JP4912755B2 - Liquid detergent composition - Google Patents

Description

  The present invention relates to a liquid detergent composition. In particular, the present invention relates to a liquid detergent composition for hard surfaces that has excellent detergency against soap scum stains or modified oil stains on hard surfaces, and is homogeneous and excellent in stability.

  Hydrophobic solvents such as terpene hydrocarbons and paraffins are widely used in liquid detergents because they have excellent cleaning effects on sebum stains, soap residue, modified oils and greases, oils, and the like. For example, Patent Document 1 discloses a water-dispersible cleaning agent for removing oily soil 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 cleaning agents containing terpene compounds, and detailed explanations and claims of the invention. In the range, it is described that a glycol ether solvent is used in combination. Patent Document 9, Patent Document 10, Patent Document 11, and Patent Document 12 disclose cleaning agents containing a terpene compound and a glycol solvent. Patent Document 13, Patent Document 14, and Patent Document 15 disclose cleaning agents containing a terpene hydrocarbon and a nonionic surfactant. Patent Document 16 discloses a cleaning agent containing a mixture of oil and a nonionic surfactant. Patent Document 17 discloses a liquid containing a nonionic compound such as a polyoxyalkylene alkyl ether having a branched chain of 2-ethylhexyl group, isononyl group and isodecyl group, a nonionic surfactant and a hydrophobic organic solvent. A cleaning composition is disclosed. Patent Document 18 discloses a liquid detergent composition containing a nonionic polyol compound having 3 to 11 carbon atoms and having an alkyl group having secondary to quaternary carbon atoms, a hydrophobic organic solvent, and water. Is described. Patent Document 19 discloses a detergent composition containing an amphoteric surfactant, an anionic surfactant, mono-2-ethylhexyl glyceryl ether or mono-2-ethylhexanoic acid glyceride and water.

Japanese Patent Laid-Open No. 2001-19999 JP 2001-98296 A JP 2000-96086 A JP 2000-303095 A JP-A-10-1698 JP-A-6-336598 JP-A-5-279699 JP-T 9-509438 JP 2001-247449 A JP 2001-342500 A JP 7-310099 A JP-A-5-320694 JP 2001-247899 A JP-A-9-59695 JP-A-9-310100 Special table 2003-522285 gazette European Patent Application No. 1466960 European Patent Application Publication No. 1365013 JP 2004-182760 A

  Hydrophobic solvents have a low affinity with water, and when used as an aqueous composition, a surfactant is generally used in combination. To obtain excellent detergency against sebum stains and soap scum adhering to hard surfaces, select a combination surfactant (including multiple combinations) so as not to interfere with the original properties of the hydrophobic solvent. There is a need to. Reduction of the amount of the surfactant is also desired from the viewpoint of cost. The present applicant has previously indicated that a compact compound and a surfactant having an alkyl chain having 3 to 11 carbon atoms, particularly 4 to 8 carbon atoms, and a plurality of hydroxy groups can sufficiently exhibit the properties of a hydrophobic solvent. (Patent documents 17 and 18). However, when the amount of the hydrophobic solvent is increased, the concentration of the compound having a hydroxy group as a stabilizer and the surfactant concentration are also increased. Patent Document 17 uses a nonionic surfactant for improving stability in order to avoid phase separation between a hydrophobic solvent and water. When the amount of the hydrophobic solvent is increased, unless other stabilizers such as nonionic surfactants are also increased, it is difficult to ensure storage stability and the effect of improving the cleaning power is lowered. Patent Document 18 describes that the storage stability can be enhanced by using a water-soluble solvent such as glycol ether in combination. However, when there are many hydrophobic solvents, there is a limit to reducing the polyol compound. Patent Document 19 does not describe a liquid hydrophobic organic solvent.

  An object of the present invention is to provide a uniform liquid phase stability (hereinafter simply referred to as stability) in a liquid detergent composition containing a specific hydrophobic solvent, which does not phase-separate after standing still with a smaller amount of surfactant. It is an object of the present invention to provide a liquid detergent composition that exhibits both excellent detergency.

In the present invention, (a) one or more compounds selected from the following (a1) and (a2) [hereinafter referred to as (a) component], (b) one or more compounds selected from anionic surfactants and amphoteric surfactants Surfactant (hereinafter referred to as component (b)), (c) a hydrophobic organic solvent that is liquid at 20 ° C. (hereinafter referred to as component (c)), and (d) water (hereinafter referred to as component (d)) [(A) + (b)] / (c) (mass ratio) is 2.5 or less, (b) / (a) (mass ratio) is 0.1 or more, (a) / (c ) (Mass ratio) is 0.1 or more, and [(a) + (b)] / surfactant total amount (mass ratio) relates to a liquid detergent composition of 0.7-1.
(A1): 2-ethylhexyl group, has one alkyl group selected from the isononyl group and an isodecyl group, a polyoxyalkylene alkyl ether is an average number of added moles of alkylene oxide having 2 or 3 carbon atoms is 1 to 6 [Hereinafter referred to as component (a1)]
(A2): Compound represented by the following general formula (I) [hereinafter referred to as component (a2)]

[Wherein, R ¹ represents one alkyl group selected from 2-ethylhexyl, isodecyl, and isononyl groups. ]

  According to the present invention, a hard surface liquid having an excellent detergency against soap scum stain or modified oil stain on a hard surface with a smaller amount of surfactant, and having a uniform and excellent stability. A cleaning composition is obtained.

<(A) component>
The component (a) of the liquid detergent composition of the present invention is a compound having a property of being easily oriented at the interface between the hydrophobic organic solvent that is the component (c) of the present invention and water. The component (a) is different from a general surfactant in that the component (a) is a component (c) due to the hydrophobic portion due to a specific branched alkyl group and the hydrophilic portion due to a limited number of hydroxy groups. It is difficult to form strong micelles while being difficult to be taken in, and as a result, the potential of the hydrophobic solvent as the component (c) against oil stains is not lost.

  The component (a1) will be described in detail below. (A1) The alkylene oxide having 2 or 3 carbon atoms of the component is ethylene oxide (hereinafter referred to as EO) or propylene oxide (hereinafter referred to as PO). However, since PO is highly hydrophobic, average addition of PO The number of moles is preferably 0 to 2, and a structure that necessarily contains EO is preferable. In the present invention, those mainly containing EO are preferred, and it is particularly preferred that all alkylene oxide groups are EO. The average added mole number of alkylene oxide is 1 to 6 moles, preferably 2 to 4 moles.

  The component (a1) having a 2-ethylhexyl group can be obtained by adding an alkylene oxide to 2-ethyl-1-hexanol obtained by hydrogenating an n-butyraldehyde after aldol condensation.

  The component (a1) having an isononyl group can be obtained by hydroformylating diisobutylene by the oxo method and then adding alkylene oxide to isononyl alcohol obtained by hydrogenation. The isononyl alcohol is mainly composed of 3,5,5-trimethyl-1-hexanol.

  The component (a1) having an isodecyl group can be obtained by hydroformylating nonene by the oxo method and then adding alkylene oxide to isodecanol obtained by hydrogenation. The isodecanol is a mixture of many isomers having methyl branches at each position, and a typical structure is 8-methyl-1-nonanol.

  The component (a1) of the present invention is preferably polyethylene glycol-2-ethylhexyl ether (EO average added mole number = 2-6).

Next, the component (a2) will be described in detail. The compound (a2) can be produced by reacting an alcohol compound represented by R ¹ OH with an epoxy compound such as epihalohydrin or glycidol using a Lewis acid catalyst such as BF ₃ . In this reaction, an aluminum catalyst described in WO-A98 / 50389 can also be used. In the present invention, 2-ethyl-1-hexanol is particularly preferable as R ¹ OH.

In the production of the component (a2), an epoxy compound such as epihalohydrin or glycidol is added to the R ¹ OH using the catalyst. In general, the epoxy compound reacts in an excess of 1 to 5 moles relative to R1OH, but in addition to the compound of general formula (I), a multimer in which an epoxy compound is further added to the compound of general formula (I) is also produced. In the present invention, the coexistence of multimers is not denied, but the multimer / (a2) component (mass ratio) is adjusted to 0.3 or less, further 0.1 or less, and particularly 0.05 or less. It is preferable to do. Such adjustment of the content of the multimer can be achieved by a method using a catalyst described in WO-A 98/50389 or a method of performing a purification operation such as distillation. In addition, the mass ratio of the multimer can be determined using gas chromatography.

  The component (a) of the present invention described above can be uniformly dispersed without changing the property of the hydrophobic solvent of the component (c) in the aqueous solution.

<(B) component>
Among the components (b), examples of the anionic surfactant include one or more compounds selected from the following (b1) to (b4).
(B1): Alkyl sulfate ester salt represented by the following general formula (1b) R ² OSO ₃ M ² (1b)
[Wherein R ² represents a linear or branched alkyl or alkenyl group having 8 to 22 carbon atoms, and M ² represents a hydrogen atom, an alkali metal, ammonia or an alkanolamine. ]

The alkyl sulfate ester salt is obtained by sulfonating a linear or branched primary alcohol or linear secondary alcohol having 8 to 22 carbon atoms, preferably 10 to 14 with SO ₃ or chlorosulfonic acid, and neutralizing. Can do.

(B2): Polyoxyethylene alkyl ether sulfate ester salt represented by the following general formula (2b) R ³ (OCH ₂ CH ₂ ) _n OSO ₃ M ³ (2b)
[Wherein R ³ represents an alkyl group having 8 to 22 carbon atoms or an alkylallyl group, n represents an integer of 0 to 16, and M ³ represents a hydrogen atom, an alkali metal, ammonia, or an alkanolamine. ]

  As the polyoxyalkylene alkyl ether sulfate ester salt, an average of 0.5 to 5 mol of EO per molecule is added to a linear or branched primary alcohol or linear secondary alcohol having an average carbon number of 8 to 22, This can be obtained by sulfation using, for example, the method described in JP-A-9-137188. The average carbon number of the alkyl group is preferably 10-16. n is preferably 1 to 5.

(B3): Fatty acid represented by the following general formula (3b) or a salt thereof R ⁴ COOM ⁴ (3b)
[Wherein, R ⁴ represents a linear or branched alkyl or alkenyl group having 7 to 17 carbon atoms, and M ⁴ represents a hydrogen atom, an alkali metal, ammonia or an alkanolamine. ]

As the fatty acid or a salt thereof, R ⁴ preferably has 9 to 15 carbon atoms, more preferably 9 to 13 from the viewpoint of stability. Fatty acids, fatty acid sodium salts, fatty acid potassium salts and the like can be used.

(B4): Ether carboxylate represented by the following general formula (4b) R ⁵ (OCH ₂ CH ₂ ) _n OCH ₂ COOM ⁵ (4b)
[Wherein, R ⁵ represents an alkyl group or alkylallyl group having 8 to 22 carbon atoms, n represents an integer of 0 to 16, and M ⁵ represents a hydrogen atom, an alkali metal, ammonia or an alkanolamine. ]

The ether carboxylate can be obtained, for example, by reacting an alcoholate of polyoxyethylene alkyl ether with sodium monochloroacetate. The carbon number of R ⁵ is preferably 10 to 14, n is preferably 2 to 15, and more preferably 3 to 12 from the viewpoint of stability.

In addition to the above (b1) to (b4), the anionic surfactant as the component (b) is an α-olefin sulfonate, α-sulfo fatty acid salt, α-sulfo fatty acid lower alkyl ester salt, dialkyl sulfosuccinate. Acid ester salts, alkyl or alkenyl succinates and the like can also be mentioned. The α-olefin sulfonate can be produced by sulfonating an α-alkene having 8 to 18 carbon atoms with SO ₃ and hydrating / neutralizing, and a compound having a hydroxy group in a hydrocarbon group. A mixture of compounds in which an unsaturated bond is present. In addition, as the α-sulfo fatty 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 washing effect. As the salt, sodium salt, potassium salt, magnesium salt, calcium salt, alkanolamine salt, and ammonium salt are suitable. As the dialkylsulfosuccinic acid ester salt, those in which both alkyl groups are 2-ethylhexyl are preferable, and a sodium salt is preferable. As the alkyl or alkenyl succinate, potassium alkenyl succinate having 10 to 14 carbon atoms or sodium alkenyl succinate is preferable.

Among the components (b), examples of the amphoteric surfactant include one or more compounds selected from the following (b5) to (b6).
(B5): Carbobetaine type surfactant represented by the following general formula (5b)

[Wherein, R ^6a is an alkyl group or alkenyl group having 9 to 23 carbon atoms, and R ^6b is an alkylene group having 1 to 6 carbon atoms. D is a group selected from —COO—, —CONH—, —OCO—, —NHCO—, and —O—, and f is a number of 0 or 1. R ^6c and R ^6d are an alkyl group having 1 to 3 carbon atoms or a hydroxyalkyl group, and R ^6e is an alkylene group having 1 to 5 carbon atoms which may be substituted with a hydroxy group. M ⁶ represents a hydrogen atom, an alkali metal, ammonia or an alkanolamine. ]

Examples of the carbobetaine-type surfactant include alkyldimethylcarboxymethylbetaines having 10 to 18 carbon atoms in R ^6a (f in the formula (5b) is 0, R ^6c and R ^6d are both methyl groups, and R ^6e is methylene. Group), R ^6a alkylamidopropylcarbobetaine having 10 to 18 carbon atoms (D in the formula (5b) is —CONH—, R ^6b is an alkylene group having 3 carbon atoms, f is 1, R ^6c and R ^6d are A methyl group, and R ^6e is a methylene group). Alkyldimethylcarboxymethylbetaine can be obtained, for example, by reacting an alkyldimethylamine having 10 to 18 carbon atoms with sodium monochloroacetate. The alkylamidopropyl carbobetaine can be obtained, for example, by reacting a fatty acid having 10 to 18 carbon atoms, dimethylaminopropylamine and an amidation reaction product with sodium monochloroacetate.

(B6): Amine oxide type surfactant represented by the following general formula (6b)

[Wherein, R ^7a is a linear alkyl group or alkenyl group having 8 to 16 carbon atoms, and R ^7c and R ^7d are an alkyl group or hydroxyalkyl group having 1 to 3 carbon atoms. R ^7b is an alkylene group having 1 to 5 carbon atoms. B is a group selected from —COO—, —CONH—, —OCO—, —NHCO—, and —O—, and e is a number of 0 or 1. ]

Examples of the amine oxide type surfactant include alkyldimethylamine oxide having 10 to 18 carbon atoms in R ^7a (e in the formula (6b) is 0, R ^7c and R ^7d are both methyl groups), carbon in R ^7a Alkylamidopropylamine oxide having a number of 10 to 18 (B in the formula (6b) is —CONH—, R ^7b is an alkylene group having 3 carbon atoms, e is 1, R ^7c and R ^7d are both methyl groups) be able to. The alkyldimethylamine oxide can be obtained, for example, by reacting an alkyldimethylamine having 10 to 18 carbon atoms with an oxidizing agent such as hydrogen peroxide. The alkylamidopropylamine oxide can be obtained, for example, by oxidizing a fatty acid having 10 to 18 carbon atoms, dimethylaminopropylamine and an amidation reaction product with an oxidizing agent such as hydrogen peroxide.

  As the component (b), an alkyl sulfate ester salt having an alkyl group having a straight chain or branched chain having 10 to 14 carbon atoms, having 10 to 14 carbon atoms, from the viewpoint that the amount of surfactant necessary for stabilization can be reduced. Polyoxyethylene alkyl sulfate ester salt having a linear or branched alkyl group and an EO average addition mole number of 1 to 3, fatty acid sodium having an alkyl group of 10 to 14 carbon atoms, alkyl of 10 to 14 carbon atoms Preferred are polyoxyethylene alkyl ether acetates having an EO average addition mole number of 4 to 10, carbon number 10 to 14 alkylamidopropylcarbobetaine, and alkyl number 10 to 14 carbon dimethylamine oxide. Among these, sodium alkylsulfate ester having a linear or branched alkyl group having 10 to 12 carbon atoms, an alkyl group having a linear or branched chain having 10 to 12 carbon atoms, and an EO average addition mole number 1 to 3 polyoxyethylene alkyl sulfate sodium, fatty acid sodium having an alkyl group having 10 to 14 carbon atoms, and polyoxyethylene alkyl ether having an alkyl group having 10 to 14 carbon atoms and an EO average addition mole number of 4 to 10 Sodium acetate is more preferred.

<(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) obtained from the following well-known formula of 10.0 to 21.0, preferably 14.0. The organic solvent is 21.0, more preferably 14.0 to 19.0, and the solubility in water at 20 ° C. is 0.5% by mass or less. An excellent detergency can be obtained by using a hydrophobic organic solvent whose sp value and solubility in water are within this range. To determine the sp value, Hoy, KL, The Hoy Tables of Solubility Parameters, Union Carbide Corporation, Solvents and Coatings Materials Division, South Charlston, WV (1985)
The stated numerical values shall be used.

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

  As a method for measuring the solubility in water, a cylindrical rotating stirrer having a diameter of 8 mm and a length of about 40 mm is used by adding a hydrophobic solvent to about 50 mL of water in a 100 mL beaker having an inner diameter of 50 mm and a height of 70 mm. When the sample that has been stirred at 600 rpm for 10 minutes and then allowed to stand for 3 hours is visually observed, the sample that is not turbid or separated is regarded as “dissolved”.

  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 in the above range. Examples of the component (c) include hydrocarbons having 6 to 30 carbon atoms, monovalent aliphatic alcohols and esters thereof, other fatty acid esters, and aliphatic ketones. In the present invention, a hydrocarbon having 8 to 20 carbon atoms, more preferably 8 to 15 carbon atoms is particularly preferable.

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

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

  Paraffin hydrocarbons include hexane, heptane, octane, nonane, decane, undecane, dodecane, tridecane, tetradecane, pentadecane, hexadecane, heptadecane, octadecane, and other linear paraffin compounds, isohexane, isoheptane, isooctane, isohexane, isododecane, and isotridecane. Branched chain paraffin compounds such as isotetradecane, isopentadecane, isohexadecane, isoheptadecane, and isooctadecane, and cyclic paraffin compounds such as cyclohexane can be used.

  Aromatic hydrocarbons include toluene, xylene and cumene.

  As the terpene compound, a monoterpene compound that is a dimer of isoprene, a sesquiterpene compound that is a trimer, and a diterpene compound that 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 kinds selected from linear paraffin compounds, branched paraffin compounds, monoterpene compounds and sesquiterpene compounds are particularly preferable. Particularly, decane, undecane, dodecane, tridecane, tetradecane, pentadecane, hexadecane, isododecane, isotridecane, iso One or more selected from tetradecane, isopentadecane, isohexadecane, isoheptadecane, isooctadecane, limonene, dipentene, and terpinolene are preferable from the viewpoint of the cleaning effect.

  As the component (c) of the present invention, a paraffinic compound having a distillation temperature of 50% in a distillation test according to JIS K 2254 is preferably 150 to 360 ° C, and more preferably 170 to 330 ° C. Not only is there no odor problem, it is also good in terms of stability and has a good cleaning effect. Further, normal paraffins having 10 to 20 carbon atoms and isoparaffins having 10 to 20 carbon atoms are preferable, and isoparaffin is particularly preferable from the viewpoint of odor. 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., Nikko N-10 (trademark), N-11 (trademark), N-12 (trademark), N-13 (trademark), N-14 (trademark) manufactured by Petrochemical Co., Ltd., Nippon Oil Corporation Isosol 300 (trademark), Isosol 400 (trademark) manufactured by Chemical Co., Ltd., IP Solvent 1620 (trademark), IP Solvent 2028 (trademark), IP Solvent 2835 (trademark) manufactured by Idemitsu Petrochemical Co., Ltd., Shell Japan Co., Ltd. Examples thereof include isoparaffins such as Shellsol 70 (trademark), Shellsol 71 (trademark), and Shellsol 72 (trademark).

  (C) A component is a thing close | similar to the property of oil, and naturally has the cleaning power superior with respect to the oil stain | pollution | contamination rather than water. Specifically, when the oil stain is washed only with the component (c), the modified oil stain can be dissolved, and the removal of the stain from the target surface can be facilitated. However, the cleaning agent containing only the component (c) has a problem that the component (c) itself remains on the cleaning surface, and is also disadvantageous in terms of safety such as ignition and economical efficiency. Thus, as described above, a system in which the component (c) is dispersed using a surfactant can be considered. However, simply dispersing the component with the surfactant changes the properties of the component (c). Detergency cannot be demonstrated. The present invention does not impair the properties of the hydrophobic solvent of component (c), and is a smaller amount of surfactants (a) and (b) than in the past, and an aqueous cleaning agent containing such a hydrophobic solvent. The composition was completed. And surprisingly, by using a specific combination of surfactants (a) and (b), the amount of surfactant ((( The total amount of (a) + (b)) can be reduced, and it is meaningful to have established a composition that can exhibit high detergency.

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

<Other ingredients>
In the present invention, a surfactant other than the component (a) and the component (b) (hereinafter referred to as the component (e)) may be contained to the extent that the effect of the present invention is not hindered mainly for the purpose of improving the sterilizing power. Good. Surfactants can be selected from those generally known to be used in detergents. A preferred example of the component (e) is a cationic surfactant.

  As a cationic surfactant, it is preferable to use the compounds of the following general formulas (e1) to (e3) from the viewpoints of cleaning effect and sterilizing effect.

[Wherein, R ^10a and R ^11a are alkyl groups or alkenyl groups having 5 to 16 carbon atoms, preferably 6 to 14 carbon atoms, preferably alkyl groups, and R ^10c and R ^10d are alkyl groups having 1 to 3 carbon atoms or A hydroxyalkyl group; T is -COO-, OCO-, -CONH-, -NHCO-, or

It is. g is a number of 0 or 1. R ^10b is an alkylene group having 1 to 6 carbon atoms or — (O—R ^10f ) _e —. Here, R ^10f 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 ^10e is an alkylene group having 1 to 5 carbon atoms, preferably 2 or 3 carbon atoms. R ^12a , R ^12b , R ^12c , and R ^12d 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. Z ^- is an anionic group, preferably a halogen ion or an alkyl sulfate ion having 1 to 3 carbon atoms. ]

  The following are mentioned as a preferable cationic surfactant of this invention.

  In the present invention, a glycol solvent (hereinafter referred to as “component (f)”) is used in combination for the purpose of improving the cleaning effect and the effect of separating the hydrophobic solvent that is component (c) at low or high temperatures and suppressing white turbidity. It is preferable to do. Specifically, the compound of the following general formula (f1) is suitable.

^R9a- ( ^OR9b ) _f- OH (f1)
[Wherein R ^9a is a hydrocarbon group having 1 to 7 carbon atoms, preferably 2 to 5 carbon atoms, f is a number of 1 to 5, preferably 1 to 4, and R ^9b has 2 or 3 carbon atoms. An alkylene group; ]

Specific examples of 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 monomer Butyl ether, propylene glycol monohexyl ether, dipropylene glycol monomethyl ether, dipropylene glycol monoethyl ether, dipropylene glycol monopropyl ether, dipropylene glycol monobutyl ether, polyoxypropylene (average number of added moles 3 to 5) monomethyl ether, poly Examples include oxypropylene (average added mole number 3 to 5) monoethyl ether, polyoxyethylene (average added mole number 1 to 5) monophenyl ether, and polyoxyethylene (average added mole number 1 to 5) monobenzyl ether.

  In the present invention, the component (f) is preferably ethylene glycol monobutyl ether, diethylene glycol monobutyl ether, diethylene glycol monohexyl ether, propylene glycol monobutyl ether, or dipropylene glycol monobutyl ether, and particularly preferably diethylene glycol monobutyl ether.

In the present invention, it is preferable to contain a metal sequestering agent (hereinafter referred to as component (g)) for the purpose of further improving detergency. 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 its derivatives, ethanehydroxy-1,1,2-triphosphonic acid, ethane-1,2-dicarboxy-1,2-diphosphonic acid, methanehydroxyphosphonic acid, and alkalis thereof Metal salts or alkanolamine salts (3) Phosphonocarboxylic acids such as 2-phosphonobutane-1,2-dicarboxylic acid, 1-phosphonobutane-2,3,4-tricarboxylic acid, α-methylphosphonosuccinic acid or alkalis thereof Metal salts or alkanolamine salts (4) Amino acids such as aspartic acid, glutamic acid, glycine or alkali metal salts thereof Alkanolamine salt (5) nitrilotriacetic acid, iminodiacetic acid, ethylenediaminetetraacetic acid, diethylenetriaminepentaacetic acid, glycol etherdiaminetetraacetic acid, hydroxyethyliminodiacetic acid, triethylenetetraaminehexaacetic acid, diencoric acid, alkylglycine-N, N -Aminopolyacetic acid such as diacetate, aspartic acid-N, N-diacetic acid, serine-N, N-diacetic acid, glutamic acid diacetic acid, ethylenediamine succinic acid, or salts thereof, preferably alkali metal salts or alkanolamine salts ( 6) Organic acids such as 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, or the like Limetal salt or alkanolamine salt (7) Alkali metal salt or alkanolamine salt of aluminosilicate represented by zeolite A (8) Aminopoly (methylenephosphonic acid) or alkali metal salt or alkanolamine salt thereof, or polyethylene polyamine poly Mention may be made of (methylenephosphonic acid) or alkali metal salts or alkanolamine salts.

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

  In the present invention, it is preferable from the viewpoint of detergency that an alkali agent (hereinafter referred to as component (h)) is contained. 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, N- (β-amino Ethyl) ethanolamine, diethylenetriamine, morpholine, N-ethylmorpholine and the like. The alkali agent used in the present invention is particularly preferably monoethanolamine, 2-amino-2-methyl-1-propanol and morpholine.

  The liquid detergent composition of the present invention preferably has a pH of 2 to 12 and more preferably 3 to 11 at 20 ° C. from the viewpoint of the cleaning effect. As pH adjusters, 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, maleic acid and other organic acids, and the above alkaline agents may be used alone or in combination. In particular, it is 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 amine compounds. From the viewpoint of ease of use, the composition of the present invention has a viscosity at 20 ° C. of 1 to 100 mPa · s, preferably 1 to 50 mPa · s. Here, the viscosity referred to in the present invention is that the sample was aged for 30 minutes in a constant temperature bath at 20 ° C., and then TOKIMEC. It is measured using INC type B viscometer model BM.

  Moreover, you may mix | blend the polyalkylene glycol for gelation prevention with the composition of this invention. Specific examples of the polyalkylene glycol for preventing gelation are preferably polypropylene glycol having a weight average molecular weight of 500 to 20000 and polyethylene glycol determined by gel permeation chromatography using polyethylene glycol as a standard. .

  The liquid detergent composition of the present invention does not impair the effects of the present invention by adding a normal dispersant, chelating agent, hydrotrope, fragrance, dye, pigment, preservative, etc. It can be added in a range.

<Liquid cleaning composition>
In general, a method of emulsifying or dispersing using a nonionic surfactant or the like is well known, but even if an appropriate nonionic surfactant is used in consideration of HLB or the like, it is a hydrophobic solvent (c In general, it is necessary to have about 3 times the amount (weight ratio) of the component, and the detergency of the component is not at the level expected from the amount of component (c), but is extremely reduced. According to the present invention, (a) which is a specific nonionic compound necessary for homogenizing the same amount of the hydrophobic solvent (c) component and an anionic surfactant and / or an amphoteric surfactant. The total amount of (b) can be reduced to 2.5 times (weight ratio) or less, particularly 1.75 times or less of (c), and (c) the original detergency is fully exhibited. In the range in which (c) can be made uniform and transparent, the smaller the total amount of (a) and (b), the higher the cleaning power. The present invention provides a specific compound having one alkyl group selected from the 2-ethylhexyl group, isononyl group and isodecyl group in order to incorporate the component (c) in an aqueous solution so as not to impair its properties. By using (a) component] and using a specific surfactant (component (b)) in combination, these problems have been solved. Although the mechanism of this action is not clear, the component (a) is different from ordinary surfactants, and because of the balance between the hydrophobicity and hydrophilicity and the branched structure, the component (a) contains a hydrophobic solvent alone. It is considered that it is difficult to form a strong micelle with a small curvature of the confined structure. Instead, it is considered that a relatively large structure can be easily formed by combining with the component (b) to form a flexible interface film having a large curvature. The size of the structure does not deviate from the speculation, but in some cases, it is conceivable that the hydrophobic solvent also forms a continuous layer like a bicontinuous structure.

  JP-A-6-306400 discloses (1) amphiphilic solvents such as triethylene glycol monohexyl ether, (2) nonpolar or weakly polar solvents such as hydrocarbons, and (3) polar solvents such as water. Is used as a cleaning agent, but the amount of the nonpolar or low polarity solvent used in the examples of the publication is 27 to 47.6 wt. % And many. Japanese Patent Application Laid-Open No. 2002-20791 discloses a liquid detergent that forms a bicontinuous phase. However, the hydrophobic component used has a high polarity, and sufficient detergency cannot be obtained. Moreover, WO01 / 059059 does not fully exhibit the excellent detergency of the oil and the surfactant in order to stabilize the oil by using the surfactants described in the description.

  According to the present invention, by using a combination of (a) and (b), a high detergency can be obtained while the amount of component (c) is relatively small (for example, 20% by weight or less). Can do.

  In addition, when the configuration of the present invention is adopted, even if an amphiphilic solvent such as the above component (g) is used in combination, the properties of the hydrophobic solvent are not changed without changing the properties of the hydrophobic solvent. Both cleaning effects can be fully demonstrated.

  The following is a summary of the features of the present invention. [(A) + (b)] / (c) (mass ratio) is 2.5 or less, preferably 2 or less, more preferably 1.75 or less. From the viewpoint of stability, the lower limit is preferably 0.1 or more, more preferably 0.2 or more. [(A) + (b)] / (c) (mass ratio) is more excellent in detergency as the value is lower, and more stable as it is higher. Further, (b) / (a) (mass ratio) is 0.1 or more, preferably 0.15 or more, more preferably 0.2 or more, and the upper limit is preferably 100 or less, more preferably 10 or less, particularly Preferably it is 2 or less. By containing the component (b) at a specific ratio or more with respect to the component (a), the blending concentration of the component (a) can be lowered and stabilization can be achieved. Moreover, in order to fully exhibit the oil stain detergency of the hydrophobic solvent which is the component (c), the content ratio of the component (b) to the component (a) is preferably a specific ratio or less. For sufficient stability, (a) / (c) (mass ratio) is 0.1 or more, preferably 0.5 or more, more preferably 0.7 or more, and the upper limit is preferably 2.5. Hereinafter, it is more preferably 2.0 or less, particularly preferably 1.2 or less. [(A) + (b)] / surfactant total amount (mass ratio) is 0.7 or more, preferably 0.9 or more, more preferably 0.95 or more, and the upper limit is 1.0 or less. That is, all the surfactants may be composed of the components (a) and (b). In the present invention, the combined use of surfactants other than (a) and (b) is likely to reduce stability and detergency and is limited. Here, the “total amount of surfactant” includes the amount of component (a).

  The composition of the present invention is a liquid detergent composition containing water as a main solvent. The liquid detergent composition of the present invention is stably blended 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. Formulated for conversion. However, when it was stabilized only with the component (a), the detergency was insufficient. In the present invention, by further using the component (b), even when the amount of the component (a) is increased, a stable and excellent detergency can be exhibited. The component (c) can be solubilized with micelles as the component (b), but the detergency of the hydrophobic solvent of the component (c) cannot be sufficiently exerted, and the detergency of the surfactant itself is also reduced.

  The specific concentration of each component in the liquid detergent composition of the present invention is preferably 2 to 25% by weight, more preferably 3 to 20% by weight, and most preferably 5 to 15% for the component (c). If the amount is too small, the detergency is insufficient. If the amount is too large, the amount of the active agent ((a) and (b)) required increases, which is not economical. The component (d) is preferably 20% by weight or more, more preferably 50% by weight or more, and most preferably 60% by weight or more. Too little is not economical. If it is 95% by weight or more, it is too thin to provide sufficient cleaning performance.

  In the present invention, the component (e) may be contained for the purpose of enhancing the cleaning effect and the sterilizing effect, and is preferably 0.01 to 1% by mass, more preferably 0.05 to 2% by mass in the composition. From the viewpoint of stabilization by the component (a) and the component (b) and from the viewpoint of the original cleaning effect of the component (c), [(a) + (b)] / surfactant total amount (mass ratio) is 0.7 or more. It is necessary to consider the amount of component (e) so that

  The component (f) of the present invention is preferably contained for the purpose of enhancing the cleaning effect and improving the stability, and the content is preferably 0.1 to 20% by mass, more preferably 1 to 20% by mass in the composition. 15 mass%, Especially preferably 2-15 mass% is good.

  The component (g) and the component (h) are preferably 0.1 to 10% by mass, more preferably 0.3 to 8% by mass, especially the component (g) in the composition for the purpose of improving the cleaning effect. Preferably 0.5 to 6% by mass, component (h) is 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 hydrotrope agent and an anti-gelling agent can be appropriately set in kind, blending amount and the like 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 modified fats and oils, greases, oils, etc., and can be used for any industrial use or general household use. It is effective as a bathroom cleaner for general households, as a cleaner for bathroom sebum and silicone stains, and as a cleaner for kitchens as a cleaner for denatured stains such as around the range and ventilation fan.

The compounding components used in the following examples are shown.
<Blending ingredients>
・ A-1: Compound obtained by adding an average of 2 mol of EO to 2-ethyl-1-hexanol ・ a-2: Compound obtained by adding an average of 2 mol of EO to isononyl alcohol ・ a-3: Average of EO to isodecanol Compound with 2 mol added: a-4: Compound with an average of 1 mol of EO added to 2-ethyl-1-hexanol a-5: Compound with an average of 4 mol of EO added to 2-ethyl-1-hexanol A-6: 2-ethyl-1-hexyl monoglyceryl ether a-7: isodecyl monoglyceryl ether a′-1: compound obtained by adding an average of 2 mol of EO to n-octanol a′-2: Compound obtained by adding an average of 2 mol of EO to n-dodecanol, a′-3: n-octyl monoglyceryl ether, b-1: sodium dodecyl sulfate ester, b-2: polyoxyethylene Down (EO average 4 moles adduct) dodecyl ether sulfate ester (dodecyl group is a straight chain)
B-3: Dovanol 23 (trademark) (manufactured by Mitsubishi Chemical Co., Ltd., 12/13 = 1/1 mixed branched chain alkyl content: 20% by mass) was added with an average of 2 mol of EO, and further sulfated Compound (sodium salt)
B-4: sodium decanoate b-5: sodium laurate b-6: sodium palmitate b-7: Kao Akipo RLM-45NV (trademark) (made by Kao Corporation, polyoxyethylene (EO average 4) .5 mol adduct) sodium dodecyl ether sulfate ester (dodecyl group is linear))
B-8: Kao Akipo RLM-100NV (trademark) (manufactured by Kao Corporation, polyoxyethylene (EO average 10 mol adduct) dodecyl ether sulfate sodium (dodecyl group is linear))
B-9: sodium α-olefin sulfonate (olefin has 12 carbon atoms)
B-10: Perex OT-P (trademark) (manufactured by Kao Corporation, dialkylsulfosuccinic acid and alkyl are both 2-ethylhexyl)
B-11: Anhitoal 20BS (trademark) (manufactured by Kao Corporation, n-dodecyldimethylcarboxymethylbetaine)
B-12: Amphital 20AB (trademark) (manufactured by Kao Corporation, n-dodecylamidopropyldimethylcarboxymethylbetaine)
B-13: Amphitol 20N (trademark) (manufactured by Kao Corporation, n-dodecyldimethylamine oxide)
B-14: Softazoline LAO (trademark) (manufactured by Kawaken Fine Chemical Co., Ltd., n-dodecylamidopropyldimethylamine oxide)
・ C-1: Dodecane (sp = 16.2)
C-2: IP2028 (trademark) (Idemitsu Petrochemicals isoparaffin, sp = 14.3)
D-1: water e-1: N-octyl-N, N-dimethyl-N-benzylammonium chloride f-1: diethylene glycol monobutyl ether g-1: sodium ethylenediaminetetraacetate g-2: citric acid・ H-1: Sodium hydroxide ・ h-2: Monoethanolamine

Example 1
The liquid cleaning composition of Tables 1-4 was prepared, and stability and detergency were investigated by the following evaluation method. The results are shown in Tables 1-4. In addition, some of the comparative products are represented by [(a) + (b)] / (c), (b) with a′-1, a′-2, and a′-3 as components (a) for convenience. / (A), (a) / (c) and [(a) + (b)] / [(a) + (b) + (e)] were calculated. However, in the comparative product 1-13, [(a) + (b)] / [(a) + (b) + (e)] is [(a) + (b)] / [(a) + ( b) + (e) + (a′−2)] (a (−) of the numerator does not include a′−2, but the (a) component of the denominator includes a′−2).

<Evaluation method>
(1-1) Stability: A stable transparent solution that does not cause phase separation or cloudiness even after standing at room temperature (10 to 30 ° C.) for 1 month or longer.
X: Phase separation, cloudiness and precipitation occur under the same conditions.

(1-2) Detergency (detergency of soap residue)
A washbasin (made of polypropylene), which is actually used for 3 months, with a soap residue fixed on it, is subjected to 5 reciprocations 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 displayed as an average value of 20 times.
5: Very good dirt removal 4: Good dirt removal 3: Unevenness in dirt removal 2: Degree of dirt slightly removed 1: Almost no dirt removed

(1-3) Detergency (detergent oil stain detergency)
Ten grams of tempura oil was evenly applied to the 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 to form a model contaminated plate. About 0.5 mL of the liquid detergent composition was dropped onto a model contamination plate fixed horizontally and left for 1 minute. Thereafter, the raised dirt was lightly removed with absorbent cotton. This operation was performed 20 times in total, and the degree of each cleaning was visually observed and evaluated according to the following criteria, and displayed as an average value of 20 times.
5: Complete stain removal 4: 60% to 80% stain removal 3: 50% to 60% stain removal 2: 30% to 50% stain removal 1: 30% stain removal 0: Dirt is not removed at all

Claims (6)

(A) one or more compounds selected from the following (a1) and (a2), (b) one or more surfactants selected from anionic surfactants and amphoteric surfactants, (c) liquid at 20 ° C. Contains a hydrophobic organic solvent and (d) water, [(a) + (b)] / (c) (mass ratio) is 2 or less, and (b) / (a) (mass ratio) is 0.1. above, (a) / (c) (mass ratio) is 0.1 or more, [(a) + (b)] / surfactant amount (mass ratio) Ri der 0.7 to 1, (c) The liquid detergent composition whose content of an ingredient is 15 mass% or less .
(A1): 2-ethylhexyl group, has one alkyl group selected from the isononyl group and an isodecyl group, a polyoxyalkylene alkyl ether is an average number of added moles of alkylene oxide having 2 or 3 carbon atoms is 1 to 6 (A2): Compound represented by the following general formula (I)

[Wherein, R ¹ represents one alkyl group selected from 2-ethylhexyl, isodecyl, and isononyl groups. ] The liquid detergent composition according to claim 1, wherein the component (b) is one or more compounds selected from the following (b1) to (b4).
(B1): Alkyl sulfate ester salt represented by the following general formula (1b) R ² OSO ₃ M ² (1b)
[Wherein R ² represents a linear or branched alkyl or alkenyl group having 8 to 22 carbon atoms, and M ² represents a hydrogen atom, an alkali metal, ammonia or an alkanolamine. ]
(B2): Polyoxyethylene alkyl ether sulfate ester salt represented by the following general formula (2b) R ³ (OCH ₂ CH ₂ ) _n OSO ₃ M ³ (2b)
[Wherein R ³ represents an alkyl group having 8 to 22 carbon atoms or an alkylallyl group, n represents an integer of 0 to 16, and M ³ represents a hydrogen atom, an alkali metal, ammonia, or an alkanolamine. ]
(B3): Fatty acid represented by the following general formula (3b) or a salt thereof R ⁴ COOM ⁴ (3b)
[Wherein, R ⁴ represents a linear or branched alkyl or alkenyl group having 7 to 17 carbon atoms, and M ⁴ represents a hydrogen atom, an alkali metal, ammonia or an alkanolamine. ]
(B4): Ether carboxylate represented by the following general formula (4b) R ⁵ (OCH ₂ CH ₂ ) _n OCH ₂ COOM ⁵ (4b)
[Wherein, R ⁵ represents an alkyl group or alkylallyl group having 8 to 22 carbon atoms, n represents an integer of 0 to 16, and M ⁵ represents a hydrogen atom, an alkali metal, ammonia or an alkanolamine. ] The liquid detergent composition according to claim 1, wherein the component (b) is one or more compounds selected from the following (b5) to (b6).
(B5): Carbobetaine type surfactant represented by the following general formula (5b)

[Wherein, R ^6a is an alkyl group or alkenyl group having 9 to 23 carbon atoms, and R ^6b is an alkylene group having 1 to 6 carbon atoms. D is a group selected from —COO—, —CONH—, —OCO—, —NHCO—, and —O—, and f is a number of 0 or 1. R ^6c and R ^6d are an alkyl group having 1 to 3 carbon atoms or a hydroxyalkyl group, and R ^6e is an alkylene group having 1 to 5 carbon atoms which may be substituted with a hydroxy group. M ⁶ represents a hydrogen atom, an alkali metal, ammonia or an alkanolamine. ]
(B6): Amine oxide type surfactant represented by the following general formula (6b)

[Wherein, R ^7a is a linear alkyl group or alkenyl group having 8 to 16 carbon atoms, and R ^7c and R ^7d are an alkyl group or hydroxyalkyl group having 1 to 3 carbon atoms. R ^7b is an alkylene group having 1 to 5 carbon atoms. B is a group selected from —COO—, —CONH—, —OCO—, —NHCO—, and —O—, and e is a number of 0 or 1. ] The component (c) is a hydrophobic organic solvent which is liquid at 20 ° C. and has a solubility parameter of 10.0 to 21.0 and a solubility in water of 20 ° C. of 0.5% by mass or less. 4. The liquid detergent composition according to any one of 3. The liquid detergent composition according to any one of claims 1 to 4, wherein the component (c) is a paraffin compound having a temperature of 50% distillation in a distillation test according to JIS K 2254 at 150 to 360 ° C. (E) The liquid cleaning composition of any one of Claims 1-5 which contains a cationic surfactant as a component.