JP4361052B2 - Liquid detergent composition - Google Patents

Description

  The present invention relates to a liquid detergent composition that is suitable mainly for hard surfaces such as kitchens, and further relates to a liquid detergent composition that is excellent in detergency to oil stains, foamability and low-temperature stability.

Conventionally, in kitchen detergents, fatty acid alkanolamides such as fatty acid diethanolamide and fatty acid monoethanolamide are used as a detergency enhancer, foam enhancer, and thickener in addition to the anionic surfactant that is the main base material. I came. However, fatty acid diethanolamide has a problem that the pH increases due to long-term storage because the stability of the compound itself is poor. Fatty acid monoethanolamide is excellent in thickening action and detergency, but its high melting point makes it poorly soluble when blended with detergents, and causes precipitation and cloudiness at low temperatures such as in winter. There was a problem that.
In order to solve such problems, in recent years, polyoxyethylene fatty acid amide type surfactants have been proposed as surfactants that are low in irritation and excellent in bubble power and detergency.
For example, Patent Document 1 discloses a composition that uses a polyoxyethylene fatty acid amide type surfactant and has excellent foaming properties and liquid stability during low-temperature storage. However, the composition has a problem that its detergency against oil stains is still insufficient. Patent Document 2 discloses a detergent composition having a high viscosity (300 mPa · s or more) containing a specific amide compound. Although this technique is said to provide a cleaning agent having excellent detergency, the composition has a high viscosity of the stock solution, so that it is inferior in foaming properties when used by directly impregnating a cleaning tool such as a sponge. There was a problem.

Japanese Patent Laid-Open No. 2003-183693 JP 2002-294293 JP

  Accordingly, an object of the present invention is to provide a liquid detergent composition having a high detergency against oil stains and excellent foaming properties.

（式中Ｒは炭素数８〜１６のアルキル基またはアルケニル基であり、ＡＯは炭素数２〜４のアルキレンオキサイド、ＥＯはエチレンオキサイドである。ｍはアルキレンオキサイドの平均付加モル数であり、ｎはエチレンオキサイドの平均付加モル数である。ｍ、ｎはそれぞれ０〜５の数であり、ｍ＋ｎは１〜６である。） As a result of intensive studies in order to solve the above problems, a cleaning composition that achieves both high detergency against oil stains and excellent foaming properties has been obtained, and the present invention has been completed. That is, the present invention relates to (a) an anionic surfactant, (b) a semipolar surfactant, (c) a compound represented by the following general formula (1), (d) a magnesium salt, and (e) an aromatic carboxylic acid. A liquid detergent composition comprising an acid / salt is provided.

(In the formula, R is an alkyl group or alkenyl group having 8 to 16 carbon atoms, AO is an alkylene oxide having 2 to 4 carbon atoms, EO is ethylene oxide, m is an average added mole number of alkylene oxide, and n Is the average number of moles of ethylene oxide added, m and n are each a number from 0 to 5, and m + n is 1 to 6.)

  According to the present invention, a liquid detergent composition having a high detergency against oil stains and excellent foaming properties can be obtained. The liquid detergent composition of the present invention is also excellent in low temperature stability.

In the present invention, examples of the anionic surfactant used as the component (a) in the present invention include polyoxyethylene alkyl sulfate, alkylbenzene sulfonate, alkyl sulfate, α-olefin sulfonate, and alkyl ether carboxylic acid. Salt, alkane sulfonate, alpha sulfo fatty acid salt, soap, amide ether carboxylate, sulfosuccinate, amino acid anionic surfactant, alkyl naphthalene sulfonate, alkyl phosphate, polyoxyethylene alkyl ether phosphate Examples include salts. These can be used alone (one kind) or in combination of two or more kinds. From the aspect of detergency, polyoxyethylene alkyl ether sulfates (preferably polyoxyethylene alkyl ether sulfates having 8 to 18 carbon atoms and 0.5 to 6 average EO addition moles), alkyl sulfates (preferably Is an alkyl sulfate ester salt having 8 to 18 carbon atoms), an alkane sulfonate (preferably an alkane sulfonate salt having 8 to 18 carbon atoms), an α-olefin sulfonate (preferably an α-olefin having 8 to 18 carbon atoms). Sulfonates) and alkylbenzene sulfonates (preferably alkylbenzene sulfonates having 8 to 18 carbon atoms) are desirable. Of these, polyoxyethylene alkyl ether sulfates having 10 to 16 carbon atoms and 1 to 4 EO average addition moles, alkane sulfonates having 10 to 16 carbon atoms, and alkylbenzene sulfonates having 10 to 16 carbon atoms are preferable.
The compounding amount of these anionic surfactants is preferably 5 to 40% by mass, more preferably 10 to 30% by mass with respect to the total amount of the liquid detergent composition. If the blending amount is less than 5%, the detergency is inferior, and if it exceeds 40%, the stability at low temperatures may be inferior.

  Examples of the semipolar surfactant used as the component (b) used in the present invention include alkyldimethylamine oxide (alkyl group carbon number: 8 to 16), alkylamidopropyldimethylamine oxide (alkyl group carbon number: 8-16), compounds represented by the following general formula (I) or (II), and the like.

[Wherein R1 is selected from an alkyl group having 8 to 16 carbon atoms, a hydroxyalkyl group, an acylamidoalkyl group and an alkylphenyl group, AO is an oxyalkylene group having 2 to 4 carbon atoms, n is 0 to 3, R2 And R3 may be the same or different and are selected from an alkyl group having 1 to 3 carbon atoms, a hydroxyalkyl group, and a polyoxyalkylene group. ]

[Wherein, R4 is a linear alkyl group or alkenyl group having 8 to 16 carbon atoms, and R6 and R7 are each independently an alkyl group or hydroxyalkyl group having 1 to 3 carbon atoms. R5 is an alkylene group having 1 to 5 carbon atoms, and X is a group selected from -COO-, -CONH-, -OCO-, -NHCO-, and -O-. ]
Of these, alkyldimethylamine oxide and alkylamidopropyldimethylamine oxide are particularly preferred. More particularly, alkyldimethylamine oxide having 10-14 carbon atoms in the alkyl group and alkylamidopropyldimethylamine oxide having 10-14 carbon atoms in the alkyl group are particularly preferable.
The amount of component (b) is preferably 0.5 to 8%, more preferably 2 to 6%, based on the total amount of the liquid detergent composition. If the blending amount is less than 0.5%, the detergency may be inferior, and if it exceeds 8%, the stability at low temperatures may be inferior.

The component (c) used in the present invention, in the above general formula (1), R is an alkyl group or alkenyl group having 8 to 16 carbon atoms, preferably 12 to 14 carbon atoms. R may be linear or branched, may be saturated or unsaturated, and may optionally contain a substituent such as a hydroxyl group. The compounds of the general formula (1) can be used alone (one kind) or as a mixture of two or more kinds.
Specific examples include polyoxypropylene (1) lauric acid monoethanolamide, polyoxypropylene (1) polyoxyethylene (2) lauric acid monoethanolamide, polyoxyethylene (2) lauric acid monoethanolamide, Examples include polyoxyethylene (5) myristic acid monoethanolamide, polyoxypropylene (2) coconut oil fatty acid monoethanolamide, and polyoxypropylene (2) coconut oil fatty acid monoethanolamide. These may be included singly or in combination of two or more. Among these, R is preferably an alkyl group having 12 carbon atoms, m is preferably 0 to 1, and n is preferably 1 to 3 in terms of excellent balance between low temperature stability and detergency. Most preferred are polyoxyethylene (2) lauric acid monoethanolamide and polyoxyethylene (3) lauric acid monoethanolamide.
The amount of component (c) is preferably 0.5 to 8%, more preferably 2 to 6%, based on the total amount of the liquid detergent composition. If the blending amount is less than 0.5%, the detergency may be inferior, and if it exceeds 8%, the stability at low temperatures may be inferior.

The magnesium salt of the component (d) used in the present invention is not limited as long as it is a water-soluble divalent magnesium salt, but its structure, production method and counter ion are not limited. For example, magnesium chloride, magnesium sulfate, nitric acid Examples thereof include magnesium, magnesium acetate and hydrates thereof, and these can be used alone (one kind) or in combination of two or more kinds. Of these, magnesium sulfate is preferred.
The content of the component (d) is preferably 0.1 to 10% by mass, more preferably 0.5 to 5% by mass with respect to the total amount of the liquid detergent composition. If the blending amount is less than 0.1%, the detergency may be inferior, and if it exceeds 10%, the stability at low temperatures may be inferior.

Examples of the aromatic carboxylic acid / salt used as the component (e) of the present invention include salicylic acid, sodium and potassium salicylate, benzoic acid, sodium and potassium benzoate, and the like. Of these, sodium benzoate is preferred.
The amount of component (e) is preferably 0.5 to 6% with respect to the total amount of the liquid detergent composition. If the blending amount is less than 0.5%, the stability at low temperatures may be inferior, and if it exceeds 6%, the viscosity may be significantly reduced.

The liquid detergent composition of the present invention preferably further contains an alcohol ethoxylate as component (f). By containing the component (f), foamability is further improved, which is preferable.
The alcohol ethoxylate (f) that can be used in the present invention is an ethylene oxide adduct of alcohol and is a kind of nonionic surfactant. The alcohol ethoxylate in the present invention is not particularly limited by its structure, production method, and the like. Preferably, the alkyl hydrophobic group has 8 to 18 carbon atoms and the average degree of polymerization of the hydrophilic oxyethylene group is 1 to 1. 50 is preferable. More preferably, the hydrophobic group has 10 to 14 carbon atoms and the hydrophilic group has an average degree of polymerization of 5 to 20 or more. Specifically, polyoxyethylene (12) decyl ether, polyoxyethylene (14) decyl ether, polyoxyethylene (7) lauryl ether, polyoxyethylene (12) lauryl ether, polyoxyethylene (15) lauryl ether, Polyoxyethylene (20) lauryl ether,
Examples include polyoxyethylene (25) myristyl ether, polyoxyethylene (18) palmityl ether, polyoxyethylene (15) oleyl ether, polyoxyethylene (15) coconut alcohol ether, polyoxyethylene (20) palm alcohol ether, and the like. However, it is not limited to these. Here, the numerical value in () is r (average oxyethylene chain length). These can be used alone or in combination.
(F) The compounding quantity of a component becomes like this. Preferably it is 0.2-15%, More preferably, it is 0.5-5%. If the blending amount is less than 0.2%, the stability at low temperature may be inferior, and if it exceeds 15%, the detergency and foam quality may be deteriorated.
Moreover, it is preferable that the mass ratio of {(c) + (f) component} / (a) component is 0.1 to 2, preferably 0.1 to 0.5. When this ratio is less than 0.1, the storage stability at low temperatures may be inferior, and when it exceeds 2, the detergency and foamability may be reduced.

The liquid detergent composition of the present invention further contains a nonionic surfactant, an amphoteric surfactant, and other compounds having a surface active action that have been used so far without impairing the effects of the present invention. Can be used in any combination. Among these, nonionic surfactants and amphoteric surfactants can be mentioned as substances having a preferable surfactant activity.
Examples of preferable nonionic surfactants that can be mixed include sorbitan fatty acid ester, polyoxyethylene fatty acid ester, alkyl polyglucoside, fatty acid glycoside ester, fatty acid methyl glycoside ester, alkyl methyl glucamide, and the like.
Examples of amphoteric surfactants that can be preferably blended include alkylbetaines, alkylhydroxysulfobetaines, alkylamidobetaines, imidazolinium betaines, and N-alkylamino acids.
These surfactants can be blended alone or in combination of two or more kinds. These surfactants are preferably used in a total amount of 1 to 20% of the total amount of the liquid detergent composition. If the total blending amount is less than 1%, the stability at low temperature may be inferior, and if it exceeds 20%, the detergency and foam quality may be deteriorated.

Moreover, you may mix | blend with the liquid cleaning composition of this invention combining arbitrarily the other additive conventionally used in the range which does not impair the effect of this invention. Preferred additive components that can be blended include, for example, metal chelating agents such as glycolic acid, citric acid, and EDTA, liquid solvents such as lower alcohol and propylene glycol, antioxidants such as BHT and ascorbic acid, and aromatic sulfonic acids. Liquid modifiers, fungicides such as zinc sulfate and polylysine, viscosity modifiers such as natural polysaccharides and viscosity minerals, coloring agents, anti-inflammatory agents, plant extracts, medicinal ingredients such as enzymes, pH adjusters, fragrances, fragrances Commonly used substances such as solvents and fragrance stabilizers can be mentioned. Further, water (purified water, ion exchange water, pure water, etc.) is usually used as the solvent.
In addition, (a)-(e) component contained in the liquid cleaning composition of this invention, (f) component added as needed, and other components may use what is obtained commercially. it can.
The liquid detergent composition of the present invention can be produced by mixing the components (a) to (e) and, if necessary, the component (f) and other optional components.

The viscosity of the liquid detergent composition of the present invention is preferably adjusted to a range of 50 to 300 mPa · s, preferably 100 to 250, at 25 ° C. When the viscosity is in such a range, it is preferable in terms of usability and foamability. In the present specification, the viscosity of the detergent composition stock solution adjusted to 25 ° C. was measured using a BL type viscometer (manufactured by TOKIMEC, PVL-B2). 2, the value after 1 minute at a rotational speed of 60 rpm (viscosity: mPa · s) is measured.
The liquid detergent composition of the present invention preferably has a pH (stock solution) of 6.0 to 8.0 with a pH adjuster or the like from the viewpoint of detergency and low-temperature stability.

EXAMPLES Next, although an Example and a comparative example demonstrate this invention further in detail, this invention is not limited to the following Example etc.
Using the compounds shown in Table 2 below, various liquid detergent compositions having the composition shown in Table 1 were prepared, and the following test methods evaluated the detergency against oil stains, foamability and low-temperature stability.
These results are shown in Table 1. In addition, the compounding quantity in Table 1 is mass% [the whole quantity is 100 mass% (the remainder is prepared with purified water), and each composition is adjusted to pH 6.5. In addition, the narrow distribution alkyl ethoxy sulfate used in the examples of the present invention was prepared by the following method.
<Alkyl ethoxy sulfate with narrow ethylene oxide addition molar distribution: S-1>
A 4 liter autoclave was charged with 400 g of lauryl alcohol and 0.4 g of a composite metal oxide Lewis acid sintered solid catalyst composed of Al / Mg / Mn, and the autoclave was purged with nitrogen and heated with stirring. Next, 54 g of ethylene oxide was introduced while maintaining the temperature at 180 ° C. and the pressure at 0.3 mPa, to obtain a reaction product. Next, 274 g of the alcohol ethoxylate thus obtained was placed in a 500 mL flask equipped with a stirrer, and after substitution with nitrogen, 81 g of liquid anhydrous sulfuric acid (sulfane) was slowly added dropwise while maintaining the reaction temperature at 40 ° C. Stirring was continued for 1 hour after the completion of the dropwise addition to obtain the desired alkyl ethoxy sulfate. The properties of the resulting alkyl ethoxy sulfate are shown in Table 3.

(Evaluation method of detergency against oil stains)
3 g of beef tallow was weighed in a frying pan having a diameter of 28 cm, and the beef tallow was dissolved by heating with high heat for 1 minute.
Next, after taking 38 g of tap water and 2 g of the detergent composition into a dishwashing sponge of 11.5 cm × 7.5 cm × 3 cm and squeezing it by hand several times, the contaminated frying pan was washed with 25 ° C. tap water. And washed in the same way as is usually done at home. After washing, the rinse was thoroughly rinsed with tap water, and the cleaning power was evaluated based on the following evaluation criteria by the touch feeling when the contaminated surface of the frying pan was touched by hand.
Evaluation criteria:
A: No sliminess due to residual oil is felt at any part of the frying pan.
○: A slight amount of luster due to residual oil is felt on a part of the side of the frying pan.
(Triangle | delta): The sliminess by oil residue is felt in the bottom face and part of side surface of a frying pan.
X: The whole frying pan was felt slim and oil remained clearly.

(Evaluation of foaming)
38 g of water and 2 g of a detergent composition are taken in a dishwashing sponge of 11.5 cm × 7.5 cm × 3 cm, and how to make bubbles after squeezing by hand 5 times is determined according to the following criteria.
Evaluation criteria:
◎: Foam covers the entire surface area of the sponge ○: Foam covers 80% of the surface area of the sponge Δ: Foam covers 50% of the surface area of the sponge ×: Foam covers 30% or less of the surface area of the sponge

(Method for evaluating liquid stability during storage at low temperatures)
100 g of each liquid detergent composition was sealed in a glass bottle and the change in appearance when it was allowed to stand at -5 ° C. for 1 month was evaluated according to the following evaluation criteria.
Evaluation criteria:
○: Precipitation or liquid separation does not occur ×: Precipitation or liquid separation occurs

Claims (4)

(A) anionic surfactant, (b) semipolar surfactant, (c) compound represented by the following general formula (1), (d) magnesium salt, (e) aromatic carboxylic acid / salt, and (f) Contains alcohol ethoxylates ,
{(C) + (f)} / (a) is 0.1 to 0.5 (mass ratio) : Liquid detergent composition characterized by:

(In the formula, R is an alkyl group or alkenyl group having 8 to 16 carbon atoms, AO is an alkylene oxide having 2 to 4 carbon atoms, EO is ethylene oxide, m is an average added mole number of alkylene oxide, and n Is the average number of moles of ethylene oxide added, m and n are each a number from 0 to 5, and m + n is 1 to 6.) (A) As an anionic surfactant, ethylene oxide 0 mol adduct 13%, 1 mol adduct 17%, 2 mol adduct 25%, 3 mol adduct 24%, 4 mol adduct 14% 5 mol adduct 5%, 6 mol adduct 2%, maximum amount adduct P is 2, P mol adduct is 26%, P ± 1 mol adduct is 66% The liquid detergent composition of Claim 1 containing the alkyl ethoxy sulfate whose average added mole number is 2 . (C) The liquid detergent composition according to claim 1 or 2, wherein the compound represented by the general formula (1) is polyoxyethylene lauric acid monoethanolamide or polyoxyethylene coconut fatty acid monoethanolamide . (A ) As an anionic surfactant, polyoxyethylene alkyl ether sulfate ester having 10 to 16 carbon atoms and 1 to 4 moles of added ethylene oxide, alkane sulfonate salt having 10 to 16 carbon atoms, or 10 to 10 carbon atoms 16 alkyl benzene sulfonates;
(b) an alkyldimethylamine oxide having an alkyl group having 10 to 14 carbon atoms as a semipolar surfactant;
(c) a compound represented by the following general formula (1);

(In the formula, R is an alkyl group or alkenyl group having 12 to 14 carbon atoms, AO is an alkylene oxide having 2 to 4 carbon atoms, EO is ethylene oxide, m is an average added mole number of alkylene oxide, and n Is the average number of moles of ethylene oxide added, m is a number from 0 to 1, and n is from 1 to 3.)
(d) Magnesium sulfate as magnesium salt;
(e) as aromatic carboxylic acid / salt, sodium benzoate and / or salicylic acid; and
(f) the alcohol ethoxylate contains an alcohol ethoxylate having an alkyl group having 10 to 14 carbon atoms and an oxyethylene group having 5 to 20 carbon atoms,
{(C) + (f)} / (a) is 0.1 to 0.5 (mass ratio)
Liquid detergent composition .