JP5020485B2 - Liquid detergent composition - Google Patents

Description

  The present invention relates to a liquid detergent composition, and more particularly to a liquid detergent composition for hard surfaces suitable as a detergent for tableware and kitchen use.

In a detergent composition for dishwashing, it has been proposed to use an anionic surfactant and an amine oxide compound in combination for the purpose of improving emulsifying power and enhancing cleaning power. For example, Patent Literatures 1 and 2 can be referred to for the technique of an acidic liquid detergent containing an anionic surfactant and an amine oxide compound. In addition, Patent Documents 3 and 4 can be referred to for the technology for applying a polyoxyethylene monophenyl ether compound to a cleaning agent. Patent Document 4 further describes a cleaning agent containing an anionic surfactant and an amine oxide compound. An agent composition is disclosed, and the detailed description of the publication describes that polyoxyethylene (p = 1 to 4) glycol phenyl ether can be used.
Japanese National Patent Publication No. 10-501275, JP-A-9-78091 JP 2002-143788 A, JP 2002-256286 A

  Patent Documents 1 and 2 disclose a technique for making a composition weakly acidic, and in particular, when washing inorganic soil around a sink using a dishwashing detergent, a weakly acidic composition may be used. preferable. However, weakly acidic compositions have poor storage stability, and in particular, compositions using a combination of an anionic surfactant and an amine oxide compound have the problem that these complexes are deposited at low temperatures and the appearance is remarkably deteriorated. . Such a problem occurs particularly remarkably when a large amount of polyvalent carboxylic acid such as citric acid is blended, and a technique for suppressing the precipitation of the complex at a low temperature is desired in terms of product quality.

  On the other hand, Patent Documents 3 and 4 are said to be excellent in storage stability. In particular, a polyvalent carboxylic acid such as citric acid is added to a composition in which an anionic surfactant and an amine oxide compound are used in combination. There is no suggestion of a technique for suppressing complex precipitation that occurs when a large amount of is added.

  Accordingly, an object of the present invention is to impart excellent storage stability, particularly storage stability at low temperatures, in a composition in which an anionic surfactant and an amine oxide compound are used in combination.

The present invention relates to (a) an anionic surfactant (hereinafter referred to as component (a)) having a hydrocarbon group having 10 to 16 carbon atoms and one or more sulfonate groups or sulfate ester bases in the molecule. To 50 mass%, (b) an amine oxide surfactant having a hydrocarbon group having 10 to 16 carbon atoms and an alkyl group having 1 to 3 carbon atoms or a hydroxyalkyl group having 1 to 3 carbon atoms [hereinafter, ( b) component] is 0.1 to 15% by mass, z in the following general formula (1) is 1 (c1) [hereinafter referred to as (c1) component], and z in the following general formula (1) 2 to 6 (hereinafter referred to as the component (c2)), the mass ratio [c1] / ([c1] of the compound (c1) and the total of the compound (c1) and the compound (c2) ] + [C2]) is 0.1 to 0.8, and the pH is 3 to less than 7 at 25 ° C. About composition [hereinafter, (c1) as component and (c2) together with component (c) component].
_{Ph- (CH 2) x (OC} y H 2y) z -OH (1)
[In the formula, Ph is a phenyl group which may be substituted by 1 to 3 alkyl groups having 1 to 3 carbon atoms, x is a number of 0 or 1 (with benzyl alcohol EO adduct added), y is a number of 2 or 3, and z is a number of 1 or 2-6. ]

  According to the present invention, a liquid detergent composition using an anionic surfactant and an amine oxide compound in combination, which has excellent storage stability, particularly excellent storage stability at low temperatures, can be obtained.

<(A) component>
The component (a) of the present invention is an anionic surfactant having a hydrocarbon group having 10 to 18 carbon atoms and one or more sulfonate groups or sulfate ester bases in the molecule, represented by the following general formula (2): Compounds are preferred.

R ¹² —O— (C ₂ H ₄ O) _a —SO _3. (1 / m) M (2)
[The meaning of each symbol in the formula is as follows.
R ¹² is an alkyl group having 10 to 18 carbon atoms.
a shows the number of 0-15, and when the compound of General formula (2) is a mixture of the compound of a = 0-15, the sum total content of the compound of a = 1-15 in a mixture is 40-90 mass. %, The content of a = 0 is 60 to 15% by mass.
The average value of a is 1-5.
M is an alkali metal or an alkaline earth metal. m represents the valence of M]

  As a preferable example of the component (a), an alkylbenzenesulfonic acid having an alkyl group having 10 to 15 carbon atoms or a salt thereof, a monoalkyl sulfate salt having 10 to 16 carbon atoms, or an alkyl group having 10 to 16 carbon atoms. , A polyoxyalkylene alkyl ether sulfate ester salt having an average (average value of a) 1.0 to 4.0 moles of an oxyalkylene group having 2 or 3 carbon atoms, an α-olefin sulfonate having 8 to 16 carbon atoms, Examples include α-sulfo fatty acid (carbon number 8 to 16) lower alkyl (carbon number 1 to 3) ester salt. Examples of the salt include sodium salt, potassium salt, magnesium salt, and alkanolamine salt, and sodium salt, potassium salt, and magnesium salt are particularly preferable from the viewpoint of viscosity.

  In the present invention, an alkyl group having 10 to 14 carbon atoms, particularly an oxyalkylene group having 2 or 3 carbon atoms, preferably an oxyethylene group is average (average value of a) of 1.0 to 3.0 mol, particularly It is preferable to use a polyoxyalkylene alkyl ether sulfate salt added with 1.5 to 3.0 mol, preferably sodium salt, potassium salt, or magnesium salt from the viewpoint of cleaning effect, and a high concentration anion. It is preferable because the storage stability of a detergent containing a surfactant at low or high temperatures can be improved.

  a shows the number of 0-15, and when the compound of General formula (2) is a mixture of the compound of a = 0-15, the sum total content of the compound of a = 1-15 in a mixture is 40-90 mass. %, More preferably 50 to 90% by mass, still more preferably 60 to 85% by mass, and the content of the compound with a = 0 is the remaining amount in the above numerical range (amount in which the total is 100% by mass). Is preferred.

  When a polyoxyalkylene alkyl ether sulfate salt is used, a polyoxyalkylene alkyl ether sulfate salt having a branched primary alkyl group produced from an alcohol obtained by hydroformylating a linear 1-alkene as a raw material is suitable. It is. Here, hydroformylation is a method in which an alcohol is obtained by adding carbon monoxide to a linear 1-alkene using a carbonyl complex such as iron, cobalt or nickel as a catalyst. An alcohol containing groups is obtained.

  The polyoxyalkylene alkyl ether sulfate ester salt further adds alkylene oxide, preferably propylene oxide (hereinafter referred to as PO) or ethylene oxide (hereinafter referred to as EO), more preferably EO, to such an alcohol, Further, it can be obtained by sulfonation with sulfur trioxide or chlorosulfonic acid and neutralization with an alkali agent. The average added mole number is preferably 1.0 to 3.0, more preferably 1.5 to 3.0, and particularly preferably 1.5 to 2.5 from the viewpoint of the cleaning effect.

  As an alkaline agent used for neutralization, sodium hydroxide, potassium hydroxide, magnesium hydroxide, sodium carbonate, potassium carbonate, and magnesium carbonate are preferable, and sodium hydroxide, potassium hydroxide, and magnesium hydroxide are more preferable.

  The polyoxyalkylene alkyl ether sulfate salt thus obtained contains a branched alkyl group, and the mass ratio of the polyoxyalkylene branched alkyl ether sulfate salt to the total polyoxyalkylene alkyl ether sulfate ester salt Is preferably 5 to 80% by mass, more preferably 10 to 70% by mass for achieving an excellent cleaning effect.

  In particular, when the polyoxyalkylene alkyl ether sulfate salt is blended in an amount exceeding 10% by mass in the composition, particularly when blended at a concentration of 15 to 40% by mass, the alkyl group of the polyoxyalkylene alkyl ether sulfate salt is used. Preferably satisfies the condition of the branching rate. The polyoxyalkylene alkyl ether sulfate salt itself has a less sticky feel than other surfactants, but with an increase in the feel of stickiness when used in combination with an amine oxide surfactant, the viscosity increases due to higher concentration. There is a concern about the feeling of slimness from being easily left on the surface to be cleaned by gelation or gelation. This problem is reduced by selecting the compound having the branched chain.

<(B) component>
The component (b) of the present invention is an amine oxide surfactant having a hydrocarbon group having 10 to 18 carbon atoms and an alkyl group having 1 to 3 carbon atoms or a hydroxyalkyl group having 1 to 3 carbon atoms. Compounds of general formula (3) are preferred.

[Wherein, R ¹³ represents an alkyl group having 10 to 18 carbon atoms or an alkenyl group having 10 to 18 carbon atoms, R ¹⁴ represents an alkylene group having 1 to 6 carbon atoms, and A represents —COO—, —CONH— , -OCO-, -NHCO-. b is a number of 0 or 1, and R ¹⁵ and R ¹⁶ are each an alkyl group having 1 to 3 carbon atoms or a hydroxyalkyl group having 1 to 3 carbon atoms. ]

In the general formula (3), R ¹³ is preferably an alkyl group having 10 to 14 or an alkenyl group having 10 to 18 carbon atoms, and particularly preferably a lauryl group (or lauric acid residue) and / or a myristyl group (or Myristic acid residue). A is preferably —COO— or —CONH—, and most preferably —CONH—. R ¹⁴ preferably has 2 or 3 carbon atoms, and R ¹⁵ and R ¹⁶ are preferably methyl groups.

In the present invention, R ¹³ may be a single alkyl (or alkenyl) chain length or a mixed alkyl group (or alkenyl group) having a different alkyl (or alkenyl) chain length. In the latter case, those having a mixed alkyl (or alkenyl) chain length derived from a vegetable oil selected from coconut oil and palm kernel oil are preferred. Specifically, it is a cleaning that the molar ratio of lauryl group (or lauric acid residue) / myristyl group (or myristic acid residue) is 95/5 to 20/80, preferably 90/10 to 30/70. It is preferable from the point of an effect and foaming property.

<(C) component>
The liquid detergent composition of the present invention comprises a compound (c1) wherein z is 1 in the following general formula (1) [(c1) component] and a compound wherein z is 2 to 6 in the following general formula (1) ( c2) [component (c2)]. And mass ratio [c1] / ([c1] + [c2]) of (c1) component and the sum total of (c1) component and (c2) component is 0.1-0.8.
_{Ph- (CH 2) x (OC} y H 2y) z -OH (1)
[In the formula, Ph is a phenyl group which may be substituted by 1 to 3 alkyl groups having 1 to 3 carbon atoms, x is a number of 0 or 1, y is a number of 2 or 3, z is a number from 1 to 6. ]

  The compound of the general formula (1) can be obtained by subjecting phenol and / or benzyl alcohol to a usual addition reaction of ethylene oxide and / or propylene oxide (hereinafter referred to as AO together). ] / ([C1] + [c2]) In order to satisfy the ratio, it is preferable to mix the following c ′ and c ″. Specifically, a mixture of compounds obtained by addition reaction of phenol and / or benzyl alcohol with AO at a molar ratio of (phenol and / or benzyl alcohol): AO = 1: 0.5 to 1: 1.5. c ′ (the mixture contains 50 to 100% of c1) and AO in phenol and / or benzyl alcohol (phenol and / or benzyl alcohol): AO = 1: 2 to 1: 4 molar ratio It is preferable to mix the compound c ″ obtained by the addition reaction with c ″ (this mixture has a c1 content of less than 10%) so as to satisfy the above ratio.

  Note that c ″ can also be produced by further adding 1 to 3 mol of AO to c ′. In the present invention, it is preferable to use c ′ having a high purity (95 to 100%) excluding phenol remaining in a purification step such as distillation.

<Other ingredients>
The liquid detergent composition of the present invention contains 2.5 to 8% by mass of (d) one or more compounds selected from hydroxycarboxylic acid and aminopolycarboxylic acid (hereinafter referred to as component (d)). Is preferred.

  Examples of the hydroxycarboxylic acid include citric acid, malic acid, tartaric acid, gluconic acid, and the like, and salts thereof can also be used. Citric acid or a salt thereof is preferable. Citric acid salts include trisodium citrate, disodium hydrogen citrate, sodium dihydrogen citrate, tripotassium citrate, dipotassium hydrogen citrate, potassium dihydrogen citrate, triammonium citrate, dihydrogen citrate Examples thereof include ammonium, ammonium dihydrogen citrate, calcium citrate, magnesium citrate, and zinc citrate.

  Examples of aminopolycarboxylic acids include ethylenediaminetetraacetic acid (EDTA) and aminopolycarboxylic acids in which one or more carboxymethyl groups are bonded to the nitrogen atom of the amino acid compound [for example, MGDA (methylglycine diacetic acid)]. These salts can also be used.

  The liquid detergent composition of the present invention preferably contains a surfactant other than the component (a) and the component (b) [hereinafter referred to as the component (e)] for the purpose of enhancing the detergency. ) A compound selected from amphoteric surfactants and nonionic surfactants other than the components is preferred.

  As the amphoteric surfactant, a compound of the following general formula (4) [hereinafter referred to as component (e-1)] is preferred.

[Wherein, R ²¹ represents an alkyl group or an alkenyl group having 9 to 23 carbon atoms, and R ²² represents an alkylene group having 1 to 6 carbon atoms. B is a group selected from —COO—, —CONH—, —OCO—, —NHCO—, and —O—, and c is a number of 0 or 1. R ²³ and R ²⁴ are each an alkyl group having 1 to 3 carbon atoms or a hydroxyalkyl group, and R ²⁵ is an alkylene group having 1 to 5 carbon atoms which may be substituted with a hydroxy group. D is a group selected from —SO ₃ ⁻ , —OSO ₃ ⁻ and —COO ⁻ . ]

In the general formula (4), R ²¹ is preferably an alkyl group having 9 to 15 carbon atoms, particularly 9 to 13 carbon atoms, and R ²² is preferably an alkylene group having 2 or 3 carbon atoms. B is preferably -CONH-, and c is preferably 0 or 1. R ²³ and R ²⁴ are preferably a methyl group or a hydroxyethyl group. D is preferably —SO ₃ ⁻ or —COO ⁻ , and when D is —SO ₃ ^— , R ²⁵ is preferably —CH ₂ CH (OH) CH ₂ —, and when D is —COO ⁻ , R is ²⁵ is preferably a methylene group.

  As the nonionic surfactant [hereinafter referred to as component (e-2)], a compound selected from the compound represented by the following general formula (5) and the compound represented by the general formula (6) is preferable.

R ³¹ -E - [(R ³² O) _d -H] _e (5)
[Wherein R ³¹ represents an alkyl group or alkenyl group having 7 to ¹⁸ carbon atoms, and R ³² represents an alkylene group having 2 or 3 carbon atoms. d shows the number of 2-100. E is —O—, —CON—, or —N—. When E is —O—, e is 1, and when E is —CON— or —N—, e is 2. ]
R ⁴¹ —O (R ⁴² O) _f G _h (6)
[Wherein R ⁴¹ is a linear alkyl group having 8 to 16, preferably 10 to 16, particularly preferably 10 to 14 carbon atoms, and R ⁴² is an alkylene group having 2 to 4 carbon atoms, preferably ethylene group or propylene. A group, in particular an ethylene group, G is a residue derived from a reducing sugar, f is an average value of 0-6, preferably 0-3, particularly preferably 0, and h is an average value of 1-10, preferably Represents a number from 1 to 5, particularly preferably from 1 to 2. ]

Specific examples of the compound of the general formula (5) include the following compounds.
^{_{R 31 -O- (C 2 H 4}} O) i -H (5-1)
[Wherein R ³¹ represents the above-mentioned meaning. i is a number from 2 to 100. ]
R ³¹ —O— (C ₂ H ₄ O) _j (C ₃ H ₆ O) _k —H (5-2)
[Wherein R ³¹ represents the above-mentioned meaning. j and k are each independently a number of 2 to 70, and ethylene oxide and propylene oxide may be random or block adducts. ]

[Wherein R ³¹ represents the above-mentioned meaning. The sum of n and m is a number from 3 to 70. ]

  In general formula (5-3), G is a residue derived from a reducing sugar, and the reducing sugar as a raw material may be either aldose or ketose, and a triose having 3 to 6 carbon atoms, Mention may be made of tetrose, pentose and hexose. Specific examples of aldose include apiose, arabinose, galactose, glucose, lyxose, mannose, galose, aldose, idose, talose and xylose, and examples of ketose include fructose. In the present invention, among these, aldopentose or aldohexose having 5 or 6 carbon atoms is particularly preferred, and glucose is most preferred.

The compound of the general formula (6) can be easily synthesized by subjecting the reducing sugar and R ⁴¹ — (OR ⁴² ) _f —OH to an acetalization reaction or a ketalization reaction using an acid catalyst. In the case of an acetalization reaction, a hemiacetal structure or a normal acetal structure may be used.

  Among the above, at least one selected from the compound of the general formula (4) and the compound of the general formula (6) is particularly preferable because it can improve foaming and enhance the cleaning effect.

  The liquid detergent of the present invention preferably contains a hydrotrope agent (hereinafter referred to as component (f)) for the purpose of improving storage stability. As the hydrotrope, toluenesulfonic acid, xylenesulfonic acid, cumenesulfonic acid and sodium salts and potassium salts thereof are preferable, and p-toluenesulfonic acid is particularly preferable. Magnesium salts can also be used.

  In the present invention, for the purpose of improving storage stability and as a viscosity modifier, a solvent other than the component (c) [hereinafter referred to as component (g)] can be contained. Specific examples of the solvent are preferably water-soluble organic solvents selected from ethanol, isopropyl alcohol, ethylene glycol, propylene glycol, diethylene glycol, dipropylene glycol, glycerin, isoprene glycol, propylene glycol monomethyl ether, and propylene glycol monoethyl ether.

  The cleaning agent of the present invention includes a polymer for preventing gelation, for example, a gelation-preventing polymer described in JP-A-11-513067 (hereinafter referred to as component (h)), particularly polyalkylene glycol. It is preferable from the viewpoint of viscosity control and storage stability. Specific examples of the polyalkylene glycol for preventing gelation include polypropylene glycol and polyethylene glycol having a weight average molecular weight of 200 to 3000 determined by gel permeation chromatography using polyethylene glycol as a standard. it can.

Moreover, it is preferable that the liquid cleaning composition of this invention contains 0.1-10 mass% of compounds (henceforth (i) component) of the following general formula (7).
R ¹¹ —O—X (7)
[Wherein R ¹¹ is a group selected from 2-ethylhexyl, isononyl, and isodecyl, and X is CH ₂ CH (OH) CH ₂ OH. ]

R ¹¹ in the general formula (1) is preferably 2-ethylhexyl from the viewpoint of detergency.

The compound of the general formula (7) as the component (i) is, for example, when R ¹¹ is 2-ethylhexyl, an epoxy compound such as 2-ethylhexanol and epihalohydrin or glycidol, an acid catalyst such as BF ₃ , or an aluminum catalyst. In general, a method of producing a mixture by reaction is used, and is a mixture containing a plurality of products as described in JP-A No. 2001-49291.

  Specifically, a compound in which 2-ethylhexanol is added to the 1-position of an epoxy compound as 2-ethylhexyl monoglyceryl ether (3- (2-ethylhexyloxy) -1,2-propanediol, hereinafter referred to as (i1)) And a compound (2- (2-ethylhexyloxy) -1,3-propanediol, hereinafter referred to as (i2)) added to the 2-position of the epoxy compound. Moreover, as a by-product, the polyaddition compound (henceforth (i3)) which further added the epoxy compound to (i1) or (i2) can be mentioned.

  In the present invention, it is suitable to use 2-ethylhexyl monoglyceryl ether in which the content of the component (i3) is 30% by mass or less, preferably 10% by mass or less, particularly preferably 1% by mass or less in the component (i). .

<Liquid cleaning composition>
(A) The content rate of a component is 5-50 mass% from a viewpoint of storage stability, Preferably it is 10-45 mass%, More preferably, it is 10-40 mass%.

  (B) From a storage-stable viewpoint, the content rate of a component is 0.1-15 mass%, Preferably it is 1-10 mass%, More preferably, it is 2-10 mass%.

  The content ratio of component (c) [total content ratio of component (c1) and component (c2)] is preferably 0.5 to 7% by mass, more preferably 1 in the composition from the viewpoint of storage stability. -6% by mass, particularly preferably 1-5% by mass. In the present invention, the mass ratio [c1] / ([c1] + [c2]) of the component (c1) and the sum of the components (c1) and (c2) is 0.1 to 0.8, preferably Is 0.3 to 0.7, more preferably 0.3 to 0.6.

  In the case where the component (d) is contained, the content is preferably 2.5 to 8% by mass, more preferably 2.5 to 7% by mass, in the composition, from the viewpoint of detergency of scale dirt and an economic viewpoint. Most preferably, it is 3-6 mass%.

  Water is the adjustment amount made into 100 mass% in total including the (a)-(c) component and the other component contained as needed.

  In the present invention, the component (e) is preferably contained for the purpose of enhancing the cleaning effect and improving the storage stability. In particular, the compound of the general formula (4) and the compound of the general formula (6) improve foamability. can do. However, a large amount of blending tends to promote luster when washing dishes, and tends to reduce the effect of component (a). Therefore, the ratio of the component (e) in the cleaning agent is preferably 0.1 to 20% by mass, more preferably 0.5 to 15% by mass, and particularly preferably 1.0 to 15% by mass.

  The component (f) of the present invention is preferably contained from the viewpoint of storage stability, and is preferably 0.1 to 10% by mass, more preferably 1 to 10% by mass, and particularly preferably 2 to 6% by mass in the cleaning agent.

  The component (g) and the component (h) of the present invention are preferable from the viewpoint of improving the storage stability, and are effective as a viscosity modifier. The component (g) is contained in the cleaning agent in an amount of 1 to 20% by mass, and further 5 -20% by mass, especially 5-15% by mass, (h) 0.05 to 10% by mass, more preferably 0.05 to 5% by mass, especially 0.1 to 3% by mass in the cleaning agent are preferred. .

  It is preferable to contain (i) component of this invention from the point of the washing | cleaning performance with respect to oil stains, and content in a composition is 0.1-10 mass%, Preferably it is 0.2-6 mass%, More preferably Is 0.5-5 mass%.

  The liquid detergent composition of the present invention is in a liquid form in which the above components are dissolved or dispersed in water, and the water content is preferably 20 to 60% by mass, more preferably 30 to 30% from the viewpoint of storage stability. 60 mass%, More preferably, it is 40-60 mass%, Most preferably, it is 45-55 mass%.

  The pH (25 ° C.) of the liquid cleaning composition of the present invention is 3 or more and less than 7 from the viewpoint of improving the cleaning performance against both oil stains (dishwashing) and scale stains (kitchen sink washing). , Preferably 4 or more and less than 7, more preferably 4 or more and less than 6.

  Examples of pH adjusters include inorganic acids such as hydrochloric acid and sulfuric acid, acid agents such as citric acid, succinic acid, malic acid, fumaric acid, tartaric acid, malonic acid, and maleic acid, sodium hydroxide and potassium hydroxide, It is preferable to use alkali agents such as sodium carbonate and potassium carbonate alone or in combination, such as ammonia and derivatives thereof, amine salts such as monoethanolamine, diethanolamine, and triethanolamine, and particularly selected from hydrochloric acid, sulfuric acid, and citric acid. It is preferable to use an acid selected from the group consisting of an acid selected from sodium hydroxide and potassium hydroxide. Any compound is blended within a range that does not have a great influence on the viscosity characteristics.

  In addition, about Mg generally used as a detergency enhancer, when used in combination with citric acid, the detergency against scale stains may be reduced, so care must be taken in the blending amount. The amount of Mg is preferably 5 to 0.0001% by mass, more preferably 1 to 0.0001% by mass, further preferably 0.4 to 0.0001% by mass, and particularly preferably 0.1 to 0.0001% by mass. preferable. The Mg-containing compound used in the blending is preferably a compound that is easily dissolved in water, and specific examples include magnesium chloride, magnesium nitrate, magnesium carbonate, and magnesium sulfate. Further, although it takes time to dissolve, magnesium hydroxide and magnesium phosphate can also be used.

  The liquid detergent composition of the present invention has a viscosity at 20 ° C. of preferably 10 to 1000 mPa · s, more preferably 30 to 700 mPa · s, and particularly preferably 30 to 500 mPa · s from the viewpoint of ease of use. Such viscosity is adjusted using, for example, the above-mentioned component (f), component (g), component (h), and the like.

  The viscosity as used in the present invention is measured as follows. First, TOKIMEC. The rotor type no. Prepare one equipped with 2 rotors. The sample is filled in a tall beaker and adjusted to 20 ° C. in a constant temperature bath at 20 ° C. A sample adjusted to a constant temperature is set in a viscometer. The rotational speed of the rotor is set to 60 r / m, and the viscosity 60 seconds after the start of rotation is taken as the viscosity of the present invention.

  As other components, as long as the viscosity characteristics are not affected, components that are usually blended in liquid detergents can be blended. For example, a fragrance | flavor component, disinfection component, antiseptic | preservative, a clouding agent, and a coloring agent can be mentioned.

  The liquid cleaning composition of the present invention is applied to a method in which a cleaning material is soaked in a flexible material such as sponge (preferably containing water) and directly brought into contact with tableware, cooking utensils, kitchen sinks, bathtubs, etc. it can.

  Since the liquid cleaning composition of the present invention has excellent cleaning performance against oil stains and scale stains, it can be applied as a cleaning agent for cleaning objects including oil stains and scale stains. Specifically, it is suitable as a dishwashing detergent and a kitchen detergent, and can also be applied as a water detergent such as a washstand detergent, a bathroom cleaner, and a toilet cleaner.

  A liquid detergent composition was prepared using the components shown in Table 1. The low temperature stability (storage stability at low temperature) of these compositions was evaluated by the following method. The results are also shown in Table 1. The pH of the composition is measured by the following method.

<Measurement method of pH>
A pH measuring composite electrode (HORIBA glass sliding sleeve type) was connected to a pH meter (HORIBA pH / ion meter F-23), and the power was turned on. A saturated potassium chloride aqueous solution (3.33 mol / L) was used as the pH electrode internal solution.

  Next, pH 4.01 standard solution (phthalate standard solution), pH 6.86 (neutral phosphate standard solution), and pH 9.18 standard solution (borate standard solution) were each filled in a 100 ml beaker. It was immersed in a constant temperature bath at 30 ° C. for 30 minutes. The pH measurement electrode was immersed in a standard solution adjusted to a constant temperature for 3 minutes, and calibration was performed in the order of pH 6.86 → pH 9.18 → pH 4.01.

  The sample was filled in a 100 ml beaker and adjusted to 25 ° C. in a constant temperature bath at 25 ° C. The pH measurement electrode was immersed in a sample adjusted to a constant temperature for 3 minutes, and the pH was measured.

<Low temperature stability>
250 ml of the liquid detergent composition shown in Table 1 was put into a PET bottle dedicated to dishwashing detergent, stored at -5 ° C for 20 days, and the change in the appearance of the liquid was evaluated according to the following criteria in comparison with immediately after preparation. .
No change in appearance ... ○
Appearance changes such as gelation, separation, and precipitation formation.

The components in the table are as follows.
ES: Sodium polyoxyethylene alkyl ether sulfate [The raw material alcohol is an alcohol obtained by hydroformylating 1-decene and 1-dodecene 50/50 (weight ratio) as raw materials. After adding 2 mol of EO to this alcohol on average, it was sulfated with sulfur trioxide and neutralized with sodium hydroxide (neutralized until the pH of 11 diluted with water was 11). The ratio of the total polyoxyethylene branched alkyl ether sulfate in the total sodium polyoxyethylene alkyl ether sulfate was 42% by weight. ]
APAO: Amidopropyl laurate-N, N-dimethylamine oxide AO: N-lauryl-N, N-dimethylamine oxide Phenoxyethanol: manufactured by Nippon Emulsifier Co., Ltd. PhG-30: polyoxyethylene monophenyl ether (Nippon Emulsifier Co., Ltd.)
Sulfobetaine: lauryl dimethyl sulfobetaine Potassium alkenyl succinate: carbon number of alkenyl group 12
Nonionic: alkyl glucoside having an alkyl group composition of C ₁₂ / C ₁₄ = 60/40 (mass ratio) and an average degree of glucoside condensation of 1.5 GE-2EH: 2-ethylhexyl monoglyceryl ether (monoglyceryl ether) 98% by mass)
-Polypropylene glycol: having an average molecular weight of 1000-Preservative: Proxel BDN (manufactured by Avicia Co., Ltd.)
In Table 1 and Example 4, even if phenoxyethanol is replaced with benzyloxyethanol in the same amount, the same effect of the present invention can be obtained.

Claims (3)

(A) 5 to 50% by mass of an anionic surfactant having a hydrocarbon group having 10 to 16 carbon atoms and one or more sulfonate groups or sulfate ester bases in the molecule, and (b) 10 to 16 carbon atoms. 0.1 to 15% by mass of an amine oxide surfactant having a hydrocarbon group of 1 to 3 and an alkyl group having 1 to 3 carbon atoms or a hydroxyalkyl group having 1 to 3 carbon atoms in the following general formula (1) one or more compounds selected from the compound (c1) wherein z is 1, the compound (c2) wherein z is 2 to 6 in the following general formula (1), and (d) hydroxycarboxylic acid and aminopolycarboxylic acid 3 to 8% by mass, and the mass ratio [c1] / ([c1] + [c2]) of the compound (c1) and the total of the compound (c1) and the compound (c2) is 0.3 to 0.8. A liquid detergent composition having a pH of 3 or more and less than 7 at 25 ° C.
_{Ph- (CH 2) x (OC} y H 2y) z -OH (1)
[In the formula, Ph is a phenyl group which may be substituted by 1 to 3 alkyl groups having 1 to 3 carbon atoms, x is a number of 0 or 1, y is a number of 2 or 3, z is 1 or a number from 2 to 6. ] Furthermore (i) the following general formula (7) compound containing 0.1 to 10 mass% claim 1 liquid detergent composition.
R ¹¹ —O—X (7)
[Wherein R ¹¹ is a group selected from 2-ethylhexyl, isononyl, and isodecyl, and X is CH ₂ CH (OH) CH ₂ OH. ] The liquid detergent composition according to claim 1 or 2, wherein the pH at 25 ° C is 4 or more and less than 6.