JP2010265333A - Liquid detergent composition - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a liquid detergent composition that contains high-concentration surfactants, is excellent in detergency and storage stability, and has no decrease in solubility due to gelling or the like. <P>SOLUTION: The liquid detergent composition contains (A) surfactants containing (a-1) a specific alkoxy-type nonionic surfactant and (a-2) an anionic surfactant, (B) a water-miscible organic solvent, and (C) water, each of which is contained within a specific range. The amount of (a-1) in (A) is 50 mass% or more, and the mass ratio [(a-1)/(a-2)] is 50/50 to 99/1. <P>COPYRIGHT: (C)2011,JPO&INPIT

Description

  The present invention relates to a liquid detergent composition excellent in cleaning performance and solubility, such as for clothing and residential use.

  In recent years, environmental awareness has increased, and there is a strong demand for the appearance of cleaning agents that have a low environmental impact. So-called concentrated type cleaning agents with higher cleaning component concentrations than conventional cleaning agents reduce the size of the cleaning agent itself, reduce the amount of container resin, reduce transportation costs, reduce waste after use, etc. It is thought that it is very effective for reducing.

  However, in a normal liquid cleaning agent, when the concentration of a surfactant as a cleaning component is increased, there is a problem that thickening or gelation occurs and the usability is significantly impaired. This is because an increase in the surfactant concentration results in the formation of a remarkably high phase such as liquid crystal or crystals in the composition. There are fluid compositions that do not form liquid crystals or crystal phases in such high-concentration systems, but the problem is that liquid crystals are formed by dilution with water, especially cold water, during washing, resulting in poor solubility. If the surfactant concentration is increased, the composition is likely to solidify during low-temperature storage, solids may precipitate, or separation such as layer separation or turbidity may occur. There was a problem with stability.

  On the other hand, recent washing machines are also in a tendency to decrease the bath ratio, decrease the stirring power, lower the temperature of washing water, and shorten the washing time in order to cope with environmental / energy problems and economy. Since these tendencies both delay the dissolution rate of the cleaning agent and thus significantly reduce the cleaning ability of the cleaning agent, a significant improvement in the dissolution rate of the cleaning agent is desired.

  Patent Documents 1 to 5 describe concentrated liquid detergent compositions containing specific fatty acid alkyl ester ethoxylates, but these increase viscosity (gelation) with increasing surfactant concentration. Although this is a technique for preventing this, the viscosity of the product itself is kept low, but there is a problem with the gelation inhibiting property at the time of dilution, and there is a particular problem with the solubility in cold water. There was also a problem with stability at low temperatures.

  Patent Document 6 discloses a concentrated liquid detergent composition in which a nonionic surfactant obtained by adding ethylene oxide (EO) or propylene oxide (PO) to a higher alcohol and a specific solvent are blended. As a preferred nonionic surfactant in the text and examples, an EO / PO block type nonionic surfactant in which EO is added and then PO is described is described.

JP 2008-7705 A JP 2008-7706 A JP 2008-7707 A JP 2009-7451 A International Publication No. 2008/001797 Pamphlet JP-A-8-157867

  An object of the present invention is to provide a liquid detergent composition containing a high concentration of a surfactant and having excellent detergency and storage stability, and having no decrease in solubility due to gelation or the like. That is. Another object of the present invention is to provide a washing method using a liquid detergent composition that does not cause a decrease in solubility due to gelation or the like when the composition is diluted with water even at a low bath ratio that results in low mechanical force.

This invention contains (A) component which consists of surfactant containing the following (a-1) component and (a-2) component, the following (B) component, and the following (C) component, (A) The component (a-1) component is 50% by mass or more, and the mass ratio of the component (a-1) to the component (a-2) is (a-1) / (a-2) = 50/50 to 99. / 1, which relates to a liquid detergent composition.
(A) component: 40-90 mass% of surfactant
Component (a-1): Nonionic surfactant represented by the following general formula (I) R ¹ COO — [(PO) _m / (EO) _n ] —R ² (I)
(Wherein R ¹ is a hydrocarbon group having 7 to 21 carbon atoms, COO— is a carbonyloxy group, R ² is an alkyl group having 1 to 3 carbon atoms, P is a propylene group, E is an ethylene group, m Is the average added mole number of PO, n is the average added mole number of EO, m is 0.3 to 5, and n is 8 to 25. / is that PO and EO may be random or block Is shown.)
(A-2) Component: Anionic surfactant (B) Component: 1-40% by mass of a water-miscible organic solvent
(C) component: Water 5-50 mass%

  Moreover, this invention relates to the washing | cleaning method which has the process of wash | cleaning textiles by the bath ratio 2-12L / kg using the washing | cleaning medium prepared from the liquid detergent composition of the said invention.

  The liquid detergent composition of the present invention has solubility, particularly solubility in cold water, and dissolution at a low bath ratio that results in low mechanical strength, even though the surfactant, which is a cleaning component, is blended at a high concentration. Excellent in storage stability and cleaning performance. Moreover, since the liquid detergent composition of this invention shows the outstanding solubility also in the washing of a low bath ratio, the washing | cleaning method in which the outstanding cleaning power is obtained is provided.

<(A) component>
The liquid detergent composition of this invention contains (A) component which consists of surfactant containing the following (a-1) component and (a-2) component.
Component (a-1): Nonionic surfactant R ¹ COO-[(PO) _m / (EO) _n ] -R ² (I) represented by the following general formula (I)
(Wherein R ¹ is a hydrocarbon group having 7 to 21 carbon atoms, COO— is a carbonyloxy group, R ² is an alkyl group having 1 to 3 carbon atoms, P is a propylene group, E is an ethylene group, m Is the average added mole number of PO, n is the average added mole number of EO, m is 0.3 to 5, and n is 8 to 25. / is that PO and EO may be random or block Is shown.)
(A-2) component: anionic surfactant

The component (a-1) is a nonionic surfactant represented by the above general formula (I), and from the viewpoints of stability, detergency, and solubility (gelation inhibiting property upon dilution), the general formula ( R ^{1 in} I) preferably has 9 to 15 carbon atoms, more preferably 11 to 13, and the hydrocarbon group is preferably an alkyl group, and more preferably a linear alkyl group. R ² is preferably a methyl group, m is preferably 0.5-4, more preferably 1-3, n is preferably 10-20, more preferably 12-18, PO and EO are preferably block sequences, PO Are more preferably ester-bonded. In particular, when m is in this range, the ability to suppress liquid crystal and crystal formation is further improved, so that the solubility and stability at low temperatures are excellent.

The component (a-1) is added, for example, by ordering alcohol (R ² —OH) with propylene oxide and ethylene oxide (hereinafter, sometimes referred to as propylene oxide and ethylene oxide together as alkylene oxide) or simultaneously by addition reaction. And then producing it by subjecting it to fatty acid or fatty acid ester by esterification or transesterification, or by sequentially or simultaneously adding alkylene oxide to fatty acid to form an adduct. It can be obtained by reacting alkyl halide. It can also be produced by a method in which an alkylene oxide is subjected to an addition reaction between an ester and an esterified product of fatty acid and alcohol (R ¹ COOR ² ) using a specific catalyst (see Japanese Patent Application Laid-Open No. 4-279552). it can.

  The component (a-2) is an anionic surfactant, and for example, an anionic surfactant selected from the following (a-2-1) to (a-2-5) can be used. An anionic surfactant selected from (a-2-1), (a-2-2), and (a-2-4) from the viewpoint of solubility and solubility (inhibition of gelation during dilution) Preferably, it further contains (a-2-1). In the case of containing (a-2-1), it is most preferable in terms of detergency, low-temperature stability, and solubility to occupy 80% by mass or more, particularly 90% by mass in the component (a-2). (A-2) A component improves stability and solubility by using with (a-1) component with a specific ratio with the effect as a washing | cleaning component. The reason for this is not clear, but by mixing the molecules of the component (a-2) between the molecules of the component (a-1), the surface activity from the electric repulsion of the anionic group of the component (a-2) The alignment of the agent molecules is suppressed, and as a result, liquid crystal and crystal formation are expected to be suppressed.

(A-2-1) Alkylbenzenesulfonate having an alkyl group having an average carbon number of 10 to 20.
(A-2-2) An alkyl group derived from a linear primary alcohol or linear secondary alcohol having an average carbon number of 10 to 20 or an alkyl group derived from a branched alcohol, and one or two oxyethylene groups are oxy A polyoxyethylene alkyl ether sulfate ester salt having an average addition mole number of 1 to 5, which may be a propylene group.
(A-2-3) Alkyl or alkenyl sulfate ester salt having an average alkyl group or alkenyl group having 10 to 20 carbon atoms.
(A-2-4) Fatty acid salt having an average carbon number of 8 to 20.
(A-2-5) An alkyl group derived from a linear primary alcohol or linear secondary alcohol having an average carbon number of 10 to 20, or an alkyl group derived from a branched alcohol, and one or two oxyethylene groups are oxy A polyoxyethylene alkyl ether carboxylate having an average addition mole number of 1 to 5, which may be a propylene group.

  Examples of the salt constituting the component (a-2) include alkali metal salts such as sodium and potassium, alkanolamine salts, and alkaline earth metal salts such as magnesium and calcium. An amine salt is preferred. The anionic surfactant may be added in an acid form in the liquid detergent and neutralized with alkali in the system. In the present invention, the component (a-2) is preferably neutralized with an alkanolamine salt or an acid form and neutralized with an alkanolamine [alkanolamine used as an alkali agent for the component (D) described later] The amount of metal-based counter ions such as alkali metals and alkaline earth metals is preferably small, and is substantially 5% by mass or less, particularly 3% by mass or less, and most preferably 1% by mass or less.

  Examples of the component (A) other than the component (a-1) and the component (a-2) include the following (a-3) to (a-5).

(A-3) Nonionic surfactant which does not correspond to the component (a-1). Examples include polyoxyalkylene alkyl ethers, alkyl polyglycosides, alkyl glycosides, sorbitan fatty acid esters, polyoxyethylene sorbitan fatty acid esters, fatty acid monoglycerides, fatty acid alkanolamides, polyhydroxy fatty acid amides, among others (a-3-1) ) To (a-3-3) are preferable.

(A-3-1) A polysaccharide surfactant represented by the following general formula.
R ³ − (OR ⁴ ) _x G _y
[Wherein R ³ is a hydrocarbon group having 8 to 18 carbon atoms, preferably an alkyl group, R ⁴ is an alkylene group having 2 to ⁴ carbon atoms, G is a reducing sugar having 5 or 6 carbon atoms, preferably glucose. Residue, x is the number of the average value 0-6, y shows the number of the average value 1-10. ]
(A-3-2) Fatty acid alkanolamide, polyhydroxy fatty acid amide.
(A-3-3) Polyoxyalkylene alkyl or alkenyl ether. For example, polyoxyalkylene alkyl or alkenyl ether represented by the following general formula is preferable.
R ⁵ —O [(EO) _p / (PO) _q ] —H
[Wherein, R ⁵ represents a hydrocarbon group, preferably an alkyl group, having 10 to 18 carbon atoms, preferably 12 to 14 carbon atoms. E represents an ethylene group, and P represents a propylene group. p represents the number of average added moles of 0 to 20, q represents the number of average added moles of 0 to 20, and the case where both p and q are 0 is excluded. Preferably, the average added mole number of p is 6 to 15, more preferably 7 to 12, and the average added mole number of q is 0 to 10, more preferably 1 to 5, particularly preferably 1 to 3. It is. / Indicates that EO and PO may be random or block. ]

(A-4) Cationic surfactant.
For example, it is a primary to tertiary amine having a long-chain alkyl group (excluding alkanolamines described later), and preferably has 8 to 8 carbon atoms which may have an ether bond, an ester bond or an amide bond in the middle. Mention may be made of cationic surfactants having 22 hydrocarbon groups, preferably one or two alkyl groups, the rest being alkyl groups which may have hydrogen atoms or hydroxy groups having 4 or less carbon atoms. it can. In the present invention, a quaternary ammonium type surfactant having one long-chain alkyl group having 8 to 22 carbon atoms and a tertiary amine having one long-chain alkyl group having 8 to 22 carbon atoms are preferable.

(A-5) Amphoteric surfactant For example, sulfobetaine or carbobetaine having an alkyl group having 10 to 18 carbon atoms can be mentioned.

  In the liquid detergent composition of the present invention, the content of the component (A) is 40 to 90% by mass from the viewpoint of detergency and solubility (gelation suppression property at the time of dilution), and 45 to 80% by mass. Preferably, 50 to 70% by mass is more preferable.

  The component (a-1) in the component (A) is 50% by mass or more, preferably 60% by mass or more, and more preferably 70% by mass from the viewpoints of detergency and solubility (inhibition of gelation during dilution). 80 mass% or more is more preferable. Moreover, 99 mass% or less is preferable, 98 mass% or less is more preferable, and 95 mass% or less is still more preferable.

  The mass ratio of the component (a-1) and the component (a-2) is (a-1) / (a-2) = 50/50 to 50% from the viewpoint of detergency and solubility (inhibition of gelation during dilution). 99/1, preferably 60/40 to 98/2, and more preferably 70/30 to 95/5. In addition, since the mass of the anionic surfactant of the component (a-2) varies depending on the molecular weight of the salt, in the present invention, the mass when the acid type, that is, the counter ion is assumed to be a hydrogen atom ion, is not a salt. (A-2) The mass of the component. By using the component (a-1) in combination with the component (a-2), it is possible to increase the detergency of the composition and further increase the solubility by suppressing liquid crystal formation.

  A feature of the present invention is that a liquid detergent composition containing a high concentration surfactant, that is, a liquid detergent composition having a surfactant concentration of 40% by mass or more, more preferably 50% by mass or more, and particularly 60% by mass or more. In the product, (a-1) component and (a-2) component are used in combination at a specific ratio and blended with a water-miscible organic solvent, which will be described later, to dissolve in water as well as excellent stability and detergency. It was succeeded in suppressing the inhibition of solubility due to gelation. This largely depends on the component (a-1), and it has been found that the region of the liquid crystal phase in the three-component phase diagram of water-surfactant-solvent can be reduced by the component (a-1). It is in the point. Furthermore, it has become possible to reduce the region of the liquid crystal phase by using a specific ratio of the component (a-1) and the component (a-2), and also contains a water-miscible organic solvent that does not greatly contribute to cleaning performance. It became possible to reduce the amount.

<(B) component>
The liquid detergent composition of the present invention contains 1 to 40% by mass of (B) a water-miscible organic solvent in terms of improving stability and solubility. 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.

  (B) Content of a component is 1-40 mass% in a composition from a stability and a soluble point, 2-30 mass% is preferable, 3-20 mass% is more preferable, 4-10 More preferred is mass%. From the viewpoint of stability and solubility, the mass ratio of the sum of the components (a-1) and (a-2) and the component (B) [(a-1) + (a-2)] / ( B) is preferably 90/10 to 65/35, more preferably 85/15 to 70/30, and still more preferably 80/20 to 70/30.

  As the component (B), a water-miscible organic solvent having a hydroxyl group and / or an ether group is preferable in terms of cleaning performance, stability, and solubility.

As a water-miscible organic solvent,
(B-1) Alkanols such as ethanol, 1-propanol, 2-propanol, 1-butanol,
(B-2) C2-C6 alkylene glycols such as ethylene glycol, propylene glycol, butylene glycol, or hexylene glycol, and glycerin,
(B-3) alkylene having 2 to 4 carbon atoms such as diethylene glycol, triethylene glycol, tetraethylene glycol, dipropylene glycol, tripropylene glycol, or polyethylene glycol or polypropylene glycol having a weight average molecular weight of 400 to 5000 and 400 to 4000 Polyalkylene glycols composed of glycol units,
(B-4) 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, diethylene glycol monobutyl ether, (Poly) alkylene glycol (mono) composed of (poly) alkylene glycol having 2 to 4 alkylene glycol units such as 1-methoxy-2-propanol or 1-ethoxy-2-propanol and alkanol having 1 to 5 carbon atoms Or di) alkyl ethers,
(B-5) Glycerol-1,3-dimethyl ether, ethyl glyceryl ether, glycerin-1,3-diethyl ether, glycerin triethyl ether, iso- or normal pentyl glyceryl ether, octyl glyceryl ether, or 2-ethylhexyl glyceryl ether, or diethylene glycol Alkyl glyceryl ethers having 1 to 8 carbon atoms such as monobutyl ether,
(B-6) ethylene glycol monophenyl ether, diethylene glycol monophenyl ether, triethylene glycol monophenyl ether, polyethylene glycol monophenyl ether having an average molecular weight of about 480, ethylene glycol monobenzyl ether, diethylene glycol monobenzyl ether, etc. Aromatic ethers of (poly) alkylene glycols having 3 alkylene glycol units,
Is mentioned.

  The component (B) is effective as a viscosity modifier and a gelation inhibitor for the composition, and preferably used in combination of two or more selected from the above classifications (b-1) to (b-6). More preferably, (b-3) is used, and in particular, a polyalkylene glycol having a weight average molecular weight of 400 to 4000 consisting of an alkylene glycol unit having 2 to 4 carbon atoms is desirably used.

<(C) component>
The liquid detergent composition of the present invention contains 5 to 50% by mass of water as the component (C) from the viewpoint of improving stability and solubility. Furthermore, it is preferable to contain 10-40 mass%, and it is more preferable to contain 15-30 mass%. It is preferable to use water that does not affect the composition, such as ion exchange water.

<Other ingredients>
Hereinafter, other components that can be blended in the liquid detergent composition of the present invention will be described.
[(D) Alkaline agent]
The liquid detergent composition of the present invention preferably contains an alkali agent [hereinafter referred to as component (D)]. Examples of the alkaline agent include alkanolamines having 1 to 3 alkanol groups having 2 to 4 carbon atoms in general alkanols in addition to alkali metal hydroxides, alkali metal carbonates, and the like. . Of these, the alkanol is preferably a hydroxyethyl group. Other than the alkanol group is a hydrogen atom, but even a methyl group can be used as an alkali agent. As alkanolamine, 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, monoethanolamine, triethanolamine, and particularly monoethanolamine are most preferred. (D) A component can be used as a pH adjuster mentioned later.

  The liquid detergent composition of the present invention preferably contains 0.5 to 8% by mass, more preferably 1 to 7% by mass of component (D). Among them, the alkanolamine is preferably contained as the component (D) in an amount of 0.5 to 8% by mass, more preferably 1 to 7% by mass. In addition, alkanolamine can also be mix | blended as counter ions, such as a salt of (a-2) component, and those amounts are also included as (D) component.

[(E) component]
The liquid detergent composition of the present invention can contain a chelating agent [hereinafter referred to as component (E)]. As the chelating agent for component (E), known ones used for liquid detergents can be used. For example, nitrilotriacetic acid, iminodiacetic acid, ethylenediaminetetraacetic acid, diethylenetriaminepentaacetic acid, glycol etherdiaminetetraacetic acid, hydroxyethyl Aminopolyacetic acid such as iminodiacetic acid, triethylenetetraamine hexaacetic acid, diencoric acid or salts thereof, diglycolic acid, oxydisuccinic acid, carboxymethyloxysuccinic acid, citric acid, lactic acid, tartaric acid, oxalic acid, malic acid, oxydisuccinic acid Organic acids such as gluconic acid, carboxymethyl succinic acid, carboxymethyl tartaric acid or salts thereof, aminotri (methylenephosphonic acid), 1-hydroxyethylidene-1,1-diphosphonic acid, ethylenediaminetetra (methylenephosphonic acid), diethylenetri Minpenta (methylene phosphonic acid), etc. These alkali metal or lower amine salts. In the present invention, the alkanolamine mentioned in the component (a-2) is preferably used as a salt, and may be a salt blended with an acid and neutralized with an alkali agent in the system.

  (E) As for the mixture ratio in the composition of a component, 0.1-5 mass% is preferable when it considers it as an acid type, More preferably, it is 0.1-4 mass%, More preferably, it is 0.1-3 mass %.

[Other ingredients]
Furthermore, the components shown in the following (i) to (xi) can be blended in the liquid detergent composition of the present invention 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 5000 or more, maleic anhydride-diisobutylene copolymer, maleic anhydride-methyl vinyl ether copolymer, maleic anhydride-vinyl acetate copolymer Recontamination preventing agents such as polymers, naphthalene sulfonate 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 (ii) Color transfer inhibitor such as polyvinylpyrrolidone (iii) Bleaching agent such as hydrogen peroxide, sodium percarbonate or sodium perborate (iv) Tetraacetylethylenediamine, general formula (I- Bleach activators such as bleach activators represented by 2) to (I-7) (v) cellulase, amylase Enzymes such as pectinase, protease, lipase (vi) Boron compounds, calcium ion sources (calcium ion supply compounds), bihydroxy compounds, formic acid and other enzyme stabilizers (vii) fluorescent dyes such as Tinopearl CBS (trade name, Ciba Fluorescent dyes (viii) butylhydroxytoluene, distyrenated cresol, sodium sulfite and sodium bisulfite, which are commercially available as Specialty Chemicals) and Whiteex SA (trade name, manufactured by Sumitomo Chemical Co.) Solubilizers such as toluene sulfonic acid, cumene sulfonic acid, meta-xylene sulfonic acid, benzoate (also effective as preservative) (x) paraffins such as octane, decane, dodecane, tridecane, decene, dodecene, etc. Olefin, methylene chloride, 1,1,1 Alkyl halides such as trichloroethane, water-immiscible organic solvent such as terpenes, such as D- limonene.
(Xi) Other antifoaming agents such as pigments, fragrances, antibacterial preservatives, and silicones

  Although the density | concentration as a parameter | index at the time of mix | blending the said arbitrary component in the liquid detergent composition of this invention below is shown, it adjusts suitably to such an extent that this effect is not impaired, and excludes when it is not suitable for a mixing | blending. The content of the anti-staining agent and dispersant (i) is preferably 0.01 to 10% by mass. The content of the color transfer inhibitor (ii) is preferably 0.01 to 10% by mass. The content of the bleaching agent (iii) is preferably 0.01 to 10% by mass. The content of the bleach activator (vi) is preferably 0.01 to 10% by mass. The content of the enzyme (v) is preferably 0.001 to 2% by mass. The content of the enzyme stabilizer (vi) is preferably 0.001 to 2% by mass. The content of the fluorescent dye (vii) is preferably 0.001 to 1% by mass. The content of the antioxidant (viii) is preferably 0.01 to 2% by mass. The solubilizer of (ix) is preferably 0.1 to 2% by mass. The water immiscible organic solvent (x) is preferably 0.001 to 2% by mass. The other components of (xi) can be blended at a known concentration, for example. In addition, since each component contains impurities derived from production during production, it may be mixed into the present composition. For example, polyethylene glycol, (poly) propylene glycol-polyethylene glycol copolymer, unreacted alcohol and the like can be mentioned as impurities that can be mixed from the surfactant such as component (a-1) and (a-3). The degree of inclusion is limited in consideration of this effect and the economic efficiency of purification.

  Of the above-mentioned optional components, (ix) and (x) affect the stability of the liquid detergent composition, so particular attention must be paid to their formulation.

  The liquid detergent composition of the present invention is measured at 20 ° C. described in 8.3 of JIS K3362: 1998. The pH of the composition is preferably from 3.0 to 9.0, more preferably from 3.5 to 8.0 from the viewpoint of stability. The pH of the 0.05 mass% aqueous solution is preferably from 5 to 11, more preferably from 5 to 10, and even more preferably from 6 to 9 from the viewpoint of cleaning performance and stability.

  Examples of the pH adjuster include inorganic acids such as hydrochloric acid, sulfuric acid, and phosphoric acid; organic acids such as polyvalent carboxylic acids and hydroxycarboxylic acids; sodium hydroxide, potassium hydroxide, ammonia, and the like. Therefore, an organic acid is preferable. Specific examples of the organic acid include polyvalent carboxylic acids such as succinic acid, maleic acid, fumaric acid, or salts thereof; hydroxy such as citric acid, malic acid, glycolic acid, p-hydroxybenzoic acid, or salts thereof. Examples thereof include carboxylic acids, and citric acid or a salt thereof is particularly preferable. A pH adjuster can be used 1 type or in mixture of 2 or more types. Specifically, the content of the pH adjuster is, for example, preferably 0.05 to 3% by mass, and more preferably 0.1 to 1.5% by mass in the liquid detergent composition. By being above the lower limit of the range, it becomes easy to keep the pH constant. On the other hand, by being below the upper limit, a pH adjusting effect for adjusting the pH to 5 to 11 can be sufficiently obtained, which is economically advantageous.

  The viscosity at 20 ° C. of the liquid detergent composition of the present invention is preferably 10 to 500 mPa · s, more preferably 50 to 400 mPa · s, and still more preferably 100 to 300 mPa · s in terms of ease of handling. It is preferable to adjust so that it may become such a range with (B) component and a solubilizer.

  The liquid detergent composition of the present invention is a composition that does not cause gelation or increase in viscosity when diluted with water.

  In the present invention, the viscosity is measured with a B-type viscometer. Select a rotor that matches the viscosity. It rotates at a rotational speed of 60 r / min, and the viscosity 60 seconds after the start of rotation is taken as the viscosity of the liquid detergent composition or diluent.

  The liquid detergent composition of the present invention is suitable for textile products such as clothing, bedding, and fabrics.

<How to wash>
In the washing method of the present invention, a textile product is washed at a bath ratio of 2 to 12 L / kg using a washing medium (washing bath) prepared from the liquid detergent composition of the present invention. The bath ratio is the amount of water (L) per kg of the textile product that is the laundry. In this range of bath ratio, the mechanical force due to stirring decreases, so the conventional concentrated liquid detergent composition (eg, Patent Documents 1 to 5) gels upon dilution and the solubility decreases, so sufficient detergency Cannot be obtained. In particular, when a fully automatic washing machine for home use is used, such a decrease in stirring force at a low bath ratio tends to be remarkable. Further, in some cases, the gelled liquid detergent composition may adhere to the laundry, but the liquid detergent composition of the present invention has sufficient solubility and low solubility even at such a low bath ratio that results in low mechanical force. Shows cleaning performance.

  The washing time is preferably 2 to 30 minutes, more preferably 3 to 20 minutes, and further preferably 5 to 15 minutes. Since the liquid detergent composition of the present invention dissolves easily without being gelled at the time of dilution, there is no fear that undissolved substances remain even after a short period of stirring. In addition, since the cleaning performance is excellent, sufficient cleaning performance can be obtained even in a short time.

  The temperature of the washing bath is preferably 3 to 40 ° C, more preferably 4 to 30 ° C, and still more preferably 5 to 25 ° C. A conventional concentrated liquid detergent composition dissolves at a high temperature, but at a low temperature it gels upon dilution and its solubility is lowered, so that a sufficient detergency cannot be obtained. Moreover, although the gelatinized liquid detergent composition may adhere to laundry, the liquid detergent composition of this invention shows sufficient solubility and washing | cleaning performance also in such low temperature.

  The concentration of the liquid detergent composition in the washing bath is preferably 0.01 to 0.5% by mass, particularly 0.01 to 0.1% by mass as the total surfactant concentration.

  The components shown in Table 1 were mixed to obtain compositions of Examples and Comparative Examples. The following evaluations were performed using the obtained compositions. The results are shown in Table 1.

(1) Evaluation of detergency A collar cloth described in JIS K3362: 1998 is prepared. The detergency of the liquid detergent composition shown in Table 1 and the index detergent for determining detergency was compared in accordance with the method for evaluating the detergency of a synthetic detergent for clothing described in JIS K 3362: 1998. The use concentration of the liquid detergent composition in Table 1 was 0.33 g / L. The determination of the cleaning power was “◎” when it was better than the index detergent, “◯” when it was equivalent to the index detergent, and “x” when it was inferior to the index detergent.

(2) Storage stability evaluation A 50 mL sample bottle (No. 6 wide-mouthed standard bottle, made of glass, cylindrical shape with a diameter of 40 mm and a height of 80 mm) was filled with 40 mL of the liquid detergent composition, capped, and then 5 It was left to stand in a constant temperature room at 20 ° C. for 20 days. The stability of the composition was determined by visually observing the appearance and following criteria.
A: A uniform liquid phase in which no liquid crystal or crystals are formed, and the liquid stability is excellent.
X: Liquid crystal formation, crystal formation, separation, or precipitation is observed.

(3) Solubility Evaluation (3-1) Solubility Model Evaluation Liquid detergent composition and ion-exchanged water [[(mass of liquid detergent composition) / (mass of liquid detergent composition + ion-exchanged water] Mass) × 100 = 5 to 95% by mass, and a total of 19 samples mixed in increments of 5% by mass were prepared and allowed to stand in a constant temperature room at 5 ° C. for 1 day, and then the viscosity of this sample at 5 ° C. Was measured under the following conditions and judged according to the following criteria, which is a solubility model test in water at 5 ° C.
Measuring instrument Tokyo Keiki Co., Ltd. digital B type viscometer (model number; DV MB)
Measurement conditions 60 r / min 60 seconds ○: The viscosity of all the samples is less than 1500 mPa · s. This means that the liquid is not thickened due to liquid crystal formation or crystal formation at the time of dilution with cold water, and can be judged to be excellent in solubility.
X: Some samples have a viscosity of 1500 mPa · s or more. This means that thickening may occur due to liquid crystal formation or crystal formation upon dilution with cold water, and it is determined that the solubility is poor.

(3-2) Solubility Evaluation by Washing Machine Using a fully automatic washing machine JW-Z20A manufactured by Haier Co., Ltd., standard course (washing 15 minutes, rinsing twice, dehydration 5 minutes, water volume 15 L), water temperature 10 ° C., After adding water at a bath ratio of 10, a washing test was conducted by adding 5 g of the liquid detergent composition. A short sleeve round neck underwear YG made by Gunze Co., Ltd. was used as the laundry.
○: Undissolved material cannot be confirmed in the washing tub after the completion of all processes.
X: Undissolved substances can be confirmed in the washing tub after completion of all the steps.

(Note) The components in the table are as follows. In addition, the monoethanolamine of (D) is described as the quantity containing the alkanolamine derived from the component (a-2).

(A) Component (a-1) Component (a-1-1): R ¹ in the general formula (I) is a linear alkyl group having 11 carbon atoms, m is 1.5, n is 15, and R ² is Nonionic surfactant (a-1-2) in which CH ₃ and PO and EO are randomly arranged: R ¹ in the general formula (I) is a linear alkyl group having 11 carbon atoms, m is 1.5, Nonionic surfactant (a-1-3) having a block arrangement in which n is 15, R ² is CH ₃ , and PO and EO are bonded to R ¹ COO in this order: R ¹ in the general formula (I) is Nonionic surfactant (a-1-4) having 11 linear carbon groups, m is 1.5, n is 15, R ² is CH ₂ CH ₃ and PO and EO are randomly arranged: General In the formula (I), R ¹ is a linear alkyl group having 11 carbon atoms, m is 4, n is 15, R ² is CH ₃ , and a non-blocking sequence in which PO and EO are bonded to R ¹ COO in this order: Ion world Active agents (a-1-5): the formula a linear alkyl group R ¹ is carbon 11 in (I), m is 0.5, n is 15, R ² is CH _3, R ¹ COO Nonionic surfactant (a-1-6) having a block arrangement in which PO and EO are bonded in this order: R ¹ in the general formula (I) is a linear alkyl group having 11 carbon atoms, m is 1.5, Nonionic surfactant (a-1-7) having a block sequence in which n is 19, R ² is CH ₃ , and PO and EO are bonded to R ¹ COO in this order: R ¹ in the general formula (I) is Nonionic surfactant having a block arrangement in which a linear alkyl group having 11 carbon atoms, m is 1.5, n is 10, R ² is CH ₃ , and is bonded to R ¹ COO in the order of PO and EO

(A-2) Component (a-2-1): Alkylbenzenesulfonic acid having a linear alkyl group having 10 to 14 carbon atoms (a-2-2): Polyoxyethylene alkyl ether sulfate (10 to 14 carbon atoms) Linear alkyl, EO average added mole number 3, monoethanolamine salt, provided that the concentrations shown in Table 1 are converted to acid type)
(A-2-3): LUNAC L-55 (trade name) (coconut oil fatty acid; manufactured by Kao Corporation)

(A-3) Component (a-3-1): non-ion in which R ¹ in the general formula (I) is a linear alkyl group having 11 carbon atoms, m is 0, n is 15, and R ² is CH ₃ Surfactant (a-3-2): R ¹ in the general formula (I) is a linear alkyl group having 11 carbon atoms, m is 0.2, n is 15, R ² is CH ₃ , PO and Nonionic surfactant (a-3-3) in which EO is a random sequence: R ¹ in the general formula (I) is a linear alkyl group having 11 carbon atoms, m is 1.5, n is 26, and R ² is Nonionic surfactant (a-3-4), which is CH ₃ and PO and EO are randomly arranged: An average of 15 moles of EO added to a primary alcohol having 10 to 14 carbon atoms (a-3-5 ): An average of 8 moles of EO added to a primary alcohol having 10 to 14 carbon atoms (a-3-6): An average of 3 moles of EO was added to a secondary alcohol having 12 to 14 carbon atoms Thing [Softanol 30 (trade name), manufactured by Nippon Shokubai Co., Ltd.]

(B) Component (B-1): Diethylene glycol monobutyl ether (B-2): Propylene glycol (B-3): Triethylene glycol monophenyl ether (B-4): Ethanol (B-5): Polyethylene glycol (weight) (Average molecular weight 1000)

Polymer (1): Polymer compound fluorescent dye synthesized by the method of Synthesis Example 1 on page 4, paragraph 0020 of JP-A-10-60476: Tinopearl CBS-X (trade name) (manufactured by Ciba Specialty Chemicals)
Enzyme: Everase 16.0L-EX (trade name) (protease, manufactured by Novozyme)
Dye (1): Green No. 202

Claims (2)

(A) component which consists of surfactant containing the following (a-1) component and (a-2) component, the following (B) component, and the following (C) component, (A) In component (a) -1) The component is 50% by mass or more, and the mass ratio of the component (a-1) to the component (a-2) is (a-1) / (a-2) = 50/50 to 99/1. , Liquid detergent composition.
(A) component: 40-90 mass% of surfactant
Component (a-1): Nonionic surfactant represented by the following general formula (I) R ¹ COO — [(PO) _m / (EO) _n ] —R ² (I)
(Wherein R ¹ is a hydrocarbon group having 7 to 21 carbon atoms, COO— is a carbonyloxy group, R ² is an alkyl group having 1 to 3 carbon atoms, P is a propylene group, E is an ethylene group, m Is the average added mole number of PO, n is the average added mole number of EO, m is 0.3 to 5, and n is 8 to 25. / is that PO and EO may be random or block Is shown.)
(A-2) Component: Anionic surfactant (B) Component: 1-40% by mass of a water-miscible organic solvent
(C) component: Water 5-50 mass%   A washing method comprising a step of washing a textile product at a bath ratio of 2 to 12 L / kg using a washing medium prepared from the liquid detergent composition according to claim 1.