JP2004323835A - Liquid detergent composition - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a liquid detergent composition for a rigid surface which has excellent detergency against soap scum or denaturated oil stains on a rigid surface, and is homogeneous and excellent in stability. <P>SOLUTION: The liquid detergent composition is characterized in that it comprises (a) a polyoxyalkylene alkyl ether oxide having one alkyl group selected from a 2-ethylhexyl group, an isononyl group and an isodecyl group, and having 2-6 average addition molar number of 2 or 3C alkylene oxide, (b) a nonionic surfactant having a 11-16C alkyl group or alkenyl group, (c) a hydrophobic organic solvent that is liquid at 20°C, and (d) water, and in that (c)/(d) and (c)+(d) are in a specified range. <P>COPYRIGHT: (C)2005,JPO&NCIPI

Description

  The present invention relates to liquid detergent compositions. In particular, the present invention relates to a liquid detergent composition for hard surfaces which has excellent detergency for soap residue stains or denatured oil stains on hard surfaces, and is homogeneous and excellent in stability.

  Hydrophobic solvents such as terpene-based hydrocarbons and paraffins are widely used in liquid cleaning agents because of their excellent cleaning effects on denatured fats, oils, greases and oils. For example, Patent Literature 1 discloses a water-dispersible cleaning agent for removing oily dirt containing a terpene compound and a surfactant. Patent Literature 2, Patent Literature 3, Patent Literature 4, Patent Literature 5, Patent Literature 6, Patent Literature 7, and Patent Literature 8 disclose a cleaning agent containing a terpene compound. Describes that a glycol ether solvent is used in combination. Patent Literature 9, Patent Literature 10, Patent Literature 11, and Patent Literature 12 disclose a cleaning agent containing a terpene compound and a glycol solvent. Patent Literature 13, Patent Literature 14, and Patent Literature 15 disclose cleaning agents containing a terpene-based hydrocarbon and a nonionic surfactant. Patent Document 16 discloses a detergent containing a mixture of oil and a nonionic surfactant.

JP 2001-19999 A JP 2001-98296 A JP-A-2000-96086 JP 2000-303095 A JP-A-10-1698 JP-A-6-336598 JP-A-5-279699 Japanese Patent Publication No. 9-509438 JP 2001-247449 A JP 2001-342500 A JP-A-7-310099 JP-A-5-320694 JP 2001-247899 A JP-A-9-59695 JP-A-9-310100 JP-T-2003-522285

  The hydrophobic solvent has a low affinity for water, and is generally used in combination with a surfactant when used as an aqueous liquid composition. Among surfactants, nonionic surfactants are the most excellent from the viewpoint of emulsifying power for a hydrophobic solvent, particularly for stability issues such as separation and cloudiness. However, in a system using only a surfactant such as a general nonionic surfactant, the hydrophobic solvent is firmly incorporated into a structure such as a micelle of the surfactant. There is a problem that the high cleaning power is impaired and the expected effect cannot be obtained. In addition, nonionic surfactants are also effective surfactants as detergents, but when used in combination with a hydrophobic solvent, the surfactant activity, which is the essence of the surfactant, is necessarily consumed in the hydrophobic solvent. Therefore, a desired cleaning effect cannot be obtained.

  That is, there is a need for a liquid detergent having excellent detergency, which does not impair the original effect of the hydrophobic solvent and brings out the cleaning effect of both the nonionic surfactant and the hydrophobic solvent.

  An object of the present invention is to provide a liquid detergent composition containing a nonionic surfactant and a specific hydrophobic solvent, without any problem in stability, without impairing the original effect of the hydrophobic solvent, and in nonionic surfactant. It is an object of the present invention to provide a liquid detergent composition having excellent detergency, which brings out the cleaning effect of both the agent and the hydrophobic solvent.

  The present invention relates to (a) a polyoxy group having one kind of an alkyl group selected from a 2-ethylhexyl group, an isononyl group and an isodecyl group and having an average addition mole number of an alkylene oxide having 2 or 3 carbon atoms of 2 to 6; Alkylene alkyl ether [hereinafter referred to as component (a)], (b) a nonionic surfactant having an alkyl group or alkenyl group having 11 to 16 carbon atoms [hereinafter referred to as component (b)], (c) 20 ° C. Containing a liquid hydrophobic organic solvent [hereinafter, referred to as component (c)] and (d) water [hereinafter, referred to as component (d)], and (c) / (d) = 0.5 / 99.5. To 40/60 (mass ratio), (c) + (d) = 50 to 99% by mass.

  According to the present invention, a liquid detergent composition for hard surfaces having excellent detergency, especially for soap scum or denatured oil stains on hard surfaces, and having excellent stability can be obtained.

<(A) component>
The component (a) of the present invention has one kind of an alkyl group (hereinafter referred to as (a1)) selected from a 2-ethylhexyl group, an isononyl group and an isodecyl group, and a compound having a 2-ethylhexyl group is particularly preferable. .

  The component (a) of the present invention is a compound obtained by adding an alkylene oxide to the component (a1). The alkylene oxide having 2 or 3 carbon atoms is ethylene oxide (hereinafter, referred to as EO) or propylene oxide (hereinafter, referred to as PO). However, since PO is more hydrophobic, the average number of moles of PO added is 0 to 0. 2 is preferable, and a structure that always includes EO is preferable. In the present invention, those mainly containing EO are preferred, and it is most preferred that all the alkylene oxide groups are EO. The average number of moles of alkylene oxide added is 2 to 6 moles, preferably 2 to 5 moles, and more preferably 3 to 5 moles.

  The component (a) having a 2-ethylhexyl group can be obtained by subjecting n-butyraldehyde to aldol condensation and then adding an alkylene oxide to 2-ethyl-1-hexanol obtained by hydrogenation.

  The component (a) having an isononyl group can be obtained by hydroformylating diisobutylene by an oxo method, and then adding an alkylene oxide to isononyl alcohol obtained by hydrogenation. Further, the isononyl alcohol is mainly composed of 3,5,5-trimethyl-1-hexanol.

  The component (a) having an isodecyl group can be obtained by hydroformylating nonene by an oxo method and then adding an alkylene oxide to isodecanol obtained by hydrogenation. The isodecanol is a mixture of many isomers having a methyl branch at each position, and a typical structure is 8-methyl-1-nonanol.

  As the component (a) of the present invention, polyethylene glycol-2-ethylhexyl ether (average number of moles of EO added = 2 to 6) is preferable.

  The component (a) enables uniform dispersion without changing the properties of the hydrophobic solvent of the component (c) in the aqueous solution.

<(B) component>
As the component (b) of the present invention, a compound represented by the following general formula (1) (hereinafter referred to as the component (b1)) can be exemplified.

^{R 1a -A - [(R 1b} O) a -R 1c] b (1)
[In the formula, R ^1a is a carbon atom bonded to A is a primary carbon atom or a secondary carbon atom, and the carbon chain bonded to the carbon atom has 11 to 16 carbon atoms having no branched chain, preferably It is an alkyl group of 11 to 14, and R ^1b is an alkylene group having 2 or 3 carbon atoms, and is preferably an ethylene group. R ^1c is an alkyl group having 1 to 3 carbon atoms or a hydrogen atom. a represents a number of 3 to 20, preferably 3 to 15, more preferably 5 to 15, and particularly preferably 5 to 10. A is -O-, -COO-,

And when A is —O— or —COO—, b is 1, and A is

In the case of b, b is 1 or 2. ]

  Specific examples of the compound of the general formula (1) include the compounds of the following general formulas (1-1) to (1-4).

^{_{R 1a -O- (C 2 H 4}} O) c -H (1-1)
[Wherein, R ^1a has the above-mentioned meaning. c is a number from 3 to 20, preferably from 3 to 15. ]
^{_{R 1a -O- (C 2 H 4}} O) d - (C 3 H 6 O) e -H (1-2)
[Wherein, R ^1a has the above-mentioned meaning. d and e each independently represent a number of 0.1 to 20, preferably 3 to 15, and (C ₂ H ₄ O) and (C ₃ H ₆ O) may be random or block adducts. ]

[Wherein, R ^1a has the above-mentioned meaning. f and g are each independently a number from 0 to 20, and f + g is a number from 0 to 20, preferably 0 to 10. R ^1d and R ^1e are each independently a hydrogen atom or an alkyl group having 1 to 3 carbon atoms. ]

  As the component (b1) of the present invention, a compound represented by the general formula (1-1) is preferable. Polyoxyethylene alkyl ethers having up to 16 linear alkyl groups and having EO added on average of 3 to 20 mol, preferably 3 to 15 mol, particularly preferably 5 to 10 mol are most preferred.

In the general formula (1-1), specific examples of the linear alkyl group R ^1a having 11 to 16 carbon atoms having a primary carbon atom bonded to an oxygen atom include natural oils and fats such as coconut oil and palm oil. An alkyl group obtained from the obtained straight-chain alcohol as a raw material, and an alkyl group obtained from a petroleum raw material system by using an alcohol containing a small amount of branch obtained by an oxo method [hydroformylation of 1-olefin having 10 to 14 carbon atoms] After that, it is obtained by hydrogenation. The alcohol obtained by the oxo method is obtained as a mixture of a straight-chain alcohol and a branched primary alcohol having a methyl group branched at the β-position with respect to the alcohol hydroxy group. In the case where an oxo alcohol is selected as the raw material of the linear alkyl group in (b1) of the present invention, the content of the branched primary alcohol is preferably 30% by mass or less, more preferably 20% by mass or less. ].

Examples of the compound of the general formula (1-1) having a linear alkyl group R ^1a having a primary carbon atom bonded to an oxygen atom include Calcol 20 (trademark), Calcol 40 (trademark) and Calcol 40 (trade name) manufactured by Kao Corporation. 60 (trademark) and the like, and when using an oxo alcohol, dovanol 23 (trademark), dovanol 25 (trademark), dovanol 45 (trademark) and the like manufactured by Mitsubishi Chemical Corporation can be used. .

Examples of the compound of the general formula (1-1) having a linear alkyl group R ^1a having a secondary carbon atom bonded to an oxygen atom include Sophtanol 33 (trademark), Sophtanol 50 (trademark), and Sophtanol 70 (trade names) manufactured by Nippon Shokubai Co., Ltd. (Trademark) and sophthanol 120 (trademark) can be used.

  As the other specific compound as the component (b) of the present invention, a compound represented by the following general formula (2) (hereinafter, referred to as a component (b2)) can be mentioned.

_{^{R 2a - (OR 2b) h}} G i (2)
[Wherein, R ^2a is a linear alkyl group having 8 to 16, preferably 9 to 14 carbon atoms, and R ^2b is an alkylene group having 2 to 4 carbon atoms, preferably an ethylene group or a propylene group, particularly an ethylene group. , G is a residue derived from a reducing sugar, h is a number having an average value of 0 to 6, preferably 0 to 3, particularly preferably 0, and i is an average value of 1 to 3, preferably 1 to 2. Indicates a number. ]

In the general formula (2), the carbon atom of R ^2a bonded to the oxygen atom is preferably primary.

  G is a residue derived from a reducing sugar, and the reducing sugar as a raw material may be any of aldose and ketose, and includes triose, tetroses, pentose, and hexose having 3 to 6 carbon atoms. Can be. Specific examples of aldose include apiose, arabinose, galactose, glucose, lyxose, mannose, growth, aldose, idose, talose, and xylose, and examples of ketose include fructose. In the present invention, among these, aldopentoses or aldohexoses having 5 or 6 carbon atoms are preferred, and glucose is most preferred.

The compound of the general formula (2) can be easily synthesized by performing an acetalization reaction or a ketalization reaction of the reducing sugar with R ^2a- (OR ^2b ) _h -OH using an acid catalyst. Further, in the case of an acetalization reaction, it may have a hemiacetal structure or a normal acetal structure.

As the component (b) in the present invention, the components (b1) and (b2) are preferable from the viewpoint of detergency. Particularly, in the compound represented by the general formula (1-1), the carbon atom of R ^1a bonded to A is preferred. Is a polyoxyethylene alkyl ether having a linear alkyl group having a secondary carbon atom or an alkylpolyglucoside having an average degree of sugar condensation of 1.2 to 1.4 among the compounds represented by the general formula (2), Most preferred in terms of effect and stability.

  The component (b) can form a stable state without impairing the property of the component (c) as a hydrophobic solvent and even when the blending concentration of the component (a) is low. In addition, when used in combination with the component (a), the detergency of the component (c) itself, which has been hindered by the micelle formation of the component (c), can be recovered, and excellent detergency can be obtained. become.

<(C) component>
The hydrophobic organic solvent which is liquid at 20 ° C. used in the present invention has a solubility parameter (hereinafter referred to as “sp value”) determined from the following well-known formula of 10.0 to 21.0, preferably 14.0 to 21.0. It is an organic solvent having an solubility of 21.0, more preferably 14.0 to 19.0, and a solubility in water at 20 ° C of 0.5% by mass or less. Within this range, excellent detergency can be obtained. In calculating the sp value, numerical values described in Hoy, KL, Hoy Tables of Solubility Parameters, Union Carbide Corporation, Solvents and Coatings Materials Division, South Charlston, WV (1985) can be used.

δ = (ΔH / V) ^1/2
δ; solubility parameter (sp value) [(J / cm ³ ) ^1/2 ]
ΔH: Molar heat of evaporation
V; molar volume

  The hydrophobic organic solvent may have an ether group, an amide group, an ester group, or the like as long as the sp value is within the above range. Examples of the component (c) include hydrocarbons having 6 to 30 carbon atoms, monohydric aliphatic alcohols and esters thereof, other fatty acid esters, and aliphatic ketones. In the present invention, hydrocarbons having 8 to 20 carbon atoms, more preferably 8 to 16 carbon atoms, are particularly preferred.

  Specific examples of the hydrocarbon include olefin hydrocarbons, paraffin hydrocarbons, aromatic hydrocarbons, and terpene hydrocarbons.

  As the olefin hydrocarbon, a linear olefin compound such as hexene, octene, decene, dodecene, and tetradecene, a branched chain olefin compound such as diisobutylene and triisobutylene, and a cyclic olefin compound such as cyclohexene and dicyclopentene can be used. .

  Examples of the paraffin hydrocarbon include linear paraffin compounds such as hexane, heptane, octane, nonane, decane, undecane, dodecane, tridecane, tetradecane, pentadecane, hexadecane, heptadecane, octadecane, isohexane, isoheptane, isooctane, isohexane, isododecane, and isotridecane. And branched paraffin compounds such as isotetradecane, isopentadecane, isohexadecane, isoheptadecane and isooctadecane, and cyclic paraffin compounds such as cyclohexane.

  Specifically, normal paraffin SL (trademark), normal paraffin L (trademark), normal paraffin M (trademark), normal paraffin MA (trademark), normal paraffin H (trademark) manufactured by Nippon Petrochemical Co., Ltd. Normal paraffin such as N-10 (trademark), N-11 (trademark), N-12 (trademark), N-13 (trademark), N-14 (trademark) manufactured by Nippon Petrochemical Co., Ltd. ISOSOL 300 (trademark) and ISOSOL 400 (trademark) manufactured by Nippon Petrochemical Co., Ltd., IP Solvent 1620 (trademark), IP Solvent 2028 (trademark), IP Solvent 2835 (trademark) manufactured by Idemitsu Petrochemical Co., Ltd. And isoparaffins such as Shellsol 70 (trademark), Shellsol 71 (trademark), and Shellsol 72 (trademark) manufactured by Shell Japan. That.

  Examples of the aromatic hydrocarbon include toluene, xylene, and cumene.

  As the terpene compound, a monoterpene compound which is a dimer of isoprene, a sesquiterpene compound which is a trimer, and a diterpene compound which is a tetramer can be used. As specific terpene compounds, α-pinene, β-pinene, camphene, limonene, dipentene, terpinolene, myrcene, β-caryophyllene, and cedrene are preferable, and limonene, dipentene and terpinolene are particularly preferable.

  In the present invention, one or more selected from linear paraffin compounds, branched paraffin compounds, monoterpene compounds and sesquiterpene compounds are particularly preferable, and decane, undecane, dodecane, tridecane, tetradecane, pentadecane, hexadecane, isododecane, isotridecane and isotridecane are particularly preferred. One or more selected from tetradecane, isopentadecane, isohexadecane, isoheptadecane, isooctadecane, limonene, dipentene, and terpinolene are preferable from the viewpoint of the cleaning effect.

  The component (c) is close to the properties of oil, and naturally has better detergency against oil stains than water. Specifically, when the oil stain is washed only with the component (c), the modified oil stain can be dissolved, and the stain can be easily removed from the target surface. However, a cleaning agent comprising only the component (c) has a problem that the component (c) itself remains on the cleaning surface, and is disadvantageous in safety such as ignition and the like and economical efficiency. Therefore, as described above, a system in which the component (c) is dispersed using a surfactant is conceivable. However, simply dispersing the component (C) with a surfactant changes the properties of the component (c) and causes the original component to disperse. Detergency cannot be demonstrated. The present invention is significant in that an aqueous detergent composition has been completed without inhibiting the properties of the hydrophobic solvent as the component (c).

<(D) component>
The component (d) of the present invention is water, and may be ion-exchanged water or distilled water from which trace amounts of metal components present in water have been removed, or sterilized water sterilized with hypochlorite or chlorine.

<Other ingredients>
In the present invention, a glycol-based solvent other than the component (a) (hereinafter referred to as (e)) is used for the purpose of improving the cleaning effect and for preventing the hydrophobic solvent (component (c)) from separating or clouding at low or high temperatures. )) Is preferably used in combination. Specifically, a compound represented by the following general formula (3) is preferable.

R ^3a- (OR ^3b ) _a -OH (3)
Wherein R ^3a is an alkyl or alkenyl group having 1 to 6, preferably 2 to 5 carbon atoms, a phenyl group or a benzyl group, and a is a number of 1 to 5, preferably 1 to 4, R ^3b is an alkylene group having 2 or 3 carbon atoms. ]

Specific preferred compounds include the following.
Ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, ethylene glycol monopropyl ether, ethylene glycol monobutyl ether, ethylene glycol monophenyl ether, ethylene glycol monobenzyl ether, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, diethylene glycol monopropyl ether, diethylene glycol mono Butyl ether, diethylene glycol monohexyl ether, diethylene glycol monophenyl ether, diethylene glycol monobenzyl ether, propylene glycol monomethyl ether, propylene glycol monoethyl ether, propylene glycol monopropyl ether, propylene glycol Butyl ether, propylene glycol monohexyl ether, dipropylene glycol monomethyl ether, dipropylene glycol monoethyl ether, dipropylene glycol monopropyl ether, dipropylene glycol monobutyl ether, polyoxypropylene (average addition mole number 1 to 5) monomethyl ether, poly Oxypropylene (average addition moles 1 to 5) monoethyl ether, polyoxyethylene (average addition moles 1 to 5) monophenyl ether, polyoxyethylene (average addition moles 1 to 5) monobenzyl ether

  In the present invention, diethylene glycol monobutyl ether is particularly preferred as the component (e).

  In the present invention, it is preferable to contain a surfactant other than the components (a) and (b) (hereinafter referred to as the component (f)) to the extent that the effects of the present invention are not impaired for the purpose of improving the detergency. Examples of the component (f) include an anionic surfactant, a cationic surfactant, and an amphoteric surfactant.

  Examples of the anionic surfactant include an alkylbenzene sulfonate having an alkyl group or an alkenyl group having 10 to 18 carbon atoms, a polyoxyalkylene alkyl ether sulfate, an alkyl sulfate, an α-olefin sulfonate, and an α-sulfo salt. It is a fatty acid salt or α-sulfo fatty acid lower alkyl ester salt.

As the alkyl benzene sulfonate, any of those generally distributed in the detergent surfactant market as long as the alkyl chain has an average carbon number of 8 to 16 can be used. For example, Kao Corporation Neopersex F25 manufactured by Shell, Dobs 102 manufactured by Shell, or the like can be used. In addition, industrially, it can also be obtained by sulfonating alkylbenzene, which is widely distributed as a detergent raw material, using an oxidizing agent such as chlorosulfonic acid or sulfur dioxide. The average carbon number of the alkyl group is preferably from 10 to 14. As the polyoxyalkylene alkyl ether sulfate, an average of 0.5 to 5 moles of EO per molecule is added to a linear or branched primary alcohol or linear secondary alcohol having an average of 10 to 18 carbon atoms. This can be obtained by, for example, sulfating using the method described in JP-A-9-137188. The average carbon number of the alkyl group is preferably from 10 to 16. The alkyl sulfate salt is obtained by sulfonating a linear or branched primary alcohol or linear secondary alcohol having 10 to 16 carbon atoms, preferably 10 to 14 carbon atoms, with SO ₃ or chlorosulfonic acid and neutralizing the same. it can. As the α-olefin sulfonate, a compound in which an α-alkene having 8 to 18 carbon atoms is sulfonated with SO ₃ and can be produced through hydration / neutralization and a hydroxy group is present in a hydrocarbon group, A mixture of compounds having an unsaturated bond. Further, as the α-sulfofatty acid lower alkyl ester salt, the alkyl group preferably has 10 to 16 carbon atoms, and methyl ester or ethyl ester is preferable from the viewpoint of the washing effect. As the salt, a sodium salt, a potassium salt, a magnesium salt, a calcium salt, an alkanolamine salt, and an ammonium salt are preferable, and a sodium salt, a potassium salt, and a magnesium salt are preferable from the viewpoint of a washing effect.

  In the present invention, it has an alkyl group having 10 to 14 carbon atoms from the viewpoint of the washing effect, and has a polyoxyethylene alkyl sulfate salt having an average EO addition mole number of 1 to 3 and an alkyl group having 11 to 15 carbon atoms. Alkyl benzene sulphonates are particularly good.

  The amphoteric surfactant preferably contains a compound selected from the following formula (4) or (5) from the viewpoint of the cleaning effect. In particular, when a hydrophobic solvent is contained, foaming is greatly reduced, so that it is preferable to contain a compound selected from the formula (4) or (5).

[Wherein, R ^4a is a linear alkyl group or alkenyl group having 8 to 16, preferably 10 to 16, particularly preferably 10 to 14 carbon atoms, and R ^4c and R ^4d are alkyl groups having 1 to 3 carbon atoms. Or a hydroxyalkyl group, preferably a methyl group, an ethyl group or a hydroxyethyl group. R ^4b is an alkylene group having 1 to 5, preferably 2 or 3 carbon atoms. A is a group selected from —COO—, —CONH—, —OCO—, —NHCO—, and —O—, and b is 0 or 1. ]

[Wherein, R ^5a is an alkyl group or alkenyl group having 9 to 23, preferably 9 to 17, and particularly preferably 9 to 15 carbon atoms, and R ^5b is an alkylene having 1 to 6, preferably 2 or 3 carbon atoms. Group. B is a group selected from —COO—, —CONH—, —OCO—, —NHCO—, and —O—, and c is a number of 0 or 1. R ^5c and R ^5d are an alkyl group or a hydroxyalkyl group having 1 to 3 carbon atoms, and R ^5e is an alkylene group having 1 to 5 carbon atoms, preferably 1 to 3 which may be substituted by a hydroxy group. . D is _{^{-COO -, -SO 3 -, -OSO}} 3 - is a group selected from. ]

  As the cationic surfactant, it is preferable to use compounds represented by the following general formulas (6) to (8) from the viewpoints of the cleaning effect and the sterilization effect.

[Wherein, R ^6a and R ^7a are an alkyl group or alkenyl group having 5 to 16, preferably 6 to 14 carbon atoms, preferably an alkyl group, and R ^6c and R ^6d are an alkyl group having 1 to 3 carbon atoms or It is a hydroxyalkyl group. E is -COO-, OCO-, -CONH-, -NHCO-, or

It is. d is a number of 0 or 1. R ^6b is an alkylene group having 1 to 6 carbon atoms or — (O—R ^6f ) _e —. Here, R ^6f is an ethylene group or a propylene group, preferably an ethylene group, and e is a number of 1 to 10, preferably 1 to 5. R ^6e is an alkylene group having 1 to 5, preferably 2 or 3 carbon atoms. R ^8a , R ^8b , R ^8c and R ^8d are two or more (preferably two) of these alkyl groups having 8 to 12 carbon atoms, and the rest are alkyl groups having 1 to 3 carbon atoms or hydroxy groups. It is an alkyl group. Further, Z ^- is an anionic group, preferably a halogen ion or an alkyl sulfate ion having 1 to 3 carbon atoms. ]

  The most preferred cationic surfactants of the present invention include the following.

  In the present invention, it is preferable to contain, as the component (f), an amphoteric surfactant of the general formula (4) and a cationic surfactant of the general formula (6) or (8).

In the present invention, for the purpose of further improving the detergency, a sequestering agent (hereinafter, referred to as component (g)) is preferably contained. As the sequestering agent used in the present invention,
(1) Phosphoric acid compounds such as phytic acid or alkali metal salts or alkanolamine salts thereof (2) ethane-1,1-diphosphonic acid, ethane-1,1,2-triphosphonic acid, ethane-1-hydroxy- Phosphonic acids such as 1,1-diphosphonic acid and derivatives thereof, ethanehydroxy-1,1,2-triphosphonic acid, ethane-1,2-dicarboxy-1,2-diphosphonic acid, methanehydroxyphosphonic acid and alkalis thereof Metal salt or alkanolamine salt (3) phosphonocarboxylic acid such as 2-phosphonobutane-1,2-dicarboxylic acid, 1-phosphonobutane-2,3,4-tricarboxylic acid, α-methylphosphonosuccinic acid, or alkali thereof Metal salt or alkanolamine salt (4) Amino acids such as aspartic acid, glutamic acid, glycine or alkali metal salts thereof Alkanolamine salts (5) nitrilotriacetic acid, iminodiacetic acid, ethylenediaminetetraacetic acid. Diethylenetriaminepentaacetic acid, glycol ether diaminetetraacetic acid, hydroxyethyliminodiacetic acid, triethylenetetraaminehexaacetic acid, diencoric acid, alkylglycine-N, N-diacetic acid, aspartic acid-N, N-diacetic acid, serine-N, Aminopolyacetic acid such as N-diacetate, glutamic acid diacetate, ethylenediamine succinic acid or a salt thereof, preferably an alkali metal salt or an alkanolamine salt (6) diglycolic acid, oxydisuccinic acid, carboxymethyloxysuccinic acid, citric acid; Organic acids such as lactic acid, tartaric acid, oxalic acid, malic acid, oxydisuccinic acid, gluconic acid, carboxymethylsuccinic acid, carboxymethyltartaric acid or alkali metal salts thereof, or alkanolamine salts (7) Aluminoke represented by zeolite A Alkali metal salt or alkanolamine salt of acid (8) Aminopoly (methylenephosphonic acid) or an alkali metal salt or alkanolamine salt thereof, or polyethylene polyamine poly (methylenephosphonic acid) or an alkali metal salt or alkanolamine salt can be mentioned. .

  Among these, at least one selected from the group consisting of the above (2), (5), (6) and (7) is preferable, and at least one selected from the group consisting of the above (5) and (6) Species are more preferred.

  In the present invention, it is preferable to contain an alkaline agent (hereinafter, referred to as a component (h)) from the viewpoint of detergency. Examples of the alkaline agent include sodium carbonate, potassium carbonate, sodium hydroxide, potassium hydroxide, ammonia, monoethanolamine, diethanolamine, N-methylpropanol, 2-amino-2-methyl-1-propanol, and N- (β-amino Ethyl) ethanolamine, diethylenetriamine, morpholine, N-ethylmorpholine and the like. As the alkali agent used in the present invention, monoethanolamine, 2-amino-2-methyl-1-propanol and morpholine are particularly preferable.

  The liquid detergent composition of the present invention preferably has a pH at 20 ° C. of 2 to 12, more preferably 3 to 11, from the viewpoint of the cleaning effect. As a pH adjuster, an inorganic acid such as hydrochloric acid or sulfuric acid, or an acid agent such as an organic acid such as citric acid, succinic acid, malic acid, fumaric acid, tartaric acid, malonic acid, or maleic acid, or the above alkali agent, alone or in combination. It is particularly preferable to use an acid selected from hydrochloric acid, sulfuric acid, and citric acid and an alkali agent selected from sodium hydroxide, potassium hydroxide, or the above-mentioned amine compounds. Further, from the viewpoint of ease of use, the viscosity of the composition of the present invention at 20 ° C. is 1 to 100 mPa · s, preferably 1 to 50 mPa · s. Here, the viscosity referred to in the present invention is such that the sample is aged for 30 minutes in a thermostat at 20 ° C. It was measured using an INC B-type viscometer model BM.

  The liquid detergent composition of the present invention preferably contains a hydrotropic agent for the purpose of improving storage stability, and specifically preferred examples of the compound include one to three alkyl groups having 1 to 3 carbon atoms. Benzenesulfonic acid or a salt thereof. More specifically, preferred examples are p-toluenesulfonic acid, m-xylenesulfonic acid, p-cumenesulfonic acid, and ethylbenzenesulfonic acid. When a salt is used, a sodium salt, a potassium salt, and a magnesium salt are preferable. is there.

  Further, the composition of the present invention may contain a polyalkylene glycol for preventing gelation. As specific examples of the polyalkylene glycol for preventing gelation, polypropylene glycol having a weight average molecular weight of 500 to 20,000 determined by gel permeation chromatography when polyethyne glycol is used as a standard, and polyethylene glycol are preferable. .

  The liquid detergent composition of the present invention, in addition to the above-mentioned components, further, if necessary, a usual dispersant, chelating agent, fragrance, dye, pigment, preservative and the like are added as long as the effects of the present invention are not impaired. be able to.

<Liquid detergent composition>
As described above, it is possible to stably blend the hydrophobic solvent [component (c)] using the surfactant [component (b)]. However, the cleaning power is extremely reduced, and the cleaning power expected from the components (b) and (c) cannot be obtained. The present invention relates to a specific polyoxy resin having one kind of alkyl group selected from the 2-ethylhexyl group, isononyl group and isodecyl group in order to mix the component (c) in an aqueous solution without impairing its properties. These problems have been solved by using an alkylene alkyl ether [component (a)]. The compound of the component (a) is different from ordinary surfactants in that it has the ability to stably incorporate a hydrophobic solvent without deteriorating its properties. The mechanism of this action is not clear, but the component (a) is different from ordinary surfactants, and has a strong micellar structure with a hydrophobic solvent confined inside due to its hydrophobicity and hydrophilicity and its branched structure. It is conceivable that a continuous layer of a hydrophobic solvent such as a bicontinuous structure is formed. Interestingly, the use of the component (a) can eliminate the effect of the surfactant of the component (b) on the hydrophobic solvent of the component (c). It has been found that by increasing the blending amount, it is possible to stabilize the hydrophobic solvent of the component (c) without ruining the properties thereof, but by using the component (b) together, it is possible to stabilize the component (a). That is, the amount can be reduced. That is, the component (b) does not degrade the properties of the component (c) and also reduces the required amount of the component (a), thereby maintaining stability and detergency. In particular, among the component (b), a polyoxyethylene alkyl ether having a structure in which EO is added to a linear secondary alcohol or an alkyl polyglucoside having a linear alkyl group is the most effective, and the stability is the highest. Excellent.

  JP-A-6-306400 discloses that (1) an amphiphilic solvent such as triethylene glycol monohexyl ether, (2) a nonpolar or weakly polar solvent such as hydrocarbon, and (3) a polar solvent such as water. It is disclosed that a near tricritical point composition composed of a compound such as triethylene glycol monohexyl ether and diethylene glycol butyl ether used in Examples of the publication is used as a homogeneous phase. In order to form the compound, the added amount increases and the compound is dissolved in the hydrophobic solvent and changes the properties of the hydrophobic solvent, so that the expected effect cannot be obtained. JP-A-2002-20791 discloses a liquid detergent that forms a bicontinuous phase. However, the polarity of the hydrophobic component used is high, and sufficient detergency cannot be obtained.

  The component (a) of the present invention is a compound that is hardly soluble in water or a hydrophobic solvent, and enables stable blending in a composition without changing the properties of the hydrophobic solvent. , Can provide a high cleaning effect.

  In addition, when the constitution of the present invention is adopted, even when an amphiphilic solvent such as the component (e) is used in combination, the properties of the hydrophobic solvent are not changed without changing the properties of the hydrophobic solvent. It is surprising that both cleaning effects can be sufficiently exhibited.

  In the present invention, the ratio of the component (c) to the component (d) is (c) / (d) = 0.5 / 99.5 to 40/60 by mass, preferably 1/99 to 30/70. It is more preferably 2/98 to 15/85, still more preferably 2/98 to 10/90, and the total (c) + (d) of the component (c) and the component (d) is 50 to 99% by mass, preferably Is a liquid detergent composition containing 55 to 98% by mass, more preferably 65 to 98% by mass, and water as a main solvent. In particular, if the mass ratio of (c) / (d) is from 1/99 to 30/70, further from 2/98 to 15/85, and further from 2/98 to 10/90, the water content is 45 mass. % Or more, that is, even if the content of the component (a) and the component (b) is reduced, the effect of the present invention is maintained, which is preferable. The liquid detergent composition of the present invention is stably compounded in the solvent of the component (d) without impairing the properties of the component (c) as a hydrophobic solvent, and the component (a) is stable. It is blended for the sake of However, in order to stabilize only with the component (a), it is necessary to increase the blending amount of the component (a), and the detergency was insufficient. In the present invention, by further using the component (b), the amount of the component (a) can be reduced, and the detergency of the component (b) can be exhibited. The component (c) can be solubilized by the micelle with the component (b), but the hydrophobic solvent of the component (c) cannot exert sufficient detergency, and the detergency of the surfactant itself decreases.

  Regarding the concentration of each specific component in the liquid detergent composition of the present invention, component (a) is preferably 0.1 to 30% by mass, more preferably 0.5 to 20% by mass, and most preferably 0.1 to 20% by mass. 5 to 10% by mass, component (b) is preferably 0.1 to 30% by mass, more preferably 0.5 to 20% by mass, most preferably 0.5 to 20% by mass, and component (c) is preferably 0.1 to 30% by mass, more preferably 0.5 to 20% by mass, most preferably 0.5 to 10% by mass, and the component (d) is preferably 30 to 98% by mass, more preferably 35 to 90% by mass. %, More preferably 45 to 90% by mass, and most preferably 60 to 90% by mass.

  Furthermore, in the liquid detergent composition of the present invention, component (a) / component (c) = 90/10 to 10/90 (mass ratio), and further 80/20, for the purpose of sufficiently exhibiting the cleaning effect of the hydrophobic solvent. (A) / (b) = 90/10 to 10/90, and more preferably 90/10 for the purpose of suppressing the separation and white turbidity of the hydrophobic solvent and enhancing the washing effect. To 40/60 (mass ratio), particularly preferably 80/20 to 50/50 (mass ratio). However, when the component (a) is polyethylene glycol-mono-2-ethylhexyl ether having an average EO addition mole number of 2 and the component (b2) is used as the component (b), the component (a) / ( c) component = 60/40 to 10/90 (mass ratio), especially 50/50 to 20/80, (a) / (b2) = 60/40 to 10/90 (mass ratio), particularly 50/50 to 20/80 is preferred.

  The component (e) of the present invention is preferably contained for the purpose of enhancing the cleaning effect and improving the stability, and the content is preferably 1 to 20% by mass, more preferably 3 to 15% by mass in the composition. .

  In the present invention, component (f) is preferably contained for the purpose of enhancing the cleaning effect, and the content is preferably 0.01 to 10% by mass, more preferably 0.05 to 8% by mass in the composition. However, a large amount of the component (f) exceeding such a range should be avoided because the cleaning effect of the hydrophobic solvent may be reduced.

  The component (g) and the component (h) preferably contain 0.1 to 10% by mass, more preferably 1 to 8% by mass of the component (g) in the composition for the purpose of improving the cleaning effect. It is preferable to contain the component in an amount of preferably 0.05 to 10% by mass, particularly preferably 0.1 to 8% by mass, from the viewpoint of the cleaning effect.

  In the present invention, other components such as a hydrotroping agent and an anti-gelling agent can be appropriately set in consideration of the purpose of use, stability, usability, and the like.

  The liquid detergent composition of the present invention exhibits a high cleaning effect on hydrophobic dirt such as denatured fats and oils, greases, and oils, and can be used for industrial use or general household use. It is effective for general household bathroom cleaners, such as detergents for sebum and silicone stains in bathrooms, and kitchen cleaners, for detergents such as denaturing stains such as around the range and ventilation fans.

Preferred embodiments of the present invention are described below.
(A) In the case of polyoxyethylene (average EO addition mole number 4 to 6) 2-ethylhexyl ether 0.5 to 10% by mass,
(B) (b1) Polyoxyethylene alkyl ether (compound in which R ^1a has 12 to 14 carbon atoms and c has 5 to 8 in the general formula (1-1)) 0.5 to 10% by mass
(C) Normal paraffin having 10 to 20 carbon atoms or isoparaffin 0.5 to 10% by mass
(D) 60 to 90% by mass of ion-exchanged water
(E) Amphoteric surfactant, cationic surfactant 0 to 8% by mass
(F) glycol solvent 3 to 15% by mass
(G) Sequestering agent (polycarboxylic acid compound having 4 to 20 carbon atoms in total) 0 to 8% by mass
(H) Alkaline agent 0 to 8% by mass
(C) / (d) = 2 / 98-15 / 85 (mass ratio), (a) / (c) containing 0.001 to 5% by mass of other components (fragrances, coloring agents, preservatives, etc.) = 80/20 to 50/50 (mass ratio), (a) / (b1) = 80/20 to 50/50 (mass ratio), (c) + (d) = 65 to 98% by mass liquid washing Agent composition.
Or,
(A) In the case of polyoxyethylene (average number of moles of added EO 2) 2-ethylhexyl ether 0.5 to 10% by mass,
(B) (b2) Alkyl polyglucoside (compound in the general formula (2), wherein R ^2a has 9 to 14 carbon atoms, R ^2b is an ethylene group, h is 0 to 3, and i is 1 to 2) 0.5 -10 mass%
(C) Normal paraffin having 10 to 20 carbon atoms or isoparaffin 0.5 to 10% by mass
(D) 60 to 90% by mass of ion-exchanged water
(E) Amphoteric surfactant, cationic surfactant 0 to 8% by mass
(F) glycol solvent 3 to 15% by mass
(G) Sequestering agent (polycarboxylic acid compound having 4 to 20 carbon atoms in total) 0 to 8% by mass
(H) Alkaline agent 0 to 8% by mass
(C) / (d) = 2 / 98-15 / 85 (mass ratio), (a) / (c) containing 0.001 to 5% by mass of other components (fragrances, coloring agents, preservatives, etc.) = 50 / 50-20 / 80 (mass ratio), (a) / (b2) = 50 / 50-20 / 80 (mass ratio), (c) + (d) = Liquid containing 65-98% by mass It is a cleaning composition.

<Ingredients>
· A-1: a compound obtained by adding an average of 4 moles of EO to 2-ethyl-1-hexanol · a-2: a compound obtained by adding an average of 5 moles of EO to 3,5,5-trimethyl-1-hexanol -3: Compound obtained by adding EO to isodecanol on average of 3 moles. A-4: Compound obtained by adding EO to 2-ethyl-1-hexanol on average of 2 moles. A'-1: Addition of 4 moles of EO to octanol Compound b-1: Softanol 70 (trademark) (manufactured by Nippon Shokubai, a compound obtained by adding an average of 7 mol of EO to a secondary alcohol having 13 carbon atoms)
B-2: alkyl polyglycoside (alkyl group having 12 carbon atoms, glucose average condensation degree 1.3)
B-3: polyoxyethylene lauryl ether (EO average addition mole number 6)
B-4: Compound obtained by adding an average of 6 moles of EO to Dovanol 23 (trade name, manufactured by Mitsubishi Chemical Corporation, having a β-methyl branch having 13 carbon atoms and a branched-chain alkyl content of 20% by mass). C-1 : Dodecane (sp = 16.2)
・ C-2: limonene (sp = 17.3)
-C-3: IP2028 (trademark) (Idemitsu Petrochemical Co., Ltd., isoparaffin, sp = 14.3)
D-1: water e-1: diethylene glycol monobutyl ether f-1: N-lauryl-N, N-dimethyl-N- (2-hydroxysulfopropyl) ammonium sulfobetaine f-2: N-octyl N, N-dimethyl-N-benzylammonium chloride · g-1: citric acid · h-1: sodium hydroxide · h-2: monoethanolamine

Example 1
The liquid detergent compositions of Tables 1 to 4 were prepared, and the stability and detergency were examined by the following evaluation methods. The results are shown in Tables 1 to 4. For some of the comparative products, (a) / (b) and (a) / (c) were calculated using a′-1 as the (a) component for convenience.

<Evaluation method>
(1-1) Stability ；: A stable transparent solution without causing phase separation or white turbidity even when left at room temperature (10 to 30 ° C.) for one month or more.
×: Under the same conditions, phase separation, cloudiness, and precipitation occur.

(1-2) Detergency (soap residue cleaning power)
A wash basin (made of polypropylene) on which soap scum is actually used for 3 months is reciprocated 5 times by applying a load of about 500 g to a polyurethane sponge containing a liquid detergent composition for evaluation. Rubbed This operation was performed 20 times, and the average value of the 20 times was displayed.
5: Very good dirt removal 4: Good dirt removal 3: Unevenness in dirt removal 2: Degree of slight dirt removal 1: Almost no dirt removal

(1-3) Detergency (denatured oil stain detergency)
10 g of tempura oil was evenly applied to an iron plate, baked at 180 ° C. for 30 minutes, and then allowed to stand at room temperature for 3 months to form an almost dry film, thereby obtaining a model contamination plate. About 0.5 mL of the liquid detergent composition was dropped on a horizontally fixed model contamination plate, and left for 1 minute. Thereafter, the floating dirt was lightly removed with absorbent cotton. This operation was performed 20 times in total, and the degree of washing was visually observed, evaluated according to the following criteria, and indicated as an average value of 20 times.
5: Complete stain removal 4: About 60% to 80% of stain removal 3: 50% to about 60% of stain removal 2: 30% to about 50% of stain removal 1: About 30% of stain removal 0: Dirt does not come off at all

  Table 5 shows a formulation example of the liquid detergent composition of the present invention. Formulation Examples 3-1 to 3-5 and 3-9 are suitably used for cleaning soap residue stains, and Formulation Examples 3-6 to 3-8 and 3-10 are preferably used for cleaning oil stains.

Claims (2)

(A) a polyoxyalkylene alkyl ether having one alkyl group selected from a 2-ethylhexyl group, an isononyl group, and an isodecyl group, and having an average addition mole number of an alkylene oxide having 2 or 3 carbon atoms of 2 to 6; (C) a nonionic surfactant having an alkyl or alkenyl group having 11 to 16 carbon atoms, (c) a hydrophobic organic solvent which is liquid at 20 ° C., and (d) water, and (c) / ( d) = 0.5 / 99.5 to 40/60 (mass ratio), and (c) + (d) = 50 to 99% by mass. The liquid detergent composition according to claim 1, wherein (a) / (b) = 90/10 to 10/90 (mass ratio) and (a) / (c) = 90/10 to 10/90 (mass ratio). object.