JPH07122072B2 - Cleaning composition - Google Patents

Description

TECHNICAL FIELD The present invention relates to a detergent composition, and more particularly to a detergent composition having an excellent feeling in use and having excellent foamability under alkaline to weakly acidic conditions.

(Prior Art) Among the functions required for a detergent composition, the five items of safety, foaming property, foam sustainability, usability, and system stability are the most important points. Conventionally, as surfactants used for detergents, alkyl sulfates, alkyl sulfonates,
Anionic surfactants such as polyoxyethylene alkyl sulfates and alkylbenzene sulfonates have been widely used, but these surfactants have good foaming properties, but have poor foam lasting properties. It was not possible to obtain a skin cleanser having a slimy feel and always having good usability. Moreover, the soap which has been widely used in general is good in terms of "slickness", but it cannot be said to be sufficient in terms of foamability, foam persistence, and smooth feeling of use. Especially in neutral to weakly acidic conditions, the detergency and foaming power are significantly reduced. Then, there is an ether carboxylate type surfactant in which the cleaning power and the foaming power are improved under neutral to weak acidity. Specifically, poly (oxyethylene) alkyl ether carboxylate [eg, Chemical Society of Japan, 1385-1389 (198
[0]] is known, but it exhibits good detergency and foaming properties under neutral to weak alkali conditions, but is not necessarily satisfactory in terms of defoaming detergency in weakly acidic and neutral regions.

(Problems to be Solved by the Invention) Therefore, in the present invention, the foaming property is good over a wide range from weakly acidic to alkaline, which is not obtained by the combination of the surfactants used in the conventional detergent, and As a result of diligent studies to obtain a detergent composition having excellent durability, usability, and system stability, the use of the monocarboxylic acids represented by the general formula (I) described above results in mild acidity to alkalinity. The inventors have found that it is possible to obtain a detergent composition having a good foaming property over a wide range and having excellent safety, foam sustainability, usability, and system stability, and completed the present invention.

(Means for Solving Problems) That is, the present invention provides the following general formula (I): (In the formula, R is a linear or branched alkyl or alkenyl group having 4 to 34 carbon atoms; _one of X ₁ and X ₂ is —CH ₂ COOM, and the other is a hydrogen atom; M Is hydrogen atom, alkali metal, alkaline earth metal, ammonium,
It is a lower alkanolamine cation, a lower alkylamine cation, or a basic amino acid cation. ) A cleaning composition comprising a monocarboxylic acid represented by the following formula.

(Detailed Description of the Invention) In the general formula (I), the linear or branched alkyl group having 4 to 34 carbon atoms of R is a butyl group, an octyl group,
Decyl group, dodecyl group, butyl group, octyl group, decyl group, dodecyl group, tetradecyl group, hexadecyl group, octadecyl group, docosyl group, 2-ethylhexyl group, 2-hexyldecyl group, 2-octylundecyl group, 2- Examples include decyltetradecyl group and 2-undecylhexadecyl group. Examples of the linear or branched alkenyl group having 4 to 34 carbon atoms include decenyl group, dodecenyl group, tetradecenyl group, hexadecenyl group and octadecenyl group. Among R, preferable is a linear alkyl group having 8 to 16 carbon atoms from the viewpoint of surface activity, and particularly preferably a decyl group or a dodecyl group. These may be a mixture of two or more kinds.

Examples of the alkali metal represented by M in X ₁ and X ₂ of the general formula (I) include sodium, potassium and lithium. Examples of alkaline earth metals include calcium, magnesium and barium. Alkanolamines forming lower alkanolamine cations include mono-, di- or tri-ethanolamine, n and is
Alkylamines forming lower alkylamine cations such as o-propanolamine include monoethylamine, diethylamine, triethylamine and the like. Examples of the basic amino acid forming the basic amino acid cation include lysine, arginine, orniline, histidine and the like. Among M, alkali metal and lower alkanolamine cations are preferable, and sodium and triethanolamine cation are particularly preferable. These may be a mixed salt of two or more kinds.

By blending the monocarboxylic acids represented by the general formula (I) above, it is possible to obtain a detergent composition which is highly safe, has an excellent feeling in use, and exhibits excellent foaming properties under alkaline to weakly acidic conditions. . When blended in the detergent composition,
Considering functions such as foamability, the above-mentioned monocarboxylic acids used in the present invention are more dicarboxylic acids (that is, both X ₁ and X _{2 in} the above general formula (I) are —CH ₂ C).
Compounds that are OOM) are more preferred. The monocarboxylic acids of the present invention may be used as a mixture with the above dicarboxylic acids, but in this case, the monocarboxylic acids are preferably used by being contained in a large proportion in these mixed carboxylic acids, and preferably 20% by weight. % Or more, particularly 50% by weight or more is preferably used. The blending amount of the monocarboxylic acid used in the present invention varies depending on the dosage form of the detergent, but is 3 to 40% by weight in the composition in the case of a liquid, and 3 to 70 in the case of a paste.
% By weight, and 3 to 95% by weight in the case of solid detergent. When mixed with the above dicarboxylic acids, the mixed carboxylic acids are blended so that the total blending amount thereof falls within the above range.
The detergent composition of the present invention includes other surfactants such as alkyl sulfate, alkyl sulfonate, polyoxyethylene alkyl sulfate, alkylbenzene sulfonate, N-acyl sarcosine salt, N-acyl-N. -Methyl taurine salt, alkyl phosphate ester salt, alpha olefin sulfone sun salt, higher fatty acid ester sulfone sun salt, alkyl ether acetate, polyoxyethylene alkyl ether acetate, anionic surfactant such as fatty acid soap, fatty acid amide, poly The effect of the present invention is not impaired even if it contains an oxyethylene alkyl ether, a nonionic surfactant such as a silicolone-based surfactant such as a polyether-modified silicone, or an imidazoline-based or betaine-based amphoteric surfactant. Absent. Further, as other additives, in the composition of the present invention, a thickener, a curing agent, a cationic polymer, a usability improving agent such as an oily raw material such as silicone oil, a preservative, a sequestering agent, a perfume colorant, etc. The effects of the present invention are not impaired by adding the above.

The monocarboxylic acids represented by the above general formula (I) used in the present invention are novel substances, and synthetic examples are shown below. The following may be mentioned as specific examples of the compound.

In addition, in Table 1 above, Compound Nos. 28 to 36 are dicarboxylic acids in which X ₁ and X ₂ in the general formula (I) both represent —CH ₂ COOM, and the dicarboxylic acids are as described above. As described above, it may be used by mixing with the monocarboxylic acid of the present invention, and thus it is described as a reference example.

Synthesis Example 1 50.0 g of 1,2-dodecanediol, 250 g of dioxane and 5.7 g of sodium metal were added to a four-necked flask, the temperature was raised under a nitrogen stream, and the mixture was stirred at 100 ° C. for 5 hours for alcoholation. 7
After cooling to 0 ° C., 28.8 g of sodium monochloroacetate was gradually added, and after the addition was completed, the reaction was further continued for 3 hours to obtain Compound No. 10 of the present invention shown in Table 1 (crude yield; 80%). After the solvent was distilled off, column chromatography was performed to separate unreacted substances and by-products to obtain 20.5 g of a purified product of compound No10 of the present invention shown in Table-1. The analysis results are shown below.

Column chromatographic conditions Silica gel column (Wakogel C-200) Developing solvent Chloroform / methanol = 10/1 → methanol Elemental analysis (unit:%) Analytical value Calculated value C; 59.8 59.6 H; 9.6 9.6 O; 22.5 22.7 Na; 8.1 8.2 NMR (D ₂ 0) (δ) 0.86 (bt, 3H) 1.28 (bs, 18H) 3.28 to 3.61 (m, 2H) 3.70 to 4.10 (m, 3H) IR (KBr) (cm ^-1 ) 3370,2960,2925 , 2875 2855,1600,1465,1455 1425,1375,1325,1115 1100,720 Weak acid value (mgKOH / g) 199.5 (calculated value; 198.8) CMC (mol /) 3.1 × 10 ^-4 Synthesis example 2 4-neck flask 1,2-tetradecanediol (50.0 g), dioxane (250 g) and metallic sodium (5.0 g) were added to the mixture, and the mixture was heated under a nitrogen stream and stirred at 100 ° C. for 5 hours for alcoholation. After cooling to 70 ° C, 27.8 g of sodium monochloroacetate was gradually added, and after the addition was completed, the reaction was continued for 3 hours.
The compound No. 16 of the present invention shown in was obtained (crude yield; 78%).
After the solvent was distilled off, column chromatography was carried out to separate unreacted by-products, and 19.8 g of a purified product of the compound No. 16 of the present invention shown in Table 1 was obtained. The analysis results are shown below.

Column chromatographic conditions Silica gel column (Wakogel C-200) Developing solvent Chloroform / methanol = 10/1 → methanol Elemental analysis (unit:%) Analytical value Calculated value C; 62.2 62.0 H; 9.9 10.0 O; 20.4 20.6 Na; 7.5 7.4 NMR (D ₂ 0) (δ) 0.86 (bt, 3H) 1.27 (bs, 22H) 3.25 to 3.60 (m, 2H) 3.70 to 4.08 (m, 3H) IR (KBr) (cm ^-1 ) 3350,2960,2925 , 2875 2855,1610,1465,1455 1425,1375,1325,1115 720 Weak acid value (mgKOH / g) 180.0 (calculated value; 180.9) Synthesis Example 3 5.0 g of sodium hydroxy ether monocarboxylate obtained in Synthesis Example 1 After dissolving in 50 g of water and acidifying with hydrochloric acid, ether extraction was carried out and hydroxy ether monocarboxylic acid
Obtained 4.5 g. The analysis results are shown below.

Elemental analysis (unit:%) Analytical value Calculated value C; 64.4 64.6 H; 10.8 10.8 O; 24.8 24.6 Acid value (mgKOH / g) 216.0 (calculated value; 215.7) Melting point (℃) 45.3 Synthetic example 4 In a 4-neck flask 1,2-Dodecanediol (50.0 g), dioxane (250 g) and sodium metal (11.4 g) were added, the temperature was raised under a nitrogen stream, and the mixture was stirred at 100 ° C. for 5 hours for alcoholation. 7
After cooling to 0 ° C, 57.7 g of sodium monochloroacetate was gradually added, and after the addition was completed, the mixture was reacted at the same temperature for 3 hours, and Table 1
The compound A of the present invention shown in was obtained (crude yield; 80%). After distilling off the solvent, column chromatography was carried out to separate unreacted substances and by-products to obtain 19.8 g of a purified product of the compound A of the present invention shown in Table 1. The analysis results are shown below.

Column chromatographic conditions Silica gel column (Wakogel C-200) Developing solvent Chloroform / methanol = 10/1 → methanol Elemental analysis (unit:%) Analytical value Calculated value C; 53.2 53.0 H; 7.5 7.7 O; 26.3 26.5 Na; 12.9 12.7 NMR (D ₂ 0) (δ) 0.86 (bt, 3H) 1.28 (bs, 16H) 1.38 to 1.69 (m, 2H) 3.40 to 3.70 (m, 3H) 3.72 to 4.08 (m, 4H) IR (KBr) (cm ^-1 ) 3430,2955,2925,2850 1610,1465,1425,1320 1090,1070,720 Weak acid value (mgKOH / g) 311.0 (calculated value; 309.9) CMC (mol /) 4.5 × 10 ^-3 Synthesis example 5 4 To a one-necked flask, 50.0 g of 1,2-tetradecanediol, 250 g of dioxane and 10.0 g of sodium metal were added, the temperature was raised under a nitrogen stream, and the mixture was stirred at 100 ° C. for 5 hours for alcoholation. After cooling to 70 ° C, 55.6 g of sodium monochloroacetate was gradually added, and after the addition was completed, the mixture was reacted at the same temperature for 3 hours,
The compound No. 30 shown in Table 1 was obtained (crude yield; 75%). After distilling off the solvent, column chromatography was performed to separate unreacted substances and by-products, and the compound No.
18.2 g of 30 purified products were obtained. The analysis results are shown below.

Column chromatographic conditions Silica gel column (Wakogel C-200) Developing solvent Chloroform / methanol = 10 / 1-methanol Elemental analysis (unit:%) Analytical value Calculated value C; 55.3 55.4 H; 8.1 8.2 O; 24.7 24.6 Na; 11.9 11.8 NMR (D ₂ 0) (δ) 0.87 (bt, 3H) 1.29 (bs, 20H) 1.37 to 1.64 (m, 2H) 3.42 to 3.72 (m, 3H) 3.72 to 4.08 (m, 4H) IR (KBr) (cm ^-1 ) 3450,2955,2925,2850 1610,1465,1455,1425 1375,1325,1090,1070 720 Weak acid value (mgKOH / g) 289.0 (calculated value; 287.7) Synthetic example 6 Synthetic example 4 Sodium ether carboxylate 5.
0 g was dissolved in 50 g of water, acidified with hydrochloric acid and extracted with ether to obtain 4.6 g of diethercarboxylic acid. The analysis results are shown below.

Elemental analysis (unit:%) Analytical value Calculated value C; 62.2 62.4 H; 9.8 9.8 O; 27.9 27.7 Acid value (mgKOH / g) 324.1 (Calculated value; 324.3) Melting point (℃) 63.5 Synthetic example 7 In a 4-neck flask 1,2-Octanediol (50.0 g), dioxane (250 g) and sodium metal (5.8 g) were added, the temperature was raised under a nitrogen stream, and the mixture was stirred at 100 ° C. for 5 hours for alcoholation. 7
After cooling to 0 ° C, 29.1 g of sodium monochloroacetate was gradually added, and after the addition was completed, the mixture was reacted at the same temperature for 3 hours, and
The compound No. 3 of the present invention shown in 1 was obtained (crude yield; 82%).
After the solvent was distilled off, column chromatography was carried out to separate unreacted by-products and 16.4 g of a purified product of Compound No. 3 of the present invention shown in Table 1 was obtained. The analysis results are shown below.

Column chromatographic conditions Silica gel column (Wakogel C-200) Developing solvent Chloroform / methanol = 10 / 1-methanol Elemental analysis (unit:%) Analytical value Calculated value C; 53.0 53.1 H; 8.5 8.5 O; 28.3 28.3 Na; 10.2 10.2 IR (KBr) (cm ^-1 ) 3370,2960,2925,2875 2855,1600,1465,1455 1425,1375,1325,1100 720 Weak acid value (mgKOH / g) 246.8 (calculated value; 247.9) Synthetic example 8 4 mouths To the flask were added 1,2-tetracosanediol (55.6 g), dioxane (300 g) and metallic sodium (3.4 g), the temperature was raised under a nitrogen stream, and the mixture was stirred at 100 ° C. for 5 hours for alcoholation. After cooling to 70 ° C, 18.1 g of sodium monochloroacetate was gradually added, and after the addition was completed, the mixture was reacted at the same temperature for 3 hours,
The compound No25 of the present invention shown in Table 1 was obtained (crude yield; 65
%). After distilling off the solvent, column chromatography was carried out to separate unreacted substances and by-products to obtain 14.2 g of the purified compound No. 25 of the present invention shown in Table 1. The analysis results are shown below. Column chromatographic conditions Silica gel column (Wakogel C-200) Developing solvent Chloroform / methanol = 10/1 → methanol Elemental analysis (unit:%) Analytical value Calculated value C; 69.3 69.5 H; 11.3 11.3 O; 14.2 14.1 Na; 5.1 5.1 Weak acid Value (mgKOH / g) 123.1 (calculated value; 124.5) Synthesis Example 9 1,4-Tetracosanediol 44.5 g, dioxane 300 g, and sodium metal 5.5 g were added to a four-necked flask, and the temperature was raised under a nitrogen stream at 100 ° C. After stirring for 5 hours, alcoholation was carried out. After cooling to 70 ° C, 28.3 g of sodium monochloroacetate was gradually added, and after the addition was completed, the mixture was reacted at the same temperature for 3 hours,
The compound No35 shown in Table-1 was obtained (crude yield; 72%). After distilling off the solvent, column chromatography was performed to separate unreacted substances and by-products, and the compound No.
16.5 g of 35 purified products were obtained. The analysis results are shown below.

Column chromatographic conditions Silica gel column (Wakogel C-200) Developing solvent Chloroform / methanol = 10 / 1-methanol Elemental analysis (unit:%) Analytical value Calculated value C; 63.2 63.4 H; 10.0 9.9 O; 18.2 18.1 Na; 8.6 8.7 Weak acid Valence (mgKOH / g) 209.8 (calculated value; 211.4) (Effect of the invention) The effect of the present invention will be specifically described below with reference to Examples, but the present invention is not limited thereto. Prior to the examples, the test methods and evaluation methods adopted will be described.

Foaming power: CaCo ₃ 70 ppm artificial hard water was used to prepare 400 ml of a 5% sample solution, and the foaming amount (foam volume) was measured using a cylindrical cylinder equipped with a stirrer at a temperature of 30 ° C.

◎ Foaming is very good, foaming amount is 2100ml or more ○ Foaming is good, foaming amount is 1800 to 2100ml △ Foaming is normal, foaming amount is 1500 to 1800ml × Foaming is poor, foaming amount is less than 1500ml Sustainability of foam: After measuring the above foaming amount , The time required for the drainage volume to reach 200 ml was measured ◎ Very good sustainability, 300 seconds or more ○ Good sustainability, 200 to 300 seconds △ Normal sustainability, 100 to 200 seconds × Poor sustainability, 100 seconds Less than smoothness: Sensory evaluation panel evaluated by 10 persons.

◎ Very good, more than 8 people answered better than control ○ Good, 6-7 people answered better than control △ Normally 4-5 people answered better than control × Poor, 4 Less than name is better than control Ease of rinsing: Sensory evaluation panel 10 evaluated.

◎ Very good, more than 8 people answered better than control ○ Good, 6-7 people answered better than control △ Normally 4-5 people answered better than control × Poor, 4 Less than name is better than control System stability: We observed conditions such as syneresis, separation, and viscosity change from -5 ° C to 50 ° C.

◎ State does not change at all ○ State hardly changes △ State changes slightly × State changes Example 1 Liquid detergent composition Compound No10 25% Dipropylene glycol 5% Hydroxypropyl methylcellulose 1% Perfume Ion-exchanged water Residual Comparative Example 1 Potassium laurate 15% Potassium myristate 10% Dipropylene glycol 5% Hydroxypropyl methylcellulose 1% Perfume A suitable amount of ion-exchanged water Residual Example 2 Liquid detergent composition Compound No8 5% Potassium laurate 10% Potassium myristate 10% Glycerin 5% Carboxyvinyl polymer 1% Fragrance Suitable amount Ion-exchanged water Residual Comparative Example 2 Potassium laurate 15% Potassium myristate 10% Glycerin 5% Carboxyvinyl polymer 1% Fragrance Suitable amount Ion-exchanged water Residual Example 3 Paste-like washing Composition Compound No27 10% Potassium myristate 10% Potassium stearate 10% Beeswax 1% Glycerin 5% Polyethylene glycol 15% Fragrance A suitable amount of deionized water Residue Comparative Example 3 Potassium myristate 10% Potassium stearate 20% Beeswax 1% Glycerin 5% Polyethylene glycol 15% Fragrance Suitable amount Ion-exchanged water Residue Example 4 Paste-like detergent composition Compound No3 10% Compound A 10% Compound No30 40% Dipropylene glycol 5% Carboxyvinyl polymer 1% Fragrance Suitable amount Ion-exchanged water Residual Comparative Example 4 Potassium myristate 60% Dipropylene glycol 5% Carboxyvinyl polymer 1% Fragrance Suitable amount Ion-exchanged water Residual Example 5 Solid detergent composition Compound No10 90% Glycerin 8% Synthetic resin powder 0.2% Perfume Suitable amount Ion-exchanged water Residual comparison 5 Soybean tallow / coconut oil type sodium soap 90% Glycerin 8% Synthetic resin powder 0.2% Fragrance proper amount Ion-exchanged water Residual Example 6 Shampoo composition Compound No16 5% Sodium lauryl sulfate 5% Lauroylmethyl taurine sodium 10% Lauroylamide betaine 10% Palm fatty acid diethanolamide 5% Polyethylene glycol stearate 2% Fragrance Suitable amount Ion-exchanged water Residual Comparative Example 6 Sodium lauryl sulfate 10% Lauroylmethyl taurine sodium 10% Lauroylamide betaine 10% Palm fatty acid diethanolamide 5% Polyethylene glycol stearate 2% Fragrance Ion-exchanged water Residual Example 7 Shampoo composition Compound No10 5% Lauryl dimethylamidoacetate betaine 20% Lauroyl-β-alanine sodium 2% Stearyl methyl ammonium chloride Loride 3% Fragrance Suitable amount Ion-exchanged water Residual Example 7 Lauryldimethylamidoacetic acid betaine 25% Lauroyl-β-alanine sodium 2% Stearylmethylammonium chloride 3% Fragrance Suitable amount Ion-exchanged water Residual (evaluation result) As is clear from Table-2 to Table-5, by using the present invention, cleaning having a good foaming property over a wide range from weakly acidic to alkaline and having excellent foam durability, usability, and system stability. It was recognized that an agent composition could be obtained.
By the way, when the safety of each example was examined, all showed good safety.

Claims (1)

[Claims] 1. The following general formula (I): (In the formula, R is a linear or branched alkyl or alkenyl group having 4 to 34 carbon atoms. One of X ₁ and X ₂ is —CH ₂ COOM, and the other is a hydrogen atom. Is a hydrogen atom, an alkali metal, an alkaline earth metal, ammonium, a lower alkanolamine cation, a lower alkylamine cation, or a basic amino acid cation.) A cleaning agent containing a monocarboxylic acid represented by the formula: Composition.