JP2010229387A - Liquid detergent composition - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a liquid detergent composition containing a high concentration surfactant, excellent in detergent power and storage stability and having no reduction in solubility caused by gel formation and the like in diluting the same with water. <P>SOLUTION: The detergent composition comprises (a) a specific alkoxyl-type nonionic surfactant having a structure containing a first carbon atom such as an alkyl group derived from a primary alcohol, or the like, (b) an anionic surfactant, (c) a water-miscible organic solvent and (d) water in a specific condition. <P>COPYRIGHT: (C)2011,JPO&INPIT

Description

  The present invention relates to a liquid detergent composition, and more particularly to a liquid detergent composition for clothing and residential use, particularly for textile products such as clothing.

  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.

  Patent Documents 1 to 3 describe concentrated liquid detergent compositions containing a specific nonionic surfactant.

  Patent Document 4 discloses a nonionic surfactant obtained by adding ethylene oxide (hereinafter sometimes referred to as EO) and propylene oxide (hereinafter also referred to as PO) to a synthetic higher alcohol having a branched chain. A concentrated liquid detergent composition containing a solvent is described. 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.

  Further, Patent Document 5 discloses a liquid detergent composition containing 5 to 50% by weight of a polyethylene oxide-polypropylene oxide addition type nonionic surfactant and 2 to 40% by weight of an anionic surfactant. Yes. Patent Document 6 describes a high-concentration liquid detergent composition containing a polyethylene oxide-polypropylene oxide addition type nonionic surfactant, an anionic surfactant and a cationic surfactant.

JP 2008-7705 A JP 2008-7706 A JP 2008-7707 A JP-A-8-157867 JP-A-11-310800 Japanese Patent Laid-Open No. 9-255989

  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. Although there are fluid compositions that do not form liquid crystals or crystal phases in such high-concentration systems, we also form liquid crystals by diluting with water, especially cold water, during washing. And found that there are problems in solubility and stability, such as causing poor solubility and being easy to solidify the composition during low-temperature storage, which becomes more prominent as the surfactant concentration increases. I found out. Among the conventional techniques, a technique considering solubility is disclosed, but it is not sufficient, and there is a problem in storage stability in the alkaline region of the base material itself, so that sufficient detergency cannot be obtained. There was a problem and was not enough.

  Therefore, the problem of the present invention is that in a liquid detergent composition containing a high concentration of surfactant, it has excellent detergency and storage stability, and has solubility due to gelation formation when the composition is diluted with water. It is to provide a liquid detergent composition without degradation.

This invention is a liquid detergent composition containing the following (a)-(d) component, Comprising: The sum total of content of (a) component and (b) component is (a) + (b) = 40- 80% by mass, the mass ratio of the component (a) to the component (b) is (a) / (b) = 50/50 to 90/10, and the content of (d) is 10% by mass or more. And a liquid detergent composition.
(A) component: 30-70 mass% of nonionic surfactant represented by following General formula (1)
^{_{R 1 O- (C 2 H 4}} O) m - (AO) n H (1)
[Wherein, R ¹ is a hydrocarbon group having 8 to 22 carbon atoms, and the carbon atom of R ¹ to which the oxygen atom of R ¹ O— is bonded is the first carbon atom. AO is an oxyalkylene group having 3 to 5 carbon atoms. m and n are average added mole numbers, m is a number of 15-30, and n is a number of 1-5. ]
(B) component: anionic surfactant (c) component: 5-40 mass% of water miscible organic solvent
(D) Component: water

  The composition of the present invention has excellent stability, particularly storage stability at low temperatures, and excellent solubility, particularly solubility in cold water, despite the high concentration of the surfactant as a cleaning component. It also has excellent cleaning performance.

<(A) component>
In general formula (1) of the component (a), R ¹ is a hydrocarbon group having 8 to 22 carbon atoms, preferably a hydrocarbon group having 10 to 16 carbon atoms, and more preferably 11 to 13 carbon atoms. R ¹ is preferably a linear hydrocarbon group. The hydrocarbon group for R ¹ is preferably an alkyl group or an alkenyl group, and more preferably an alkyl group. R ¹ is preferably a linear or branched alkyl group, and more preferably a linear alkyl group.

  Prior art 4 mentioned in the background art uses a synthetic surfactant having a branched chain as a surfactant as one of the means for solving the problem. However, when a surfactant derived from a linear primary alcohol, that is, a surfactant derived from a natural alcohol is used, it is insufficient and there is no recognition of gelation upon dilution during washing. The present invention is an effective technique when a linear alkyl group is contained in a high ratio, and a sufficient effect can be obtained even with a surfactant system having a linearity ratio of 90% or more, particularly a substantially linearity ratio of 100%. It differs from the prior art in that it can be demonstrated.

In the component (a) of the present invention, in the general formula (1), the carbon atom of R ¹ to which the oxygen atom of R ¹ O— is bonded is the first carbon atom. The compound of the general formula (1) can be obtained by subjecting a primary alcohol having 8 to 22 carbon atoms to block addition reaction of ethylene oxide and then alkylene oxide having 3 to 5 carbon atoms, preferably propylene oxide. .

  Moreover, m in General formula (1) is the average addition mole number of ethylene oxide, 16-25 are preferable from the point of low-temperature solubility and a detergency, 16-22 are more preferable, and 18-22 are the most preferable. n is the average number of added moles of alkylene oxide having 3 to 5 carbon atoms, preferably 1 to 3, and more preferably 1 to 2 in terms of detergency. By increasing the average number of moles of ethylene oxide added and further adding a small amount of propylene oxide, the formation of a liquid crystal phase in water dilution during washing can be suppressed. However, from the viewpoint of sufficient detergency, the added mole number of m and n is not more than the upper limit value. In addition, the combined use of the component (b) described later is important for the suppression of liquid crystal phase formation and detergency during dilution.

  The oxyalkylene group which is AO in the general formula (1) (hereinafter sometimes referred to as AO group) is obtained by addition reaction of a C 3-5 alkylene oxide, and is a moiety bonded by addition reaction. Has a methyl branched or propyl branched structure. We believe this structure is important. The AO group is preferably an oxypropylene group obtained by addition reaction of propylene oxide (hereinafter sometimes referred to as PO group).

In the liquid detergent composition of the present invention, the blending amount of the component (a) is 30 to 70% by mass from the viewpoint of cleaning performance, preferably 35 to 70% by mass, more preferably 40 to 65% by mass, 45 -60 mass% is most preferred. In the case of using an alkyl group compound in which R ¹ has a straight chain ratio of 90% or more, and particularly a substantially straight chain ratio of 100%, the component (a) is preferably 40 to 60% by weight. In the present invention, even when the surfactant concentration is high, excellent detergency can be obtained without causing gelation due to water dilution during washing.

<(B) component>
The liquid detergent composition of the present invention is blended with (b) an anionic surfactant in terms of improving the washing performance, stability and solubility. The content of the component (b) needs to satisfy the ratio described later from the relationship with the component (a). The component (b) improves the stability and solubility by using the component (a) at a specific ratio together with the effect as a cleaning component. The reason for this is not clear, but by mixing the molecules of component (b) between the molecules of component (a), the alignment of surfactant molecules is suppressed from the electrical repulsion of the anionic group of component (b). As a result, liquid crystal and crystal formation are expected to be suppressed.

  As the anionic surfactant, for example, the following (b1) to (b5) can be used, and (b1), (b2), and (b4) are preferable in terms of cleaning performance, stability, and solubility, and ( It is more preferable to contain one or more selected from b1) and (b2). When containing at least one selected from (b1) and (b2), it is most preferable in terms of detergency, low-temperature stability, and solubility to account for 80% by mass or more, particularly 90% by mass in the component (b). . Moreover, when (b4) is contained for reasons such as a foam modifier and a mud dispersant, it is preferably 1 to 30% by mass, more preferably 1 to 20% by mass in the component (b) from the viewpoint of low temperature stability. .

(B1) Alkylbenzenesulfonate having an alkyl group having an average carbon number of 10 to 20.
(B2) having an alkyl group derived from a linear primary alcohol or linear secondary alcohol having an average carbon number of 10 to 20 or a branched alcohol, and having an average addition mole number of an oxyalkylene group of 1 to 5. The polyoxyethylene alkyl ether sulfate ester salt (b3) having an average carbon number of 10 to 10, which contains an oxyethylene group as an oxyalkylene group and may contain an oxypropylene group in the range of an average addition mole number of 0.2 to 2 moles. An alkyl or alkenyl sulfate ester salt having 20 alkyl groups or alkenyl groups.
(B4) Fatty acid salt having an average carbon number of 8 to 20.
(B5) It has 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 the average added mole number of the oxyalkylene group is 1 to 5. A polyoxyethylene alkyl ether carboxylate which contains an oxyethylene group as an oxyalkylene group and may contain an oxypropylene group in an average addition mole number range of 0.2 to 2 mol.

  Examples of the salt constituting the component (b) include alkali metal salts such as sodium and potassium, alkanolamine salts, and alkaline earth metal salts such as magnesium and calcium. In particular, alkanolamine salts from the viewpoint of stability. It is preferable that 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 (b) is preferably neutralized with an alkanolamine salt or an acid form and then added in the system with an alkanolamine [alkanolamine used as an alkali agent for the component (f) described later]. Metal-based counter ions such as alkali metals and alkaline earth metals may be mixed in the manufacturing process of component (a), or may contain sulfites, particularly sodium sulfite, in addition to sequestering agents and hydrotropes. It may be contained in the composition by blending an oxidation or anti-coloring agent, etc. at a concentration described later, but the metal ion concentration is preferably low from the viewpoint of storage stability, substantially It is preferable that it is 5 mass% or less in a composition, especially 3 mass% or less.

In the liquid detergent composition of the present invention, from the viewpoint of detergency and stability, the total content of the component (a) and the component (b) is (a) + (b) = 40 to 80% by mass, 50-80 mass% is preferable and 60-70 mass% is more preferable. (A) In the case of using an alkyl group compound in which R ¹ has a linear ratio of 90% or more, particularly substantially 100% as the component, 50 to 70% by mass is preferable, and 60 to 70% by mass is more preferable. In addition, since the mass of the anionic surfactant of the component (b) 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 instead of the salt (b ) The mass of the component.

  Moreover, in the liquid cleaning composition of this invention, (a) / (b) is 50 / 50-90 / 10 as mass ratio from a viewpoint of cleaning performance, solubility, and stability, and 50 / 50-85 / 15 is preferable, and 55/45 to 80/20 is more preferable. From the viewpoint of detergency, the proportion of the component (a) is not less than the lower limit and not more than the upper limit from the viewpoint of solubility and stability. By using the component (a) in combination with the component (b), it is possible to increase the detergency of the composition and further increase the solubility by suppressing liquid crystal formation.

<(C) component>
The liquid detergent composition of the present invention contains 5 to 40% by mass of (c) a water-miscible organic solvent from the viewpoint 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.

The content of the component (c), stability, in terms of solubility, in the composition, 5 to 40 wt%, preferably 10 to 35 mass%, R ¹ is a linear rate as the component (a) When using a compound having an alkyl group of 90% or more, particularly substantially 100%, 15 to 30% by mass is preferable.

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

  Examples of the water-miscible organic solvent include (c1) alkanols such as ethanol, 1-propanol, 2-propanol, 1-butanol, (c2) carbon number 2 such as ethylene glycol, propylene glycol, butylene glycol, or hexylene glycol. -6 alkylene glycols and glycerin, (c3) 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 4000, 2 to 4 carbon atoms Polyalkylene glycols consisting of the following alkylene glycol units: (c4) diethylene glycol monomethyl ether, diethylene glycol dimethyl ether, triethylene Recall 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, 1-methoxy-2-propanol, or 1-ethoxy-2 A (poly) alkylene glycol (mono or di) alkyl ether composed of a (poly) alkylene glycol having 2 to 4 carbon atoms such as propanol and an alkanol having 1 to 5 carbon atoms, (c5) glycerin-1,3 -Dimethyl ether, ethyl glyceryl ether, glycerin-1,3-diethyl ether, glycerin triethyl ether, iso or no Alkyl glyceryl ethers having an alkyl having 1 to 8 carbon atoms such as malpentyl glyceryl ether, octyl glyceryl ether or 2-ethylhexyl glyceryl ether, (c6) ethylene glycol monophenyl ether, diethylene glycol monophenyl ether, triethylene glycol monophenyl And (poly) alkylene glycol aromatic ethers having a C2-C3 alkylene glycol unit, such as ether, polyethylene glycol monophenyl ether having an average molecular weight of about 480, ethylene glycol monobenzyl ether, diethylene glycol monobenzyl ether, and the like. .

  The component (c) is effective as a viscosity modifier and a gelation inhibitor of the composition, and one or more selected from the above classifications (c1) to (c6), particularly two or more may be used in combination. More preferably, two or more kinds selected from the classifications (c1), (c2), (c4) and (c6), particularly preferably 2 selected from the classifications (c2), (c4) and (c6). More than one species, more specifically, by using two or more selected from propylene glycol, diethylene glycol monobutyl ether, and mono-triethylene glycol monophenyl ether, it is possible to effectively achieve viscosity adjustment and gelation suppression of the composition. Most preferred.

<(D) component>
The liquid detergent composition of the present invention contains water as the component (d) in terms of improving stability and solubility. Content of water is 10 mass% or more in a composition, 10-40 mass%, Especially 15-30 mass% is preferable. It is preferable to use water that does not affect the composition, such as ion exchange water. When the water content is less than 10% by mass, the composition is easily crystallized.

  In the liquid detergent composition of the present invention, the total of the components (a) to (d) is preferably 85% by mass or more, preferably 90% by mass or more, and particularly preferably 95% by mass or more.

<Other ingredients>
Hereinafter, other components that can be blended in the liquid detergent composition of the present invention will be described.
[(E) component]
The liquid detergent composition of the present invention can contain a surfactant other than the component (a) and the component (b) [hereinafter referred to as the component (e)] in a range that does not impair the effects of the present invention. Examples of the component (e) include the following (e1) to (e3).
(E1) Nonionic surfactants that do not fall under component (a).
For example, the following (e1-1), (e1-2), and (e1-3) are mentioned.
(E1-1) A polysaccharide surfactant represented by the following general formula.
R ^1e − (OR ^2e ) _x G _y
[Wherein, R ^1e is a linear or branched alkyl group or alkenyl group having 8 to 18 carbon atoms, R ^2e is an alkylene group having 2 to 4 carbon atoms, and G is derived from a reducing sugar having 5 or 6 carbon atoms. Residue, x is a number having an average value of 0-6, and y is a number having an average value of 1-10. ]
(E1-2) Fatty acid alkanolamide, polyhydroxy fatty acid amide.
(E1-3) Nonionic surfactant represented by the following general formula: R ² O (C ₂ H ₄ O) _p / (C ₃ H ₆ O) _q H
[Wherein, R ² represents an alkyl group having 8 to 22 carbon atoms, preferably 8 to 20 carbon atoms, and preferably a linear alkyl group. The carbon atom of R ² to which the oxygen atom of R ² O— is bonded is the second carbon atom. p and q are average addition mole numbers, p is a number of 6-20, and q is a number of 0-5. / Indicates that EO and PO may be random or block. ]
(E2) Cationic surfactant.
For example, it is a primary to tertiary amine having a long-chain alkyl group (except for alkanolamine described later) or a quaternary ammonium compound, preferably having an ether bond, an ester bond or an amide bond in the middle. Examples thereof include a cationic surfactant having one or two alkyl groups having 8 to 22 carbon atoms, and the remaining alkyl group optionally having a hydroxy group having 4 or less carbon atoms. 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.
(E3) Amphoteric surfactant For example, sulfobetaine or carbobetaine having an alkyl group having 10 to 18 carbon atoms can be mentioned.

  Of the nonionic surfactants that do not fall under component (a), the combined use of primary alcohol-derived polyoxyethylene alkyl ethers may cause gelation when dissolved in cold water. On the other hand, from the viewpoint of suppressing gelation, it is preferably used in a proportion of 30% by mass or less, more preferably 20% by mass or less, and particularly preferably less than 10% by mass. If it is a nonionic surfactant of (e1-3), from the point of detergency, it is 10-30 mass% with respect to (a) component, and also the detergency by mix | blending in the ratio of 10-20 mass%. Can be increased.

  The content of the component (e) is preferably 0.5 to 15% by mass, more preferably 0.5 to 10% by mass in the liquid detergent composition of the present invention. The nonionic surfactant (e1) in the component (e) is combined with the component (a) as [(a) + (e1)] / (b). It is preferable to fall within the range of the mass ratio. For the quaternary ammonium salt, the mass excluding the counter anion is the mass of the quaternary ammonium salt, and for the tertiary amine, hydrogen atoms other than organic groups are substituted among the groups bonded to the nitrogen atom. The mass of the resulting structure is defined as the mass of the tertiary amine.

[(F) Alkaline agent]
The liquid detergent composition of the present invention preferably contains an alkali agent [hereinafter referred to as component (f)]. 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. The alkanolamine 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. The component (f) can be used as a pH adjuster described 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 the component (f). In addition, alkanolamine can also be mix | blended as counter ions, such as a salt of (b) component, and those amounts are also included as (f) component.

[(G) component]
The liquid detergent composition of the present invention can contain a chelating agent [hereinafter referred to as component (g)]. (G) The chelating agent of a component can use the well-known thing used for a liquid detergent, 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 metal or lower amine salts thereof. In the present invention, the alkanolamine mentioned in the component (b) is preferably used as a salt, and may be a salt blended with an acid and neutralized with an alkali agent in the system.

  (G) The mixture ratio in the composition of a component is 0.1-5 mass% when it considers that it is an acid type, Preferably it is 0.1-4 mass%, More preferably, it is 0.1-3 mass%. It is.

[Other optional 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.

  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 pH of the composition of the present invention is measured at 25 ° C. as described in JIS K3362: 1998. The pH is preferably 6 to 11, particularly 8 to 10 (25 ° C.) from the viewpoint of cleaning performance and stability.

  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. (C) It is preferable to adjust so that it may become such a range with a component and a solubilizing agent.

  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 can be filled into a container, for example, a plastic container including a measuring cap and a bottle to obtain a liquid detergent article in a container. As a material of the bottle, plastics such as polypropylene (PP), polyethylene terephthalate (PET), high density polyethylene (HDPE), medium density polyethylene (MDPE), vinyl chloride (PVC) can be used. The container for filling the liquid detergent composition of the present invention is a plastic container having a container for containing a liquid detergent composition, from the viewpoint of suppressing deformation under reduced pressure due to a decrease in the internal pressure of the plastic material molding container, The container is preferably a plastic container having a flexural modulus (JIS K7171) of 2000 MPa or more, preferably 5000 MPa or less, more preferably 3000 MPa or less, and a wall thickness of 0.3 to 1.5 mm. A bottle that satisfies such a flexural modulus and thickness is used. As a reason for the container deformation, since the liquid detergent composition of the present invention contains a nonionic surfactant at a high concentration, it is presumed that oxygen present in the space in the bottle dissolves. Moreover, since light transmission promotes oxygen solubility, the light transmittance of the container of the liquid detergent composition is preferably 15% or less for light in the wavelength range of 600 nm to 700 nm. Usually, the bottle has such light transmittance. In order to improve the light shielding property, titanium oxide or carbon black can be added to the plastic constituting the container.

  Further, as an article filled in a refill container, the liquid detergent composition of the present invention is preferably enclosed in a bag formed by laminating a flexible laminated resin film from the viewpoint of storage stability. .

  In addition, a nozzle part with a dispensing channel is provided in a part of the upper edge of the bag body, laser processing, score processing, etc. are performed, and the nozzle upper part edge is opened by hand to form the nozzle part discharge port What can be made is preferable from the viewpoint of ease of use, and as a bag shape, a standing pouch type bag is easy to handle and is a preferable type.

  As the film forming the bag, a flexible single layer resin film can be used, but a laminated resin film is generally used. As the base layer of the laminated resin film, stretched nylon film (ONy), polyethylene terephthalate (PET), stretched polypropylene (OPP), sealant layer as unstretched polypropylene (CPP), linear low density polyethylene (LLDPE), high Examples thereof include high density polyethylene (HDPE), low density polyethylene (LDPE), and aluminum vapor-deposited polyethylene terephthalate (VM-PET), ceramic vapor-deposited polyethylene terephthalate, and aluminum foil as the barrier layer.

  In particular, from the viewpoint of suppressing the occurrence of delamination (delamination) during long-term storage, the laminated resin film is composed of three or more layers, and is configured such that printing ink (ink layer) is not interposed between the intermediate layer and the innermost layer. Is preferred. Considering production aptitude, drop strength, openability and packaging material cost, the delamination is highly effective in suppressing delamination, and PET (preferably with a thickness greater than the outer layer (the layer farthest from the layer in contact with the liquid detergent composition)). A laminated film of 9 to 25 μm) / [ink layer + adhesive layer] / ONy (preferably having a thickness of 15 to 25 μm) / adhesive layer / LLDPE (preferably having a thickness of 60 to 200 μm) is most preferable.

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

  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. In Table 1, some of the comparative examples are (a) + (b) (mass%) and (a) / (b) (mass ratio) as (a) component (e-2) to (e− The numerical value of 5) was used.

(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 After filling a 50 mL sample bottle (No. 6 wide-mouth standard bottle, glass, cylindrical shape with a diameter of 40 mm and a height of 80 mm) with 40 mL of the liquid detergent composition, capping, 7 It was allowed to stand for 20 days in a constant temperature room at 5 ° C. 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 model evaluation Liquid detergent composition and ion-exchanged water [(mass of liquid detergent composition) / (mass of liquid detergent composition + mass of ion-exchanged water) × 100 = 5 A total of 19 samples mixed at 5% by mass increments to 95% by mass were prepared and allowed to stand in a constant temperature room at 7.5 ° C. for 1 day, and then the viscosity of this sample at 10 ° C. was measured under the following conditions. The determination was made according to the following criteria, which is a solubility model test in water at 10 ° 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.
Δ: Some samples have a viscosity of 2000 mPa · s or more, but some have a viscosity of 1500 mPa · s or more and less than 2000 mPa · s.
X: Some samples have a viscosity of 2000 mPa · s or more.
When the viscosity of all the samples is less than 1500 mPa · s, it means that the viscosity does not increase due to liquid crystal formation or crystal formation at the time of dilution with cold water, and it can be determined that the solubility is excellent. On the other hand, if it exceeds 1500 mPa · s, it means that the liquid crystal formation or the crystal formation becomes easier upon dilution with cold water, and it is judged that the solubility is poor. In particular, when a sample of 2000 mPa · s or more exists, the viscosity tends to increase upon dilution with cold water.

(Note) The components in the table are as follows. In addition, about the composition which uses (a) component and other surfactant together like Example 7, the quantity ratio which added other surfactant to (a) component was displayed in parenthesis. Monoethanolamine of (f) is described as an amount containing alkanolamine derived from component (b-2).
(A) Component
(A-1): C10 to C14 primary linear alcohol in which EO is added in the order of 15 mol on average and PO in the order of 2 mol on average. It means a compound obtained by addition reaction of 15 moles of ethylene oxide per mole of primary alcohol of 14 and then addition reaction of 2 moles of propylene oxide. In the general formula (1) of component (a), m = 15, also means compounds with n = 2. The following (a-2) to (a-4) shall be similarly interpreted. The same interpretation is applied to (e-2) to (e-5). In addition, (e-1) used the commercial item as it was.
(A-2): a primary linear alcohol having 10 to 14 carbon atoms, in which EO is added in an average of 20 moles and PO is added in block order in an average of 2 moles (a-3): primary having 10 to 14 carbon atoms A linear alcohol in which EO is added in an average of 25 moles and PO is added in an order of 2 moles in the order (a-4): Dovanol 23 (trademark) (Mitsubishi Chemical Co., Ltd., carbon 13 β-position methyl branched, branched chain) Alkyl content is 20% by mass) and EO is added in an average of 20 mol and PO is added in blocks in the order of 2 mol

(B) Component (b-1): C10-14 linear alkylbenzene sulfonic acid (* Comparative Example 11 uses sodium salt of the compound)
(B-2): Polyoxyethylene alkyl ether sulfate (linear alkyl having 10 to 14 carbon atoms, EO average added mole number 3, monoethanolamine salt, but the concentrations shown in Table 1 are converted to acid type)
(B-3): Polyoxyethylene alkyl ether sulfate (linear alkyl having 10 to 14 carbon atoms, EO average addition mole number of 2, monoethanolamine salt, provided that the concentration in the table is the acid type concentration and the salt (Monoethanolamine in (f) was added to component (f).)
(B-4): LUNAC L-55 (trade name) (coconut oil fatty acid; manufactured by Kao Corporation)

(C) Component (c-1): Diethylene glycol monobutyl ether (also called butoxy diglycol)
(C-2): Propylene glycol (c-3): Triethylene glycol monophenyl ether (c-4): Ethanol

(Other)

(E-1): An average of 3 moles of EO added to a secondary alcohol having 12 to 14 carbon atoms [Softanol 30 (trade name), manufactured by Nippon Shokubai Co., Ltd.]
(E-2): An average of 20 moles of EO added to a primary linear alcohol having 10 to 14 carbon atoms (e-3): An average of 40 moles of EO to a primary linear alcohol having 10 to 14 carbon atoms , PO added in block order in an average of 2 moles (e-4): a primary linear alcohol having 10 to 14 carbon atoms in block order with an average of 6 moles of EO and 2 moles of PO in average order ( e-5): primary linear alcohol having 10 to 14 carbon atoms with EO added in the order of 20 mol on average and PO in the order of 6 mol on average (e-6): primary straight chain having 10 to 14 carbon atoms Polymer obtained by block addition of chain alcohol in the order of 12 moles of EO and 2 moles of PO in the order of polymer (1): Polymer compound synthesized by the method of Synthesis Example 1 on page 4, paragraph 0020 of JP-A-10-60476 pTS: sodium sulfonate Fluorescent dye: Tinopal 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

<Product example>
(1) Product example 1
The liquid detergent composition of the present invention can be provided as a product filled in a bag-like container. An example is shown below.

  As a film forming the container, a laminated film of PET 12 μm / [ink layer + adhesive layer] / ONy 15 μm / adhesive layer / LLDPE 150 μm is used from the outer layer (the layer farthest from the layer in contact with the liquid detergent composition), and the width is 120 mm. X A self-supporting bag having a height of 215 mm and a bottom folding width of 34.5 mm was formed. The bag was filled with 320 g of the liquid detergent composition of the present invention (e.g., the composition of Examples 1 to 10), and the upper part was heat-sealed to be sealed and packaged in a plastic container. Get. Containerized liquid detergents packaged in plastic containers are usually sold on the market for refill purposes.

(2) Product example 2
In addition, the liquid detergent composition of the present invention can be provided as a product filled in a bottle, a main body cap attached to the mouth of the bottle, and if necessary, a container including a cap having a measuring function in the main body. it can. An example is shown below.

  As a container, a full capacity of 438 mL manufactured using a PET resin added with 1.0% by mass of titanium oxide (flexural modulus [JIS K7171]: 2400 MPa, light transmittance between wavelengths of 600 to 700 nm: 10% or less), The liquid detergent composition of the present invention (for example, the compositions of Examples 1 to 10) is applied to a cylindrical bottle having a maximum outer diameter of 61 mm, a barrel outer diameter of 59 mm, a height of 190 mm, and a bottle barrel average thickness of 0.5 mm. ), And a main body cap previously fitted with a cap (capacity 26 mL) is fitted into the bottle to obtain a containerized liquid cleaning agent filled in a sealed plastic container.

Claims (4)

It is a liquid detergent composition containing the following (a)-(d) component, Comprising: The sum total of content of (a) component and (b) component is (a) + (b) = 40-80 mass% A liquid detergent having a mass ratio of the component (a) to the component (b) of (a) / (b) = 50/50 to 90/10 and a content of (d) of 10% by mass or more Composition.
(A) component: 30-70 mass% of nonionic surfactant represented by following General formula (1)
^{_{R 1 O- (C 2 H 4}} O) m - (AO) n H (1)
[Wherein R ¹ is a hydrocarbon group having 8 to 22 carbon atoms, and the carbon atom of R ¹ to which the oxygen atom of R ¹ O— is bonded is the first carbon atom. AO is an oxyalkylene group having 3 to 5 carbon atoms. m and n are average added mole numbers, m is a number of 15-30, and n is a number of 1-5. ]
(B) component: anionic surfactant (c) component: 5-40 mass% of water miscible organic solvent
(D) Component: Water   The liquid detergent composition of Claim 1 whose said C3-C5 oxyalkylene group is an oxypropylene group. The liquid detergent composition according to claim 1 or 2, wherein R ¹ is a linear hydrocarbon group.   The liquid cleaning composition in any one of Claims 1-3 in which the sum total of (a)-(d) component occupies 85 mass% or more in a composition.