JPH0411698A - Liquid detergent composition - Google Patents

Abstract

PURPOSE:To make mild to the skin and improve the detergency for oil stains, lathering in washing and feeling of bubbles by providing a composition containing a nonionic surfactant, an anionic surfactant and a specific surfactant. CONSTITUTION:The title composition is prepared by blending 3-40wt.% nonionic surfactant represented by formula I (wherein R is a 7-15C alkyl or alkenyl; and n is a molar number of addition of ethylene oxide) and satisfying formula III (wherein Yi is the wt.% of a component with a molar number of addition of (i)) when the average molar number of addition (nAV) of ethylene oxide is 3-15, the component of n=0 that is an unreacted alcohol being 10wt.% or less, and the molar number of addition of the component of a maximum wt.% is represented by formula II, 0.5-20wt.% anionic surfactant having a group selected among -COO, -OSO3 and -SO3, and 0.5-20wt.% surfactant selected among an amine oxide, a sugar ester-based surfactant that is an ester of a 6-18C fatty acid and a (monoalkyl ether of) 5-6C monosaccharide and an alkanolamide of a fatty acid, in such a way that their weight ratio is in the range enclosed by (a) to (d) in the diagram, and adding thereto a hydrotrope, perfume, water, etc., as required.

Description

[Detailed description of the invention] Industrial applications The present invention relates to liquid cleaning agents such as kitchen cleaning agents.

Kitchen detergents and the like are desired to be mild and cause little skin irritation, as they often come into contact with the skin during use, in addition to having excellent oil stain cleaning properties.

Furthermore, for cleaning agents that are used in contact with the skin, foaming and the feel of the foam during cleaning are also important.

If the foam does not foam well or if the foam gives the impression of being ``slimy'', it will not be pleasant to use.

Product value will drop significantly. In addition, when cleaning, it is generally diluted and used, but if the cleaning solution has a slimy feel, it not only feels unpleasant to use as described above, but also requires the use of a large amount of water for rinsing after cleaning. This poses a problem in terms of workability and economy.

The present invention is mild to the skin and has excellent oil stain cleaning power, and it also foams well during cleaning, making the foam feel dry, and also improves the 1' sliminess of the washing liquid. The present invention provides a liquid cleaning composition.

The liquid detergent composition of the present invention includes the following (A) and (B).
) and (C) components, and the weight ratio of the above (A), (B) and (C) components is an area surrounded by points a, b, c, and d of the triangular diagram shown in Figure 1. Characterized by being within.

(A) The following - maximum (I), and (a)
A nonionic surfactant satisfying the conditions of , (b) and (c): 3 to 40% by weight.

RO+ CH2CH20+ n H・= (1) (R:
Alkyl group or alkenyl group n having an average carbon number of 7 to 15: number of added moles of ethylene oxide) (a) Average added mole nAV of ethylene oxide is 3 to 1
5゜(b) The component of n=o, which is unreacted alcohol, is 10% by weight or less.

(c) The following formula is satisfied when the number of added moles with the largest weight % is n MAX.

(Yi: number of moles added is weight % of number of moles i) (B) Anionic surfactant having -COO-2-〇503- or -S O3- group = 0.5 to 20% by weight.

(C) 0.5 to 20% by weight of at least one surfactant selected from the following (C-1) to (C-3).

(C-1) Amine oxide.

(C-2) A sugar ester surfactant comprising an ester of a fatty acid having 6 to 18 carbon atoms and a monosaccharide having 5 to 6 carbon atoms or a monoalkyl ether thereof.

(C-3) Fatty acid alkanolamide.

The present invention will be explained in more detail below.

The nonionic surfactant as component (A) used in the present invention is an ethylene oxide adduct of alcohol (alcohol ethoxylate), and this alcohol can be saturated or unsaturated, or linear or branched. Good too. The average carbon chain length of the alcohol is 7 to I5.

Generally, alcohol ethoxylates are obtained as a mixture with a wide distribution of the number of added moles (n) of ethylene oxide, with a large amount of n=o, a component with a small number of added moles such as 1.2, or a component with a small number of added moles (n) such as Contains too many ingredients.

If a component with a small number of added moles is present in a large amount, the foam or cleaning solution will have a "slimy" feel, the skin mildness will deteriorate, and no improvement effect will be shown. Furthermore, the number of added moles is /
When JX becomes thinner, the foam during cleaning disappears and remains as a film on the surface of dishes and other items to be washed after cleaning.In particular, n = Q, that is, unreacted alcohol, is almost similar in character to oily dirt. Also, if the average number of added moles nAV becomes too large,
If the hydrophilicity becomes too large, the liquid becomes cloudy, which is not desirable as a product.

Therefore, in the present invention, in the nonionic surfactant of general formula (I), the average number of added moles of ethylene oxide nAV
is 3 to 15, preferably 5 to 12, and has a narrow molecular weight distribution range, and moreover, the nonionic surfactant contains more than 10% by weight of the component n=o, which is unreacted alcohol, preferably Use a material that does not contain more than 5% by weight.

To specifically describe the narrow molecular weight distribution range, in general formula (1), the number of added moles with the largest weight% is n
A nonionic surfactant with a narrow fractionation width in which a large number of additional molar components is included in a narrow range that satisfies the following formula (II) when MAX is used is used. Also, preferably ΣY
i≧65%.

(Yi: % by weight of the number of moles of i) Here, this formula will be briefly explained in detail with reference to the drawings. The white dots in Figure 2 indicate the distribution of the number of added moles of ethylene oxide (E○), a nonionic surfactant with a narrow distribution width of the present invention, while the black dots indicate nonionic surfactants outside the scope of the present invention (comparative examples). The distribution of the agent is shown.

In the nonionic surfactant of the present invention, nAV” about 7
and nM^8=7. Therefore, the above formula (II)
is as follows, and the components from n=5 to 9 (Ys=
Y-Y7- The total weight percentage of Ys and YJ is 84 weight percent, which satisfies the condition (C) [called narrow degree] required for the present invention.

On the other hand, the nonionic surfactant of the comparative example had nAV=about 7,
nMAX"7, but the degree of narrowness is 46%, which does not meet the requirements of the present invention.

When the degree of narrowness is less than 55%, the "sliminess" of the foam during washing, the "sliminess" of the washing liquid, and the mildness to hand skin deteriorate.

A nonionic surfactant with a high degree of narrowness that satisfies the conditions of the present invention may be synthesized by applying conventional methods and strictly controlling the synthesis conditions, or after synthesis, it may be separated into a number within the required distribution range by topping, etc. The degree of narrowness and the average number of added moles may be adjusted accordingly. Further, by using the method described in JP-A-1-164437, alcohol ethoxylates with a high degree of narrowness can be easily obtained.

The nonionic surfactant as component (A) of the present invention is blended in the cleaning composition in an amount of 3 to 40% by weight, preferably 5 to 20% by weight. If this amount is too small, the effect of improving 'slipiness' and skin mildness will not be sufficient.On the other hand, even if the amount is increased, the performance will already be saturated, and on the contrary, a sufficient amount of water will be ensured. As a result, the viscosity of the product increases and it becomes a gel, which is not appropriate.

As the anionic surfactant of component (B), -COO-
(carboxylic acid type), -〇S O, - (sulfuric acid ester type)
Alternatively, -8○, - (sulfonic acid type) activators are used, and specific examples thereof include the following.

(1) Carboxylic acid-based anionic surfactant/C technology. ~0.
Fatty acid salt, succinic acid monoalkyl ester salt having 3 to 15 carbon atoms in the ester moiety, and mono- or di-salt R-CHCOOY of a sulfonated fatty acid represented by the following general formula.

S○, Zl (R: alkyl group or alkenyl group having 10 to 20 carbon atoms, Zl: counter ion) (2) Sulfate ester-based anionic surfactant/C□. ~,
Alkyl sulfate of 1 - Alkyl (or alkenyl) polyethoxy sulfate with an alkyl group or alkenyl group having 10 to 18 carbon atoms (average number of added moles of ethylene oxide β = 2 to 7) (3) Sulfonic acid-based anionic surfactant. C engineering. ~, 8
Alkanesulfonate + C10-18 olefin sulfonate - Alkylbenzene sulfonate whose alkyl group has CII to 6 carbon atoms - Sulfonate of fatty acid lower alkyl ester represented by the following general formula R-CHCO○Y2 S O, Z2 (R: alkyl group or alkenyl group having 10 to 20 carbon atoms Y2: alkyl group having 1 to 3 carbon atoms Z2: counter ion) These salts include alkali metal salts, alkaline earth metal salts, ammonium Salts, alkanolamine salts, etc. are used.

The anionic surfactant (B) component is blended in the cleaning composition in an amount of 0.5 to 20% by weight, preferably 1.5 to 10% by weight. If the amount is less than 0.5% by weight, foaming will not be improved, while if it exceeds 20% by weight, the effect of improving sliminess and skin mildness will be impaired.

Component (C) includes (C-1) amine oxide, (C
At least one of -2) sugar ester surfactant and (C-3) fatty acid alkanolamide is used.

The alkylamine oxide (C-1) is a surfactant that is mild to the skin with little skin irritation, and is preferably a compound represented by the following general formula (III). Here, R
R2 is an alkyl group or hydroxyalkyl group having 1 to 5 carbon atoms, and R3 is an alkyl group having 8 to 20 carbon atoms.

R, -N-+0...(I) R3 may be saturated or unsaturated, and may be linear or branched.

The sugar ester surfactant (C-2) is a surfactant that has good biodegradability and is mild to the skin with little skin irritation. 8 fatty acid or a fatty acid derivative thereof,
Obtained from monopentoses, monohexoses, or their monoalkyl ethers.

Here, the fatty acid may be saturated or unsaturated, and may be linear or branched. Specific examples of such fatty acids include, for example, caproic acid, caprylic acid, capric acid, lauric acid, myristic acid, palmitic acid, stearic acid, caproleic acid, lauroleic acid, myristoleic acid, palmitoleic acid, oleic acid, methyl Examples include undecanoic acid.

Examples of monopentoses include monopentoses such as xylose, arabinose, ribulose, xylulose, and lyxose, as well as monoalkylated products such as methylxylose and ethylarabinose. Examples of monohexoses include monohexoses such as glucose, galactose, and fructose, as well as monoalkylated products such as methylglucose and ethylglucose. Further, the alkyl group of the monoalkyl ether is methyl, ethyl, or propyl.

In the sugar ester surfactant of the present invention, it is not particularly important how many of the hydroxyl groups of the monosaccharide form an ester with the fatty acid residues of CG~, 8, but it is preferable that the surfactant is mainly composed of monoesters. Polyester of ester or higher is 1
It is desirable that it is less than % by weight.

Sugar ester surfactants can be obtained by any appropriate method, but according to the method for producing sugar monofatty acid esters previously filed by the applicant as Japanese Patent Application No. 1-210495, Esters can be advantageously synthesized industrially. An example of this synthesis will be shown below.

Synthesis Example Adding the third
grade butyl alcohol 25a+ Q was added, and heat-stable lipase derived from Candida antarctica (sp.
-382, manufactured by Novo Corporation) immobilized on an acrylic resin, 10 g of Molecular Sieves 5A was added as a demethanol agent, and the mixture was heated to reflux with stirring for 24 hours to produce glucose monocaprylic acid ester (CS glucose ester). I got it.

Next, 0.5 mΩ of the reaction solution was taken into a screw tube.

Add 2.5 ml of pyridine, further add 10 μQ of n-tetradecane as an internal standard substance, mix thoroughly, then go door to door, add acetic anhydride IIIQ as an acetylating agent to 1 mΩ of P solution, and react at 60°C for 30 minutes. Ta.

When 1μ of the reaction solution was analyzed by gas chromatography, 98% of glucose monocaprylate was found.
It was obtained with a purity of 70% and a production rate of 70%, and the content of polyester higher than triester was 1% by weight or less.

The fatty acid alkanolamide (C-3) is an amide of fatty acid and ethanolamine, and fatty acid jetanolamide is a typical example. The number of carbon atoms in this fatty acid is 8 to 18
In particular, fatty acids with 12 carbon atoms (C1□
Ethanolamide of fatty acids) is preferred.

Component (C), the surfactant, is present in the detergent composition in an amount of 0.5 to
It is blended in an amount of 20% by weight, preferably 1 to 10% by weight. If this amount is less than 0.5% by weight, the oil stain cleaning power will not be improved, while if it exceeds 20% by weight, the performance will already be saturated, and on the contrary, the viscosity will increase and the product will gel. etc. is not appropriate.

In the liquid detergent composition of the present invention, the above (A).

It is necessary that the blending ratio of the three components (B) and (C) is within the area surrounded by points a, b, c, and d shown in FIG. 1 in terms of weight ratio. If the blending range is outside this range, it will not be possible to obtain a detergent that is mild to the skin, has foaming properties, and has oil stain detergency.

For boat fishing, if the amount of nonionic surfactant (A) is too small, the effect of improving "sliminess" and skin mildness will not be sufficient. If the amount is too low, the foaming properties will deteriorate, and if the surfactant (C) component is too low, the cleaning power for oil stains will decrease.

In the triangular diagram in Figure 1, the vertices of the triangle ^, B, and C are the components (A), (B), and (C) respectively] -00%
The opposite side is 0%.

The triangular coordinates of points a, b, c, and d in Figure 1 and the ratios of the (A), (B), and (C) components at those points are shown in Table 1 below.

a (86,96,4,35,8,70)
20/1/2b (32, 30, 64, 60,
3,23) 10/20/1c (20,0
0,40,00,40,00) 1/2/2d
32.79 1.64 65.57 20/
1/40 Furthermore, various additives used in ordinary liquid detergent compositions can be blended. These additives include, for example, anionic, nonionic, cationic, and amphoteric surfactants other than components (A), (B), and (C), foam enhancers such as alkanolamines, lower alcohols, polyhydric alcohols, Examples include hydrotropes such as polyethylene glycol and lower aryl sulfonates, sequestering agents such as ethylenediaminetetraacetic acid, diethylenetriaminepentaacetic acid, citric acid and its metal salts, fungicides such as benzoic acid, pigments, fragrances, etc. .

According to the present invention, the average number of moles of ethylene oxide (E○) added is 3 to 15, the unreacted alcohol content is 10% by weight or less, and the number of moles of E○ added has a specific distribution width. narrow(
By using A) nonionic surfactant together with specific (B) anionic surfactant and (C) surfactant, it has excellent oil stain cleaning power and reduces foaming, foaming and sliminess of cleaning liquid during cleaning. A liquid detergent composition can be obtained which has an improved dryness, provides a light feeling, has an excellent feeling of use, has good rinsability, and is mild to the skin.

Hereinafter, the present invention will be explained in more detail with reference to Examples, but prior to this, the analytical methods and evaluation methods used in the Examples will be explained.

(1) Analysis method of EO addition mole distribution method E of nonionic surfactant (alcohol ethoxylate)
○The distribution of the number of added moles and the average number of added moles (nAv) are:
Asahi Kasei HODP-50 (6mmφX 150+++m)
High performance liquid chromatography (HPL) manufactured by Hitachi
C, L series).

(2) Evaluation method for foam's "sliminess" Sponge (3M, Scotch Brite)
% detergent solution and squeeze 20 to 30 times with one hand to create foam.

Using the other hand, the feel of the obtained foam was checked with the hands and fingers, and the results were expressed as the average value of 5 or more testers based on the following criteria.

(3) How to evaluate the "sliminess" of a cleaning solution: Put 500g of a 10% cleaning solution into an IQ poly beaker, dip one hand in it, observe the feel of the solution, and use the following criteria to determine the average value of 5 or more testers. Indicated.

(4) Mildness for hand skin Soak your hands up to your wrists in a 1% detergent solution for 30 minutes a day, repeat for 3 days, and then self-evaluate on the next day based on the following criteria.More than 20 testers Shown as the average.

(5) Take 20g of detergent solution with foaming property of 10% into a 100m Q nibton tube, add 0.5g of pharmacopoeial soybean oil, shake vigorously 20 times, and observe the foam height from the foam-liquid interface after 20 minutes. .

0: 50 ■ weight or more Δ: 20 to 50 m Garden X: Less than 20 + m weight (6) Oil stain cleaning power 60% of each 10 g of soybean oil and beef tallow specified in the Japanese Pharmacopoeia
After dissolving m Q in chloroform.

Add 0.1 g of Oil Red and mix well to prepare a stain solution. Dip a glass plate in this solution to contaminate it,
Chloroform is removed by air-drying at a temperature of 25° C. for 30 minutes or more, and soil pieces are prepared (amount of soil: 20 to 23 mg/sheet).

0.15wt of these 6 pieces of dirt at 25℃, 700m
% detergent solution for 3 minutes at a rotational speed of 250 rpm, air-dried, weighed, and the oil removal rate after washing was calculated using the following formula to determine the detergency.

-W Cleaning power (%) = (1-w knee.) Δ: 30-60% ×: Less than 30% Example 1 A liquid cleaning composition having the composition shown in Table 2 below was prepared,
"Sliminess" of foam, "sliminess" of diluted cleaning solution,
The mildness to hand skin, foaming, and oil stain cleaning ability were evaluated, and the results are shown in Table 2.

(Margin below) 4,

[Brief explanation of the drawing]

FIG. 1 is a triangular diagram showing the blending ratio (weight ratio) of the three components (A), (B), and (C). FIG. 2 is a graph showing the distribution of the number of moles of ethylene oxide added (n).

Claims (1)

[Claims] 1. (A) General formula (I) ▲ Numerical formulas, chemical formulas, tables, etc. are included ▼... (I) (R: alkyl group or alkenyl group having an average carbon number of 7 to 15 n: ethylene oxide A nonionic surfactant represented by (number of added moles of ethylene oxide), in which (a) the average added mole n_A_V of ethylene oxide is 3 to 15, (b) the component of n=0, which is unreacted alcohol, is 10% by weight or less, and ( c) When the number of added moles with the largest weight% is n_M_A_X, the following formula ▲ Numerical formula, chemical formula, table, etc. ▼ Yi ≧ 55% (Yi: number of added moles is weight % of the number of i moles). Nonionic surfactant: 3 to 40% by weight, (B) -COO^-, -OSO_3^- or -SO_
Anionic surfactant having a 3^- group: 0.5 to 20% by weight, (C) At least one surfactant selected from the following (C-1) to (C-3): 0.5 to 20% by weight 20% by weight (C-1) Amine oxide (C-2) Sugar ester surfactant (C- 3) Contains fatty acid alkanolamide, and the weight ratio of the components (A), (B), and (C) is within the area surrounded by points a, b, c, and d shown in attached Figure 1. A liquid cleaning composition comprising: