as follows. First, from the bottom of a 250 ml polypropylene wide-mouthed bottle (manufactured by ASONE: I-boy wide-mouthed bottle) to the main body part having a height of about one third was excised. Next, as shown in FIG. 2, a polyethylene perforated plate having 13 holes with a diameter of 2 mm at 9 mm intervals was prepared for a thin circular polyethylene plate with a diameter of 4 cm. Finally, the polyethylene perforated plate was fixed as the opening 4 to the lid opening (diameter 4 cm) at the top of the excised wide-mouth bottle to produce hard water introducing means 3 (handmade watering device). The hard water introducing means 3 (manufactured by hand) thus produced was fitted into the opening of the graduated cylinder 1 while being kept in an inverted state as shown in FIG. Hard water was introduced from the excised side of the wide-mouth bottle.
Figure JPOXMLDOC01-appb-T000005
Figure JPOXMLDOC01-appb-T000005

Claims (14)

  1.  (a)下記一般式(1)で表されるスルホコハク酸アルキルエステル又はその塩、(b)炭素数8~21の炭化水素基と、硫酸エステル塩基又はスルホン酸塩基とを有する陰イオン界面活性剤〔但し(a)を除く〕5~35質量%、及び(c)スルホベタイン型界面活性剤を含有する手洗い用食器洗浄剤組成物。
    Figure JPOXMLDOC01-appb-C000001
    〔式中、R1、R2は、それぞれ、炭素数5~18のアルキル基又は水素原子であり、R1、R2の少なくとも一方は炭素数5~18のアルキル基である。即ち、R1とR2が同時に水素原子である場合を除く。A1、A2はそれぞれ独立に炭素数2~4のアルキレン基、x、yは平均付加モル数でありそれぞれ独立に0~6である。M1は陽イオンである。〕
    (A) a sulfosuccinic acid alkyl ester represented by the following general formula (1) or a salt thereof; (b) an anionic surfactant having a hydrocarbon group having 8 to 21 carbon atoms and a sulfate ester base or a sulfonate group. [However, (a) is excluded] A dishwashing detergent composition for hand washing containing 5 to 35% by mass and (c) a sulfobetaine surfactant.
    Figure JPOXMLDOC01-appb-C000001
    [Wherein, R 1 and R 2 are each an alkyl group having 5 to 18 carbon atoms or a hydrogen atom, and at least one of R 1 and R 2 is an alkyl group having 5 to 18 carbon atoms. That is, the case where R 1 and R 2 are hydrogen atoms at the same time is excluded. A 1 and A 2 are each independently an alkylene group having 2 to 4 carbon atoms, and x and y are average added mole numbers, and are each independently 0 to 6. M 1 is a cation. ]
  2.  更に、(d)含マグネシウム無機化合物及び/又はアルキレンジアミン(アルキレン基は炭素数2~6)を含有する請求項1記載の手洗い用食器洗浄剤組成物。 The dishwashing composition for hand washing according to claim 1, further comprising (d) a magnesium-containing inorganic compound and / or an alkylenediamine (the alkylene group has 2 to 6 carbon atoms).
  3.  (e)アミンオキシド型界面活性剤、カルボベタイン型界面活性剤及びアルカノールアミド型界面活性剤から選ばれる界面活性剤の含有量が、組成物中5質量%以下である、請求項1又は2記載の手洗い用食器洗浄剤組成物。 (E) Content of surfactant chosen from an amine oxide type surfactant, a carbobetaine type surfactant, and an alkanolamide type surfactant is 5 mass% or less in a composition, The claim 1 or 2 Dishwashing composition for hand washing.
  4.  (b)が、炭素数8~18のアルキル基を有するアルキル硫酸エステル塩、炭素数8~18のアルキル基を有し炭素数2~3のオキシアルキレン基の平均付加モル数が0.1~6であるポリオキシアルキレンアルキルエーテル硫酸エステル塩、炭素数8~15のアルキル基を有するアルキルベンゼンスルホン酸塩、並びに炭素数10~15のアルカンスルホン酸塩から選ばれる陰イオン界面活性剤である請求項1~3の何れか1項記載の手洗い用食器洗浄剤組成物。 (B) is an alkyl sulfate ester salt having an alkyl group having 8 to 18 carbon atoms, and an average added mole number of an oxyalkylene group having 2 to 3 carbon atoms having an alkyl group having 8 to 18 carbon atoms is 0.1 to 6. An anionic surfactant selected from polyoxyalkylene alkyl ether sulfate ester salt of 6, alkylbenzene sulfonate having an alkyl group having 8 to 15 carbon atoms, and alkane sulfonate having 10 to 15 carbon atoms. 4. The dishwashing composition for hand washing according to any one of 1 to 3.
  5.  組成物中の全界面活性剤の含有量に対する(a)、(b)、及び(c)の合計質量が50~100質量%である請求項1~4の何れか1項記載の手洗い用食器洗浄剤組成物。 The tableware for hand-washing according to any one of claims 1 to 4, wherein the total mass of (a), (b), and (c) with respect to the total surfactant content in the composition is 50 to 100 mass%. Cleaning composition.
  6.  更に、(f)炭素数10~18の脂肪酸又はその塩を、組成物中、0.5質量%以下含有する請求項1~5の何れか1項記載の手洗い用食器洗浄剤組成物。 6. The dishwashing composition for hand washing according to any one of claims 1 to 5, further comprising (f) 0.5 mass% or less of a fatty acid having 10 to 18 carbon atoms or a salt thereof in the composition.
  7. (e)アミンオキシド型界面活性剤、カルボベタイン型界面活性剤及びアルカノールアミド型界面活性剤から選ばれる界面活性剤の含有量が、組成物中2質量%以下である、請求項1~6の何れか1項記載の手洗い用食器洗浄剤組成物。 The content of a surfactant selected from (e) an amine oxide type surfactant, a carbobetaine type surfactant, and an alkanolamide type surfactant is 2% by mass or less in the composition. The dishwashing agent composition for hand-washing any one of Claims.
  8. (a)成分が、スルホコハク酸ジアルキルエステル又はその塩である、請求項1~7の何れか1項記載の手洗い用食器洗浄剤組成物。 The dishwashing composition for hand washing according to any one of claims 1 to 7, wherein the component (a) is a dialkyl ester of sulfosuccinic acid or a salt thereof.
  9.  (b)成分が、下記一般式(2)の化合物である、請求項1~8の何れか1項記載の手洗い用食器洗浄剤組成物。
       R3-O-(R4O)n-SO32    (2)
    〔式中、R3は、炭素数8~18のアルキル基であり、R4は、エチレン基及び/又はプロピレン基であり、nは平均付加モル数であり0以上6以下の数である。M2は陽イオンである。〕
    The dishwashing composition for hand washing according to any one of claims 1 to 8, wherein the component (b) is a compound of the following general formula (2).
    R 3 —O— (R 4 O) n —SO 3 M 2 (2)
    [Wherein R 3 is an alkyl group having 8 to 18 carbon atoms, R 4 is an ethylene group and / or a propylene group, and n is an average added mole number, which is a number of 0 or more and 6 or less. M 2 is a cation. ]
  10. 組成物中に、(a)成分を1~30質量%、(b)成分を5~35質量%、(c)成分1~20質量%含有する請求項1~9の何れか1項記載の手洗い用食器洗浄剤組成物。 The composition according to any one of claims 1 to 9, wherein the composition contains 1 to 30% by mass of component (a), 5 to 35% by mass of component (b), and 1 to 20% by mass of component (c). A dishwashing composition for hand washing.
  11. (b)成分を7~20質量%含有する、請求項1~10の何れか1項記載の手洗い用食器洗浄剤組成物。 The dishwashing composition for hand washing according to any one of claims 1 to 10, comprising 7 to 20% by mass of component (b).
  12. (a)成分/(b)成分の質量比が0.03~2.5であり、(b)成分/(c)成分の質量比が0.3~6であり、(a)成分/(c)成分の質量比が0.1~5である、請求項1~11の何れか1項記載の手洗い用食器洗浄剤組成物。 The mass ratio of component (a) / component (b) is 0.03 to 2.5, the mass ratio of component (b) / component (c) is 0.3 to 6, and component (a) / ( The dishwashing composition for hand washing according to any one of claims 1 to 11, wherein the mass ratio of the component c) is 0.1 to 5.
  13. (c)成分/〔(a)成分+(b)成分〕の質量比が0.02~2である請求項1~12の何れか1項記載の手洗い用食器洗浄剤組成物。 The dishwashing composition for hand-washing according to any one of claims 1 to 12, wherein the mass ratio of component (c) / [component (a) + component (b)] is 0.02 to 2.
  14.  請求項1~13の何れか1項記載の手洗い用食器洗浄剤組成物を用いた洗浄液で食器を手洗い洗浄し、その後、水を用いてすすぎを行う、食器の洗浄方法。 A method for washing dishes, wherein the dishes are washed by hand with a cleaning solution using the dishwashing composition for washing hands according to any one of claims 1 to 13, and then rinsed with water.
PCT/JP2012/073562 2011-10-12 2012-09-14 Composition for dishwashing liquid for cleaning hands WO2013054635A1 (en)

Priority Applications (2)

Application Number Priority Date Filing Date Title
CN201280050578.7A CN103890156B (en) 2011-10-12 2012-09-14 Composition for dishwashing liquid for cleaning hands
IN1969DEN2014 IN2014DN01969A (en) 2011-10-12 2012-09-14

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
JP2011225125 2011-10-12
JP2011-225125 2011-10-12

Publications (1)

Publication Number Publication Date
WO2013054635A1 true WO2013054635A1 (en) 2013-04-18

Family

ID=48081693

Family Applications (1)

Application Number Title Priority Date Filing Date
PCT/JP2012/073562 WO2013054635A1 (en) 2011-10-12 2012-09-14 Composition for dishwashing liquid for cleaning hands

Country Status (5)

Country Link
JP (1) JP5654537B2 (en)
CN (1) CN103890156B (en)
IN (1) IN2014DN01969A (en)
TW (1) TWI548735B (en)
WO (1) WO2013054635A1 (en)

Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2016199754A (en) * 2016-05-27 2016-12-01 花王株式会社 Liquid detergent composition for hard surface
US12018230B2 (en) 2020-03-17 2024-06-25 Kao Corporation Surfactant composition

Families Citing this family (8)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP6678381B2 (en) * 2014-08-01 2020-04-08 花王株式会社 Biofilm remover composition for hard surfaces
JP6771952B2 (en) * 2015-12-25 2020-10-21 花王株式会社 Liquid cleaning agent composition for hard surfaces
WO2017110773A1 (en) 2015-12-25 2017-06-29 花王株式会社 Liquid detergent composition for hard surfaces
JP6707294B2 (en) * 2016-05-27 2020-06-10 花王株式会社 How to clean hard surfaces
WO2017204148A1 (en) * 2016-05-27 2017-11-30 花王株式会社 Method for washing hard surface
MX2022011389A (en) 2020-03-17 2022-10-10 Kao Corp Method for cleaning hard article.
CN116348578A (en) * 2020-10-15 2023-06-27 罗地亚经营管理公司 Structured surfactant blends and sulfate-free aqueous personal cleansing compositions prepared therefrom
JP7450518B2 (en) 2020-10-30 2024-03-15 ライオン株式会社 dishwashing detergent

Citations (12)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPS62127396A (en) * 1985-11-28 1987-06-09 花王株式会社 Low irritant detergent composition
JPH01297500A (en) * 1988-05-25 1989-11-30 Kao Corp Liquid cleaning agent composition
JPH0436223A (en) * 1990-05-29 1992-02-06 Kao Corp Low irritation detergent composition
JPH05132699A (en) * 1991-04-15 1993-05-28 Colgate Palmolive Co Low-boiling liquid detergent composition
JPH08199187A (en) * 1995-01-20 1996-08-06 Kao Corp Liquid detergent composition
JPH0967325A (en) * 1995-08-29 1997-03-11 Kawaken Fine Chem Co Ltd Mixture of polyoxypropylene fatty acid alkanol amide sulfosuccinic acid ester salt compound, its production and detergent composition
JPH09176107A (en) * 1995-12-27 1997-07-08 Lion Corp New sulfosuccinic acid ester, anionic surfactant and detergent composition
JP2005162932A (en) * 2003-12-04 2005-06-23 Lion Corp Solubility improver for alpha-sulfo long-chain fatty acid alkyl ester salt and method for improving solubility of detergent composition
JP2008507611A (en) * 2004-07-23 2008-03-13 ザ プロクター アンド ギャンブル カンパニー Liquid detergent composition that improves detergency at low temperatures against oil and starch stains
JP2008143947A (en) * 2006-12-06 2008-06-26 Kao Corp Liquid detergent composition
JP2009256527A (en) * 2008-04-21 2009-11-05 Kao Corp Liquid cleaning agent composition
JP2012140572A (en) * 2011-01-06 2012-07-26 Kao Corp Tableware detergent composition for hand washing

Family Cites Families (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US7259131B2 (en) * 2004-07-20 2007-08-21 Unilever Home & Personal Care Usa, Division Of Conopco, Inc. Mild, moisturizing cleansing compositions
JP5801319B2 (en) * 2009-12-17 2015-10-28 ステパン カンパニー Foamed light liquid detergent composition, method for its preparation and use

Patent Citations (12)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPS62127396A (en) * 1985-11-28 1987-06-09 花王株式会社 Low irritant detergent composition
JPH01297500A (en) * 1988-05-25 1989-11-30 Kao Corp Liquid cleaning agent composition
JPH0436223A (en) * 1990-05-29 1992-02-06 Kao Corp Low irritation detergent composition
JPH05132699A (en) * 1991-04-15 1993-05-28 Colgate Palmolive Co Low-boiling liquid detergent composition
JPH08199187A (en) * 1995-01-20 1996-08-06 Kao Corp Liquid detergent composition
JPH0967325A (en) * 1995-08-29 1997-03-11 Kawaken Fine Chem Co Ltd Mixture of polyoxypropylene fatty acid alkanol amide sulfosuccinic acid ester salt compound, its production and detergent composition
JPH09176107A (en) * 1995-12-27 1997-07-08 Lion Corp New sulfosuccinic acid ester, anionic surfactant and detergent composition
JP2005162932A (en) * 2003-12-04 2005-06-23 Lion Corp Solubility improver for alpha-sulfo long-chain fatty acid alkyl ester salt and method for improving solubility of detergent composition
JP2008507611A (en) * 2004-07-23 2008-03-13 ザ プロクター アンド ギャンブル カンパニー Liquid detergent composition that improves detergency at low temperatures against oil and starch stains
JP2008143947A (en) * 2006-12-06 2008-06-26 Kao Corp Liquid detergent composition
JP2009256527A (en) * 2008-04-21 2009-11-05 Kao Corp Liquid cleaning agent composition
JP2012140572A (en) * 2011-01-06 2012-07-26 Kao Corp Tableware detergent composition for hand washing

Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2016199754A (en) * 2016-05-27 2016-12-01 花王株式会社 Liquid detergent composition for hard surface
US12018230B2 (en) 2020-03-17 2024-06-25 Kao Corporation Surfactant composition

Also Published As

Publication number Publication date
CN103890156B (en) 2017-02-15
TWI548735B (en) 2016-09-11
CN103890156A (en) 2014-06-25
JP2013100462A (en) 2013-05-23
JP5654537B2 (en) 2015-01-14
IN2014DN01969A (en) 2015-05-15
TW201317336A (en) 2013-05-01

Similar Documents

Publication Publication Date Title
JP5654537B2 (en) Dishwashing composition for hand washing
JP5775788B2 (en) Dishwashing composition for hand washing
TWI609078B (en) Hand wash food detergent composition
JP5642598B2 (en) Dishwashing composition for hand washing
JP5659038B2 (en) Detergent composition for dishwashing
JP5642599B2 (en) Dishwashing composition for hand washing
JP5875766B2 (en) Dishwashing composition for hand washing
JP5700553B2 (en) Cleaning composition for hard surface
JP5774315B2 (en) Dishwashing composition for hand washing
JP5700523B2 (en) Dishwashing composition for hand washing
JP5878327B2 (en) Dishwashing composition for hand washing
JP5602199B2 (en) Dishwashing composition for hand washing
JP6549383B2 (en) Dishwashing composition for hand washing
JP5875827B2 (en) Dishwashing composition for hand washing
KR102410873B1 (en) Liquid detergent for dishwashing
JP5805493B2 (en) Dishwashing composition for hand washing
JP6192231B2 (en) Liquid detergent for dishwashing
JP5802604B2 (en) Liquid detergent for kitchen
JP5957198B2 (en) Dishwashing composition for hand washing
JP5809006B2 (en) Dishwashing composition for hand washing
JP5592781B2 (en) Dishwashing composition for hand washing
JP2018184495A (en) Tableware detergent
JP6472984B2 (en) Dishwashing composition for hand washing
JP2016094503A (en) Hand washing tableware detergent composition

Legal Events

Date Code Title Description
121 Ep: the epo has been informed by wipo that ep was designated in this application

Ref document number: 12839426

Country of ref document: EP

Kind code of ref document: A1

NENP Non-entry into the national phase

Ref country code: DE

122 Ep: pct application non-entry in european phase

Ref document number: 12839426

Country of ref document: EP

Kind code of ref document: A1