JPH1112594A - Liquid cleaner composition - Google Patents

Abstract

PROBLEM TO BE SOLVED: To obtain a liquid cleaner composition excellent in foaming force, activities for lowering the oil/water interface tension while maintaining the low temperature stability excellent. SOLUTION: This liquid cleaner composition comprises (a) 0.5-20 wt.% compound of the formula; RO-(EO)x -(PO)y -(EO)x '-H [R is an 8-22C alkyl group, etc.; EO is an oxyethylene group; PO is an oxypropylene group; (x) and (x') are each a number of >=1, with the proviso that the sum of (x) and (x') is 4-20; (y) is a number of 0.5-6; with the proviso that (EO)x , (PO)y , and (EO)x ', forms block bonds in the order], (b) 1-50 wt.% sulfate type or sulfonate type anionic surfactant and, (c) 0.1-10 wt.% ampholytic, amine oxide-based or fatty acid diethanolamide-based surfactant.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a liquid detergent composition, and more particularly to a liquid detergent composition having excellent foaming power and oil / water interfacial tension lowering ability while maintaining good low-temperature stability. is there.

[0002]

2. Description of the Related Art The most basic performance required of household cleaning compositions is detergency and foaming power. It is generally said that there is no universal relationship between detergency and foaming power. However, consumers often judge the detergency based on disappearance of bubbles during washing, and also tend to prefer rich foaming in terms of palatability. For this reason, as a commercial product, a cleaning agent having foaming power, particularly rich foaming even in the presence of oil stains, is preferable.

[0003] Conventional cleaning agents mainly use an anionic surfactant as a main cleaning base for the reason of foaming power, and furthermore, for the purpose of enhancing foaming power in the presence of oil stains and alleviating the effect on the skin. Nitrogen-containing amphoteric, cationic or nonionic surfactants such as tertiary amine oxides, higher fatty acid alkanolamides and alkyl betaines are used in combination. However, in the case of a detergent composition using a combination of these surfactants, the foaming power tends to be impaired as the emulsifying power for oil and fat stains increases in general, due to the surface chemistry of the surfactant.

[0004] Sulfate-type or sulfonate-type anionic surfactants are surfactants having excellent detergency and foaming power, and have been widely used as raw materials for liquid detergents. However, since the low-temperature stability of the formulation is poor, low-temperature stabilizers include lower alcohols such as ethanol, lower alkylbenzene sulfonates such as benzenesulfonate and p-toluenesulfonate, ethylene glycol and propylene glycol. Glycols, urea and the like have been used alone or in combination. Of these, urea is widely used because it shows excellent effects and is economical, but it decomposes when stored at high temperatures to produce unpleasant odors such as ammonia odor and to increase pH. There are drawbacks. On the other hand, other low-temperature stabilizers have little effect when used in a small amount, and a sufficient low-temperature stabilizing effect is not recognized even when mixed in large amounts, and is uneconomical.

Therefore, it has a detergency as a surfactant,
Attempts have also been made to use alcohol ethoxylate-based nonionic surfactants that have a low-temperature stabilizing effect, but the low-temperature stabilizing effect is not yet sufficient, and when used in a large amount, the detergency and foaming properties deteriorate. was there.

Accordingly, an object of the present invention is to provide a detergent composition which is excellent in foaming power and oil / water interfacial tension lowering ability while maintaining good low-temperature stability.

[0007]

Means for Solving the Problems As a result of intensive studies, the present inventors have found that the above problems can be solved by blending a ternary block copolymer having a specific number of moles of alkylene oxide added and a specific form of addition. The present invention has been completed. That is, the present invention provides a liquid detergent composition comprising the following components (a), (b) and (c).

[0008] (a) the compound represented by formula _{(I) RO- (EO) x} - (PO) y - in _{(EO) x '-H (I} ) [wherein, R 8 to 22 carbon atoms Represents a linear or branched alkyl or alkenyl group, EO is an oxyethylene group, PO
Represents an oxypropylene group. x and x 'are numbers of 1 or more indicating the average number of moles of ethylene oxide added, and the sum of x and x' is 4 to 20. y is a number of 0.5 to 6 indicating the average number of moles of propylene oxide added. (EO) _x , (PO) _y ,
(EO) _{x '} is block-connected in this order. (B) Sulfate type or sulfonate type anionic surfactant (c) Amphoteric surfactant, amine oxide surfactant or fatty acid diethanolamide surfactant

[0009]

Embodiments of the present invention will be described below in detail.

[Component (a)] The cleaning composition of the present invention comprises (a)
It contains a compound represented by the above general formula (I) as a component. The compound represented by the general formula (I) is obtained by adding ethylene oxide to an alcohol represented by the general formula (II) R-OH (II) (wherein R has the above-mentioned meaning), then propylene oxide,
Further, it can be obtained by sequentially adding ethylene oxide in blocks.

The alcohol represented by the general formula (II) includes a saturated or unsaturated primary or secondary straight-chain or branched-chain alcohol having 8 to 22 carbon atoms, preferably 10 to 14 carbon atoms. , Specific examples include decyl alcohol,
Linear alcohols such as lauryl alcohol, myristyl alcohol, stearyl alcohol, etc., mixed alcohols mixed in the range of 8 to 22 carbon atoms, and branched alcohols having 8 to 22 carbon atoms synthesized by the oxo method or the Ziegler method. And the like, and lauryl alcohol is particularly preferred.

As a method of adding an alkylene oxide to these alcohols, there is a method of adding a known alkoxylation method in the presence of a catalyst. The order of addition of the alkylene oxide is as follows. It is necessary to add propylene oxide and then add ethylene oxide in order. If ethylene oxide or propylene oxide is added at random, foaming is undesirably hindered.

The total (x + x ') of the average number of moles of ethylene oxide added to the compound represented by formula (I) of the present invention is 4 to 20 mol, preferably 5 to 8 mol.
Mol or less. If the sum of the average number of moles of ethylene oxide added is less than 4 moles, the compatibility of the compound represented by the general formula (I) with water will be poor, and if it exceeds 20 moles, the handleability will be poor.

The average addition mole number y of propylene oxide of the compound represented by formula (I) is 0.5 mol or more and 6 mol or less, preferably 2 mol or more and 4 mol or less, and particularly preferably 2 mol. When the average number of moles of propylene oxide added is less than 0.5 mole, the change in viscosity is large and the handleability deteriorates. When the amount exceeds 6 moles, the detergency is reduced.

The content of the component (a) in the cleaning composition of the present invention is preferably 0.5 to 20% by weight, more preferably 1 to 10% by weight.

[Component (b)] The cleaning composition of the present invention comprises (b)
As a component, it contains a sulfate type or a sulfonate type anionic surfactant. Examples of the sulfate type or sulfonate type anionic surfactant used in the present invention include one or more selected from the following groups (i) to (v).

(I) a linear alkyl benzene sulfonate having 9 to 15, preferably 11 to 14, particularly preferably 12 carbon atoms of the alkyl group; and (ii) an alcohol having 8 to 22 carbon atoms, preferably 12 to 16 carbon atoms. Alkyl sulfate obtained by sulfation (iii) Alkane sulfonate having 8 to 22 carbon atoms, preferably 12 to 16 carbon atoms (iv) α-olefin sulfonate having 8 to 22 carbon atoms, preferably 12 to 16 carbon atoms (v) polyoxyethylene alkyl ether sulfates derived from the ethoxylation of alcohols having 8 to 22 carbon atoms, preferably 12 to 16 carbon atoms, with 1 to 30 moles, preferably 1 to 12 moles of ethylene oxide; ) Among the components, polyoxyethylene alkyl ether sulfate in terms of detergency and skin mildness, particularly the following general formula (III) R ¹ O (CH ₂ CH ₂ O) _m SO ₃ M (III) (wherein , R ¹ represents an alkyl group having 12 to 16 carbon atoms, or alkenylene The group, M represents an alkali metal, ammonium or alkanolamine, m polyoxyethylene alkyl ether sulfate represented by the average the number of 1-12.) Are preferred.

The content of the component (b) in the cleaning composition of the present invention is preferably 1 to 50% by weight, more preferably 5 to 30% by weight.

[Component (c)] The detergent composition of the present invention contains, as component (c), an amphoteric surfactant or an amine oxide-based surfactant in order to improve the foaming power and the effect on the skin. Or it contains a fatty acid diethanolamide surfactant.

Examples of the amphoteric surfactant used in the present invention include alkylcarbobetaines and alkylsulfobetaines represented by the following general formulas (IV) to (VI).

[0021]

Embedded image

(Wherein R ² represents an alkyl or alkenyl group having 8 to 22 carbon atoms, R ³ and R ⁴ each independently represent an alkyl group having 1 to 3 carbon atoms, and A represents a hydrogen atom or a hydroxyl group. are shown, B is -COO ^- or -SO ₃ ^-. indicates, n) also represents an integer of 1-5, the amine oxide-based surfactant used in the present invention, the following general formula (VII) or And tertiary amine oxides represented by (VIII).

[0023]

Embedded image

(In the formula, R ² , R ³ , R ⁴ and n have the same meanings as above.) The fatty acid diethanolamide surfactant used in the present invention is represented by the following general formula (IX). Compounds to be used.

[0025]

Embedded image

(In the formula, R ⁵ CO- represents a saturated or unsaturated fatty acid residue having 10 to 20 carbon atoms.) In the general formula (IX), the fatty acid residue represented by R ⁵ CO- is laurin. Acid, myristic acid, palmitic acid, oleic acid, stearic acid, isostearic acid, coconut oil fatty acid, palm kernel oil fatty acid, tallow fatty acid, castor oil fatty acid,
Examples of the residue include fatty acid residues such as rapeseed oil fatty acid. Of these, lauric acid, coconut oil fatty acid, and palm kernel oil fatty acid are preferable.

The content of the component (c) in the detergent composition of the present invention is preferably from 0.1 to 10% by weight, more preferably from 1 to 8% by weight.

The balance of the above-mentioned components of the detergent composition of the present invention is water. In addition, anionic surfactants other than sulfate-type or sulfonate-type anionic surfactants,
Nonionic surfactants such as fatty acid alkanolamides other than fatty acid diethanolamide can be included. Furthermore, conventionally known low-temperature stabilizers, for example, lower alcohols such as ethanol and isopropanol, glycols such as ethylene glycol, polyethylene glycol, propylene glycol and polypropylene glycol, benzenesulfonate, p-toluenesulfonate, xylene Lower alkylbenzene sulfonates such as sulfonates, acetamides, and aromatic carboxylate salts such as benzoates and salicylates can be used in combination.
In addition, various substances already known as compounds that can be blended with the liquid cleaning agent can be appropriately used in accordance with the purpose. Examples of such substances include citric acid, malic acid, organic builders and inorganic builders for improving detergency such as gluconic acid or salts thereof, as well as anti-rough agents, enzymes, bactericides, antibacterial agents,
Additives such as protein derivatives, opacifiers, coloring agents, preservatives, fragrances, bleaching agents, rust inhibitors, chelating agents and the like can be mentioned.

The detergent composition of the present invention comprises a kitchen detergent,
Residential cleaning agents, hard surface cleaning agents such as metal plastic,
It is suitably used as a detergent for clothing, a detergent for hair, a detergent for body, and the like, and is particularly preferably used as a detergent for kitchen.

[0030]

EXAMPLES Hereinafter, the cleaning composition of the present invention will be described in more detail with reference to examples, but the present invention is not limited to these examples. Parts and percentages in the examples are by weight unless otherwise specified.

The component (a) used in the examples was synthesized under the following conditions by changing the amount of ethylene oxide or propylene oxide added according to the number of moles added. The synthesis conditions are shown below. 500 g of lauryl alcohol (trade name: Calcol 2098, manufactured by Kao Corporation) in a 5 ml rotary stirring type autoclave equipped with two measuring tanks for ethylene oxide and propylene oxide, potassium hydroxide 3.0 g,
After purging with nitrogen, the temperature was raised to 110 ° C., and dehydration was performed at 40 torr for 1 hour. Next, the temperature was raised to 150 ° C., and an amount of ethylene oxide [amount corresponding to x in the general formula (I)] corresponding to the target compound was introduced into the autoclave at a pressure of 3.5 kg / m ² , and the pressure was reduced. After reacting until constant, 12
After cooling to 0 ° C., an amount of propylene oxide [amount corresponding to y in the general formula (I)] corresponding to the target compound is introduced into the autoclave at a pressure of 3.5 kg / m ² , and the pressure is reduced and becomes constant. Until the reaction. Thereafter, the temperature was raised again to 150 ° C., and ethylene oxide [amount corresponding to x ′ in general formula (I)]
Was introduced into the autoclave at a pressure of 3.5 kg / m ² , and reacted until the pressure was reduced to a constant level. After the reaction was completed, the temperature was lowered, and 3.2 g of acetic acid was added to neutralize the target. The final product was obtained.

Examples 1 to 6 and Comparative Examples 1 to 4 Base formulations shown in Tables 1 and 2 were prepared, and the components (a) or (a ') shown in Tables 1 and 2 were added to the base formulations. Was added at the ratios shown in Tables 1 and 2 to prepare a detergent composition. The resulting detergent composition was treated with oil /
The water interface tension lowering effect, foam increasing effect, Kraft point lowering effect and oil stain cleaning power were evaluated. The results are shown in Tables 1 and 2.

<Effect of lowering oil / water interfacial tension>
The interfacial tension at the interface between water and water diluted twice with water is Wilhelmy
It was measured by the plate method (25 ° C.), and the effect was determined based on the following criteria. The value of a solution obtained by diluting the base formulation with water 40 times was used as a reference value. Judgment criteria +: The measured value of each composition is lower than the reference value ±: The measured value of each composition is not different from the reference value-: The measured value of each composition is higher than the reference value

<Effect of increasing foam> 40 ml of a detergent solution having a detergent composition concentration of 0.2% (water used was German hardness of 3.5 ° DH) was placed in a glass cylinder having a diameter of 5 cm and stirred with a rotating blade. Was measured and judged according to the following criteria. In addition, the value in a base compound was made into the reference value. Criteria +: The measured value of each composition is higher than the reference value ±: The measured value of each composition is not different from the reference value −: The measured value of each composition is lower than the reference value

<Kraft point lowering effect> The Kraft point of each composition was measured, and the effect was judged based on the following criteria. In addition, the value in a base compound was made into the reference value. Judgment criteria +: The measured value of each composition is lower than the reference value ±: The measured value of each composition is not different from the reference value −: The measured value of each composition is higher than the reference value <oil stain>Detergency> 0.1% of Sudan III (red dye) is added to beef tallow as an indicator, and 2.5 g of this is added to a porcelain dish (diameter 25).
cm). This was mixed with 3 g of detergent composition in water (hardness)
Using a sponge impregnated with a solution dissolved in 27 g of (3.5 ° DH), the solution was rubbed and washed at a liquid temperature of 20 ° C., and the number of dishes from which tallow was sufficiently washed / removed was represented as the detergency.

[0036]

[Table 1]

[0037]

[Table 2]

Note) * 1: Shown by the value of R, x, y, x 'in the compound represented by the general formula (I).

* 2: Comparative product of component (a), represented by the value of R, x, y, x 'in the compound represented by formula (I).

──────────────────────────────────────────────────の Continued on the front page (51) Int.Cl. ⁶ Identification code FI C11D 1/75 C11D 1/75 1/83 1/83 1/835 1/835 1/90 1/90 1/92 1/92 1/94 1/94

Claims (3)

[Claims] 1. A liquid detergent composition comprising the following components (a), (b) and (c). (a) the compound represented by the general formula _{(I) RO- (EO) x} - (PO) y - (EO) x '-H (I) wherein, R represents a straight-chain or having 8 to 22 carbon atoms EO represents an oxyethylene group, PO represents a branched alkyl group or an alkenyl group.
Represents an oxypropylene group. x and x 'are numbers of 1 or more indicating the average number of moles of ethylene oxide added, and the sum of x and x' is 4 to 20. y is a number of 0.5 to 6 indicating the average number of moles of propylene oxide added. (EO) _x , (PO) _y ,
(EO) _{x '} is block-connected in this order. (B) Sulfate type or sulfonate type anionic surfactant (c) Amphoteric surfactant, amine oxide surfactant or fatty acid diethanolamide surfactant 2. The composition according to claim 1, wherein the content of the component (a) is 0.5 to 20% by weight,
When the content of the component (b) is 1 to 50% by weight and the content of the component (c) is
The liquid detergent composition according to claim 1, which is 0.1 to 10% by weight. 3. The liquid detergent composition according to claim 1, which is for kitchen use.