JP5806526B2 - Foam enhancer and detergent composition containing the same - Google Patents

Description

  An object of the present invention is to provide a foam-increasing agent that imparts high foaming properties and quick foaming properties. The present invention also relates to a cleaning composition such as a hair cleaning composition, a body cleaning composition, a dish detergent, and a facial cleansing foam using the same.

  Cleaning agents such as shampoos, solid soaps, body shampoos, kitchen detergents, clothing detergents, and residential detergents are required to have high foaming power and rich foaming.

  Conventionally, as a foaming surfactant in these detergents, anionic surfactants, nonionic surfactants, amphoteric surfactants, amphoteric surfactants, semipolar surfactants, cationic surfactants have been used. Used as the main agent.

  In addition, when these are used alone as the main component of the cleaning agent, generally, there is a drawback that the quick foaming property (speed of foaming), the amount of foam, the foam quality and the like are not sufficient. Various studies have been made on blending of.

  In recent years, fatty acid monoethanolamide (Patent Document 1), polyoxypropylene fatty acid isopropanolamide mixture (Patent Document 2), hydroxyalkyl polyvalent An alcohol ether compound (Patent Document 3), glyceryl ether (Patent Document 4) and the like have been proposed.

  However, although these cleaning compositions also improve the cleaning properties, the amount of foam, and the foam quality, they are still not fully satisfactory in terms of quick foaming properties.

Japanese Patent Laid-Open No. 11-080785 Japanese Patent Application Laid-Open No. 09-020740 JP 2003-096435 A JP 2001-107097 A

  The object of the present invention is to be used together with anionic surfactants, nonionic surfactants, amphoteric surfactants, amphoteric surfactants, semipolar surfactants, foaming surfactants of cationic surfactants It is providing the foaming agent which is excellent in foaming speed by this, and the cleaning composition containing them.

  As a result of intensive studies to solve the above problems, the present inventors have determined that the tertiary amine compound having a specific structure having a specific structure of the present invention is a foaming property of a foamable surfactant, The present invention was completed by finding that it can be used as a foam-increasing agent having a function of increasing the rapid foaming property.

  That is, this invention relates to the foam increasing agent which consists of a tertiary amine compound which has a specific structure of General formula (1).

[However Shikichu ^{R 1} represents an alkyl group having 5-9 carbon atoms, X is Ri linking group Der - (OR ⁵⁾ pO- (provided that wherein ^{R 5} is the number may be branched carbon 1-3 An alkylene group, p is a number from 0 to 3), and n is a number from 1 to 3. R ² and R ³ each independently represent a C 1-3 alkyl group that may contain a hydroxyl group. ]

  More preferably, it relates to a foam-increasing agent wherein the substance of general formula (1) is octanoic acid dimethylaminoethyl ester.

  Further, (A) the aforementioned foam increasing agent and (B) anionic surfactant, nonionic surfactant (except for the compound of formula 1), amphoteric surfactant, amphoteric surfactant, cationic surfactant The present invention relates to a detergent composition containing a foaming surfactant composed of at least one selected from the group consisting of 2 or more.

  By adding the foam increasing agent of the present invention together with a foaming surfactant, it is possible to obtain a high foaming detergent having unprecedented fast foaming properties.

  Hereinafter, embodiments of the present invention will be described.

  The foaming agent component of the present invention is a compound containing a tertiary amine group having a specific structure specified by the general formula (1).

[However Shikichu ^{R 1} represents an alkyl group having 5-9 carbon atoms, X is Ri linking group Der - (OR ⁵⁾ pO- (provided that wherein ^{R 5} is the number may be branched carbon 1-3 An alkylene group, p is a number from 0 to 3), and n is a number from 1 to 3. R ² and R ³ each independently represent a C 1-3 alkyl group that may contain a hydroxyl group. ]

In the foam increasing agent of the present invention, it is important that R ¹ is an alkyl group having 5 to 9 carbon atoms. When the carbon number of R ¹ is less than 5, it is not preferable because the effect of increasing bubbles and rapid foaming does not occur, and when the number of carbon atoms of R ¹ exceeds 9, it is not preferable because the effect of fast foaming disappears. More preferably, R ¹ is an alkyl group having 7 carbon atoms.

  m is a number of 0 or 1, but m = 1, that is, it is preferable from the viewpoint of foaming property that a carbonyl group is included in the intermediate group.

X is a linking group and represents — (OR ⁵ ) pO—, —NR ⁴ —, and n represents a number of 1 to 3. In particular, — (OR ⁵ ) pO— is preferable in terms of excellent quick-foaming performance.

  n is a number of 1 to 3, but 2 to 3 is more preferable.

R ² and R ³ are alkyl groups having 1 to 3 carbon atoms which may have a hydroxyl group independently of each other, but it is more preferable that both R ² and R ³ are methyl groups.

  The compound containing a tertiary amine group having a specific structure specified by the general formula (1), which is the foaming agent component of the present invention, can be used for a halide containing a lipophilic group as shown in the following chemical formula. Can be easily obtained by subjecting the corresponding alkanolamine or diamine compound to a condensation reaction.

[However, L represents a halogen atom. Others are the same as in the general formula (1)]

Preferred examples of the compound of the general formula (1) include octanoic acid dimethylaminoethyl ester (R ¹ = alkyl having 7 carbons; m = 1; n = 2; R ² , R ³ = methyl group), dimethyl hexanoate Aminoethyl ester, isohexanoic acid dimethylaminoethyl ester, heptanoic acid dimethylaminoethyl ester, octanoic acid dimethylaminoethyl ester, 2-ethylhexanoic acid dimethylaminoethyl ester, hexanoic acid diethylaminoethyl ester, isohexanoic acid diethylaminoethyl ester, heptanoic acid diethylamino acid Ethyl ester, octanoic acid diethylaminoethyl ester, 2-ethylhexanoic acid diethylaminoethyl ester, hexanoic acid dihydroxyethylaminoethyl ester, isohexanoic acid dihydroxyethylamino ester Ester, heptanoic acid dihydroxyethylaminoethyl ester, octanoic acid dihydroxyethylaminoethyl ester, 2-ethylhexanoic acid dihydroxyethylaminoethyl ester, hexanoic acid dimethylaminopropyl ester, isohexanoic acid dimethylaminopropyl ester, heptanoic acid dimethylaminopropyl ester, Octanoic acid dimethylaminopropyl ester, 2-ethylhexanoic acid dimethylaminopropyl ester, hexanoic acid dimethylamino 2-propyl ester, isohexanoic acid dimethylamino 2-propyl ester, heptanoic acid dimethylamino 2-propyl ester, octanoic acid dimethylamino 2- ester Propyl ester, 2-ethylhexanoic acid dimethylamino 2-propyl ester, hexyl dimethylamino ester Ether, isohexyldimethylaminoethyl ether, heptyldimethylaminoethyl ether, octyldimethylaminoethyl ether, 2-ethylhexyldimethylaminoethyl ether, hexanoic acid dimethylaminoethylamide, isohexanoic acid dimethylaminoethylamide, heptanoic acid dimethylaminoethylamide, Octanoic acid dimethylaminoethylamide, 2-ethylhexanoic acid dimethylaminoethylamide, hexanoic acid dimethylaminopropylamide, isohexanoic acid dimethylaminopropylamide, heptanoic acid dimethylaminopropylamide, octanoic acid dimethylaminopropylamide, 2-ethylhexanoic acid Dimethylaminopropylamide is mentioned, but dimethylaminoethyl octoate is effective due to the effect of quick foaming and foaming. Esters are particularly preferred.

  The cleaning composition relating to the use of the present foam increasing agent will be described.

  The foaming agent of the present invention can be combined with a foaming surfactant to obtain a high foaming detergent having unprecedented fast foaming properties.

  Examples of the foaming surfactant include an anionic surfactant, a nonionic surfactant (excluding the compound of Formula 1), an amphoteric surfactant, a zwitterionic surfactant, and a cationic surfactant.

  Foaming surfactants alone vary in foaming performance depending on the type, and fatty acid salts and N-acyl amino acid surfactants are characterized by low irritation, but are well known to have weak foaming. Yes. The rapid foaming effect and the foam increasing effect by the combination with an anionic surfactant that is slow or difficult to foam are remarkable.

  The blending amount of the foam increasing agent of the present invention into the cleaning agent will be described in detail.

  Although this invention cleaning agent can be implemented by mix | blending (A) this invention foam increasing agent and (B) foaming surfactant, More preferably, A: B is 0.5: 19. A ratio of 5 to 6:14 is preferred. More preferably, it is 2.0: 18-3.0: 17.

  In the cleaning agent of the present invention, when the ratio of the foaming agent of the present invention is less than 0.5: 19.5, the quick foaming performance and foaming performance of the present invention are exhibited but the effect is small. If more than 6:14 is blended, the antifoaming property becomes strong, which is not preferable.

  When this invention cleaning agent is a liquid cleaning agent, the total compounding quantity of (A) this invention foam increasing agent and (B) foaming surfactant is 0.1 to 50 weight% of the whole liquid cleaning composition. It is preferable. More preferably, it is 5 to 30% by weight.

  As long as the effects of the present invention are not impaired, other components usually used in cosmetics, pharmaceuticals, and the like can be blended in the foam-containing detergent containing the present invention according to the purpose. For example, polymer compounds such as cationized cellulose, hydroxylated cellulose, and highly polymerized polyethylene oxide; anti-dandruff agents such as zinc pyrithione and benzalkonium chloride; vitamins; bactericides; anti-inflammatory agents; antiseptics; chelating agents; Moisturizing agents such as dyes, pigments, etc .; polar solvent extract of eucalyptus, shells or pearls having a nacre layer or hydrolysates thereof, proteins obtained from silk or hydrolysates thereof, legumes Protein-containing extracts obtained from plant seeds, ginseng extract, rice germ extract, hibermata extract, camellia extract, aloe extract, moon peach leaf extract, chlorella extract, etc .; Pearl such as titanium oxide Powders, fragrances, pigments, ultraviolet absorbers, antioxidants, and the like can be blended as necessary.

  Examples of the cleaning composition of the present invention include body cleaning compositions such as shampoos, hand soaps, body shampoos, and bar soaps, kitchen detergents, and laundry detergents.

  Hereinafter, the present invention will be described in more detail with reference to examples. The present invention is not limited to these examples. The blending amount is expressed in mass% unless otherwise specified.

  The foam increasing agents of the present invention were synthesized in the combinations shown in Table 1.

  The combination of Example 1 was octanoic acid dimethylaminoethyl ester. Specifically, 86 g (1 mol) of N, N-dimethylaminoethanol and 100 g of THF were stirred in a reaction vessel. The dropping funnel was used there, and 65 g (0.4 mol) of octanoic acid chloride was dripped over 30 minutes, cooling with ice so that reaction temperature might be 35 degrees C or less. After completion of dropping, the mixture was kept at room temperature for 2 hours. The completion of the reaction was confirmed by the disappearance of the starting octanoic acid chloride spot by TLC. The reaction solution was transferred to a separatory funnel and washed twice with saturated brine, and then the organic phase was dried over anhydrous sodium sulfate for 2 hours. After anhydrous sodium sulfate was removed by filtration, the solvent was distilled off under reduced pressure to obtain octamino acid dimethylaminoethyl ester.

  According to Table 2 and Table 3, the prepared samples were foamed surfactants (“Karaken Fine Chemical Co., Ltd.“ Alanon ALE ”: Lauroyl-N-methyl-β-alanine sodium, coconut soap: potassium laurate) and foam increase. An agent was blended, and the speed of foaming and the amount of foaming were evaluated for each detergent sample. “Amizole CME” in Comparative Examples 3 and 7 is coconut oil fatty acid monoethanolamide manufactured by Kawaken Fine Chemical Co., Ltd. The evaluation method is as follows.

(A) Fast-foaming property A detergent sample was diluted with water and adjusted so that the surfactant concentration was 1 wt%. A dynamic surface tension meter (“BUBBLE PRESURE TENSIOTER-BP-2” manufactured by KRUSS) was used to measure the dynamic surface tension accompanying the change over time by the maximum bubble pressure method at a measurement temperature of 25 ° C. Based on the obtained data, the dynamic surface tension curves at 0.1 to 1 second estimated as the initial foaming time were compared. Compared with the dynamic surface tension results of a 1% aqueous solution of a foaming surfactant alone component, which is the sample containing the foam increasing agent of the present invention (Examples 1 to 3) and its peripheral substances (Comparative Example 1)? The dynamic surface tension curve like this was drawn or analyzed. If the surface tension value is higher than the dynamic surface tension of the 1% aqueous solution of the foaming surfactant alone, it takes a long time for the surfactant adsorbing on the gas-liquid interface to reach saturated adsorption. Therefore, it can be said that the adsorption speed is slow, that is, it lacks fast foaming property. On the contrary, when the surface tension value is lower than the dynamic surface tension result of the 1% aqueous solution of the foaming surfactant alone component, it can be said that the rapid foaming property is high because the time until saturation adsorption is short. .

  Using the surface tension value at 0.5 second, which is the middle of 0.1 to 1 second, which is the initial foaming time, the difference in surface tension change was calculated from the following equation.

Γ ₀ in formula (I) is the dynamic surface tension value (mN / m) of a 1% aqueous solution of the foaming surfactant alone component in 0.5 seconds, and γ is the dynamic surface of the detergent sample. The tension value (mN / m). The larger the value calculated by the formula (I), the better the surface tension lowering ability, that is, the fast foaming property. Conversely, when the value is small or negative, it can be said that the fast foaming property is low or absent.

  Among the values calculated by the formula (I), the present inventors have a correlation that the samples exhibit a value of 3 mN / m or more, and have a rapid foam property even in sensory evaluation. I found out. Therefore, in this evaluation, it is preferably 3 mN / m or more in order to have high foamability.

(B) Foaming amount Sample produced as trial product in Table 2 Take 1 mL of active agent concentration 20%, and evaluate the foaming speed and foaming property (foaming property) for 30 seconds by hand washing by 10 panelists. Evaluation was made on the basis of Comparative Example 2 in Table 2. When the rapid foaming property and foaming property were inferior to those, “X” was indicated, and when it was excellent, “◯” was indicated.

(C) Foam quality Sensory evaluation by hand washing by 10 panelists was performed for each detergent sample. Comparative Example 2 in Table 2 was evaluated as a standard (ordinary), and evaluated according to an evaluation standard as to whether it was fine or coarse.

  As is clear from the results in Table 2, all the tertiary amine compounds within the scope of the present invention have excellent quick foaming properties and foam increasing properties. This effect is not found in the sample of Comparative Example 2 which is outside the range of the present foaming agent. This means that the foam increasing agent of the present invention is expressed only in a tertiary amine compound having a specific structure. Moreover, the effect as a foaming agent is excellent compared with the sample (Comparative Examples 1 and 2) using the conventionally used foaming agent. The above evaluation of the foam performance is a quantitative evaluation in accordance with the user's senses, and the cleaning composition in which all these evaluations are within the above range is recognized as having an effective feeling with high foam performance for all users. It is done.

  Further, as is apparent from the results of Table 3, it shows a higher Δγ value than the sample using the conventional foam increasing agent (Comparative Example 2), and it is understood that it is excellent in quick foaming property. .

The following detergent composition was prototyped by combining the foam increasing agent of the present invention and various foaming surfactants.
All showed excellent quick foaming properties and foam amount, and the overall evaluation was good.

Example 10 Shampoo composition (blending ingredients) (wt%)
Polyoxyethylene (3) sodium lauryl ether sulfate 12.0%
Coconut oil fatty acid amidopropyl betaine 4.0%
The amine of Example 1 5.0%
Ethylene glycol distearate 0.5%
Cationized cellulose 0.5%
Quaternium-33 1.0%
Cetyl alcohol 0.5%
Dimethylpolysiloxane (20cs) 1.0%
Glutamic acid 5% distilled water diluted solution pH = 4.0
Preservative 0.2%
Pigment proper amount Fragrance 0.3%
Purified water residue

Example 11 Hand soap composition for sterilization (blending component) (% by weight)
Lauric acid 5.5%
Lauric acid amidopropyldimethylamine oxide 3.0%
POE (3) lauryl ether acetic acid 3.0%
Benzalkonium chloride 1.0%
Benzethonium chloride 0.5%
The amine of Example 1 2.0%
N-coconut fatty acid acyl-N′-carboxymethyl-N′-ethylenediamine sodium salt
9.5%
Amount of triethanolamine pH = 7.8 Glycerol 3.0%
Purified water residue

Example 12 Body Shampoo (Compounding ingredients) (wt%)
Lauric acid 6.0%
Myristic acid 8.0%
Palmitic acid 2.0%
Potassium hydroxide 3.89%
Lauric acid amidopropyl hydroxysulfobetaine 3.0%
Lauroyl-N-methyl-β-alanine potassium 2.0%
The amine of Example 2 3.0%
Palm oil fatty acylglycine potassium salt 0.5%
Glycerin 5.0%
Ethylene glycol distearate 1.5%
Hydroxypropyl methylcellulose 0.2%
EDTA.4 sodium 0.2%
Methylparaben 0.2%
Purified water residue

Example 13 Transparent solid detergent composition (formulation component) (wt%)
Tallow fatty acid sodium 2.0%
Sodium palm fatty acid 8.0%
The amine of Example 1 5.0%
N-cocoyl-sodium glutamate 2.0%
Concentrated glycerin 8.0%
Sucrose 10.0%
Ethanol 15.0%
Lauric acid amidopropyldimethylamine oxide 7.0%
Hydroxyethane diphosphonic acid 0.5%
Purified water residue * Dry to 80% of the weight immediately after production to obtain a transparent solid detergent.

Example 14 Solid detergent composition (formulation component) (wt%)
Amisoft GS-11 (Ajinomoto Co., Inc.) 49.10%
Amisoft CK-11 (Ajinomoto Co., Inc.) 25.00%
Behenyl alcohol 2.00%
Isostearyl alcohol 3.00%
Allantoin 0.20%
The amine of Example 3 15.00%
EDTA · 2Na 0.10%
Titanium oxide 0.10%
Purified water 5.50%

  The foam increasing agent of the present invention is useful as a foam increasing agent for a cleaning agent because it is excellent in foaming speed when used with a foaming surfactant.

Claims (2)

(A) a foam increasing agent comprising a tertiary amine compound having the structure of the general formula (1) ;

[However Shikichu ^{R 1} represents an alkyl group having 5-9 carbon atoms, X is Ri linking group Der - (OR ⁵⁾ pO- (provided that wherein ^{R 5} is the number may be branched carbon 1-3 An alkylene group, p is a number from 0 to 3), and n is a number from 1 to 3. R ² and R ³ each independently represent a C 1-3 alkyl group that may contain a hydroxyl group. ]
(B) At least one or more selected from anionic surfactants, nonionic surfactants (excluding the compound of formula 1), amphoteric surfactants, zwitterionic surfactants, and cationic surfactants A detergent composition comprising a surfactant comprising: The cleaning composition according to claim 1, wherein the substance of the general formula (1) is octanoic acid dimethylaminoethyl ester .