WO2011114876A1

WO2011114876A1 - Liquid detergent composition

Info

Publication number: WO2011114876A1
Application number: PCT/JP2011/054559
Authority: WO
Inventors: 村田大也; 窪田裕一; 吉岡佐知子; 矢野誠二
Original assignee: 花王株式会社
Priority date: 2010-03-16
Filing date: 2011-03-01
Publication date: 2011-09-22
Also published as: JP2011213993A; TW201137113A

Abstract

Disclosed is a liquid detergent composition that includes water, (A) a specific amphoteric compound, (B) a specific polyether compound, (C) a non-soap anionic surfactant, and (D) a fatty acid and/or a salt thereof, and that has a pH measured at 25˚C, as set forth in JIS K3362:1998, of at least 8.

Description

Liquid detergent composition

The present invention relates to a liquid detergent composition, and more particularly to a liquid detergent composition suitable for hand-washing laundry.
Background art

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.

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.

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.

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.

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

The present invention relates to (A) a compound represented by the following general formula (A1) [hereinafter referred to as component (A)], (B) a compound represented by the following general formula (B1) [hereinafter referred to as component (B). ], (C) a non-soap anionic surfactant (hereinafter referred to as component (C)), (D) a fatty acid and / or a salt thereof (hereinafter referred to as component (D)), and water, JIS K3362 : It relates to the liquid detergent composition whose pH measured at 25 degreeC of 1998 description is 8 or more.

[Wherein, R ^1a is a hydrocarbon group having 9 to 23 carbon atoms, and R ^2a 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 ^3a and R ^4a are each independently an alkyl group having 1 to 3 carbon atoms or a hydroxyalkyl group having 1 to 3 carbon atoms, and R ^5a 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 ^1b — (OR ^2b ) _q —OH (B1)
[Wherein R ^1b is a hydrocarbon group having 6 to 18 carbon atoms, R ^2b 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 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

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.

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.

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) component>
The component (A) is a compound represented by the general formula (A1). In general formula (A1), R ^1a 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 ^2a is preferably an alkylene group having 2 or 3 carbon atoms, 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 ^3a and R ^4a 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 ^- is -SO ₃ ^- in the case ^{of, R 5a} is _{_{-CH 2 CH (OH) CH 2}} - -SO 3 is preferably, Y ^- if the ^- is -COO In this case, R ^5a is preferably a methylene group (—CH ₂ —).

<(B) component>
The component (B) is a compound represented by the general formula (B1). The compound (B1) is necessary for enhancing the foaming power, but at the same time it must satisfy the rinsing properties. In order to make these compatible, it has been found that both the hydrophilic group structure and the hydrophobic structure of (B1) are limited as follows. Although it is not necessarily certain, it seems that the orientation to the gas-liquid interface is higher than the orientation to clothing and dirt by adopting the following structure. In the general formula (B1), R ^1b is preferably an alkyl group or alkenyl group having 6 to 18 carbon atoms, more preferably 6 to 14, and even more preferably 6 to 10. When R ^2b is a propylene group, q is preferably 2 to 4 from the viewpoints of foamability and rinsing properties. From the same viewpoint, when R ^2b 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 ^2b is preferably a residue obtained by removing two hydroxy groups from glycerin.

As component (B), R ^1b in the general formula (B1) is an alkyl group or alkenyl group having 6 to 10 carbon atoms, R ^2b 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.

<(C) component>
The non-soap anionic surfactant as the component (C) is not particularly limited. For example, polyoxyalkylene alkyl ether sulfate and / or salt thereof, alkyl sulfate and / or salt thereof, alkylbenzenesulfone Acid and / or salt thereof, α-olefin sulfonic acid and / or salt thereof, α-sulfo fatty acid ester and / or salt thereof, alkyl phosphate ester and / or salt thereof, alkyl ether phosphate ester and / or salt thereof, N-acyl-N-methyltaurine and / or a salt thereof.

Examples of the salt constituting the component (C) include alkali metal salts such as sodium and potassium, alkanolamine salts, and alkaline earth metal salts such as magnesium and calcium. The component (C) may be added to the composition of the present invention in an acid form and neutralized with an alkali [used as an alkali agent for the component (E) described later] in the system.

In the present invention, as component (C), (C1) polyoxyalkylene alkyl ether sulfate and / or salt thereof (hereinafter referred to as (C1) component) and (C2) alkylbenzenesulfonic acid and / or salt thereof (hereinafter referred to as ( C2) component] is preferably contained.

(C1) Component includes a polyoxyalkylene alkyl ether sulfate ester salt having an alkyl group having 10 to 20 carbon atoms. For example, it has an alkyl group having 10 to 20 carbon atoms, preferably an alkyl group derived from a linear primary alcohol or linear secondary alcohol or an alkyl group derived from a branched alcohol, and the average number of added moles of an alkyleneoxy group is 0. -5, preferably 0.5-4, more preferably 1-3. The component (C1) 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.

As the component (C2), an alkylbenzene sulfonate having an alkyl group having 8 to 20 carbon atoms, preferably 10 to 15 carbon atoms, preferably a linear alkyl benzene sulfonate is exemplified.

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, or ammonium hydroxide or a component (E) described later can be used.

<(D) component>
The fatty acid and / or salt thereof as component (D) is not particularly limited, but for example, it has 7 to 43 carbon atoms, preferably 9 to 23, more preferably 11 to 17, and still more preferably 12 to 14. Examples thereof include those having a linear or branched alkyl group, more preferably a fatty acid having 12 to 14 carbon atoms and / or a salt thereof having a linear or methyl branched chain. The component (D) may have an unsaturated bond, but the number is preferably 2 or less from the viewpoint of rinsing properties. Specific examples of the component (D) include lauric acid and / or its salt, myristic acid and / or its salt, lauric acid, a mixture of fatty acids derived from coconut rich in myristic acid and / or its salt, and the like. From the viewpoints of detergency, foamability and rinsability, it is preferable to include lauric acid and / or a salt thereof and fatty acid and / or a salt thereof selected from myristic acid and / or a salt thereof. Or it is more preferable that the salt is included.

Examples of the salt constituting the component (D) include alkali metal salts such as sodium and potassium, alkanolamine salts, and alkaline earth metal salts such as magnesium and calcium. It is preferably a salt or an alkanolamine salt. 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 (E) described later can be used.

<Liquid cleaning composition>
In the liquid detergent composition of the present invention, the component (A) is 0.1 to 10% by mass, further 0.2 to 5% by mass, and further 0.4 to 2% from the viewpoint of foamability and rinsing properties. It is preferable to contain 7 mass%.

In addition, the liquid detergent composition of the present invention has a component (B) of 0.1 to 10% by mass, further 0.2 to 5% by mass, and further 0.4 to 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 has a mass ratio of (A) / (B) of 80/20 to 20/80, more preferably 70/30 to 30/70, from the viewpoint of foamability and rinsing properties. More preferably, it is 60/40 to 40/60.

In addition, the liquid detergent composition of the present invention has a component (C) of 1 to 50% by mass, further 2 to 30% by mass, and further 3 to 20% by mass from the viewpoint of foamability, rinsability and detergency. %, And more preferably 4 to 15% by mass. Among them, the total of the component (C1) and the component (C2) is 10 to 100% by mass, further 50 to 100% by mass, further 80 to 100% by mass, and further 90 to 100% by mass in the component (C). % Is preferred. Further, the total may be 100% by mass. In addition, from the viewpoint of foaming properties, rinsing properties, and detergency, the mass ratio of (C1) / (C2) is 85/15 to 30/70, preferably 80/20 to 40/60. 75/25 to 50/50, and further 70/30 to 55/45. If the ratio of the component (C1) in this mass ratio is within this range, the rinsability is improved more 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.

From the viewpoints of foaming properties and rinsing properties, particularly from the viewpoint of foaming properties, a mass ratio of [(A) + (B)] / (C), and further [(A) + (B)] / [(C1) + (C2)] has a mass ratio of 0.5 / 99.5 to 50/50, more preferably 2/98 to 40/60, still more 4/96 to 30/70, still more 6/94 to 25/75, and more. Further, 8/92 to 23/77 is preferable.

Further, from the viewpoint of foamability and rinsability, the liquid detergent composition of the present invention is obtained by calculating the amount of component (D) in terms of sodium salt in an amount of 1 to 50% by mass, and further 1.5 to 30% by mass. %, Further 2 to 20% by mass, and more preferably 4 to 10% by mass. Moreover, when using alkyl sulfate ester and / or its salt as (C) component, the liquid detergent composition of this invention is (C) alkyl sulfate ester and / or its from the viewpoint of foamability and a rinse property. 1 to 50% by mass, further 1.5 to 30% by mass, further 2 to 20% by mass, further 4 to 14% by mass, and further 6 to 12% in total amount of salt and component (D) (sodium salt equivalent) It is preferable to contain by mass.

From the viewpoints of foaming properties and rinsing properties, the mass ratio of [(A) + (B)] / (D) is 2/98 to 80/20, more preferably 5/95 to 60/40, still more preferably 10/90 to 50/50, more preferably 20/80 to 40/60 is preferable.

The liquid detergent composition of the present invention preferably further contains (E) an alkali agent (hereinafter referred to as component (E)). The alkali agent is not particularly limited, but preferably has a pKa of 8.0 or more, more preferably 9.0 to 10.6, and still more preferably, from the viewpoint of detergency, foamability and rinsing properties. Mention may be made of the compounds of 9.3 to 10.6. Specific examples include alkanolamines having 1 to 3 alkanol groups having 2 to 4 carbon atoms, in addition to alkali metal hydroxides, alkali metal carbonates such as potassium carbonate and sodium carbonate. That is, the alkali metal carbonate and / or the alkanolamine 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 an alkali agent. 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. Furthermore, it is preferable to use these alkanolamines in combination with alkali metal carbonates such as potassium carbonate from the viewpoint that the rinsing properties and storage stability can be further improved.

The component (E) can be used as a pH adjuster described later. The component (E) may also be used for neutralization of the component (C) and the component (D) described above.

In the liquid cleaning composition of the present invention, the content of the component (E) is preferably an amount necessary for the pH of the cleaning composition to fall within the range described later.

The liquid cleaning composition of the present invention can contain a chelating agent, but has a low content of a chelating agent having a molecular weight of 1,000 or less (hereinafter referred to as “component (F)”). Among them, the content is preferably 0.001 to 10% by mass, more preferably 0.01 to 3% by mass, and 0.03 to 1% by mass. The chelating agent of (F) component is, for example,
Aminopolyacetic acid or salts thereof such as nitrilotriacetic acid, iminodiacetic acid, ethylenediaminetetraacetic acid, diethylenetriaminepentaacetic acid, glycol etherdiaminetetraacetic acid, hydroxyethyliminodiacetic acid, triethylenetetraaminehexaacetic acid, diencoric acid,
Diglycolic acid, oxydisuccinic acid, carboxymethyloxysuccinic acid, citric acid, lactic acid, tartaric acid, oxalic acid, malic acid, oxydisuccinic acid, gluconic acid, carboxymethyl succinic acid, carboxymethyl tartaric acid and the like, or salts thereof,
Examples include aminotri (methylenephosphonic acid), 1-hydroxyethylidene-1,1-diphosphonic acid, ethylenediaminetetra (methylenephosphonic acid), diethylenetriaminepenta (methylenephosphonic acid), and alkali metals or amine salts thereof. In the present invention, the alkanolamine mentioned in the component (F) is preferably used as a salt, and may be a salt blended with an acid and neutralized with an alkali agent in the system.

From the viewpoint of improving stability and solubility, it is preferable to contain a water-miscible organic solvent as the component (G). 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, more preferably 1.5 to 10% by mass, more preferably from the viewpoint of stability and solubility. 2 to 5% by mass is preferred. When the surfactant concentration is not a concentrated system, it may be less than 10% by mass.

As the component (G), a water-miscible organic solvent having a hydroxyl group and / or an ether group is preferable.

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.

The component (G) is effective as a viscosity modifier and gelation inhibitor for the composition, and the above (G1) alkanols, (G2) glycols, (G4) alkyl ethers, and (G5) aromatic ethers. It is preferable to use at least one selected from the group consisting of (G2) glycols, (G4) alkyl ethers, and (G5) aromatic ethers, particularly preferably (G4). . In particular, diethylene glycol monobutyl ether is preferable. The component (G) is effective for adjusting the viscosity and suppressing gelation.

In the liquid detergent composition of the present invention, the water content is preferably 5 to 90% by mass, more preferably 10 to 85% by mass, and still more preferably 20 to 80% by mass in the composition. It is preferable to use water that does not affect the composition, such as ion exchange water.

In the liquid detergent composition of the present invention, the content of the nonionic surfactant is preferably 2% by mass or less, more preferably 1.5% by mass or less, from the viewpoint of rapid foam extinction during rinsing. 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 a nonionic surfactant. The nonionic surfactant referred to here is not particularly limited, and examples thereof include polyoxyalkylene alkyl ethers. For example, an average of 4 to 15 moles of ethylene oxide in an alcohol having 10 to 18 carbon atoms, preferably Includes polyoxyalkylene alkyl ethers added with 4 to 10 moles of propylene oxide and an average of 0 to 5 moles, 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, and there is a risk of impeding rapid bubble disappearance during rinsing. However, among polyoxyalkylene alkyl ethers, those having a large added mole number of alkylene oxide, for example, an average of more than 15 moles of ethylene oxide in an alcohol having 10 to 18 carbon atoms, preferably an average of 18 moles or more, more preferably an average of 20 moles. As described above, an average of 0 to 5 moles of propylene oxide added may be used in the liquid detergent composition of the present invention as long as the amount is small.

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.

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. It should be noted that an average of more than 10 to 60 moles, preferably 12 to 50, more preferably 18 to 40, more preferably 20 to 30 moles of propylene oxide, and an average of 0 to 5 moles of ethylene oxide in an alcohol having 10 to 18 carbon atoms. In the case of using a polyoxyalkylene alkyl ether added in a molar amount, the content in the composition is 2% by mass or less, preferably 0.1 to 1.8% by mass, more preferably 1 to 1.6% by mass (however, In the case where other nonionic surfactants are contained, the total is within these ranges.)

Here, the mass ratio of the polyoxyalkylene alkyl ether added with an average of less than 18 mol of ethylene oxide to the polyoxyalkylene alkyl ether added with an average of 18 mol or more of ethylene oxide is preferably 0/100 to 60/40, more It is preferably 0/100 to 50/50, more preferably 0/100 to 30/70, and particularly preferably 0/100 to 15/85.

Further, the mass ratio of the polyoxyalkylene alkyl ether added with less than 20 moles of ethylene oxide to the polyoxyalkylene alkyl ether added with an average of 20 moles or more of ethylene oxide is preferably 0/100 to 70/30, more preferably Is 0/100 to 60/40, more preferably 0/100 to 50/50, still more preferably 0/100 to 30/70, and particularly preferably 0/100 to 15/85.

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) 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 dyes, fragrances, antibacterial preservatives, and silicones

The viscosity at 20 ° C. of the liquid detergent composition of the present invention is preferably 10 to 2,000 mPa · s, more preferably 100 to 1,500 mPa · s, and more preferably 300 to 1,000 mPa · s in terms of ease of handling. Is more preferable. Considering use in winter, the viscosity at 5 ° C. is preferably from 100 to 2,000 mPa · s, more preferably from 300 to 1,500 mPa · s in view of ease of handling. It is preferable to adjust so that it may become such a range with (G) component, a solubilizer, or an inorganic salt. In the present invention, the viscosity is measured with a B-type viscometer. Select a rotor that matches the viscosity. The liquid is rotated at a rotational speed of 60 r / min, and the viscosity 60 seconds after the start of rotation is defined as the viscosity of the liquid detergent composition.

In the liquid detergent composition of the present invention, the pH measured at 25 ° C. described in JIS K3362: 1998 is 8 or more, preferably 8.5 or more, more preferably 8.5 to from the viewpoint of foamability and detergency. It is preferably 10.5, more preferably 9-10.

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. . 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.

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.

A liquid detergent composition was prepared using the ingredients shown in Tables 1 to 3, and the following evaluations were performed. The results are shown in Tables 1 to 3.

(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. 15 g of the liquid detergent composition is added thereto and dissolved uniformly with stirring by hand. Next, 3 pieces of underwear (Gunze, YG1614 round neck L size, made of cotton) in which the adjustment oil shown below was uniformly dropped to 0.7 g per sheet were thrown there, and 15 soaked in the cleaning solution. Leave for a minute. After leaving for 15 minutes, it is washed 50 times per piece of undergarment (converted to 1 in 1 reciprocation (about 1 second) while rubbing the cloths together). Thereafter, the underwear is taken out, and the state of the washing liquid immediately after squeezing three sheets is squeezed on the basin so that the moisture content of the underwear is about 40 to 60% of the underwear. As for the evaluation criteria, when the entire washing liquid surface was covered with foam, the height of the foam was measured by inserting a ruler and evaluated according to the following criteria. In Examples 17 to 19, underwear was used in which 1.0 g of the adjustment oil was uniformly dropped per sheet.

* 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.

Evaluation criteria A: Bubble height is 2 cm or more. O: Bubble height is 1 cm or more and less than 2 cm. Δ: Bubble height is less than 1 cm.

(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) Detergency evaluation <Production of artificially contaminated cloth>
Artificial stain used was 6cm x 6cm cotton / polyester broad blended dyeing fabric (cotton / polyester ratio = 35/65 purchased from Tanigami Shoten). Gravure coating.

* 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%

<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. .
Washing rate (%) = 100 × [(reflectance after washing−reflectance before washing) / (reflectance of base fabric−reflectivity before washing)]

<Evaluation of cleaning power>
When the average value of the washing rate of the four artificially contaminated cloths is 0% or more and less than 2% compared to the value of Example 14 (average value of the washing rate of four sheets), “◯” is 2% or more. In some cases, the cleaning power was evaluated as “として”.

* Detergency evaluation of Example 17 was performed by washing and rinsing with water having a hardness of 2 ° DH.

** Foaming property evaluation and rinsing property evaluation of Examples 18 to 24 were performed using underwear in which 1.0 g of adjustment oil was uniformly dropped per sheet. Since Examples 18, 19, and 20 correspond to Examples 1, 4, and 5, respectively, evaluation of the cleaning power was omitted.

The components in the table are as follows. In the table, “appropriate amount” is an amount for adjusting the pH to the value in the table. In some comparative examples, for convenience, each mass ratio was calculated using A′-1 as the component (A) and B′-1 to B′-3 as the component (B).
A-1: Sulfobetaine represented by the following formula, Amphithol 20HD (manufactured by Kao Corporation)

A-2: Betaine represented by the following formula, Amhitor 20AB (manufactured by Kao Corporation)

A'-1: Lauryldimethylamine oxide, Amhitoal 20N (manufactured by Kao Corporation)
B-1: 2-ethylhexyl monoglyceryl ether

B-2: propylene oxide adduct of n-octanol represented by the following formula (average propylene oxide addition mole number: 2.7)

B-3: Isodecyl monoglyceryl ether

B'-1: n-dodecanol with an average of 8 moles of ethylene oxide added B'-2: hexaglycerin lauric acid monoester B'-3: lauryl polyglucoside, mydol 12 (Kao Corporation) Made)
-B'-4: An average of 12 moles of ethylene oxide added to a primary alcohol having 10 to 14 carbon atoms-B'-5: An average of 21 moles of ethylene oxide added to a primary alcohol having 10 to 14 carbon atoms Food / Myristic acid: LUNAC MY-98 (manufactured by Kao Corporation)
AES-Na: polyoxyethylene (average number of moles added 2) sodium lauryl ether sulfate, Emar 270J (manufactured by Kao Corporation)
・ LAS-Na: Sodium laurylbenzenesulfonate, Neoperex G-15 (manufactured by Kao Corporation)
AS-Na: Sodium lauryl sulfate ester, Emar 10 powder (manufactured by Kao Corporation)
MAP-K: Potassium salt of phosphate ester produced using Diadol 115L (synthetic higher alcohol, manufactured by Mitsubishi Chemical Corporation) as the raw material alcohol

Claims

(A) a compound represented by the following general formula (A1), (B) a compound represented by the following general formula (B1), (C) a non-soap anionic surfactant, (D) a fatty acid and / or its A liquid detergent composition containing a salt and water and having a pH of 8 or more as measured at 25 ° C. described in JIS K3362: 1998.

[Wherein, R 1a is a hydrocarbon group having 9 to 23 carbon atoms, and R 2a 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 3a and R 4a are each independently an alkyl group having 1 to 3 carbon atoms or a hydroxyalkyl group having 1 to 3 carbon atoms, and R 5a 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 1b — (OR 2b ) q —OH (B1)
[Wherein R 1b is a hydrocarbon group having 6 to 18 carbon atoms, R 2b is a residue obtained by removing two hydroxy groups from a propylene group or glycerin, and q is a number of 1 to 5. ]
Anionic groups in the general formula (A) of (A) Y - is, -SO 3 -, -OSO 3 - , -COO - a group selected from claim 1 liquid detergent composition.
The liquid detergent composition according to claim 1, wherein R 1a in the general formula (A1) of (A) is an alkyl group having 11 to 13 carbon atoms.
(A) is a compound in which Y − in general formula (A1) is —SO 3 — and R 5a is —CH 2 CH (OH) CH 2 —, and Y − in general formula (A1) There -COO - a is and R 5a is a compound selected from the compounds which are methylene group, claim 1 liquid detergent composition.
The liquid detergent composition according to claim 1, wherein R 1b in the general formula (B1) of (B) is an alkyl group or an alkenyl group having 6 to 10 carbon atoms.
(B) is a compound in which R 2b in the general formula (B1) is a propylene group and q is a number of 2 to 4, and R 2b in the general formula (B1) has two hydroxy groups from glycerin. 2. The liquid detergent composition according to claim 1, wherein the liquid detergent composition is a compound selected from compounds which are residues and q is a number of 1 to 3.
(B) is R 1b in the general formula (B1) is an alkyl group or alkenyl group having 6 to 10 carbon atoms, R 2b is a residue obtained by removing two hydroxy groups from glycerin, and q is a glyceryl ether of 1. The liquid detergent composition according to claim 1.
(C) is a polyoxyalkylene alkyl ether sulfate and / or salt thereof, alkylbenzene sulfonic acid and / or salt thereof, α-olefin sulfonic acid and / or salt thereof, α-sulfo fatty acid ester and / or salt thereof, alkyl The liquid detergent composition according to claim 1, which is a phosphate ester and / or salt thereof, an alkyl ether phosphate ester and / or salt thereof, or N-acyl-N-methyltaurine and / or salt thereof.
2. The liquid detergent composition according to claim 1, comprising (C1) both (C1) polyoxyalkylene alkyl ether sulfate and / or a salt thereof and (C2) alkylbenzenesulfonic acid and / or a salt thereof.
10. The liquid detergent composition according to claim 9, wherein (C1) is a polyoxyalkylene alkyl ether sulfate having an alkyl group having 10 to 20 carbon atoms and an average addition mole number of an alkyleneoxy group of 0 to 5. .
10. The liquid detergent composition according to claim 9, wherein (C2) is an alkylbenzene sulfonate having an alkyl group having 8 to 20 carbon atoms.
2. The liquid detergent composition according to claim 1, wherein (D) is a fatty acid having a linear or branched alkyl group having 11 to 17 carbon atoms and / or a salt thereof.
The liquid detergent composition according to claim 1, wherein the component (D) 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.
The liquid detergent composition according to claim 1, comprising 0.1 to 10% by mass of (A).
The liquid detergent composition according to claim 1, comprising 0.1 to 10% by mass of (B).
The liquid detergent composition according to claim 1, comprising 2 to 30% by mass of (C).
The sum of (C1) and (C2) is 50 to 100% by mass in (C), and the mass ratio of (C1) / (C2) is 80/20 to 40/60. Liquid detergent composition.
The liquid detergent composition according to claim 1, comprising 2 to 20% by mass of (D).
The liquid detergent composition according to claim 1, wherein the mass ratio of (A) / (B) is 80/20 to 20/80.
2. The liquid detergent composition according to claim 1, wherein the mass ratio of [(A) + (B)] / (C) is 0.5 / 99.5 to 50/50.
The liquid detergent composition according to claim 1, wherein the mass ratio of [(A) + (B)] / (D) is 2/98 to 80/20.
The liquid detergent composition according to claim 1, wherein the content of the nonionic surfactant is 2% by mass or less.
The liquid according to claim 22, wherein the nonionic surfactant is a polyoxyalkylene alkyl ether obtained by adding an average of 4 to 15 mol of ethylene oxide and an average of 0 to 5 mol of propylene oxide to an alcohol having 10 to 18 carbon atoms. Cleaning composition.
The liquid detergent composition according to claim 23, wherein the content of the polyoxyalkylene alkyl ether is 1% by mass or less.
The liquid detergent composition according to claim 23, wherein the content of the polyoxyalkylene alkyl ether is 0.5% by mass or less.
The liquid detergent composition according to claim 23, which does not contain the polyoxyalkylene alkyl ether.
The liquid detergent composition according to claim 1, further comprising (E) an alkaline agent.
28. The liquid detergent composition according to claim 27, wherein (E) is a compound having a pKa of 8.0 or more.
28. The liquid detergent composition according to claim 27, wherein (E) is a compound having a pKa of 9.0 to 10.6.
28. The liquid detergent composition according to claim 27, wherein (E) is an alkali metal carbonate and / or alkanolamine.
28. The liquid detergent composition according to claim 27, wherein (E) is monoethanolamine or triethanolamine.
Furthermore, as component (F), aminopolyacetic acid such as nitrilotriacetic acid, iminodiacetic acid, ethylenediaminetetraacetic acid, diethylenetriaminepentaacetic acid, glycol etherdiaminetetraacetic acid, hydroxyethyliminodiacetic acid, triethylenetetraaminehexaacetic acid, diencoric acid or the like These salts, organic acids such as diglycolic acid, oxydisuccinic acid, carboxymethyloxysuccinic acid, citric acid, lactic acid, tartaric acid, oxalic acid, malic acid, oxydisuccinic acid, gluconic acid, carboxymethylsuccinic acid, carboxymethyltartaric acid, or these Salts of aminotri (methylenephosphonic acid), 1-hydroxyethylidene-1,1-diphosphonic acid, ethylenediaminetetra (methylenephosphonic acid), diethylenetriaminepenta (methylenephosphonic acid), their alkali metals or The Min salts containing 0.01 to 3 wt%, claim 1 liquid detergent composition.
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 to 20 mass%, claim 1 liquid detergent composition.
2. The liquid detergent composition according to claim 1, which is for hand-washing laundry.
2. The liquid detergent composition according to claim 1, which is for hand washing of textile products.
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.
The hand-washing washing method according to claim 36, wherein the hardness of water used for the preparation of washing water is 5 ° DH to 25 ° DH.
The hand-washing washing method according to claim 36, wherein the hardness of water used for the preparation of washing water is 10 ° DH to 20 ° DH.