WO2011114875A1 - Liquid detergent composition - Google Patents

Liquid detergent composition Download PDF

Info

Publication number
WO2011114875A1
WO2011114875A1 PCT/JP2011/054558 JP2011054558W WO2011114875A1 WO 2011114875 A1 WO2011114875 A1 WO 2011114875A1 JP 2011054558 W JP2011054558 W JP 2011054558W WO 2011114875 A1 WO2011114875 A1 WO 2011114875A1
Authority
WO
WIPO (PCT)
Prior art keywords
liquid detergent
detergent composition
mass
composition according
ether
Prior art date
Application number
PCT/JP2011/054558
Other languages
French (fr)
Japanese (ja)
Inventor
窪田裕一
村田大也
吉岡佐知子
矢野誠二
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 CN201180012173XA priority Critical patent/CN102803461A/en
Publication of WO2011114875A1 publication Critical patent/WO2011114875A1/en

Links

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
    • C11D1/00Detergent compositions based essentially on surface-active compounds; Use of these compounds as a detergent
    • C11D1/02Anionic compounds
    • C11D1/37Mixtures of compounds all of which are anionic
    • 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
    • C11D3/20Organic compounds containing oxygen
    • C11D3/2075Carboxylic acids-salts thereof
    • C11D3/2079Monocarboxylic acids-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
    • C11D1/22Sulfonic acids or sulfuric acid esters; Salts thereof derived from aromatic 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
    • C11D1/29Sulfates of polyoxyalkylene ethers

Definitions

  • the present invention relates to a liquid detergent composition, and more particularly to a liquid detergent composition suitable for hand-washing laundry.
  • hand washing and washing machine washing There are two types of laundry washing methods: hand washing and washing machine washing. In recent years, there is a tendency for washing machines to increase due to the spread of washing machines. However, from the viewpoint of being able to confirm the degree of dirt removal and economical efficiency, hand washing is still widely performed worldwide. Yes. In particular, hand-washing laundry is often adopted so that it can be washed with as little water as possible in an area where water resources are low.
  • hand-washed washing enables fine washing according to the situation, such as the degree of dirt removal and the type of object to be washed. Accompanied by.
  • “rubbing” in which objects to be cleaned are rubbed together is one of the most natural hand washing methods because it is easy to apply mechanical force to the parts to be cleaned.
  • the amount of foam generated at the time of washing clothes and the like is a factor that causes a sense of fulfillment and a sense of security that washing is sufficient for consumers who do laundry.
  • Many detergents mainly composed of anionic surfactants such as alkylbenzene sulfonates are manufactured and sold.
  • liquid detergent compositions are mainly known as laundry detergent compositions.
  • the liquid detergent composition has advantages such as no generation of fine powder during use and quick dissolution and dispersion in washing water.
  • JP 10-504049 includes a surfactant system including a specific anionic surfactant and a specific nonionic surfactant mixture, a detergency builder, and an auxiliary detergent component.
  • Laundry detergent compositions that can be in liquid form for use are disclosed.
  • JP-T-10-504056 discloses a hand-washing laundry detergent composition which can take a liquid form containing an anionic surfactant, a nonionic surfactant and a cationic surfactant under specific conditions.
  • JP-A-52-82909 discloses an aqueous liquid detergent composition containing a specific surfactant, a higher fatty acid salt, a sulfonate of benzene or lower alkylbenzene, an inorganic builder, and an alkali salt of a polyvalent carboxylic acid.
  • the present invention comprises (A) polyoxyalkylene alkyl ether sulfate ester salt (hereinafter referred to as component (A)), (B) alkylbenzene sulfonate salt (hereinafter referred to as component (B)), (C) fatty acid and / or its A salt (hereinafter referred to as component (C)), (D) a compound having a pKa of 8.0 or more, preferably 9.0 to 10.6 (hereinafter referred to as component (D)), and water, ) / (B) has a mass ratio of 85/15 to 30/70 and [(A) + (B)] / (C) has a mass ratio of 85/15 to 30/70, [(A) + (B)] / (D) is a mass ratio of 85/15 to 40/60, the content of the nonionic surfactant is 2% by mass or less, and measurement is performed at 25 ° C.
  • component (A)) polyoxyalkylene alkyl ether
  • the present invention relates to a liquid detergent composition having a pH of 9.0 to 10.5.
  • mass% and mass ratio shall respectively calculate by the quantity of sodium salt conversion, respectively.
  • (A) polyoxyalkylene alkyl ether sulfate salt, (B) alkylbenzene sulfonate, (C) fatty acid and / or salt thereof (hereinafter referred to as (C) component), (D) pKa is 9. Containing 0 to 10.6 compound and water, the mass ratio of (A) / (B) is 85/15 to 30/70, and the mass ratio of [(A) + (B)] / (C) Is 85/15 to 30/70, the mass ratio of [(A) + (B)] / (D) is 85/15 to 40/60, and the content of the nonionic surfactant is 2% by mass.
  • a liquid detergent composition having a pH of 9.0 to 10.5 as measured at 25 ° C. described in JIS K3362: 1998.
  • the present invention also relates to a hand-washing washing method for hand-washing an object to be cleaned that has been brought into contact with cleaning water containing the liquid detergent composition of the present invention, wherein the mass of the cleaning water relative to the mass of the object to be cleaned is 2 to 100 It is related to the hand-washing washing method.
  • a washing detergent composition for washing has excellent foaming properties that exhibit appropriate foaming during washing and excellent rinsing properties such as foam disappearing quickly during rinsing.
  • JP-T-10-504049 and JP-T-10-504056 are said to have good foaming properties and low irritation, they have not yet sufficiently achieved rapid foam disappearance during rinsing.
  • Japanese Patent Laid-Open No. 52-82909 is said to be excellent in cleanability and stability, but cannot achieve both proper foaming and quick foam disappearance in hand-washing.
  • liquid detergent composition having excellent detergency in washing clothes and the like and excellent in both foaming and rinsing properties.
  • the polyoxyalkylene alkyl ether sulfate salt of component (A) is not particularly limited, but for example, an alkyl group having 10 to 20 carbon atoms, preferably 12 to 14 carbon atoms, preferably a linear primary alcohol or It has an alkyl group derived from a linear secondary alcohol or an alkyl group derived from a branched alcohol, and an average addition mole number of an alkyleneoxy group is 0 to 5, preferably 0.5 to 4, more preferably 1 to 3. Can be mentioned.
  • the component (A) preferably contains an ethyleneoxy group as an alkyleneoxy group, and may contain a propyleneoxy group in an average addition mole number range of 0.2 to 2 mol.
  • the salt is preferably an alkali metal salt, particularly preferably a sodium salt and / or potassium salt, and particularly preferably a sodium salt.
  • the alkylbenzene sulfonate of component (B) is not particularly limited, and examples thereof include alkylbenzene sulfonates having 8 to 20 carbon atoms, preferably 10 to 15 carbon atoms, and preferably having a linear alkyl group. .
  • alkylbenzene sulfonate examples include alkali metal salts such as sodium and potassium, alkanolamine salts, and alkaline earth metal salts such as magnesium and calcium. From the viewpoint of detergency and storage stability of the composition. , An alkali metal salt, or an alkanolamine salt is preferable.
  • an alkylbenzene sulfonic acid (acid type) is added to the composition, and it may be neutralized with an alkali in the system to obtain an alkyl benzene sulfonate. It may be added to the product.
  • a strong base such as sodium hydroxide, potassium hydroxide, lithium hydroxide, ammonium hydroxide or the component (D) described later can be used.
  • the fatty acid and / or salt thereof as the component (C) is not particularly limited, but for example, a linear or branched alkyl having 7 to 43 carbon atoms, preferably 9 to 23 carbon atoms, more preferably 11 to 17 carbon atoms.
  • a fatty acid having a group, more preferably a linear or methyl branched chain and having 14 to 14 carbon atoms and / or a salt thereof may be mentioned.
  • the component (C) may have an unsaturated bond, but the number thereof is 2 or less, preferably 1 or less, more preferably 0 from the viewpoint of rinsing properties.
  • component (C) examples include lauric acid and / or a salt thereof, myristic acid and / or a salt thereof, a mixture of lauric acid and fatty acid derived from coconut rich in myristic acid, and / or a salt thereof.
  • lauric acid and / or a salt thereof a mixture of lauric acid and fatty acid derived from coconut rich in myristic acid, and / or a salt thereof.
  • the fatty acid salt of the component (C) is preferably an alkali metal salt such as sodium or potassium, or an alkanolamine salt from the viewpoint of rinsing properties.
  • a fatty acid (acid type) may be added to the composition and neutralized with an alkali in the system, or after neutralization in advance and added to the composition. Also good.
  • a strong base such as sodium hydroxide, potassium hydroxide, lithium hydroxide, or ammonium hydroxide or a component (D) described later can be used.
  • the component (D) is a compound having a pKa of 8.0 or more, preferably 8.0 to 10.6, more preferably 9.0 to 10.6, still more preferably 9.3 to 10.6,
  • alkali metal carbonates such as potassium carbonate and sodium carbonate and / or alkanolamines, especially alkanolamines having 1 to 3 alkanol groups having 2 to 4 carbon atoms can be mentioned.
  • the alkanol group is preferably a hydroxyethyl group.
  • Other than the alkanol group is a hydrogen atom, but an alkyl group having 1 to 5 carbon atoms, particularly a methyl group, can also be used as the component (D).
  • Alkanolamines include 2-aminoethanol, N-methylethanolamine, N, N-dimethylethanolamine, N, N-diethylethanolamine, diethanolamine, N-methyldiethanolamine, N-butyldiethanolamine, triethanolamine, triisopropanol Alkanolamines such as amine and isopropanolamine mixtures (mono, di and tri mixtures) can be mentioned.
  • alkanolamine is preferable, monoethanolamine or triethanolamine is more preferable, and monoethanolamine is most preferable from the viewpoint of detergency.
  • alkanolamines are used in combination with alkali metal carbonates such as potassium carbonate because the storage stability can be further improved.
  • the component (D) may be used for neutralizing the component (B) and component (C) described above. From the viewpoint of detergency and mildness to the hand skin, it is preferable that the pH buffering ability of the liquid detergent composition of the present invention is well expressed in the range of pH 9.0 to 10.5. It is desirable to combine a weak acid such as component C) with a compound having a pKa of component (D) in the range of 9.0 to 10.6.
  • the liquid detergent composition of the present invention has a mass ratio of (A) / (B) of 85/15 to 30/70, preferably 80/20 to 40/60, and more preferably 75/25 to 50 / 50, and 70/30 to 55/45. If the ratio of the component (A) in this mass ratio is within this range, the rinsability is improved particularly if it is 85/15 or less, while the washability is improved if it is 30/70 or more, and Excellent foaming properties when washing.
  • the mass ratio of [(A) + (B)] / (C) is from the viewpoint of appropriate foaming properties during cleaning, quick foam disappearance during rinsing, and cleaning properties. 85/15 to 30/70, preferably 80/20 to 45/55, more preferably 75/25 to 55/45, and more preferably 70/30 to 60/40.
  • [(A) + (B)] / () from the viewpoint of moderate foaming property during cleaning, cleanability and low irritation to the hand skin, particularly from the viewpoint of foaming property.
  • the mass ratio of D) is 85/15 to 40/60, preferably 82/18 to 50/50, more preferably 79/21 to 55/45, more preferably 76/24 to 60/40, and more preferably Is 73/27 to 65/35.
  • the component (B) is 0.5 to 20% by mass, further 1.2 to 12% by mass, further 2 to 8% by mass, and further 2.2 to 7.5% by mass. %, And more preferably 3 to 5% by mass.
  • the component (C) is calculated in terms of sodium salt, and is contained in an amount of 1 to 50% by mass, further 1.5 to 30% by mass, further 2 to 20% by mass, and further 4 to 10% by mass. preferable.
  • the component (D) is preferably contained in an amount of 2 to 10% by mass, further 2.5 to 8% by mass, further 3.5 to 6% by mass, and further 3.8 to 5.5% by mass.
  • the content of each component is selected within a range that satisfies the mass ratio.
  • the liquid detergent composition of the present invention has a total of 5 to 30% by mass of the component (A) and the component (B), and further 6 to 20% from the viewpoint of appropriate foaming properties and quick foam disappearance at the time of rinsing.
  • the content is preferably 7% by mass, more preferably 7 to 15% by mass, and still more preferably 8 to 12% by mass. If this content is 5% by mass or more, a composition having better detergency and foaming properties can be obtained. On the other hand, if it is 30% by mass or less, it has a good viscosity and dissolves and disperses quickly in the washing liquid. Or a composition having a clear liquid feeling is obtained.
  • the water content in the composition is preferably 30 to 90% by mass, more preferably 40 to 85% by mass, and even more preferably 50 to 80% by mass.
  • the content of the nonionic surfactant is 2% by mass or less, 1.5% by mass or less, and further 1% by mass or less from the viewpoint of rapid foam extinction at the time of rinsing. More preferably, it is 0.5% by mass or less, and further, it is not blended at all, that is, the liquid detergent composition of the present invention does not contain a nonionic surfactant.
  • the nonionic surfactant referred to herein is not particularly limited, and examples thereof include polyoxyalkylene alkyl ether. For example, an average of 4 to 15, preferably, ethylene oxide is added to an alcohol having 10 to 18 carbon atoms.
  • Examples include polyoxyalkylene alkyl ethers in which 4 to 10 moles and 0 to 5 moles of propylene oxide are added on average, and the content is preferably kept within the above range.
  • nonionic surfactants have high orientation to the gas-liquid interface, and c. m. c. Since the (critical micelle concentration) is small, bubbles remain persistently even at low concentrations, impeding rapid bubble disappearance during rinsing.
  • those having a large added mole number of alkylene oxide for example, an alcohol having 10 to 18 carbon atoms with an average of more than 15 moles, preferably an average of 20 moles or more, and an average of 0 to propylene oxide.
  • Those added in an amount of ⁇ 5 mol may be used in the liquid detergent composition of the present invention as long as the amount is small (desirably 2% by mass or less).
  • the liquid detergent composition of the present invention is an average of 4 to 60 mol, preferably 4 to 30, more preferably 4 to 15, more preferably 4 to 15 moles of ethylene oxide as a nonionic surfactant in an alcohol having 10 to 18 carbon atoms.
  • the content of the polyoxyalkylene alkyl ether in the liquid detergent composition of the present invention is preferably 2% by mass or less, more preferably 1.5% by mass or less, and further It is most desirable that it is 1% by mass or less, further 0.5% by mass or less, and further not blended at all, that is, the liquid detergent composition of the present invention does not contain the polyoxyalkylene alkyl ether.
  • the nonionic surfactant whose content in the composition is limited to 2% by mass or less is an average of 4 to 15 moles, preferably 4 to 5 moles of ethylene oxide in an alcohol having 10 to 18 carbon atoms. It may be a polyoxyalkylene alkyl ether to which 10 mol and 0 to 5 mol of propylene oxide is added on average.
  • the liquid detergent composition of the present invention comprises a polyoxyalkylene alkyl ether obtained by adding an average of more than 15 to 60 mol of ethylene oxide and an average of 0 to 5 mol of propylene oxide to an alcohol having 10 to 18 carbon atoms. It can contain in the range which does not inhibit the effect of invention, desirably 2 mass% or less.
  • the liquid cleaning composition of this invention can contain the nonionic surfactant represented by the following general formula (e1) as (E) component.
  • n and n are average added mole numbers, m is a number from more than 15 to 60, and n is a number from 0 to 5. “/” Indicates that the C 2 H 4 O group and the C 3 H 6 O group may be bonded to either random or block. ]
  • R 1e is a hydrocarbon group having 10 to 18 carbon atoms, preferably a hydrocarbon group having 10 to 16 carbon atoms, and more preferably 10 to 14 carbon atoms.
  • R 1e is preferably a chain hydrocarbon group, and more preferably a linear hydrocarbon group.
  • a hydrocarbon group of R 1e an alkyl group or an alkenyl group is preferable, and an alkyl group is more preferable.
  • R 1e is preferably a linear or branched alkyl group, and more preferably a linear alkyl group.
  • the carbon atom of R 1e bonded to the oxygen atom may be the first carbon atom.
  • Such an alkyl group can use a fatty alcohol derived from natural fats and oils as a raw material.
  • a compound in which the carbon atom of R 1e bonded to the oxygen atom of R 1e —O— in the general formula (e1) is the first carbon atom is more excellent in detergency than the compound having the second carbon atom.
  • R 1e is preferably a linear alkyl group having the first carbon atom.
  • the method for obtaining the compound of the general formula (e1) is not particularly limited, but can be obtained by addition reaction of ethylene oxide with an alcohol having 10 to 18 carbon atoms or addition reaction of ethylene oxide and propylene oxide. it can.
  • M in the general formula (e1) is the average number of added moles of ethyleneoxy group
  • the lower limit of m is preferably 18 or more, more preferably 20 or more, more preferably from the viewpoint of rinsing properties and cleaning performance. It is 22 or more, more preferably 26 or more, more preferably 30 or more, and the upper limit is preferably 45 or less, more preferably 35 or less, from the viewpoint of ease of production. Therefore, as the component (E), a nonionic surfactant having a number m in the general formula (e1) of 18 to 60, preferably 26 to 60 can be used.
  • n is the average number of moles of propyleneoxy group added, and the lower limit is 0 or more, preferably 1 or more, and the upper limit is 5 or less, preferably 4 or less, more preferably 3 or less, from the viewpoint of cleaning performance.
  • the propyleneoxy group in general formula (e1) has a methyl-branched structure in the case of propylene oxide addition reaction.
  • the component (E) of the present invention is such that the proportion of the compound that is R 1e —O—C 2 H 4 O— is 75 mol% or more in the compound constituting the component (E). Furthermore, it is preferably 80 mol% or more (the upper limit is 100 mol% or less). Such a compound can also be obtained by removing unreacted alcohol.
  • the component (E) has a ratio of —C 2 H 4 O—H at the terminal after satisfying the condition of R 1e —O—C 2 H 4 O— in the general formula (e1). Higher ones are preferable because the adsorptivity of the fibers is lower than when the terminal is —C 3 H 6 O—H having a hydrophobic propyleneoxy group. In particular, it is more preferable that the amount of the compound having a structure of —C 2 H 4 O—H at the terminal is 70 mol% or more, and further 80 mol% or more (the upper limit is 100 mol% or less).
  • Such a compound is produced by first adding ethylene oxide under the above-mentioned conditions in the production of the general formula (e1), or after adding ethylene oxide, removing unreacted alcohol, and then propylene oxide, preferably propylene. It can be obtained by conducting an oxide addition reaction step and finally adding only 6 mol or more, particularly 8 mol or more of ethylene oxide. This rule may also be applied to the general formula (e1-5) described later.
  • the ratio of R 1e —O—C 2 H 4 O— or —C 2 H 4 O—H can be determined by quantitative measurement using C 13 -NMR.
  • the compound represented by the general formula (e1) of the present invention may be a compound represented by the following general formulas (e1-1) to (e1-5).
  • the compounds represented by the general formulas (e1-1) to (e1-5) can be prepared by taking into consideration the reaction ratio and reaction sequence of the alkylene oxide with respect to R 1e OH.
  • the compound of the general formula (e1-2), (e1-4) or (e1-5), particularly the compound of the general formula (e1-2) or (e1-5) is more preferable in terms of rinsing properties. preferable.
  • Component (E) of the present invention is a compound represented by R 1e —OH (R 1e is a hydrocarbon group having 10 to 18 carbon atoms, preferably the same as R 1e in formula (e1)) per mole.
  • Nonionic surfactants having a number of 26 to 35 are more preferable.
  • m2 can be determined from m1 and m1 + m2.
  • m2 is preferably a number of 3 to 30, more preferably a number of 7 to 25, and preferably a number of 8 to 20.
  • PO is not bonded to the terminal and R 1e
  • R 1e , m1, m2 and n have the same meaning as in the general formula (e1-5).
  • examples of the catalyst used for alkoxylation of R 1e —OH include a base catalyst and an acid catalyst.
  • a base catalyst is preferably used from the viewpoint of cost, sodium hydroxide or potassium hydroxide is more preferable as the base, and potassium hydroxide is most preferably used.
  • potassium hydroxide is charged into a higher alcohol having 10 to 18 carbon atoms (compound represented by R 1e —OH) as a raw material, and then purged with nitrogen, and at 100 to 110 ° C. and 1 to 7 kPa for 30 minutes to 1 hour. Perform dehydration. Then, ethylene oxide is added at 100 to 170 ° C. and 0.3 to 0.6 MPa, and then propylene oxide is added at 100 to 150 ° C. and 0.3 to 0.7 MPa.
  • each ethylene oxide and propylene oxide is selected according to the number-of-moles of raw material alcohol so that the conditions of the average value of m and n in a composition may be satisfy
  • the liquid detergent composition of the present invention has the effect of the present invention as a component (F) with surfactants other than the components (A), (B), (C) and the nonionic surfactant. It can contain in the range which is not impaired.
  • the proportion of the component (F) is preferably 20% by mass or less, more preferably 10% by mass or less, and even more preferably 5% by mass or less in the total surfactant.
  • Component is not particularly limited, and examples thereof include aliphatic alcohols, alkanolamides, amine oxides and betaines. Since these have a function as a foam booster, for example, as described in “Foam Engineering” (published by Techno System Co., Ltd., 2005), the foaming power of the cleaning composition of the present invention is increased. be able to.
  • the foam booster selected from aliphatic alcohol, alkanolamide, amine oxide, and betaine is 5% by mass or less, more preferably 3% by mass in the total surfactant in order not to impair the rinsing property. Hereinafter, it is more preferably 1.5% by mass or less.
  • Examples of the aliphatic alcohol include aliphatic alcohols having 8 to 18, preferably 10 to 16, and more preferably 12 to 14 carbon atoms. Among these, dodecyl alcohol is preferable.
  • Examples of the alkanolamide monoethanolamide, diethanolamide, N-methylethanolamide and the like are preferable, but those having an isopropanolamide type or an alkylene oxide added thereto can be used.
  • Examples of the amine oxide include mono long chain alkyl amine oxides having a long chain length alkyl group having 8 to 18 carbon atoms, preferably 12 to 14 carbon atoms, and an alkyl group having 1 to 3 carbon atoms, preferably a methyl group. be able to.
  • Examples of betaines include alkylamidopropyl betaines. Among them, lauramidopropyl betaine having 12 carbon atoms and cocoamidopropyl betaine having a coconut oil composition are generally used.
  • the component (F) is selected from (F1) a compound represented by the following general formula (f1) and (F2) a compound represented by the following general formula (f2). It is preferable to use a surfactant. Two or more of these can be used.
  • R 1f is a hydrocarbon group having 9 to 23 carbon atoms
  • R 2f is an alkylene group having 1 to 6 carbon atoms
  • X is a group selected from an ester group, an amide group, and an ether group
  • p is a number of 0 or 1.
  • R 3f and R 4f are each independently an alkyl group having 1 to 3 carbon atoms or a hydroxyalkyl group having 1 to 3 carbon atoms
  • R 5f is an alkylene group having 1 to 5 carbon atoms which may be substituted with a hydroxy group. It is.
  • Y - is an anionic group.
  • R 6f- (OR 7f ) q -OH (f2) [Wherein R 6f is a hydrocarbon group having 6 to 18 carbon atoms, R 7f is a residue obtained by removing two hydroxy groups from a propylene group or glycerin, and q is a number of 1 to 5. ]
  • the component (F1) is a compound represented by the general formula (f1).
  • R 1f is a hydrocarbon group having 9 to 23 carbon atoms, preferably an alkyl group or an alkenyl group, more preferably an alkyl group having 10 to 15 carbon atoms, and more preferably 11 to 13 carbon atoms.
  • R 2f is preferably an alkylene group having 2 or 3 carbon atoms, and more preferably an alkylene group having 3 carbon atoms.
  • X is a group selected from an ester group, an amide group, and an ether group, and specific examples include groups selected from —COO—, —OCO—, —CONH—, —NHCO—, and —O—. .
  • X is preferably an amide group, and more preferably a group represented by —CONH—.
  • p is preferably 0 or 1.
  • R 3f and R 4f are each preferably a methyl group or a hydroxyethyl group, more preferably a methyl group.
  • Y ⁇ is an anionic group, and examples thereof include a group selected from —SO 3 ⁇ , —OSO 3 ⁇ , and —COO 2 — .
  • Y - or -COO - - are preferred, Y - -SO 3 has -SO 3 - in the case of, R 5f is -CH 2 CH (OH) CH 2 - if the - preferably, Y- is -COO In this case, R 5f is preferably a methylene group (—CH 2 —).
  • the component (F2) is a compound represented by the general formula (f2).
  • the compound of the general formula (f2) is suitable for increasing the foaming power, but at the same time, it is desired that the rinsing property is also good.
  • both the hydrophilic group structure and the hydrophobic structure of the compound represented by the general formula (f2) are limited as follows. Although it is not necessarily certain, it is considered that the orientation to the gas-liquid interface is higher than the orientation to clothing and dirt by adopting the following structure.
  • R 6f is preferably an alkyl or alkenyl group having 6 to 18, more preferably 6 to 14, and even more preferably 6 to 10 carbon atoms.
  • R 7f is a propylene group
  • q is preferably 2 to 4 from the viewpoint of foamability and rinsing properties.
  • q is preferably a number of 1 to 3, and more preferably 1.
  • R 7f is preferably a residue obtained by removing two hydroxy groups from glycerin.
  • R 6f in the general formula (f2) is an alkyl group or alkenyl group having 6 to 10 carbon atoms
  • R 7f is a residue obtained by removing two hydroxy groups from glycerin
  • glyceryl ether having q 1 Is preferred.
  • examples thereof include 2-ethylhexyl monoglyceryl ether, isononyl monoglyceryl ether, and isodecyl monoglyceryl ether.
  • 2-ethylhexyl monoglyceryl ether is preferable in order to achieve both foaming properties and rinsing properties.
  • the component (F1) is 0.1 to 10% by mass, more preferably 0.2 to 5% by mass, and still more preferably 0.4 to 2. It is preferable to contain 7 mass%.
  • the liquid detergent composition of the present invention has a component (F2) of 0.1 to 10% by mass, more preferably 0.2 to 5% by mass, and still more preferably 0.4 to 0.4% from the viewpoint of foamability and rinsing properties. It is preferable to contain 2.7 mass%.
  • the liquid detergent composition of the present invention can contain both the component (F1) and the component (F2) from the viewpoint of foamability.
  • the mass ratio of (F1) / (F2) is preferably 80/20 to 20/80, more preferably 70/30 to 30/70, and still more preferably 60/40 to 40/60.
  • the liquid detergent composition of the present invention has a pH measured at 25 ° C. described in JIS K3362: 1998 of 9.0 to 10.5, preferably 9.3, from the viewpoint of detergency and mildness to the hand skin. To 10.2, more preferably 9.5 to 10.
  • the pH can be adjusted depending on the type and amount of the component to be blended in the composition, and in particular, the type and blending amount of the component (B), the component (C), and the component (D). It may be adjusted using an acid agent such as 6N-HCl).
  • the liquid detergent composition of the present invention has an excellent detergency in washing clothes and the like by specifying the mass ratio of each component and the content of the nonionic surfactant described above, and has a foaming property. It exhibits excellent performance in both rinsing properties.
  • nitrilotriacetic acid iminodiacetic acid, ethylenediaminetetraacetic acid, diethylenetriaminepentaacetic acid, glycol etherdiaminetetraacetic acid, hydroxyethyliminodiacetic acid, triethylenetetraamine Aminopolyacetic acid such as hexaacetic acid and diencoric acid or salts thereof, diglycolic acid, oxydisuccinic acid, carboxymethyloxysuccinic acid, citric acid, lactic acid, tartaric acid, oxalic acid, malic acid, oxydisuccinic acid, gluconic acid, carboxymethylsuccinic acid Chelating agents such as organic acids such as carboxymethyl tartaric acid or salts thereof, preferably chelating agents having a molecular weight of 1,000 or less can be blended. The content of the chelating agent is preferably 0.001 to 10% by mass
  • component (G) a water-miscible organic solvent
  • the water-miscible organic solvent referred to in the present invention refers to a solvent that dissolves 50 g or more in 1 L of ion-exchanged water at 25 ° C., that is, a solvent having a degree of dissolution of 50 g / L or more.
  • the content of the component (G) is 0.5 to 40% by mass, further 1 to 20% by mass, further 1.5 to 10% by mass in the composition from the viewpoint of improving the solution stability and transparency. Furthermore, 2 to 5% by mass is preferable.
  • (G1) alkanols such as ethanol, 1-propanol, 2-propanol and 1-butanol
  • (G2) glycols such as propylene glycol, butylene glycol and hexylene glycol
  • Glycols such as triethylene glycol, tetraethylene glycol, dipropylene glycol, tripropylene glycol
  • the water-miscible organic solvent is effective at the same time as a viscosity modifier and gelation inhibitor of the composition, and the above (G1) alkanols, (G2) glycols, (G4) alkyl ethers, (G5) aromatics It is preferable to use one or more selected from ethers, more preferably selected from (G2) glycols, (G4) alkyl ethers, and (G5) aromatic ethers, particularly preferably (G4). It is. In particular, diethylene glycol monobutyl ether is preferable.
  • the component (G) is effective for adjusting the viscosity and suppressing gelation.
  • the following components (i) to (xiii) can be blended to such an extent that the effects of the present invention are not impaired.
  • Solubilizers such as paratoluenesulfonic acid, cumenesulfonic acid, metaxylenesulfonic acid, benzoate (also effective as a preservative)
  • x polyethylene having an average molecular weight of about 200 to about 400 Glycol, polyalkylene glycol-based anti-gelling polymers such as polypropylene glycol having an average molecular weight of about 1,000 to about 2,000
  • paraffins such as octane, decane, dodecane, tridecane, olefins such as decene, dodecene
  • Water immiscible organic solvents such as methylene chloride, alkyl halides such as 1,1,1-trichloroethane, and terpenes such as D-limonene
  • Metal ion exchangers such as zeolite and crystalline layered silicate
  • Other antifoaming agents such as pigments,
  • liquid detergent composition of the present invention for example, a predetermined amount of the components (A) and (D) and, if necessary, (G) in ion-exchanged water heated to a predetermined temperature (about 80 ° C.) Add ingredients and dissolve. If necessary, a strong base such as sodium hydroxide is added at this stage. Next, the acid type (B) component and the acid type (C) component are added and mixed until it becomes transparent, then other components are added as appropriate, and after cooling to room temperature, a fragrance, a pigment, and the like are added. be able to.
  • the liquid detergent composition of the present invention is suitable for washing at home and also for hand washing, and is suitably used for hand washing of textile products such as clothing, fabrics, bedding, towels and the like.
  • the present invention relates to a hand-washing laundry method for hand-washing an object to be cleaned that has been brought into contact with cleaning water containing the liquid detergent composition of the present invention.
  • Examples of the hand-washing washing method using the liquid detergent composition of the present invention include a method of hand washing by bringing the washing water containing the liquid detergent composition of the present invention into contact with an object to be washed such as a fabric and soaking. .
  • the contact time and / or immersion time is long, the cleaning effect is high, and when the contact time and / or immersion is 5 to 15 minutes, a better effect is obtained.
  • the composition is applied directly to a soiled part and left for 5 to 15 minutes, a higher effect can be obtained.
  • the composition of the present invention or a water dilution of the composition for example, an aqueous solution
  • the mass of washing water with respect to the mass of an object to be cleaned such as a fabric is preferably 2 to 100 times, more preferably 3 to 50 times, and particularly preferably 5 to 25 times.
  • the object to be cleaned such as the fabric brought into contact with the cleaning water according to the present invention is sufficiently rubbed by hand, not only a high detergency is obtained but also abundant foaming is visually preferred.
  • the fabric is taken out from the washing water, squeezed to drain the water, or drained using a dehydrator, and immersed again in fresh water (hereinafter referred to as rinsing water).
  • the rinsing water may be either water stored in a basin or running water.
  • the mass of rinsing water with respect to the fabric is preferably 2 to 1,000 times, more preferably 5 to 500 times, and particularly preferably 10 to 100 times based on the total amount of rinsing water used for rinsing. Since the surfactant remaining in the fabric at the stage of immersing the rinse water is redissolved in the rinse water, foaming is observed. When this operation is repeated several times, the foaming disappears and the rinsing is completed. In general washing by hand, for example, when a normal cleaning agent is used, it is generally required 5 times or more. However, in the present invention, rinsing can be completed in 3 times or less, and rinsing is performed with very little rinsing water. Can be terminated.
  • the hardness of water used for the preparation of cleaning water and / or the hardness of rinsing water is preferably 1 ° DH to 50 ° DH, more preferably 2 ° DH to 40 ° DH, more preferably from the viewpoint of cleaning power and rinsing properties.
  • a liquid detergent composition was prepared using the ingredients shown in Tables 1 and 2, and the following evaluations were performed. The results are shown in Tables 1 and 2.
  • Point 6 Foam with a height of 1 cm or more remains on the entire liquid surface 5: Foam remains on the entire liquid surface (less than 1 cm) 4: Bubbles remain at about 1/2 of the liquid level 3: Bubbles remain at about 1/4 of the liquid level 2: Fine bubbles remain at the liquid level 1: Bubbles remain at the liquid level Absent
  • A Adjustment oil used in the evaluation of foaming properties (mass% in artificial dirt is 0.44 mass% lauric acid, 3.15 mass% myristic acid, 2.35 mass% pentadecanoic acid, 6.31 palmitic acid) Wt%, heptadecanoic acid 0.44 wt%, stearic acid 1.6 wt%, oleic acid 7.91 wt%, triolein 13.33 wt%, n-hexadecyl palmitate 2.22 wt%, squalene 6.66 (Use in an amount of mass%)
  • B Hard water obtained by weighing 105 mg of calcium chloride (dihydrate) and dissolving in distilled water to obtain 1,000 ml C: 1.98% by mass of egg white lecithin liquid crystal
  • AES-Na polyoxyethylene (average number of moles added 2) sodium lauryl ether sulfate (Emar 270J, manufactured by Kao Corporation)
  • Nonionic surfactant (1) polyoxyethylene (average addition mole number 8) alkyl (carbon number 10-14) ether
  • Nonionic surfactant (2) polyoxyethylene (average addition mole number 21) alkyl (C12)
  • Ether F1-1 Sulfobetaine represented by the following formula, Amphital 20HD (manufactured by Kao Corporation)
  • F1-1 Betaine represented by the following formula, Amhitor 20AB (manufactured by Kao Corporation)
  • Examples 1 to 9 and Examples 10 to 14 have excellent results in any evaluation.
  • Comparative Examples 1, 6, and 8 are in terms of rinsing properties
  • Comparative Examples 2, 3, 7, and 9 are in terms of foaming properties and cleaning properties
  • Comparative Examples 4 and 5 are in terms of foaming properties and irritation, It turned out that it is inferior to an Example.

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)
  • Health & Medical Sciences (AREA)
  • Emergency Medicine (AREA)
  • Detergent Compositions (AREA)

Abstract

Disclosed is a liquid detergent composition that includes water, (A) a polyoxyalkylene alkyl ether sulfate, (B) an alkylbenzene sulfonate, (C) a fatty acid and/or a salt thereof, and (D) a compound with a pKa of at least 8.0, wherein the mass ratio of (A)/(B) is 85/15 to 30/70, the mass ratio of [(A)+(B)]/(C) is 85/15 to 30/70, the mass ratio of [(A)+(B)]/(D) is 85/15 to 40/60, the content of a nonionic surfactant is no more than 2 mass%, and the pH measured at 25˚C, as set forth in JIS K3362:1998, is 9.0 to 10.5.

Description

液体洗浄剤組成物Liquid detergent composition
 本発明は、液体洗浄剤組成物、詳しくは手洗い洗濯用として好適な液体洗浄剤組成物に関する。
背景技術
The present invention relates to a liquid detergent composition, and more particularly to a liquid detergent composition suitable for hand-washing laundry.
Background art
 衣料等の洗濯方法としては、大きく分けて手洗い洗濯と洗濯機洗濯の2種類がある。近年では、洗濯機の普及により洗濯機による洗濯が増加する傾向にあるが、汚れの落ち具合をしっかり確認できることや経済性の観点などから、世界的にみれば依然、手洗い洗濯が広く行われている。特に、水資源の少ない地域では出来るだけ少ない水で洗濯できるように手洗い洗濯を採用する場合が多い。 There are two types of laundry washing methods: hand washing and washing machine washing. In recent years, there is a tendency for washing machines to increase due to the spread of washing machines. However, from the viewpoint of being able to confirm the degree of dirt removal and economical efficiency, hand washing is still widely performed worldwide. Yes. In particular, hand-washing laundry is often adopted so that it can be washed with as little water as possible in an area where water resources are low.
 手洗い洗濯は、洗濯機による洗濯と比較した場合、汚れの落ち具合、被洗浄物の種類など、状況に応じたきめ細かい洗浄が可能となる一方、洗濯をする者にとって、肉体的、精神的疲労感を伴う。特に、被洗浄物同士をこすり合わせる「もみ洗い」は、被洗浄部位に機械力をかけやすく、最も自然な手洗い方法の1つである。 Compared to washing with a washing machine, hand-washed washing enables fine washing according to the situation, such as the degree of dirt removal and the type of object to be washed. Accompanied by. In particular, “rubbing” in which objects to be cleaned are rubbed together is one of the most natural hand washing methods because it is easy to apply mechanical force to the parts to be cleaned.
 衣料等の洗濯時に発生する泡の量は、洗濯を行う消費者にとっては、洗濯が充分にされているという充実感、安心感を生じさせる要因となるものであり、経済性及び泡立ち(速泡性)等の観点から、陰イオン界面活性剤、例えばアルキルベンゼンスルホネートが主体の洗剤が多く製造・販売されている。 The amount of foam generated at the time of washing clothes and the like is a factor that causes a sense of fulfillment and a sense of security that washing is sufficient for consumers who do laundry. Many detergents mainly composed of anionic surfactants such as alkylbenzene sulfonates are manufactured and sold.
 一方、洗濯用の洗浄剤組成物としては、主として、粒状(固体状)のものと液状のものが知られている。液状の洗浄剤組成物は、使用時に微粉の発生がない、洗濯水に速やかに溶解、分散するといった利点がある。 On the other hand, granular (solid) and liquid compositions are mainly known as laundry detergent compositions. The liquid detergent composition has advantages such as no generation of fine powder during use and quick dissolution and dispersion in washing water.
 特表平10-504049には、特定の陰イオン界面活性剤及び特定の非イオン界面活性剤混合物を包含する界面活性剤系と、洗浄性ビルダーと、補助洗剤成分とを含有する、手洗い操作で使用するための、液体の形態をとり得る洗濯洗剤組成物が開示されている。また、特表平10-504056には、アニオン界面活性剤、非イオン界面活性剤及びカチオン界面活性剤を特定条件で含む、液体の形態をとり得る手洗い洗濯洗剤組成物が開示されている。また、特開昭52-82909には、特定の界面活性剤、高級脂肪酸塩、ベンゼン又は低級アルキルベンゼンのスルホン酸塩、無機質ビルダー、及び多価カルボン酸アルカリ塩を含有する水性液体洗剤組成物が開示されている。
発明の要約
JP 10-504049 includes a surfactant system including a specific anionic surfactant and a specific nonionic surfactant mixture, a detergency builder, and an auxiliary detergent component. Laundry detergent compositions that can be in liquid form for use are disclosed. In addition, JP-T-10-504056 discloses a hand-washing laundry detergent composition which can take a liquid form containing an anionic surfactant, a nonionic surfactant and a cationic surfactant under specific conditions. JP-A-52-82909 discloses an aqueous liquid detergent composition containing a specific surfactant, a higher fatty acid salt, a sulfonate of benzene or lower alkylbenzene, an inorganic builder, and an alkali salt of a polyvalent carboxylic acid. Has been.
Summary of invention
 本発明は、(A)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〔以下、(A)成分という〕、(B)アルキルベンゼンスルホン酸塩〔以下、(B)成分という〕、(C)脂肪酸及び/又はその塩〔以下、(C)成分という〕、(D)pKaが8.0以上、好ましくは9.0~10.6の化合物〔以下、(D)成分という〕、並びに水を含有し、(A)/(B)の質量比が85/15~30/70であり、〔(A)+(B)〕/(C)の質量比が85/15~30/70であり、〔(A)+(B)〕/(D)の質量比が85/15~40/60であり、非イオン界面活性剤の含有量が2質量%以下であり、JIS K3362:1998記載の25℃で測定するpHが9.0~10.5である、液体洗浄剤組成物に関する。なお、(A)成分、(B)成分及び(C)成分の量は、それぞれ、全てナトリウム塩換算の量で質量%や質量比を算出するものとする。 The present invention comprises (A) polyoxyalkylene alkyl ether sulfate ester salt (hereinafter referred to as component (A)), (B) alkylbenzene sulfonate salt (hereinafter referred to as component (B)), (C) fatty acid and / or its A salt (hereinafter referred to as component (C)), (D) a compound having a pKa of 8.0 or more, preferably 9.0 to 10.6 (hereinafter referred to as component (D)), and water, ) / (B) has a mass ratio of 85/15 to 30/70 and [(A) + (B)] / (C) has a mass ratio of 85/15 to 30/70, [(A) + (B)] / (D) is a mass ratio of 85/15 to 40/60, the content of the nonionic surfactant is 2% by mass or less, and measurement is performed at 25 ° C. described in JIS K3362: 1998. The present invention relates to a liquid detergent composition having a pH of 9.0 to 10.5. In addition, as for the quantity of (A) component, (B) component, and (C) component, mass% and mass ratio shall respectively calculate by the quantity of sodium salt conversion, respectively.
 本発明は、(A)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、(B)アルキルベンゼンスルホン酸塩、(C)脂肪酸及び/又はその塩〔以下、(C)成分という〕、(D)pKaが9.0~10.6の化合物並びに水を含有し、(A)/(B)の質量比が85/15~30/70であり、〔(A)+(B)〕/(C)の質量比が85/15~30/70であり、〔(A)+(B)〕/(D)の質量比が85/15~40/60であり、非イオン界面活性剤の含有量が2質量%以下であり、JIS K3362:1998記載の25℃で測定するpHが9.0~10.5である、液体洗浄剤組成物を包含する。 In the present invention, (A) polyoxyalkylene alkyl ether sulfate salt, (B) alkylbenzene sulfonate, (C) fatty acid and / or salt thereof (hereinafter referred to as (C) component), (D) pKa is 9. Containing 0 to 10.6 compound and water, the mass ratio of (A) / (B) is 85/15 to 30/70, and the mass ratio of [(A) + (B)] / (C) Is 85/15 to 30/70, the mass ratio of [(A) + (B)] / (D) is 85/15 to 40/60, and the content of the nonionic surfactant is 2% by mass. And a liquid detergent composition having a pH of 9.0 to 10.5 as measured at 25 ° C. described in JIS K3362: 1998.
 また、本発明は、上記本発明の液体洗浄剤組成物を含む洗浄水を接触させた被洗浄物を手洗いする手洗い洗濯方法であって、被洗浄物の質量に対する洗浄水の質量が2~100倍である、手洗い洗濯方法に関する。
発明の詳細な説明
The present invention also relates to a hand-washing washing method for hand-washing an object to be cleaned that has been brought into contact with cleaning water containing the liquid detergent composition of the present invention, wherein the mass of the cleaning water relative to the mass of the object to be cleaned is 2 to 100 It is related to the hand-washing washing method.
Detailed Description of the Invention
 洗濯用の洗浄剤組成物においては、優れた洗浄力を有することに加え、洗浄時に適度な泡立ちを示す起泡性と、濯ぎ時には泡が速やかに消える等の濯ぎ性に優れることが望まれる。特表平10-504049や特表平10-504056は起泡性が良く低刺激性であるとされているが、濯ぎ時の速やかな泡消えを未だ十分に達成できていない。 In addition to having an excellent detergency, it is desirable that a washing detergent composition for washing has excellent foaming properties that exhibit appropriate foaming during washing and excellent rinsing properties such as foam disappearing quickly during rinsing. Although JP-T-10-504049 and JP-T-10-504056 are said to have good foaming properties and low irritation, they have not yet sufficiently achieved rapid foam disappearance during rinsing.
 特開昭52-82909は、洗浄性と安定性に優れるとされているが、手洗い洗濯における適度な泡立ちと速やかな泡消えの両立を達成できない。 Japanese Patent Laid-Open No. 52-82909 is said to be excellent in cleanability and stability, but cannot achieve both proper foaming and quick foam disappearance in hand-washing.
 本発明によれば、衣料等の洗濯において、優れた洗浄力を有し、起泡性と濯ぎ性の両方に優れた液体洗浄剤組成物が提供される。 According to the present invention, there is provided a liquid detergent composition having excellent detergency in washing clothes and the like and excellent in both foaming and rinsing properties.
<(A)成分>
 (A)成分の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としては、特に限定されるものではないが、例えば、炭素数10~20、好ましくは12~14のアルキル基、好ましくは直鎖1級アルコール若しくは直鎖2級アルコール由来のアルキル基又は分岐アルコール由来のアルキル基を有し、アルキレンオキシ基の平均付加モル数が0~5、好ましくは0.5~4、更に好ましくは1~3のものが挙げられる。(A)成分は、アルキレンオキシ基としてエチレンオキシ基を含むことが好ましく、平均付加モル数0.2~2モルの範囲でプロピレンオキシ基を含んでいてもよい。塩はアルカリ金属塩が好ましく、特にナトリウム塩及び/又はカリウム塩が好ましく、特にナトリウム塩好ましい。
<(A) component>
The polyoxyalkylene alkyl ether sulfate salt of component (A) is not particularly limited, but for example, an alkyl group having 10 to 20 carbon atoms, preferably 12 to 14 carbon atoms, preferably a linear primary alcohol or It has an alkyl group derived from a linear secondary alcohol or an alkyl group derived from a branched alcohol, and an average addition mole number of an alkyleneoxy group is 0 to 5, preferably 0.5 to 4, more preferably 1 to 3. Can be mentioned. The component (A) preferably contains an ethyleneoxy group as an alkyleneoxy group, and may contain a propyleneoxy group in an average addition mole number range of 0.2 to 2 mol. The salt is preferably an alkali metal salt, particularly preferably a sodium salt and / or potassium salt, and particularly preferably a sodium salt.
<(B)成分>
 (B)成分のアルキルベンゼンスルホン酸塩としては、特に限定されるものではないが、例えば炭素数8~20、好ましくは10~15の、好ましくは直鎖アルキル基を有するアルキルベンゼンスルホン酸塩が挙げられる。
<(B) component>
The alkylbenzene sulfonate of component (B) is not particularly limited, and examples thereof include alkylbenzene sulfonates having 8 to 20 carbon atoms, preferably 10 to 15 carbon atoms, and preferably having a linear alkyl group. .
 アルキルベンゼンスルホン酸塩は、ナトリウム、カリウムなどのアルカリ金属塩、アルカノールアミン塩、又はマグネシウム、カルシウムなどのアルカリ土類金属塩などを挙げることができるが、洗浄性や組成物の保存安定性の観点から、アルカリ金属塩、又はアルカノールアミン塩であることが好ましい。本発明の組成物を調製する場合、アルキルベンゼンスルホン酸(酸型)を組成物中に添加し、系内でアルカリと中和反応させアルキルベンゼンスルホン酸塩としてもよいし、予め中和した後、組成物中に添加してもよい。アルキルベンゼンスルホン酸の中和には、水酸化ナトリウム、水酸化カリウム、水酸化リチウム、水酸化アンモニウムなどの強塩基や後述する(D)成分を用いることができる。 Examples of the alkylbenzene sulfonate include alkali metal salts such as sodium and potassium, alkanolamine salts, and alkaline earth metal salts such as magnesium and calcium. From the viewpoint of detergency and storage stability of the composition. , An alkali metal salt, or an alkanolamine salt is preferable. When preparing the composition of the present invention, an alkylbenzene sulfonic acid (acid type) is added to the composition, and it may be neutralized with an alkali in the system to obtain an alkyl benzene sulfonate. It may be added to the product. For neutralization of the alkylbenzene sulfonic acid, a strong base such as sodium hydroxide, potassium hydroxide, lithium hydroxide, ammonium hydroxide or the component (D) described later can be used.
<(C)成分>
 (C)成分の脂肪酸及び/又はその塩としては、特に限定されるものではないが、例えば炭素数7~43、好ましくは9~23、より好ましくは11~17の直鎖又は分岐鎖のアルキル基を有するもの、より好ましくは直鎖又はメチル分岐鎖を有する炭素数12~14の脂肪酸及び/又はその塩が挙げられる。(C)成分は、不飽和結合を有しても構わないが、その数は2以下、好ましくは1以下、より好ましくは0であることが濯ぎ性の観点からより望ましい。(C)成分としては、具体的には、ラウリン酸及び/又はその塩、ミリスチン酸及び/又はその塩、ラウリン酸、ミリスチン酸を多く含むココヤシ由来の脂肪酸の混合物及び/又はその塩などが挙げられ、特に洗浄力、起泡性、濯ぎ性の観点から、ラウリン酸及び/又はその塩、又はミリスチン酸及び/又はその塩を含むことが好ましく、更にミリスチン酸及び/又はその塩を含むことがより好ましい。
<(C) component>
The fatty acid and / or salt thereof as the component (C) is not particularly limited, but for example, a linear or branched alkyl having 7 to 43 carbon atoms, preferably 9 to 23 carbon atoms, more preferably 11 to 17 carbon atoms. A fatty acid having a group, more preferably a linear or methyl branched chain and having 14 to 14 carbon atoms and / or a salt thereof may be mentioned. The component (C) may have an unsaturated bond, but the number thereof is 2 or less, preferably 1 or less, more preferably 0 from the viewpoint of rinsing properties. Specific examples of the component (C) include lauric acid and / or a salt thereof, myristic acid and / or a salt thereof, a mixture of lauric acid and fatty acid derived from coconut rich in myristic acid, and / or a salt thereof. In particular, from the viewpoints of detergency, foamability and rinsability, it is preferable to contain lauric acid and / or a salt thereof, or myristic acid and / or a salt thereof, and further contain myristic acid and / or a salt thereof. More preferred.
 (C)成分の脂肪酸塩は、ナトリウム、カリウムなどのアルカリ金属塩、又はアルカノールアミン塩であることが、濯ぎ性の観点から好ましい。本発明の組成物を調製する場合、脂肪酸(酸型)を組成物中に添加し、系内でアルカリと中和反応させてもよいし、予め中和した後、組成物中に添加してもよい。脂肪酸の中和には、水酸化ナトリウム、水酸化カリウム、水酸化リチウム、水酸化アンモニウムなどの強塩基や後述する(D)成分を用いることができる。 The fatty acid salt of the component (C) is preferably an alkali metal salt such as sodium or potassium, or an alkanolamine salt from the viewpoint of rinsing properties. When preparing the composition of the present invention, a fatty acid (acid type) may be added to the composition and neutralized with an alkali in the system, or after neutralization in advance and added to the composition. Also good. For the neutralization of the fatty acid, a strong base such as sodium hydroxide, potassium hydroxide, lithium hydroxide, or ammonium hydroxide or a component (D) described later can be used.
<(D)成分>
 (D)成分はpKaが8.0以上、好ましくは8.0~10.6、より好ましくは9.0~10.6、更に好ましくは9.3~10.6の化合物であれば、特に限定されるものではないが、例えば炭酸カリウムや炭酸ナトリウムなどのアルカリ金属炭酸塩及び/又はアルカノールアミン、中でも炭素数2~4のアルカノール基を1つから3つ有するアルカノールアミンを挙げることができる。このうちアルカノール基はヒドロキシエチル基であるものが好ましい。アルカノール基以外は水素原子であるが、炭素数1~5のアルキル基、特にはメチル基であっても(D)成分として使用することができる。アルカノールアミンとしては、2-アミノエタノール、N-メチルエタノールアミン、N,N-ジメチルエタノールアミン、N,N-ジエチルエタノールアミン、ジエタノールアミン、N-メチルジエタノールアミン、N-ブチルジエタノールアミン、トリエタノールアミン、トリイソプロパノールアミン、イソプロパノールアミン混合物(モノ、ジ、トリの混合物)等のアルカノールアミン類が挙げられる。本発明ではアルカノールアミンが好ましく、モノエタノールアミン又はトリエタノールアミンがより好ましく、洗浄性の観点からモノエタノールアミンが最も好ましい。
<(D) component>
If the component (D) is a compound having a pKa of 8.0 or more, preferably 8.0 to 10.6, more preferably 9.0 to 10.6, still more preferably 9.3 to 10.6, Although not limited thereto, for example, alkali metal carbonates such as potassium carbonate and sodium carbonate and / or alkanolamines, especially alkanolamines having 1 to 3 alkanol groups having 2 to 4 carbon atoms can be mentioned. Of these, the alkanol group is preferably a hydroxyethyl group. Other than the alkanol group is a hydrogen atom, but an alkyl group having 1 to 5 carbon atoms, particularly a methyl group, can also be used as the component (D). Alkanolamines include 2-aminoethanol, N-methylethanolamine, N, N-dimethylethanolamine, N, N-diethylethanolamine, diethanolamine, N-methyldiethanolamine, N-butyldiethanolamine, triethanolamine, triisopropanol Alkanolamines such as amine and isopropanolamine mixtures (mono, di and tri mixtures) can be mentioned. In the present invention, alkanolamine is preferable, monoethanolamine or triethanolamine is more preferable, and monoethanolamine is most preferable from the viewpoint of detergency.
 更に、これらのアルカノールアミンを炭酸カリウムなどのアルカリ金属炭酸塩と併用することがより保存安定性を向上できる点で好ましい。 Furthermore, it is preferable that these alkanolamines are used in combination with alkali metal carbonates such as potassium carbonate because the storage stability can be further improved.
 (D)成分は前述した(B)成分や(C)成分の中和にも用いても良い。洗浄性、及び手肌への低刺激性の観点から、本発明の液体洗浄剤組成物のpH緩衝能がpH9.0~10.5の範囲で良好に発現することが好ましく、そのためには(C)成分のような弱酸と、(D)成分であるpKaを9.0~10.6の範囲に持つ化合物とを組み合わせることが望ましい。 The component (D) may be used for neutralizing the component (B) and component (C) described above. From the viewpoint of detergency and mildness to the hand skin, it is preferable that the pH buffering ability of the liquid detergent composition of the present invention is well expressed in the range of pH 9.0 to 10.5. It is desirable to combine a weak acid such as component C) with a compound having a pKa of component (D) in the range of 9.0 to 10.6.
<液体洗浄剤組成物>
 本発明の液体洗浄剤組成物は、(A)/(B)の質量比が85/15~30/70であり、好ましくは80/20~40/60であり、更に75/25~50/50、更に70/30~55/45である。この質量比において(A)成分の比率がこの範囲内であれば、特に85/15以下であればより濯ぎ性が向上する一方、30/70以上であればより洗浄性が向上し、且つ、洗っているときの泡立ち性に優れる。
<Liquid cleaning composition>
The liquid detergent composition of the present invention has a mass ratio of (A) / (B) of 85/15 to 30/70, preferably 80/20 to 40/60, and more preferably 75/25 to 50 / 50, and 70/30 to 55/45. If the ratio of the component (A) in this mass ratio is within this range, the rinsability is improved particularly if it is 85/15 or less, while the washability is improved if it is 30/70 or more, and Excellent foaming properties when washing.
 本発明の液体洗浄剤組成物では、洗浄時の適度な泡立ち性、濯ぎ時の速やかな泡消え性及び洗浄性の観点から、〔(A)+(B)〕/(C)の質量比が85/15~30/70であり、好ましくは80/20~45/55、より好ましくは75/25~55/45、より好ましくは70/30~60/40である。 In the liquid detergent composition of the present invention, the mass ratio of [(A) + (B)] / (C) is from the viewpoint of appropriate foaming properties during cleaning, quick foam disappearance during rinsing, and cleaning properties. 85/15 to 30/70, preferably 80/20 to 45/55, more preferably 75/25 to 55/45, and more preferably 70/30 to 60/40.
 本発明の液体洗浄剤組成物では、洗浄時の適度な泡立ち性、洗浄性及び手肌への低刺激性の観点から、特に泡立ち性の観点から、〔(A)+(B)〕/(D)の質量比が85/15~40/60であり、好ましくは82/18~50/50、より好ましくは79/21~55/45、より好ましくは76/24~60/40、より好ましくは73/27~65/35である。 In the liquid detergent composition of the present invention, [(A) + (B)] / () from the viewpoint of moderate foaming property during cleaning, cleanability and low irritation to the hand skin, particularly from the viewpoint of foaming property. The mass ratio of D) is 85/15 to 40/60, preferably 82/18 to 50/50, more preferably 79/21 to 55/45, more preferably 76/24 to 60/40, and more preferably Is 73/27 to 65/35.
 本発明の液体洗浄剤組成物は、(B)成分を0.5~20質量%、更に1.2~12質量%、より更に2~8質量%、より更に2.2~7.5質量%、より更に3~5質量%含有することが好ましい。また、(C)成分をナトリウム塩換算の量で算出したもので1~50質量%、更に1.5~30質量%、更に2~20質量%、より更に4~10質量%含有することが好ましい。また、(D)成分を2~10質量%、更に2.5~8質量%、より更に3.5~6質量%、より更に3.8~5.5質量%含有することが好ましい。各成分の含有量は、前記質量比を満たす範囲で選択される。 In the liquid detergent composition of the present invention, the component (B) is 0.5 to 20% by mass, further 1.2 to 12% by mass, further 2 to 8% by mass, and further 2.2 to 7.5% by mass. %, And more preferably 3 to 5% by mass. The component (C) is calculated in terms of sodium salt, and is contained in an amount of 1 to 50% by mass, further 1.5 to 30% by mass, further 2 to 20% by mass, and further 4 to 10% by mass. preferable. Further, the component (D) is preferably contained in an amount of 2 to 10% by mass, further 2.5 to 8% by mass, further 3.5 to 6% by mass, and further 3.8 to 5.5% by mass. The content of each component is selected within a range that satisfies the mass ratio.
 本発明の液体洗浄剤組成物は、適度な泡立ち性と濯ぎ時の速やかな泡消え性の観点から、(A)成分と(B)成分とを合計で5~30質量%、更に6~20質量%、より更に7~15質量%、より更に8~12質量%含有することが好ましい。この含有量が5質量%以上であればより良好な洗浄性及び泡立ち性を有する組成物が得られる一方、30質量%以下であれば良好な粘度を有し、洗濯液に速やかに溶解、分散でき、又は透明な液感を有する組成物が得られる。 The liquid detergent composition of the present invention has a total of 5 to 30% by mass of the component (A) and the component (B), and further 6 to 20% from the viewpoint of appropriate foaming properties and quick foam disappearance at the time of rinsing. The content is preferably 7% by mass, more preferably 7 to 15% by mass, and still more preferably 8 to 12% by mass. If this content is 5% by mass or more, a composition having better detergency and foaming properties can be obtained. On the other hand, if it is 30% by mass or less, it has a good viscosity and dissolves and disperses quickly in the washing liquid. Or a composition having a clear liquid feeling is obtained.
 本発明の液体洗浄剤組成物において、水の含有量は、組成物中、30~90質量%、更に40~85質量%、より更に50~80質量%が好ましい。 In the liquid detergent composition of the present invention, the water content in the composition is preferably 30 to 90% by mass, more preferably 40 to 85% by mass, and even more preferably 50 to 80% by mass.
 本発明の液体洗浄剤組成物は、すすぎ時の速やかな泡消え性の観点から、非イオン界面活性剤の含有量が2質量%以下であり、1.5質量%以下、更に1質量%以下、より更に0.5質量%以下、更には全く配合しないこと、すなわち、本発明の液体洗浄剤組成物が非イオン界面活性剤を含有しないことが最も好ましい。ここで言う非イオン界面活性剤としては、特に限定されるものではないが、例えばポリオキシアルキレンアルキルエーテルが挙げられ、例えば炭素数10~18のアルコールにエチレンオキサイドを平均で4~15、好ましくは4~10モル、プロピレンオキサイドを平均で0~5モル付加したポリオキシアルキレンアルキルエーテルが挙げられ、その含有量を前記範囲内に留めることが好ましい。一般にこうした非イオン界面活性剤は、気液界面への配向性が高く、またc.m.c.(臨界ミセル濃度)が小さいことから、低濃度であってもしつこく泡が残り、すすぎ時の速やかな泡消え性を阻害する。ただし、ポリオキシアルキレンアルキルエーテルの中でも、アルキレンオキサイドの付加モル数が大きいもの、例えば炭素数10~18のアルコールにエチレンオキサイドを平均15モル超、好ましくは平均20モル以上、プロピレンオキサイドを平均で0~5モル付加したものは、少量(望ましくは2質量%以下)であれば本発明の液体洗浄剤組成物に使用してもよい。 In the liquid detergent composition of the present invention, the content of the nonionic surfactant is 2% by mass or less, 1.5% by mass or less, and further 1% by mass or less from the viewpoint of rapid foam extinction at the time of rinsing. More preferably, it is 0.5% by mass or less, and further, it is not blended at all, that is, the liquid detergent composition of the present invention does not contain a nonionic surfactant. The nonionic surfactant referred to herein is not particularly limited, and examples thereof include polyoxyalkylene alkyl ether. For example, an average of 4 to 15, preferably, ethylene oxide is added to an alcohol having 10 to 18 carbon atoms. Examples include polyoxyalkylene alkyl ethers in which 4 to 10 moles and 0 to 5 moles of propylene oxide are added on average, and the content is preferably kept within the above range. In general, such nonionic surfactants have high orientation to the gas-liquid interface, and c. m. c. Since the (critical micelle concentration) is small, bubbles remain persistently even at low concentrations, impeding rapid bubble disappearance during rinsing. However, among the polyoxyalkylene alkyl ethers, those having a large added mole number of alkylene oxide, for example, an alcohol having 10 to 18 carbon atoms with an average of more than 15 moles, preferably an average of 20 moles or more, and an average of 0 to propylene oxide. Those added in an amount of ˜5 mol may be used in the liquid detergent composition of the present invention as long as the amount is small (desirably 2% by mass or less).
 本発明の液体洗浄剤組成物は、非イオン界面活性剤として、炭素数10~18のアルコールにエチレンオキサイドを平均で4~60モル、好ましくは4~30、より好ましくは4~15、より好ましくは4~10モル、プロピレンオキサイドを平均で0~5モル付加したポリオキシアルキレンアルキルエーテルを含有することもできる。 The liquid detergent composition of the present invention is an average of 4 to 60 mol, preferably 4 to 30, more preferably 4 to 15, more preferably 4 to 15 moles of ethylene oxide as a nonionic surfactant in an alcohol having 10 to 18 carbon atoms. Can also contain 4 to 10 mol of polyoxyalkylene alkyl ether added with 0 to 5 mol of propylene oxide on average.
 ここで、炭素数10~18のアルコールにエチレンオキサイドを平均で4~15モル、好ましくは4~10モル、プロピレンオキサイドを平均で0~5モル付加したポリオキシアルキレンアルキルエーテルを用いる場合は、すすぎ時の速やかな泡消え性の観点から、本発明の液体洗浄剤組成物中の当該ポリオキシアルキレンアルキルエーテルの含有量が2質量%以下であることが好ましく、更に1.5質量%以下、更に1質量%以下、更に0.5質量%以下、より更には全く配合しないこと、すなわち、本発明の液体洗浄剤組成物が当該ポリオキシアルキレンアルキルエーテルを含有しないことが最も望ましい。従って、本発明において、組成物中の含有量が2質量%以下に制限される非イオン界面活性剤は、炭素数10~18のアルコールにエチレンオキサイドを平均で4~15モル、好ましくは4~10モル、プロピレンオキサイドを平均で0~5モル付加したポリオキシアルキレンアルキルエーテルであってもよい。 Here, when polyoxyalkylene alkyl ether in which ethylene oxide is added to alcohol having 10 to 18 carbon atoms on average in an amount of 4 to 15 moles, preferably 4 to 10 moles and propylene oxide in an average of 0 to 5 moles is used, rinsing is performed. From the viewpoint of rapid foam extinction, the content of the polyoxyalkylene alkyl ether in the liquid detergent composition of the present invention is preferably 2% by mass or less, more preferably 1.5% by mass or less, and further It is most desirable that it is 1% by mass or less, further 0.5% by mass or less, and further not blended at all, that is, the liquid detergent composition of the present invention does not contain the polyoxyalkylene alkyl ether. Therefore, in the present invention, the nonionic surfactant whose content in the composition is limited to 2% by mass or less is an average of 4 to 15 moles, preferably 4 to 5 moles of ethylene oxide in an alcohol having 10 to 18 carbon atoms. It may be a polyoxyalkylene alkyl ether to which 10 mol and 0 to 5 mol of propylene oxide is added on average.
 一方、本発明の液体洗浄剤組成物は、炭素数10~18のアルコールにエチレンオキサイドを平均で15超~60モル、プロピレンオキサイドを平均で0~5モル付加したポリオキシアルキレンアルキルエーテルを、本発明の効果を阻害しない範囲、望ましくは2質量%以下の範囲で含有することができる。本発明の液体洗浄剤組成物は、(E)成分として、下記一般式(e1)で表される非イオン界面活性剤を含有することができる。
 R1eO-[(CO)/(CO)]H        (e1)
〔式中、R1eは炭素数10~18の炭化水素基である。m、nは平均付加モル数であって、mは15超~60の数であり、nは0~5の数である。“/”はCO基及びCO基が、ランダム又はブロックのいずれに結合したものであってもよいことを示す。〕
On the other hand, the liquid detergent composition of the present invention comprises a polyoxyalkylene alkyl ether obtained by adding an average of more than 15 to 60 mol of ethylene oxide and an average of 0 to 5 mol of propylene oxide to an alcohol having 10 to 18 carbon atoms. It can contain in the range which does not inhibit the effect of invention, desirably 2 mass% or less. The liquid cleaning composition of this invention can contain the nonionic surfactant represented by the following general formula (e1) as (E) component.
R 1e O — [(C 2 H 4 O) m / (C 3 H 6 O) n ] H (e1)
[Wherein, R 1e is a hydrocarbon group having 10 to 18 carbon atoms. m and n are average added mole numbers, m is a number from more than 15 to 60, and n is a number from 0 to 5. “/” Indicates that the C 2 H 4 O group and the C 3 H 6 O group may be bonded to either random or block. ]
 (E)成分の一般式(e1)中、R1eは炭素数10~18の炭化水素基であり、炭素数10~16、更に10~14の炭化水素基が好ましい。また、R1eは鎖式炭化水素基、更に直鎖の炭化水素基が好ましい。また、R1eの炭化水素基としては、アルキル基又はアルケニル基が好ましく、アルキル基がより好ましい。R1eは、直鎖又は分岐鎖のアルキル基が好ましく、直鎖アルキル基がより好ましい。本発明では酸素原子に結合するR1eの炭素原子が第一炭素原子であってもよい。このようなアルキル基は天然油脂由来の脂肪族アルコールを原料として用いることができる。一般式(e1)中のR1e-O-の酸素原子に結合するR1eの炭素原子が第1炭素原子であるものは、第2炭素原子による化合物よりも洗浄力に優れる。特にR1eは第1炭素原子を有する直鎖アルキル基が好ましい。 In the general formula (e1) of component (E), R 1e is a hydrocarbon group having 10 to 18 carbon atoms, preferably a hydrocarbon group having 10 to 16 carbon atoms, and more preferably 10 to 14 carbon atoms. R 1e is preferably a chain hydrocarbon group, and more preferably a linear hydrocarbon group. Moreover, as a hydrocarbon group of R 1e , an alkyl group or an alkenyl group is preferable, and an alkyl group is more preferable. R 1e is preferably a linear or branched alkyl group, and more preferably a linear alkyl group. In the present invention, the carbon atom of R 1e bonded to the oxygen atom may be the first carbon atom. Such an alkyl group can use a fatty alcohol derived from natural fats and oils as a raw material. A compound in which the carbon atom of R 1e bonded to the oxygen atom of R 1e —O— in the general formula (e1) is the first carbon atom is more excellent in detergency than the compound having the second carbon atom. In particular, R 1e is preferably a linear alkyl group having the first carbon atom.
 一般式(e1)の化合物を得る方法は、特に限定されるものではないが、炭素数10~18のアルコールにエチレンオキシドを付加反応すること、あるいはエチレンオキシドとプロピレンオキシドを付加反応することによって得ることができる。 The method for obtaining the compound of the general formula (e1) is not particularly limited, but can be obtained by addition reaction of ethylene oxide with an alcohol having 10 to 18 carbon atoms or addition reaction of ethylene oxide and propylene oxide. it can.
 一般式(e1)中のmはエチレンオキシ基の平均付加モル数であって、mの下限値は、すすぎ性、洗浄性能の点から、好ましくは18以上、より好ましくは20以上、より好ましくは22以上、より好ましくは26以上、より好ましくは30以上であり、上限値は、製造し易さの点から、好ましくは45以下、より好ましくは35以下である。従って、(E)成分として、一般式(e1)中のmが18~60、好ましくは26~60の数の非イオン界面活性剤を用いることができる。nはプロピレンオキシ基の平均付加モル数であり、洗浄性能の点から下限値は0以上、好ましくは1以上であり、上限値は5以下、好ましくは4以下、より好ましくは3以下である。 M in the general formula (e1) is the average number of added moles of ethyleneoxy group, and the lower limit of m is preferably 18 or more, more preferably 20 or more, more preferably from the viewpoint of rinsing properties and cleaning performance. It is 22 or more, more preferably 26 or more, more preferably 30 or more, and the upper limit is preferably 45 or less, more preferably 35 or less, from the viewpoint of ease of production. Therefore, as the component (E), a nonionic surfactant having a number m in the general formula (e1) of 18 to 60, preferably 26 to 60 can be used. n is the average number of moles of propyleneoxy group added, and the lower limit is 0 or more, preferably 1 or more, and the upper limit is 5 or less, preferably 4 or less, more preferably 3 or less, from the viewpoint of cleaning performance.
 一般式(e1)中のプロピレンオキシ基は、プロピレンオキシドの付加反応による場合はメチル分岐した構造を有する。 The propyleneoxy group in general formula (e1) has a methyl-branched structure in the case of propylene oxide addition reaction.
 ところで、R1eO-の近い位置にCOが存在する構造の場合、COは疎水性基であることから、R1eである鎖式炭化水素基が延長された構造に類似する構造になり、疎水性が高まる傾向を示す。本発明の(E)成分は、一般式(e1)において、R1e-O-CO-である化合物の割合が、(E)成分を構成している化合物中の75モル%以上、更に80モル%以上(上限は100モル%以下)であることが好ましい。このような化合物は未反応アルコールを除去することによっても得られるが、本発明では特に、R1eOHの1モルに対して、エチレンオキシドを6モル以上、特には8モル以上付加させることで、この要件を達成することができる。この規定は、後述する一般式(e1-2)、(e1-4)及び(e1-5)においても適用してもよい。 By the way, in the case where C 3 H 6 O is present at a position close to R 1e O—, since C 3 H 6 O is a hydrophobic group, a structure in which a chain hydrocarbon group as R 1e is extended. It shows a tendency to increase the hydrophobicity. In the general formula (e1), the component (E) of the present invention is such that the proportion of the compound that is R 1e —O—C 2 H 4 O— is 75 mol% or more in the compound constituting the component (E). Furthermore, it is preferably 80 mol% or more (the upper limit is 100 mol% or less). Such a compound can also be obtained by removing unreacted alcohol. In the present invention, particularly, 6 mol or more, particularly 8 mol or more of ethylene oxide is added to 1 mol of R 1e OH. The requirement can be achieved. This rule may be applied to general formulas (e1-2), (e1-4), and (e1-5) described later.
 更には(E)成分は、一般式(e1)において、前記の、R1e-O-CO-の条件を満たした上で、末端が-CO-Hの割合も高いものが、末端が疎水性基のプロピレンオキシ基の-CO-Hである場合よりも、繊維の吸着性が低いことから好ましい。特には末端が-CO-Hの構造を有する化合物が70モル%以上、更に80モル%以上(上限は100モル%以下)であることがより好ましい。このような化合物は、一般式(e1)を製造する上で、最初にエチレンオキシドを前記条件で付加反応させるか、エチレンオキシドの付加後、未反応アルコールを除去させた後、次いでプロピレンオキシド、好ましくはプロピレンオキシドの付加反応工程を行い、最後にエチレンオキシドだけを6モル以上、特には8モル以上付加させることで得ることができる。この規定は後述する一般式(e1-5)においても適用してもよい。なおR1e-O-CO-や-CO-Hの割合はC13-NMRを用いた定量測定で求めることができる。 Furthermore, the component (E) has a ratio of —C 2 H 4 O—H at the terminal after satisfying the condition of R 1e —O—C 2 H 4 O— in the general formula (e1). Higher ones are preferable because the adsorptivity of the fibers is lower than when the terminal is —C 3 H 6 O—H having a hydrophobic propyleneoxy group. In particular, it is more preferable that the amount of the compound having a structure of —C 2 H 4 O—H at the terminal is 70 mol% or more, and further 80 mol% or more (the upper limit is 100 mol% or less). Such a compound is produced by first adding ethylene oxide under the above-mentioned conditions in the production of the general formula (e1), or after adding ethylene oxide, removing unreacted alcohol, and then propylene oxide, preferably propylene. It can be obtained by conducting an oxide addition reaction step and finally adding only 6 mol or more, particularly 8 mol or more of ethylene oxide. This rule may also be applied to the general formula (e1-5) described later. The ratio of R 1e —O—C 2 H 4 O— or —C 2 H 4 O—H can be determined by quantitative measurement using C 13 -NMR.
 本発明の一般式(e1)で示される化合物としては下記一般式(e1-1)~(e1-5)の化合物であってもよい。一般式(e1-1)~(e1-5)で示される化合物は、R1eOHに対するアルキレンオキシドの反応割合及び反応順序を考慮することで調製することができる。
 R1eO-(PO)-(EO)H             (e1-1)
 R1eO-(EO)-(PO)H             (e1-2)
 R1eO-[(EO)m1・(PO)]-(EO)m2H    (e1-3)
 R1eO-(EO)m1-[(PO)・(EO)m2]H    (e1-4)
 R1eO-(EO)m1-(PO)-(EO)m2H      (e1-5)
〔式中、EO、POは夫々エチレンオキシ基、プロピレンオキシ基であり、R1e、m、nは前記の意味であり、m1、m2は平均付加モル数であって、m=m1+m2である。“・”はランダム結合であることを示す。〕
The compound represented by the general formula (e1) of the present invention may be a compound represented by the following general formulas (e1-1) to (e1-5). The compounds represented by the general formulas (e1-1) to (e1-5) can be prepared by taking into consideration the reaction ratio and reaction sequence of the alkylene oxide with respect to R 1e OH.
R 1e O— (PO) n — (EO) m H (e1-1)
R 1e O— (EO) m — (PO) n H (e1-2)
R 1e O-[(EO) m1 · (PO) n ]-(EO) m2 H (e1-3)
R 1e O— (EO) m1 — [(PO) n · (EO) m2 ] H (e1-4)
R 1e O— (EO) m1 — (PO) n — (EO) m2 H (e1-5)
[In the formula, EO and PO are an ethyleneoxy group and a propyleneoxy group, respectively, R 1e , m and n have the same meanings as described above, and m1 and m2 are the average number of added moles, and m = m1 + m2. “·” Indicates a random bond. ]
 本発明では一般式(e1-2)、(e1-4)又は(e1-5)の化合物が、特に一般式(e1-2)又は(e1-5)の化合物が、すすぎ性の点からより好ましい。 In the present invention, the compound of the general formula (e1-2), (e1-4) or (e1-5), particularly the compound of the general formula (e1-2) or (e1-5) is more preferable in terms of rinsing properties. preferable.
 本発明の(E)成分は、R1e-OHで表される化合物(R1eは炭素数10~18の炭化水素基、好ましくは、前記一般式(e1)におけるR1eと同じ)1モル当りに、エチレンオキシドをm1モル付加させた後、プロピレンオキシドをnモル付加させた後、更にエチレンオキシドをm2モル付加させて得られる非イオン界面活性剤であって、m1が3~30の数、好ましくは5~25、より好ましくは8~20の数であり、nが1~5の数、好ましくは1~3の数であり、m1とm2は合計でm1+m2=18~60、好ましくは22~45、より好ましくは26~35の数である非イオン界面活性剤が好ましい。m2は前記m1とm1+m2より求めることができるが、本発明で、m2が好ましくは3~30の数、より好ましくは7~25の数、好ましくは8~20の数である。本発明では特にPOが末端、及びR1eに結合していないことが好ましく、m1とm2は、m1/(m1+m2)=0.2~0.8、更に0.3~0.7が好ましい。この場合、R1e、m1、m2及びnは前記一般式(e1-5)と同じ意味である。 Component (E) of the present invention is a compound represented by R 1e —OH (R 1e is a hydrocarbon group having 10 to 18 carbon atoms, preferably the same as R 1e in formula (e1)) per mole. A nonionic surfactant obtained by adding m1 mol of ethylene oxide, then adding n mol of propylene oxide and then adding m2 mol of ethylene oxide, wherein m1 is a number of 3 to 30, preferably 5 to 25, more preferably 8 to 20, n is a number from 1 to 5, preferably 1 to 3, and m1 and m2 are in total m1 + m2 = 18 to 60, preferably 22 to 45 Nonionic surfactants having a number of 26 to 35 are more preferable. m2 can be determined from m1 and m1 + m2. In the present invention, m2 is preferably a number of 3 to 30, more preferably a number of 7 to 25, and preferably a number of 8 to 20. In the present invention, it is particularly preferable that PO is not bonded to the terminal and R 1e , and m1 and m2 are preferably m1 / (m1 + m2) = 0.2 to 0.8, more preferably 0.3 to 0.7. In this case, R 1e , m1, m2 and n have the same meaning as in the general formula (e1-5).
 (E)成分の製造に関して、R1e-OHのアルコキシル化に用いられる触媒は塩基触媒、酸触媒が挙げられる。このうち特に、コストの面から塩基触媒を使用することが好ましく、塩基として水酸化ナトリウム又は水酸化カリウムがより好ましく、水酸化カリウムを使用することが最も好ましい。 Regarding the production of component (E), examples of the catalyst used for alkoxylation of R 1e —OH include a base catalyst and an acid catalyst. Of these, a base catalyst is preferably used from the viewpoint of cost, sodium hydroxide or potassium hydroxide is more preferable as the base, and potassium hydroxide is most preferably used.
 水酸化カリウムを触媒として使用する場合の製造条件の一例を以下に示す。まず原料となる炭素数10~18の高級アルコール(R1e-OHで表される化合物)に水酸化カリウムを仕込んだ後、窒素置換し、100~110℃、1~7kPaで30分~1時間脱水を行う。次いで100~170℃、0.3~0.6MPaでエチレンオキシドの付加を行い、次に100~150℃、0.3~0.7MPaの条件でプロピレンオキシドの付加を行い、再度100~170℃、0.3~0.7MPaの条件でエチレンオキシドを付加した後、添加した水酸化カリウムと当モル量の酸剤(酢酸、乳酸、グリコール酸等)で中和することによって得られる。なお各エチレンオキシド及びプロピレンオキシドの使用量は、組成物中のm、nの平均値の条件を満たすように、原料アルコールのモル数に応じて選定される。 An example of production conditions when potassium hydroxide is used as a catalyst is shown below. First, potassium hydroxide is charged into a higher alcohol having 10 to 18 carbon atoms (compound represented by R 1e —OH) as a raw material, and then purged with nitrogen, and at 100 to 110 ° C. and 1 to 7 kPa for 30 minutes to 1 hour. Perform dehydration. Then, ethylene oxide is added at 100 to 170 ° C. and 0.3 to 0.6 MPa, and then propylene oxide is added at 100 to 150 ° C. and 0.3 to 0.7 MPa. It can be obtained by adding ethylene oxide under the condition of 0.3 to 0.7 MPa, and then neutralizing with added potassium hydroxide and an equimolar amount of an acid agent (acetic acid, lactic acid, glycolic acid, etc.). In addition, the usage-amount of each ethylene oxide and propylene oxide is selected according to the number-of-moles of raw material alcohol so that the conditions of the average value of m and n in a composition may be satisfy | filled.
 また、本発明の液体洗浄剤組成物は、(F)成分として、(A)成分、(B)成分、(C)成分及び上記非イオン界面活性剤以外の界面活性剤を本発明の効果を損なわない範囲で含有することができる。本発明では、(F)成分の割合が、全界面活性剤中の20質量%以下、更に10質量%以下、より更には5質量%以下であることが好ましい。 In addition, the liquid detergent composition of the present invention has the effect of the present invention as a component (F) with surfactants other than the components (A), (B), (C) and the nonionic surfactant. It can contain in the range which is not impaired. In the present invention, the proportion of the component (F) is preferably 20% by mass or less, more preferably 10% by mass or less, and even more preferably 5% by mass or less in the total surfactant.
 (F)成分としては、特に限定されるものでないが、脂肪族アルコール、アルカノールアミド、アミンオキシド、ベタインなどが挙げられる。これらは、例えば、「泡のエンジニアリング」(株式会社テクノシステム発行、2005年)に記載されているように、泡ブースターとしての機能を持つため、本発明の洗浄剤組成物の起泡力を高めることができる。(F)成分のうち、脂肪族アルコール、アルカノールアミド、アミンオキシド、及びベタインから選ばれる泡ブースターは、すすぎ性を損なわないために、全界面活性剤中の5質量%以下、更には3質量%以下、より更には1.5質量%以下が好ましい。 (F) Component is not particularly limited, and examples thereof include aliphatic alcohols, alkanolamides, amine oxides and betaines. Since these have a function as a foam booster, for example, as described in “Foam Engineering” (published by Techno System Co., Ltd., 2005), the foaming power of the cleaning composition of the present invention is increased. be able to. Among the components (F), the foam booster selected from aliphatic alcohol, alkanolamide, amine oxide, and betaine is 5% by mass or less, more preferably 3% by mass in the total surfactant in order not to impair the rinsing property. Hereinafter, it is more preferably 1.5% by mass or less.
 脂肪族アルコールとしては、炭素数8~18、好ましくは10~16、より好ましくは12~14の脂肪族アルコールが挙げられる。中でも、ドデシルアルコールが好ましい。アルカノールアミドとしては、モノエタノールアミド、ジエタノールアミドやN-メチルエタノールアミドなどが好ましいが、イソプロパノールアミドタイプやアルキレンオキシドを付加したものなどを用いることができる。アミンオキシドとしては、炭素数8~18、好ましくは12~14の長鎖長のアルキル基と炭素数1~3のアルキル基、好ましくはメチル基とを有する、モノ長鎖アルキルアミンオキシドなどを挙げることができる。ベタインとしては、アルキルアミドプロピルベタインを挙げることができる。中でも、炭素数が12のラウラミドプロピルベタインやヤシ油組成のココアミドプロピルベタインが一般的である。 Examples of the aliphatic alcohol include aliphatic alcohols having 8 to 18, preferably 10 to 16, and more preferably 12 to 14 carbon atoms. Among these, dodecyl alcohol is preferable. As the alkanolamide, monoethanolamide, diethanolamide, N-methylethanolamide and the like are preferable, but those having an isopropanolamide type or an alkylene oxide added thereto can be used. Examples of the amine oxide include mono long chain alkyl amine oxides having a long chain length alkyl group having 8 to 18 carbon atoms, preferably 12 to 14 carbon atoms, and an alkyl group having 1 to 3 carbon atoms, preferably a methyl group. be able to. Examples of betaines include alkylamidopropyl betaines. Among them, lauramidopropyl betaine having 12 carbon atoms and cocoamidopropyl betaine having a coconut oil composition are generally used.
 特に、起泡力、すすぎ性の観点から、(F)成分として、(F1)下記一般式(f1)で表される化合物及び(F2)下記一般式(f2)で表される化合物から選ばれる界面活性剤を用いるのが好ましい。これらは、2種以上を用いることができる。 In particular, from the viewpoint of foaming power and rinsability, the component (F) is selected from (F1) a compound represented by the following general formula (f1) and (F2) a compound represented by the following general formula (f2). It is preferable to use a surfactant. Two or more of these can be used.
Figure JPOXMLDOC01-appb-C000001
Figure JPOXMLDOC01-appb-C000001
〔式中、R1fは炭素数9~23の炭化水素基であり、R2fは炭素数1~6のアルキレン基である。Xはエステル基、アミド基、及びエーテル基から選ばれる基であり、pは0又は1の数である。R3f及びR4fはそれぞれ独立に炭素数1~3のアルキル基又は炭素数1~3のヒドロキシアルキル基であり、R5fはヒドロキシ基で置換していてもよい炭素数1~5のアルキレン基である。Yは陰イオン性基である。〕
   R6f-(OR7f-OH   (f2)
〔式中、R6fは炭素数6~18の炭化水素基、R7fはプロピレン基又はグリセリンから2つのヒドロキシ基を除いた残基、qは1~5の数である。〕
[Wherein R 1f is a hydrocarbon group having 9 to 23 carbon atoms, and R 2f is an alkylene group having 1 to 6 carbon atoms. X is a group selected from an ester group, an amide group, and an ether group, and p is a number of 0 or 1. R 3f and R 4f are each independently an alkyl group having 1 to 3 carbon atoms or a hydroxyalkyl group having 1 to 3 carbon atoms, and R 5f is an alkylene group having 1 to 5 carbon atoms which may be substituted with a hydroxy group. It is. Y - is an anionic group. ]
R 6f- (OR 7f ) q -OH (f2)
[Wherein R 6f is a hydrocarbon group having 6 to 18 carbon atoms, R 7f is a residue obtained by removing two hydroxy groups from a propylene group or glycerin, and q is a number of 1 to 5. ]
 (F1)成分は上記一般式(f1)で表される化合物である。一般式(f1)において、R1fは炭素数9~23の炭化水素基であり、アルキル基又はアルケニル基が好ましく、炭素数10~15、更に11~13のアルキル基がより好ましい。また、R2fは炭素数2又は3のアルキレン基が好ましく、炭素数3のアルキレン基がより好ましい。また、Xはエステル基、アミド基、及びエーテル基から選ばれる基であり、具体的には-COO-、-OCO-、-CONH-、-NHCO-、-O-から選ばれる基が挙げられる。Xは、アミド基、更に-CONH-で表される基が好ましい。pは0又は1が好ましい。R3f及びR4fはそれぞれメチル基又はヒドロキシエチル基が好ましいが、メチル基がより好ましい。Yは陰イオン性基であり、-SO 、-OSO 、-COOから選ばれる基が挙げられる。Yは-SO 又は-COOが好ましく、Yが-SO の場合には、R5fは-CHCH(OH)CH-が好ましく、Y-が-COOの場合には、R5fはメチレン基(-CH-)が好ましい。 The component (F1) is a compound represented by the general formula (f1). In the general formula (f1), R 1f is a hydrocarbon group having 9 to 23 carbon atoms, preferably an alkyl group or an alkenyl group, more preferably an alkyl group having 10 to 15 carbon atoms, and more preferably 11 to 13 carbon atoms. R 2f is preferably an alkylene group having 2 or 3 carbon atoms, and more preferably an alkylene group having 3 carbon atoms. X is a group selected from an ester group, an amide group, and an ether group, and specific examples include groups selected from —COO—, —OCO—, —CONH—, —NHCO—, and —O—. . X is preferably an amide group, and more preferably a group represented by —CONH—. p is preferably 0 or 1. R 3f and R 4f are each preferably a methyl group or a hydroxyethyl group, more preferably a methyl group. Y is an anionic group, and examples thereof include a group selected from —SO 3 , —OSO 3 , and —COO 2 . Y - or -COO - - are preferred, Y - -SO 3 has -SO 3 - in the case of, R 5f is -CH 2 CH (OH) CH 2 - if the - preferably, Y- is -COO In this case, R 5f is preferably a methylene group (—CH 2 —).
 (F2)成分は上記一般式(f2)で表される化合物である。一般式(f2)の化合物は起泡力を高めるために好適であるが、同時にすすぎ性も良好であることが望まれる。これらを両立させるには一般式(f2)で表される化合物の親水基構造と疎水性構造の両方が以下のように限定された構造であることが好ましい。必ずしも定かではないが、以下の構造にすることで、衣類や汚れへ配向性よりも気液界面への配向性が高まるものと思われる。一般式(f2)において、R6fは炭素数6~18、更に6~14、より更に6~10のアルキル基又はアルケニル基が好ましい。R7fがプロピレン基の場合、起泡性とすすぎ性の観点から、qは2~4が好ましい。また、同様の観点から、R7fが、グリセリンから2つのヒドロキシ基を除いた残基の場合、qは1~3の数が、更に1の数が好ましい。R7fは、グリセリンから2つのヒドロキシ基を除いた残基が好ましい。 The component (F2) is a compound represented by the general formula (f2). The compound of the general formula (f2) is suitable for increasing the foaming power, but at the same time, it is desired that the rinsing property is also good. In order to make these compatible, it is preferable that both the hydrophilic group structure and the hydrophobic structure of the compound represented by the general formula (f2) are limited as follows. Although it is not necessarily certain, it is considered that the orientation to the gas-liquid interface is higher than the orientation to clothing and dirt by adopting the following structure. In general formula (f2), R 6f is preferably an alkyl or alkenyl group having 6 to 18, more preferably 6 to 14, and even more preferably 6 to 10 carbon atoms. When R 7f is a propylene group, q is preferably 2 to 4 from the viewpoint of foamability and rinsing properties. From the same viewpoint, when R 7f is a residue obtained by removing two hydroxy groups from glycerin, q is preferably a number of 1 to 3, and more preferably 1. R 7f is preferably a residue obtained by removing two hydroxy groups from glycerin.
 (F2)成分としては、一般式(f2)中のR6fが炭素数6~10のアルキル基又はアルケニル基、R7fがグリセリンから2つのヒドロキシ基を除いた残基、qが1のグリセリルエーテルが好ましい。例えば、2-エチルヘキシルモノグリセリルエーテル、イソノニルモノグリセリルエーテル、イソデシルモノグリセリルエーテルなどが挙げられる。特に、起泡性とすすぎ性を両立するには2-エチルヘキシルモノグリセリルエーテルが好ましい。 As the component (F2), R 6f in the general formula (f2) is an alkyl group or alkenyl group having 6 to 10 carbon atoms, R 7f is a residue obtained by removing two hydroxy groups from glycerin, and glyceryl ether having q = 1 Is preferred. Examples thereof include 2-ethylhexyl monoglyceryl ether, isononyl monoglyceryl ether, and isodecyl monoglyceryl ether. In particular, 2-ethylhexyl monoglyceryl ether is preferable in order to achieve both foaming properties and rinsing properties.
 本発明の液体洗浄剤組成物は、起泡性とすすぎ性の観点から、(F1)成分を0.1~10質量%、更に0.2~5質量%、より更に0.4~2.7質量%含有することが好ましい。 In the liquid cleaning composition of the present invention, the component (F1) is 0.1 to 10% by mass, more preferably 0.2 to 5% by mass, and still more preferably 0.4 to 2. It is preferable to contain 7 mass%.
 また、本発明の液体洗浄剤組成物は、起泡性とすすぎ性の観点から、(F2)成分を0.1~10質量%、更に0.2~5質量%、より更に0.4~2.7質量%含有することが好ましい。 In addition, the liquid detergent composition of the present invention has a component (F2) of 0.1 to 10% by mass, more preferably 0.2 to 5% by mass, and still more preferably 0.4 to 0.4% from the viewpoint of foamability and rinsing properties. It is preferable to contain 2.7 mass%.
 また、本発明の液体洗浄剤組成物は、起泡性の観点から、(F1)成分と(F2)成分の両方を含むことができる。このとき、(F1)/(F2)の質量比が80/20~20/80、更に70/30~30/70、より更に60/40~40/60であることが好ましい。 In addition, the liquid detergent composition of the present invention can contain both the component (F1) and the component (F2) from the viewpoint of foamability. At this time, the mass ratio of (F1) / (F2) is preferably 80/20 to 20/80, more preferably 70/30 to 30/70, and still more preferably 60/40 to 40/60.
 本発明の液体洗浄剤組成物は、洗浄性と手肌への低刺激性の観点から、JIS K3362:1998記載の25℃で測定するpHが9.0~10.5、好ましくは9.3~10.2、より好ましくは9.5~10である。pHは、組成物中に配合される成分の種類や配合量、なかでも、(B)成分、(C)成分、(D)成分の種類や配合量により調整でき、必要に応じて塩酸(例えば6N-HCl)等の酸剤を用いて調整してもよい。 The liquid detergent composition of the present invention has a pH measured at 25 ° C. described in JIS K3362: 1998 of 9.0 to 10.5, preferably 9.3, from the viewpoint of detergency and mildness to the hand skin. To 10.2, more preferably 9.5 to 10. The pH can be adjusted depending on the type and amount of the component to be blended in the composition, and in particular, the type and blending amount of the component (B), the component (C), and the component (D). It may be adjusted using an acid agent such as 6N-HCl).
 本発明の液体洗浄剤組成物は、前述した各成分の質量比及び非イオン界面活性剤の含有量を特定することにより、衣料等の洗濯において、優れた洗浄力を有し、起泡性と濯ぎ性の両方に優れた性能を発現するものである。 The liquid detergent composition of the present invention has an excellent detergency in washing clothes and the like by specifying the mass ratio of each component and the content of the nonionic surfactant described above, and has a foaming property. It exhibits excellent performance in both rinsing properties.
 本発明の液体洗浄剤組成物に配合できるその他の成分として、例えば、ニトリロ三酢酸、イミノ二酢酸、エチレンジアミン四酢酸、ジエチレントリアミン五酢酸、グリコールエーテルジアミン四酢酸、ヒドロキシエチルイミノ二酢酸、トリエチレンテトラアミン六酢酸、ジエンコル酸等のアミノポリ酢酸又はこれらの塩、ジグリコール酸、オキシジコハク酸、カルボキシメチルオキシコハク酸、クエン酸、乳酸、酒石酸、シュウ酸、リンゴ酸、オキシジコハク酸、グルコン酸、カルボキシメチルコハク酸、カルボキシメチル酒石酸等の有機酸又はこれらの塩などのキレート剤、好ましくは分子量が1,000以下のキレート剤を配合できる。キレート剤の含有量は、組成物中、0.001~10質量%、0.01~3質量%、0.03~1質量%であることが好ましい。 Other components that can be incorporated into the liquid detergent composition of the present invention include, for example, nitrilotriacetic acid, iminodiacetic acid, ethylenediaminetetraacetic acid, diethylenetriaminepentaacetic acid, glycol etherdiaminetetraacetic acid, hydroxyethyliminodiacetic acid, triethylenetetraamine Aminopolyacetic acid such as hexaacetic acid and diencoric acid or salts thereof, diglycolic acid, oxydisuccinic acid, carboxymethyloxysuccinic acid, citric acid, lactic acid, tartaric acid, oxalic acid, malic acid, oxydisuccinic acid, gluconic acid, carboxymethylsuccinic acid Chelating agents such as organic acids such as carboxymethyl tartaric acid or salts thereof, preferably chelating agents having a molecular weight of 1,000 or less can be blended. The content of the chelating agent is preferably 0.001 to 10% by mass, 0.01 to 3% by mass, and 0.03 to 1% by mass in the composition.
 その他、洗浄剤組成物の溶液安定性や透明性の向上を目的に水混和性有機溶剤〔以下、(G)成分という〕を含有することが好ましい。本発明でいう水混和性有機溶剤とは、25℃のイオン交換水1Lに50g以上溶解するもの、すなわち、溶解の程度が50g/L以上である溶剤を指す。(G)成分の含有量は、溶液安定性と透明性の向上の観点から、組成物中、0.5~40質量%、更に1~20質量%、更に1.5~10質量%、より更に2~5質量%が好ましい。 In addition, it is preferable to contain a water-miscible organic solvent [hereinafter referred to as component (G)] for the purpose of improving the solution stability and transparency of the cleaning composition. The water-miscible organic solvent referred to in the present invention refers to a solvent that dissolves 50 g or more in 1 L of ion-exchanged water at 25 ° C., that is, a solvent having a degree of dissolution of 50 g / L or more. The content of the component (G) is 0.5 to 40% by mass, further 1 to 20% by mass, further 1.5 to 10% by mass in the composition from the viewpoint of improving the solution stability and transparency. Furthermore, 2 to 5% by mass is preferable.
 (G)成分としては、(G1)エタノール、1-プロパノール、2-プロパノール、1-ブタノールなどのアルカノール類、(G2)プロピレングリコール、ブチレングリコール、ヘキシレングリコールなどのグリコール類、(G3)ジエチレングリコール、トリエチレングリコール、テトラエチレングリコール、ジプロピレングリコール、トリプロピレングリコールなどのグリコール類、(G4)ジエチレングリコールモノメチルエーテル、ジエチレングリコールジメチルエーテル、トリエチレングリコールモノメチルエーテル、ジエチレングリコールモノエチルエーテル、ジエチレングリコールジエチルエーテル、ジプロピレングリコールモノメチルエーテル、ジプロピレングリコールモノエチルエーテル、トリプロピレングリコールモノメチルエーテル、1-メトキシ-2-プロパノール、1-エトキシ-2-プロパノール、1-メチルグリセリンエーテル、2-メチルグリセリンエーテル、1,3-ジメチルグリセリンエーテル、1-エチルグリセリンエーテル、1,3-ジエチルグリセリンエーテル、トリエチルグリセリンエーテル、1-ペンチルグリセリルエーテル、2-ペンチルグリセリルエーテル、1-オクチルグリセリルエーテル、2-エチルヘキシルグリセリルエーテル、ジエチレングリコールモノブチルエーテル(ブトキシジグリコールとも呼ばれる)などのアルキルエーテル類、(G5)2-フェノキシエタノール、ジエチレングリコールモノフェニルエーテル、トリエチレングリコールモノフェニルエーテル、平均分子量約480のポリエチレングリコールモノフェニルエーテル、2-ベンジルオキシエタノール、ジエチレングリコールモノベンジルエーテル等の芳香族エーテル類、が挙げられる。 As the component (G), (G1) alkanols such as ethanol, 1-propanol, 2-propanol and 1-butanol, (G2) glycols such as propylene glycol, butylene glycol and hexylene glycol, (G3) diethylene glycol, Glycols such as triethylene glycol, tetraethylene glycol, dipropylene glycol, tripropylene glycol, (G4) diethylene glycol monomethyl ether, diethylene glycol dimethyl ether, triethylene glycol monomethyl ether, diethylene glycol monoethyl ether, diethylene glycol diethyl ether, dipropylene glycol monomethyl ether , Dipropylene glycol monoethyl ether, tripropylene glycol Nomethyl ether, 1-methoxy-2-propanol, 1-ethoxy-2-propanol, 1-methylglycerol ether, 2-methylglycerol ether, 1,3-dimethylglycerol ether, 1-ethylglycerol ether, 1,3- Alkyl ethers such as diethyl glyceryl ether, triethyl glyceryl ether, 1-pentyl glyceryl ether, 2-pentyl glyceryl ether, 1-octyl glyceryl ether, 2-ethylhexyl glyceryl ether, diethylene glycol monobutyl ether (also called butoxy diglycol), (G5 ) 2-phenoxyethanol, diethylene glycol monophenyl ether, triethylene glycol monophenyl ether, polyethylene glycol having an average molecular weight of about 480 Over mono phenyl ether, 2-benzyloxy ethanol, aromatic ethers such as diethylene glycol monobenzyl ether, and the like.
 水混和性有機溶剤は同時に、組成物の粘度調整剤、ゲル化抑制剤として有効であり、上記の(G1)アルカノール類、(G2)グリコール類、(G4)アルキルエーテル類、(G5)芳香族エーテル類から選ばれる1種以上を用いることが好ましく、より好ましくは(G2)グリコール類、(G4)アルキルエーテル類、(G5)芳香族エーテル類から選ばれるものであり、特に好ましくは(G4)である。特に、ジエチレングリコールモノブチルエーテルが好ましい。(G)成分は粘度調整やゲル化抑制に効果的である。 The water-miscible organic solvent is effective at the same time as a viscosity modifier and gelation inhibitor of the composition, and the above (G1) alkanols, (G2) glycols, (G4) alkyl ethers, (G5) aromatics It is preferable to use one or more selected from ethers, more preferably selected from (G2) glycols, (G4) alkyl ethers, and (G5) aromatic ethers, particularly preferably (G4). It is. In particular, diethylene glycol monobutyl ether is preferable. The component (G) is effective for adjusting the viscosity and suppressing gelation.
 本発明の液体洗浄剤組成物に配合できるその他の成分として、次の(i)~(xiii)に示す成分を本発明の効果を損なわない程度で配合することができる。 As other components that can be blended in the liquid detergent composition of the present invention, the following components (i) to (xiii) can be blended to such an extent that the effects of the present invention are not impaired.
(i)ポリアクリル酸、ポリマレイン酸、カルボキシメチルセルロース、重量平均分子量5,000以上のポリエチレングリコール、無水マレイン酸-ジイソブチレン共重合体、無水マレイン酸-メチルビニルエーテル共重合体、無水マレイン酸-酢酸ビニル共重合体、ナフタレンスルホン酸塩ホルマリン縮合物、及び特開昭59-62614の請求項1~21(1頁3欄5行~3頁4欄14行)記載のポリマーなどの再汚染防止剤及び分散剤 0.1~10質量%、好ましくは0.5~5質量%、より好ましくは1~3質量%
(ii)ポリビニルピロリドン等の色移り防止剤
(iii)過酸化水素、過炭酸ナトリウム又は過硼酸ナトリウム等の漂白剤
(iv)テトラアセチルエチレンジアミン、特開平6-316700の一般式(I-2)~(I-7)で表される漂白活性化剤等の漂白活性化剤
(v)セルラーゼ、アミラーゼ、ペクチナーゼ、プロテアーゼ、リパーゼ等の酵素
(vi)ホウ素化合物、カルシウムイオン源(カルシウムイオン供給化合物)、ビヒドロキシ化合物、蟻酸等の酵素安定化剤
(vii)蛍光染料、例えばチノパールCBS(商品名、チバスペシャリティケミカルズ製)やホワイテックスSA(商品名、住友化学社製)として市販されている蛍光染料
(viii)ブチルヒドロキシトルエン、ジスチレン化クレゾール、亜硫酸ナトリウム及び亜硫酸水素ナトリウム等の酸化防止剤
(ix)パラトルエンスルホン酸、クメンスルホン酸、メタキシレンスルホン酸、安息香酸塩(防腐剤としての効果もある)などの可溶化剤
(x)平均分子量約200~約400のポリエチレングリコール、平均分子量約1,000~約2,000のポリプロピレングリコールなどのポリアルキレングリコール系ゲル化防止重合体
(xi)オクタン、デカン、ドデカン、トリデカンなどのパラフィン類、デセン、ドデセンなどのオレフィン類、塩化メチレン、1,1,1-トリクロロエタンなどのハロゲン化アルキル類、D-リモネンなどのテルペン類などの水非混和性有機溶剤
(xii)ゼオライトや結晶性層状シリケートなどの金属イオン交換剤
(xiii)その他、色素、香料、抗菌防腐剤、シリコーン等の消泡剤。
(I) Polyacrylic acid, polymaleic acid, carboxymethyl cellulose, polyethylene glycol having a weight average molecular weight of 5,000 or more, maleic anhydride-diisobutylene copolymer, maleic anhydride-methyl vinyl ether copolymer, maleic anhydride-vinyl acetate Recontamination preventives such as copolymers, naphthalenesulfonate formalin condensates, and polymers described in claims 1 to 21 (page 1, column 3, line 5 to page 3, column 4, line 14) of JP-A-59-62614; Dispersant 0.1-10% by weight, preferably 0.5-5% by weight, more preferably 1-3% by weight
(Ii) Color transfer inhibitor such as polyvinylpyrrolidone (iii) Bleaching agent such as hydrogen peroxide, sodium percarbonate or sodium perborate (iv) Tetraacetylethylenediamine, general formula (I-2) to JP-A-6-316700 Bleach activators such as bleach activators represented by (I-7) (v) enzymes such as cellulase, amylase, pectinase, protease, lipase (vi) boron compounds, calcium ion sources (calcium ion supply compounds), Enzyme stabilizers (vii) fluorescent dyes such as bihydroxy compounds and formic acid, for example, fluorescent dyes commercially available as Chino Pearl CBS (trade name, manufactured by Ciba Specialty Chemicals) and Whitetex SA (trade name, manufactured by Sumitomo Chemical Co., Ltd.) viii) Butylhydroxytoluene, distyrenated cresol, sodium sulfite, sodium bisulfite, etc. (Ix) Solubilizers such as paratoluenesulfonic acid, cumenesulfonic acid, metaxylenesulfonic acid, benzoate (also effective as a preservative) (x) polyethylene having an average molecular weight of about 200 to about 400 Glycol, polyalkylene glycol-based anti-gelling polymers such as polypropylene glycol having an average molecular weight of about 1,000 to about 2,000 (xi) paraffins such as octane, decane, dodecane, tridecane, olefins such as decene, dodecene, Water immiscible organic solvents such as methylene chloride, alkyl halides such as 1,1,1-trichloroethane, and terpenes such as D-limonene (xii) Metal ion exchangers such as zeolite and crystalline layered silicate (xiii) Other antifoaming agents such as pigments, fragrances, antibacterial preservatives, and silicones.
 本発明の液体洗浄剤組成物は、例えば、所定温度(80℃程度)に加温したイオン交換水に、所定量の(A)成分、及び(D)成分、及び必要に応じて(G)成分を加えて溶解させる。必要であればこの段階で水酸化ナトリウムなどの強塩基を加えておく。次いで酸型の(B)成分、及び酸型の(C)成分を加え、透明になるまで混合した後、その他の成分を適宜加え、室温まで冷却後、香料や色素などを加えることにより製造することができる。 In the liquid detergent composition of the present invention, for example, a predetermined amount of the components (A) and (D) and, if necessary, (G) in ion-exchanged water heated to a predetermined temperature (about 80 ° C.) Add ingredients and dissolve. If necessary, a strong base such as sodium hydroxide is added at this stage. Next, the acid type (B) component and the acid type (C) component are added and mixed until it becomes transparent, then other components are added as appropriate, and after cooling to room temperature, a fragrance, a pigment, and the like are added. be able to.
 本発明の液体洗浄剤組成物は、家庭での洗濯用、更には手洗い洗濯用として好適であり、衣料、布帛、寝具、タオル等の繊維製品の手洗い洗濯に好適に用いられる。 The liquid detergent composition of the present invention is suitable for washing at home and also for hand washing, and is suitably used for hand washing of textile products such as clothing, fabrics, bedding, towels and the like.
 本発明は、本発明の液体洗浄剤組成物を含む洗浄水を接触させた被洗浄物を手洗いする手洗い洗濯方法に関する。本発明の液体洗浄剤組成物を用いた手洗い洗濯方法としては、布帛のような被洗浄物に、本発明の液体洗浄剤組成物を含む洗浄水を接触、浸漬させて手洗いする方法が挙げられる。接触時間及び/又は浸漬時間が長いと洗浄効果が高く、5~15分接触及び/又は浸漬するとより良好な効果が得られる。特に汚れた部分に直接組成物を塗布して5~15分放置すると更に高い効果が得られる。洗浄水は、本発明の組成物又は組成物の水希釈物(例えば水溶液)が用いられる。布帛のような被洗浄物の質量に対する洗浄水の質量は、好ましくは2~100倍、より好ましくは3~50倍、特に好ましくは5~25倍である。本発明に係る洗浄水を接触させた布帛等の被洗浄物を十分に手でこすり洗いすると高い洗浄力が得られるばかりか豊かな泡立ちがあるため、視覚的に好ましい。こすり洗い後は洗浄水から布帛を取り出し、絞って水を切るか脱水機を用いて水を切り、新しい水〔以下すすぎ水という〕に再度浸漬させる。すすぎ水は、洗面器などにためた水でも流水でもどちらでも良い。布帛に対するすすぎ水の質量は、すすぎに用いたすすぎ水の全量基準で、好ましくは2~1,000倍、より好ましくは5~500倍、特に好ましくは10~100倍である。すすぎ水を浸漬させた段階で布帛に残存している界面活性剤などが、すすぎ水に再溶解するため、泡立ちが見られる。この操作を数回繰り返すと泡立ちがなくなりすすぎ終了となる。手洗いによる一般的な洗濯では、例えば通常の洗浄剤を用いた場合には一般的に5回以上必要となるが、本発明では3回以下ですすぎを終了でき、非常に少ないすすぎ水ですすぎを終了させることができる。 The present invention relates to a hand-washing laundry method for hand-washing an object to be cleaned that has been brought into contact with cleaning water containing the liquid detergent composition of the present invention. Examples of the hand-washing washing method using the liquid detergent composition of the present invention include a method of hand washing by bringing the washing water containing the liquid detergent composition of the present invention into contact with an object to be washed such as a fabric and soaking. . When the contact time and / or immersion time is long, the cleaning effect is high, and when the contact time and / or immersion is 5 to 15 minutes, a better effect is obtained. In particular, when the composition is applied directly to a soiled part and left for 5 to 15 minutes, a higher effect can be obtained. As the washing water, the composition of the present invention or a water dilution of the composition (for example, an aqueous solution) is used. The mass of washing water with respect to the mass of an object to be cleaned such as a fabric is preferably 2 to 100 times, more preferably 3 to 50 times, and particularly preferably 5 to 25 times. When the object to be cleaned such as the fabric brought into contact with the cleaning water according to the present invention is sufficiently rubbed by hand, not only a high detergency is obtained but also abundant foaming is visually preferred. After scrubbing, the fabric is taken out from the washing water, squeezed to drain the water, or drained using a dehydrator, and immersed again in fresh water (hereinafter referred to as rinsing water). The rinsing water may be either water stored in a basin or running water. The mass of rinsing water with respect to the fabric is preferably 2 to 1,000 times, more preferably 5 to 500 times, and particularly preferably 10 to 100 times based on the total amount of rinsing water used for rinsing. Since the surfactant remaining in the fabric at the stage of immersing the rinse water is redissolved in the rinse water, foaming is observed. When this operation is repeated several times, the foaming disappears and the rinsing is completed. In general washing by hand, for example, when a normal cleaning agent is used, it is generally required 5 times or more. However, in the present invention, rinsing can be completed in 3 times or less, and rinsing is performed with very little rinsing water. Can be terminated.
 洗浄水の調製に用いる水の硬度、及び/又はすすぎ水の硬度は、洗浄力とすすぎ性の観点から1°DH~50°DHが好ましく、より好ましくは2°DH~40°DH、より好ましくは3°DH~30°DH、より好ましくは5°DH~25°DH、より好ましくは10°DH~20°DHである。
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。
The hardness of water used for the preparation of cleaning water and / or the hardness of rinsing water is preferably 1 ° DH to 50 ° DH, more preferably 2 ° DH to 40 ° DH, more preferably from the viewpoint of cleaning power and rinsing properties. Is 3 ° DH to 30 ° DH, more preferably 5 ° DH to 25 ° DH, and more preferably 10 ° DH to 20 ° DH.
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.
 表1、2に示す配合成分を用いて液体洗浄剤組成物を調製し、以下の評価を行った。結果を表1、2に示す。 A liquid detergent composition was prepared using the ingredients shown in Tables 1 and 2, and the following evaluations were performed. The results are shown in Tables 1 and 2.
(1)泡立ち性評価
 円形洗面器(底面の直径25cm、上面の直径30cm、高さ12cm、新輝合成株式会社、洗桶33型)に、水温20℃、炭酸カルシウム換算で179mg/Lの硬水〔塩化カルシウムCaCl1.19gと硫酸マグネシウムMgSO・7HO1.76gにイオン交換水を加えて10Lとしたもの、Ca/Mg=7/3(モル比)、本硬水はドイツ硬度で10°DHに相当する〕3Lを注入する。そこに液体洗浄剤組成物を20g添加し、手で攪拌しながら均一に溶解させる。次いでそこに下記に示す調整油を、1枚当り0.5gになるよう均一に滴下した肌着(グンゼ社製(YG1614丸首Lサイズ、木綿製)を3枚投じ、洗浄液に完全に浸る状態で15分間放置する。15分間放置後、肌着1枚に付き50回もみ洗い(布と布を擦り合わせながら1往復(約1秒)で1回と換算)する。その後、肌着を取り出し、肌着の含水量が肌着に対して40~60%程度になるように洗面器の上で絞り、3枚絞った直後の洗濯液面の状態を確認する。評価基準は、洗濯液面全体を泡が覆っている場合は、その泡高さを、ものさしを差し込んで計測しセンチメートルで表記した。洗濯液面全体を覆っていない場合は、泡が覆っている面積比で表記した(例えば、液面半分を泡が覆っている場合は、1/2と表記する)。
(1) Evaluation of foaming property A circular washbasin (diameter 25 cm at the bottom, diameter 30 cm at the top, height 12 cm, Shinki Gosei Co., Ltd., Washing Type 33), water temperature 20 ° C., 179 mg / L in terms of calcium carbonate [Calcium chloride CaCl 2 1.19 g and magnesium sulfate MgSO 4 .7H 2 O 1.76 g added with ion exchange water to make 10 L, Ca / Mg = 7/3 (molar ratio), hard water is 10 in German hardness [Corresponds to DH] 3L is injected. 20g of liquid detergent composition is added there, and it is made to melt | dissolve uniformly, stirring by hand. Next, three underwears (Gungze Co., Ltd. (YG1614 round neck L size, made of cotton)) in which the adjustment oil shown below was uniformly dropped so as to be 0.5 g per sheet were thrown there, and the underwear was completely immersed in the cleaning solution. After leaving for 15 minutes, wash 50 times with each undergarment (convert to 1 time in 1 reciprocation (approx. 1 second) while rubbing the cloth and cloth). Squeeze on the washbasin so that the amount of water is about 40 to 60% of the underwear, and check the condition of the washing liquid immediately after squeezing three. If it does not cover the entire surface of the washing liquid, it is expressed as the ratio of the area covered by the foam (for example, half the liquid level). If it is covered by bubbles, it is written as 1/2).
*調整油
 ラウリン酸1質量%、ミリスチン酸7.1質量%、ペンタデカン酸5.3質量%、パルチミチン酸14.2質量%、ヘプタデカン酸1質量%、ステアリン酸3.6質量%、オレイン酸17.8質量%、トリオレイン30質量%、パルミチン酸n-ヘキサデシル5質量%、スクアレン15質量%を約60℃に加温し、均一に溶解混合したものを調整油とした。
* Adjusted oil Lauric acid 1% by mass, myristic acid 7.1% by mass, pentadecanoic acid 5.3% by mass, palmitic acid 14.2% by mass, heptadecanoic acid 1% by mass, stearic acid 3.6% by mass, oleic acid 17 0.8% by mass, 30% by mass of triolein, 5% by mass of n-hexadecyl palmitate, and 15% by mass of squalene were heated to about 60 ° C., and uniformly dissolved and mixed to obtain a prepared oil.
(2)すすぎ性評価
 円形洗面器(底面の直径25cm、上面の直径30cm、高さ12cm、新輝合成株式会社、洗桶33型)に、水温20℃、炭酸カルシウム換算で179mg/Lの硬水(前記泡立ち性評価で用いたものと同様に調製したもの)5Lを注入し、上記泡立ち性評価で絞った肌着3枚を投入する。肌着をすすぎ水中でほぐした後、ほぐした肌着を1枚ずつ浴中から上に持ち上げ(浴中から衣類全体が抜け切るまで)、その後再び浴中へ戻す。このような上下運動によるすすぎを1枚の肌着につき10回繰り返した後、肌着の含水量が肌着に対して40~60%程度になるように手で絞る。3枚の肌着のすすぎ、脱水が終わった直後のすすぎ水の液面状態を観察し、下記の基準でポイントをつける。脱水した肌着に新しいすすぎ水を投入し、この評価をあと2回繰り返す(上記泡立ち性評価から含めて1つの液体洗浄剤組成物について用いる肌着は3枚)行い、ポイントの総和ですすぎ性を評価した。
ポイント
 6:液面全体を泡高さ1cm以上の泡が残っている
 5:液面全体に泡が残っている(1cm未満)
 4:液面の1/2程度に泡が残っている
 3:液面の1/4程度に泡が残っている
 2:液面に細かい泡が残っている
 1:液面に泡が残っていない
(2) Rinse evaluation Hard water with a water temperature of 20 ° C. and calcium carbonate equivalent of 179 mg / L in a circular washbasin (diameter 25 cm at the bottom, diameter 30 cm at the top, height 12 cm, Shinki Gosei Co., Ltd., Wash 33) 5L is injected (prepared in the same manner as that used in the evaluation of foaming properties), and three underwears squeezed in the evaluation of foaming properties are introduced. After rinsing the underwear in the water, lift the loose underwear one by one from the bath (from the bath until all the clothes are removed), and then return to the bath again. After rinsing by such up and down movements is repeated 10 times for each undergarment, it is squeezed by hand so that the moisture content of the undergarment is about 40 to 60% of the undergarment. Rinse the three underwears and observe the level of the rinse water immediately after the dehydration is finished. New rinse water is added to the dehydrated underwear, and this evaluation is repeated two more times (three underwears are used for one liquid detergent composition, including the above-mentioned foaming property evaluation), and the rinsability is evaluated with the sum of points. did.
Point 6: Foam with a height of 1 cm or more remains on the entire liquid surface 5: Foam remains on the entire liquid surface (less than 1 cm)
4: Bubbles remain at about 1/2 of the liquid level 3: Bubbles remain at about 1/4 of the liquid level 2: Fine bubbles remain at the liquid level 1: Bubbles remain at the liquid level Absent
(3)洗浄力評価
<人工汚染布の作製>
 使用した人工汚染布は、6cm×6cmの木綿/ポリエステル混紡ブロード染着布(木綿/ポリエステル比=65/35 谷頭商店より購入)に、下記組成から成る人工汚垢を1枚当り100mgになるようグラビア塗工したものである。
(3) Detergency evaluation <Production of artificially contaminated cloth>
Artificial stains used were 6cm x 6cm cotton / polyester blended broad-dyed fabric (cotton / polyester ratio = 65/35 purchased from Tanigami Shoten). Gravure coating.
*人工汚垢
 下記A、B、C、D、Eを含有する組成物を人工汚垢とした。それぞれの質量%は、最終組成の人工汚垢中の割合であり、合計が100質量%となるようにBの量を調節した。
A:前記泡立ち性評価で用いた調整油(人工汚垢中の質量%が、ラウリン酸0.44質量%、ミリスチン酸3.15質量%、ペンタデカン酸2.35質量%、パルチミチン酸6.31質量%、ヘプタデカン酸0.44質量%、ステアリン酸1.6質量%、オレイン酸7.91質量%、トリオレイン13.33質量%、パルミチン酸n-ヘキサデシル2.22質量%、スクアレン6.66質量%となる量で用いる)
B:塩化カルシウム(2水塩)105mgを秤量し、蒸留水に溶かして1,000mlとして得た硬水
C:卵白レシチン液晶物1.98質量%(蒸留水80mlにアルギニン塩酸塩11.37g、ヒスチジン4.20g、セリン2.44gを溶解し、濃塩酸でpHを5.0に調整した後、この溶液と卵白レシチンをミキサーで十分混ぜ合わせて得た卵白レシチン液晶物)
D:鹿沼赤土8.11質量%
E:カーボンブラック0.025質量%
* Artificial dirt The composition containing the following A, B, C, D, E was used as artificial dirt. Each mass% is a ratio in the artificial dirt of the final composition, and the amount of B was adjusted so that the total was 100 mass%.
A: Adjustment oil used in the evaluation of foaming properties (mass% in artificial dirt is 0.44 mass% lauric acid, 3.15 mass% myristic acid, 2.35 mass% pentadecanoic acid, 6.31 palmitic acid) Wt%, heptadecanoic acid 0.44 wt%, stearic acid 1.6 wt%, oleic acid 7.91 wt%, triolein 13.33 wt%, n-hexadecyl palmitate 2.22 wt%, squalene 6.66 (Use in an amount of mass%)
B: Hard water obtained by weighing 105 mg of calcium chloride (dihydrate) and dissolving in distilled water to obtain 1,000 ml C: 1.98% by mass of egg white lecithin liquid crystal (11.37 g of arginine hydrochloride, 80 ml of distilled water, histidine 4. After dissolving 20.20 g and 2.44 g of serine and adjusting the pH to 5.0 with concentrated hydrochloric acid, this solution and egg white lecithin were sufficiently mixed with a mixer to obtain an egg white lecithin liquid crystal product)
D: Kanuma red soil 8.11 mass%
E: Carbon black 0.025 mass%
<洗浄条件>
 液体洗浄剤組成物3gを、炭酸カルシウム換算で179mg/Lの硬水(前記泡立ち性評価で用いたものと同様に調製したもの)1Lに溶解し、そこに上記人工汚染布4枚入れてターゴトメーターにて以下の条件で洗浄した。
 洗浄時間10分
 水温20℃
 洗浄力は、汚染前の原布、及び洗浄前後の550nmにおける反射率を測色色差計(日本電色株式会社製 Z-300A)にて測定し、次式によって洗浄率(%)を求めた(表中の値は4枚の洗浄率の平均値)。
洗浄率(%)=100×[(洗浄後の反射率-洗浄前の反射率)/(原布の反射率-洗浄前の反射率)]
<Cleaning conditions>
3 g of the liquid detergent composition is dissolved in 1 liter of hard water (prepared in the same manner as that used in the evaluation of foaming property) in terms of calcium carbonate, and 4 pieces of the above artificially contaminated cloth are added to the targot. Washing was performed with a meter under the following conditions.
Washing time 10 minutes Water temperature 20 ° C
The detergency was determined by measuring the reflectance at 550 nm before and after cleaning with a colorimetric colorimeter (Nippon Denshoku Co., Ltd., Z-300A), and calculating the cleaning rate (%) by the following formula. (The values in the table are average values of the cleaning rates of 4 sheets).
Washing rate (%) = 100 × [(reflectance after washing−reflectance before washing) / (reflectance of base fabric−reflectivity before washing)]
(4)手肌への刺激性試験
 健常な女性パネラー3名が、素手で前記(1)の泡立ち性評価、及び(2)のすすぎ性評価を連続して実施した後、手肌の感触を下記の基準で評価した。3人の評価点の平均値を表1、2に示した。
(評価点)
 0:特に手肌に違和感を感じなかった
 1:洗濯後、つっぱり感を覚えた
 2:手肌が荒れた
(4) Irritation test on hand skin After three healthy female panelists continuously performed the foaming property evaluation of (1) and the rinsing property evaluation of (2) with bare hands, the hand skin feel was evaluated. Evaluation was made according to the following criteria. Tables 1 and 2 show the average values of the three evaluation points.
(Evaluation points)
0: No particular discomfort in the hand skin 1: After washing, I felt a sense of tension 2: The hand skin was rough

Figure JPOXMLDOC01-appb-T000002
Figure JPOXMLDOC01-appb-T000002
Figure JPOXMLDOC01-appb-T000003
Figure JPOXMLDOC01-appb-T000003
 表中の成分は以下のものである。また、pHの調整には、必要に応じて6N-HClも用いた。
・AES-Na:ポリオキシエチレン(平均付加モル数2)ラウリルエーテル硫酸エステルナトリウム(エマール270J 花王株式会社製)
・LAS-Na:アルキルベンゼンスルホン酸ナトリウム〔アルキルベンゼン(新日本石油株式会社製 商品名:アルケンL)にSOガスを接触させ、SO/アルキルベンゼンの反応モル比=1.030の条件でスルホン化したアルキルベンゼンスルホン酸を原料として配合し、組成物の製造過程で水酸化ナトリウムで中和した。ここで、アルキル基の炭素数は10~13である。〕
・ミリスチン酸:表1にはナトリウム塩換算の量で算出した質量%と質量比を示した。
・非イオン界面活性剤(1):ポリオキシエチレン(平均付加モル数8)アルキル(炭素数10~14)エーテル
・非イオン界面活性剤(2):ポリオキシエチレン(平均付加モル数21)アルキル(炭素数12)エーテル
・F1-1:下記式で表されるスルホベタイン、アンヒトール20HD(花王(株)製)
The components in the table are as follows. Moreover, 6N-HCl was also used for adjusting the pH as required.
AES-Na: polyoxyethylene (average number of moles added 2) sodium lauryl ether sulfate (Emar 270J, manufactured by Kao Corporation)
LAS-Na: Sodium alkylbenzene sulfonate [Alkylbenzene (trade name: Alkene L, manufactured by Nippon Oil Corporation) was contacted with SO 3 gas, and sulfonated under a reaction molar ratio of SO 3 /alkylbenzene=1.030. Alkylbenzenesulfonic acid was blended as a raw material, and neutralized with sodium hydroxide during the process of producing the composition. Here, the alkyl group has 10 to 13 carbon atoms. ]
-Myristic acid: Table 1 shows mass% and mass ratio calculated in terms of sodium salt.
Nonionic surfactant (1): polyoxyethylene (average addition mole number 8) alkyl (carbon number 10-14) ether Nonionic surfactant (2): polyoxyethylene (average addition mole number 21) alkyl (C12) Ether F1-1: Sulfobetaine represented by the following formula, Amphital 20HD (manufactured by Kao Corporation)
Figure JPOXMLDOC01-appb-C000004
Figure JPOXMLDOC01-appb-C000004
・F1-1:下記式で表されるベタイン、アンヒトール20AB(花王(株)製) F1-1: Betaine represented by the following formula, Amhitor 20AB (manufactured by Kao Corporation)
Figure JPOXMLDOC01-appb-C000005
Figure JPOXMLDOC01-appb-C000005
・F2-1:2-エチルヘキシルモノグリセリルエーテル F2-1: 2-ethylhexyl monoglyceryl ether
 表1に示すように、実施例1~9及び実施例10~14は、何れの評価においても優れた結果が得られている。一方、比較例1、6、8はすすぎ性の点で、比較例2、3、7、9は泡立ち性と洗浄性の点で、比較例4、5は泡立ち性と刺激性の点で、実施例よりも劣ることが分かった。 As shown in Table 1, Examples 1 to 9 and Examples 10 to 14 have excellent results in any evaluation. On the other hand, Comparative Examples 1, 6, and 8 are in terms of rinsing properties, Comparative Examples 2, 3, 7, and 9 are in terms of foaming properties and cleaning properties, and Comparative Examples 4 and 5 are in terms of foaming properties and irritation, It turned out that it is inferior to an Example.

Claims (35)

  1.  (A)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、(B)アルキルベンゼンスルホン酸塩、(C)脂肪酸及び/又はその塩、(D)pKaが8.0以上の化合物、並びに水を含有し、(A)/(B)の質量比が85/15~30/70であり、〔(A)+(B)〕/(C)の質量比が85/15~30/70であり、〔(A)+(B)〕/(D)の質量比が85/15~40/60であり、非イオン界面活性剤の含有量が2質量%以下であり、JIS K3362:1998記載の25℃で測定するpHが9.0~10.5である、液体洗浄剤組成物。 (A) a polyoxyalkylene alkyl ether sulfate ester salt, (B) an alkylbenzene sulfonate, (C) a fatty acid and / or a salt thereof, (D) a compound having a pKa of 8.0 or more, and water, ) / (B) has a mass ratio of 85/15 to 30/70 and [(A) + (B)] / (C) has a mass ratio of 85/15 to 30/70, [(A) + (B)] / (D) is a mass ratio of 85/15 to 40/60, the content of the nonionic surfactant is 2% by mass or less, and measurement is performed at 25 ° C. described in JIS K3362: 1998. A liquid detergent composition having a pH of 9.0 to 10.5.
  2.  (A)が、炭素数10~20のアルキル基を有し、アルキレンオキシ基の平均付加モル数が0~5の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である、請求項1記載の液体洗浄剤組成物。 The liquid detergent composition according to claim 1, wherein (A) is a polyoxyalkylene alkyl ether sulfate salt having an alkyl group having 10 to 20 carbon atoms and having an average addition mole number of alkyleneoxy groups of 0 to 5. object.
  3.  (A)が、炭素数10~20のアルキル基を有し、アルキレンオキシ基の平均付加モル数が0.5~4の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である、請求項1記載の液体洗浄剤組成物。 The liquid washing according to claim 1, wherein (A) is a polyoxyalkylene alkyl ether sulfate salt having an alkyl group having 10 to 20 carbon atoms and an average addition mole number of alkyleneoxy groups of 0.5 to 4. Agent composition.
  4.  (A)が、炭素数10~20のアルキル基を有し、アルキレンオキシ基の平均付加モル数が1~3の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である、請求項1記載の液体洗浄剤組成物。 The liquid detergent composition according to claim 1, wherein (A) is a polyoxyalkylene alkyl ether sulfate ester salt having an alkyl group having 10 to 20 carbon atoms and having an average addition mole number of alkyleneoxy groups of 1 to 3. object.
  5.  (C)が、炭素数11~17の直鎖又は分岐鎖のアルキル基を有する脂肪酸及び/又はその塩である、請求項1記載の液体洗浄剤組成物。 The liquid detergent composition according to claim 1, wherein (C) is a fatty acid having a linear or branched alkyl group having 11 to 17 carbon atoms and / or a salt thereof.
  6.  (C)が、ラウリン酸及び/又はその塩並びにミリスチン酸及び/又はその塩から選ばれる脂肪酸又はその塩である、請求項1記載の液体洗浄剤組成物。 2. The liquid detergent composition according to claim 1, wherein (C) is a fatty acid or a salt thereof selected from lauric acid and / or a salt thereof and myristic acid and / or a salt thereof.
  7.  (B)を2~8質量%含有する、請求項1記載の液体洗浄剤組成物。 The liquid detergent composition according to claim 1, comprising 2 to 8% by mass of (B).
  8.  (B)を2.2~7.5質量%含有する、請求項1記載の液体洗浄剤組成物。 The liquid detergent composition according to claim 1, comprising 2.2 to 7.5% by mass of (B).
  9.  (D)が、pKaが9.0~10.6の化合物である、請求項1記載の液体洗浄剤組成物。 2. The liquid detergent composition according to claim 1, wherein (D) is a compound having a pKa of 9.0 to 10.6.
  10.  (D)が、pKaが9.0~10.6のアルカリ金属炭酸塩又はアルカノールアミンである、請求項1記載の液体洗浄剤組成物。 The liquid detergent composition according to claim 1, wherein (D) is an alkali metal carbonate or alkanolamine having a pKa of 9.0 to 10.6.
  11.  (D)が、モノエタノールアミン又はトリエタノールアミンである、請求項1記載の液体洗浄剤組成物。 2. The liquid detergent composition according to claim 1, wherein (D) is monoethanolamine or triethanolamine.
  12.  (A)と(B)とを合計で5~30質量%含有する、請求項1記載の液体洗浄剤組成物。 The liquid detergent composition according to claim 1, comprising 5 to 30% by mass in total of (A) and (B).
  13.  (A)と(B)とを合計で7~15質量%含有する、請求項1記載の液体洗浄剤組成物。 The liquid detergent composition according to claim 1, comprising 7 to 15% by mass in total of (A) and (B).
  14.  (A)/(B)の質量比が70/30~55/45である、請求項1記載の液体洗浄剤組成物。 2. The liquid detergent composition according to claim 1, wherein the mass ratio of (A) / (B) is 70/30 to 55/45.
  15.  (C)を1~50質量%含有する、請求項1記載の液体洗浄剤組成物。 The liquid detergent composition according to claim 1, comprising 1 to 50% by mass of (C).
  16.  (C)を4~10質量%含有する、請求項1記載の液体洗浄剤組成物。 The liquid detergent composition according to claim 1, comprising 4 to 10% by mass of (C).
  17.  (D)を2~10質量%含有する、請求項1記載の液体洗浄剤組成物。 The liquid detergent composition according to claim 1, comprising 2 to 10% by mass of (D).
  18.  (D)を3.5~6質量%含有する、請求項1記載の液体洗浄剤組成物。 The liquid detergent composition according to claim 1, comprising 3.5 to 6% by mass of (D).
  19.  〔(A)+(B)〕/(C)の質量比が75/25~55/45である、請求項1記載の液体洗浄剤組成物。 2. The liquid detergent composition according to claim 1, wherein the mass ratio of [(A) + (B)] / (C) is 75/25 to 55/45.
  20.  〔(A)+(B)〕/(D)の質量比が79/21~55/45である、請求項1記載の液体洗浄剤組成物。 The liquid cleaning composition according to claim 1, wherein the mass ratio of [(A) + (B)] / (D) is 79/21 to 55/45.
  21.  非イオン界面活性剤の含有量が、1質量%以下である、請求項1記載の液体洗浄剤組成物。 The liquid detergent composition according to claim 1, wherein the content of the nonionic surfactant is 1% by mass or less.
  22.  非イオン界面活性剤の含有量が、0.5質量%以下である、請求項1記載の液体洗浄剤組成物。 The liquid detergent composition according to claim 1, wherein the content of the nonionic surfactant is 0.5% by mass or less.
  23.  非イオン界面活性剤を含有しない、請求項1記載の液体洗浄剤組成物。 The liquid detergent composition according to claim 1, which does not contain a nonionic surfactant.
  24.  非イオン界面活性剤が、炭素数10~18のアルコールにエチレンオキシドを平均で4~15モル、プロピレンオキシドを平均で0~5モル付加したポリオキシアルキレンアルキルエーテルである請求項1記載の液体洗浄剤組成物。 The liquid detergent according to claim 1, wherein the nonionic surfactant is a polyoxyalkylene alkyl ether obtained by adding an average of 4 to 15 moles of ethylene oxide and an average of 0 to 5 moles of propylene oxide to an alcohol having 10 to 18 carbon atoms. Composition.
  25.  前記ポリオキシアルキレンアルキルエーテルの含有量が、2質量%以下である、請求項24記載の液体洗浄剤組成物。 The liquid detergent composition according to claim 24, wherein the content of the polyoxyalkylene alkyl ether is 2% by mass or less.
  26.  前記ポリオキシアルキレンアルキルエーテルの含有量が、1質量%以下である、請求項24記載の液体洗浄剤組成物。 The liquid detergent composition according to claim 24, wherein the content of the polyoxyalkylene alkyl ether is 1% by mass or less.
  27.  前記ポリオキシアルキレンアルキルエーテルの含有量が、0.5質量%以下である、請求項24記載の液体洗浄剤組成物。 The liquid detergent composition according to claim 24, wherein the content of the polyoxyalkylene alkyl ether is 0.5% by mass or less.
  28.  前記ポリオキシアルキレンアルキルエーテルを含有しない、請求項24記載の液体洗浄剤組成物。 The liquid detergent composition according to claim 24, which does not contain the polyoxyalkylene alkyl ether.
  29.  更に、(G)成分として、(G4)ジエチレングリコールモノメチルエーテル、ジエチレングリコールジメチルエーテル、トリエチレングリコールモノメチルエーテル、ジエチレングリコールモノエチルエーテル、ジエチレングリコールジエチルエーテル、ジプロピレングリコールモノメチルエーテル、ジプロピレングリコールモノエチルエーテル、トリプロピレングリコールモノメチルエーテル、1-メトキシ-2-プロパノール、1-エトキシ-2-プロパノール、1-メチルグリセリンエーテル、2-メチルグリセリンエーテル、1,3-ジメチルグリセリンエーテル、1-エチルグリセリンエーテル、1,3-ジエチルグリセリンエーテル、トリエチルグリセリンエーテル、1-ペンチルグリセリルエーテル、2-ペンチルグリセリルエーテル、1-オクチルグリセリルエーテル、2-エチルヘキシルグリセリルエーテル、又はジエチレングリコールモノブチルエーテルを1.5~10質量%含有する、請求項1記載の液体洗浄剤組成物。 Furthermore, as component (G), (G4) diethylene glycol monomethyl ether, diethylene glycol dimethyl ether, triethylene glycol monomethyl ether, diethylene glycol monoethyl ether, diethylene glycol diethyl ether, dipropylene glycol monomethyl ether, dipropylene glycol monoethyl ether, tripropylene glycol monomethyl Ether, 1-methoxy-2-propanol, 1-ethoxy-2-propanol, 1-methylglycerol ether, 2-methylglycerol ether, 1,3-dimethylglycerol ether, 1-ethylglycerol ether, 1,3-diethylglycerol Ether, triethylglycerin ether, 1-pentylglyceryl ether, 2-pentylglyceride Ether, 1-octyl glyceryl ether, 2-ethylhexyl glyceryl ether, or diethylene glycol monobutyl ether containing 1.5-10 wt%, claim 1 liquid detergent composition.
  30.  更に、ポリアクリル酸、ポリマレイン酸、カルボキシメチルセルロース、重量平均分子量5,000以上のポリエチレングリコール、無水マレイン酸-ジイソブチレン共重合体、無水マレイン酸-メチルビニルエーテル共重合体、無水マレイン酸-酢酸ビニル共重合体、又はナフタレンスルホン酸塩ホルマリン縮合物を0.5~5質量%含有する、請求項1記載の液体洗浄剤組成物。 Further, polyacrylic acid, polymaleic acid, carboxymethyl cellulose, polyethylene glycol having a weight average molecular weight of 5,000 or more, maleic anhydride-diisobutylene copolymer, maleic anhydride-methyl vinyl ether copolymer, maleic anhydride-vinyl acetate copolymer The liquid detergent composition according to claim 1, comprising 0.5 to 5% by mass of a polymer or a naphthalenesulfonate formalin condensate.
  31.  手洗い洗濯用である請求項1記載の液体洗浄剤組成物。 2. The liquid detergent composition according to claim 1, which is for hand-washing laundry.
  32.  繊維製品の手洗い洗濯用である請求項1記載の液体洗浄剤組成物。 2. The liquid detergent composition according to claim 1, which is for hand washing of textile products.
  33.  請求項1記載の液体洗浄剤組成物を含む洗浄水を接触させた被洗浄物を手洗いする手洗い洗濯方法であって、被洗浄物の質量に対する洗浄水の質量が2~100倍である、手洗い洗濯方法。 A hand-washing laundry method for hand-washing an object to be cleaned that has been brought into contact with cleaning water comprising the liquid cleaning composition according to claim 1, wherein the mass of the cleaning water is 2 to 100 times the mass of the object to be cleaned. How to wash.
  34.  洗浄水の調製に用いる水の硬度が5°DH~25°DHである、請求項33記載の手洗い方法。 The hand washing method according to claim 33, wherein the hardness of water used for the preparation of washing water is 5 ° DH to 25 ° DH.
  35.  洗浄水の調製に用いる水の硬度が10°DH~20°DHである、請求項33記載の手洗い方法。 The hand washing method according to claim 33, wherein the hardness of water used for the preparation of washing water is 10 ° DH to 20 ° DH.
PCT/JP2011/054558 2010-03-15 2011-03-01 Liquid detergent composition WO2011114875A1 (en)

Priority Applications (1)

Application Number Priority Date Filing Date Title
CN201180012173XA CN102803461A (en) 2010-03-15 2011-03-01 Liquid detergent composition

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
JP2010-057181 2010-03-15
JP2010057181 2010-03-15

Publications (1)

Publication Number Publication Date
WO2011114875A1 true WO2011114875A1 (en) 2011-09-22

Family

ID=44648978

Family Applications (1)

Application Number Title Priority Date Filing Date
PCT/JP2011/054558 WO2011114875A1 (en) 2010-03-15 2011-03-01 Liquid detergent composition

Country Status (4)

Country Link
JP (1) JP2011213992A (en)
CN (1) CN102803461A (en)
TW (1) TWI491728B (en)
WO (1) WO2011114875A1 (en)

Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2013038750A1 (en) * 2011-09-15 2013-03-21 花王株式会社 Liquid detergent composition
WO2015176221A1 (en) * 2014-05-20 2015-11-26 The Procter & Gamble Company Low surfactant, high carbonate liquid laundry detergent compositions with improved suds profile

Families Citing this family (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP6503844B2 (en) * 2015-03-31 2019-04-24 日油株式会社 Liquid detergent composition
WO2017070917A1 (en) 2015-10-30 2017-05-04 The Procter & Gamble Company Direct-foam cleaning products

Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPS63397A (en) * 1986-03-31 1988-01-05 ザ、プロクタ−、エンド、ギヤンブル、カンパニ− Liquid detergent containing anionic surfactant, succinate builder and fatty acid
JP2006291069A (en) * 2005-04-12 2006-10-26 Kao Corp Liquid detergent composition for clothing
JP2009173700A (en) * 2008-01-22 2009-08-06 Kao Corp Liquid detergent composition

Family Cites Families (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN1037912C (en) * 1993-03-01 1998-04-01 上海锦华科技开发公司 Emulsion suspending heavy-duty liquid detergent and its preparation method
WO1995010585A1 (en) * 1993-10-12 1995-04-20 Stepan Company Liquid detergent compositions comprising salts of alpha sulfonated fatty acid methyl esters, and anionic surfactants
US5573702A (en) * 1993-11-22 1996-11-12 Colgate-Palmolive Co. Liquid cleaning compositions with grease release agent
CN101514307B (en) * 2008-12-31 2011-07-20 北京绿伞化学股份有限公司 Transparent and high-concentration laundry detergent and preparation method thereof

Patent Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPS63397A (en) * 1986-03-31 1988-01-05 ザ、プロクタ−、エンド、ギヤンブル、カンパニ− Liquid detergent containing anionic surfactant, succinate builder and fatty acid
JP2006291069A (en) * 2005-04-12 2006-10-26 Kao Corp Liquid detergent composition for clothing
JP2009173700A (en) * 2008-01-22 2009-08-06 Kao Corp Liquid detergent composition

Cited By (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2013038750A1 (en) * 2011-09-15 2013-03-21 花王株式会社 Liquid detergent composition
WO2015176221A1 (en) * 2014-05-20 2015-11-26 The Procter & Gamble Company Low surfactant, high carbonate liquid laundry detergent compositions with improved suds profile
US9340753B2 (en) 2014-05-20 2016-05-17 The Procter & Gamble Company Low surfactant, high carbonate liquid laundry detergent compositions with improved suds profile

Also Published As

Publication number Publication date
JP2011213992A (en) 2011-10-27
TWI491728B (en) 2015-07-11
TW201137111A (en) 2011-11-01
CN102803461A (en) 2012-11-28

Similar Documents

Publication Publication Date Title
WO2011114876A1 (en) Liquid detergent composition
JP5686638B2 (en) Liquid detergent composition for clothing
JP5341023B2 (en) Liquid detergent composition
JP5545911B2 (en) Liquid detergent composition
JP5946720B2 (en) Liquid detergent composition for textile products
JP6052777B2 (en) Liquid detergent composition
WO2011114875A1 (en) Liquid detergent composition
CN111534388A (en) Low-foam easy-to-bleach sterilization laundry detergent and preparation method thereof
JP4176317B2 (en) Liquid detergent composition
WO2011037219A1 (en) Detergent composition
JP5638227B2 (en) Cleaning composition
JP5148060B2 (en) Liquid detergent composition for clothing
JP2012007155A (en) Liquid detergent composition
JP5495641B2 (en) Liquid detergent composition
JP5250715B2 (en) Powder detergent composition for clothing
WO2007032435A1 (en) Liquid detergent composition for clothes
JPH08231996A (en) Liquid detergent composition
JP6058392B2 (en) Liquid detergent composition for clothing
JP5628537B2 (en) Cleaning composition for clothing
JP5642383B2 (en) Liquid detergent composition for clothing
JP5253712B2 (en) Liquid detergent composition for clothing
JPH10195489A (en) Liquid cleaner composition
JP2009173908A (en) Liquid detergent composition
JP2010138266A (en) Liquid detergent composition

Legal Events

Date Code Title Description
WWE Wipo information: entry into national phase

Ref document number: 201180012173.X

Country of ref document: CN

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

Ref document number: 11756064

Country of ref document: EP

Kind code of ref document: A1

WWE Wipo information: entry into national phase

Ref document number: 1201004698

Country of ref document: TH

NENP Non-entry into the national phase

Ref country code: DE

122 Ep: pct application non-entry in european phase

Ref document number: 11756064

Country of ref document: EP

Kind code of ref document: A1