JPH0420038B2 - - Google Patents

Description

[Detailed description of the invention]

The present invention relates to a novel solid detergent based on N-(N'-acylglycyl)glycine groups. In recent years, there has been a demand for detergents that have excellent surfactant properties as well as other properties such as safety and irritation to the eyes and skin. The field of solid detergents is no exception. Fatty acid soaps, solid synthetic detergents, composite soaps of fatty acid soaps and synthetic detergents, etc. have already been widely used, but all of these have various disadvantages. In other words, fatty acid soap has the disadvantage that the free alkali contained in the soap and the alkali generated by hydrolysis during use irritate the skin, and that when used in hard water, the foaming property decreases due to the formation of lime soap. There is. Composite soaps solve the problem of poor foaming in hard water, but adding synthetic detergents increases their degreasing ability, promotes skin irritation, and also reduces the gelling properties of soaps. Therefore, if the water is not sufficiently drained after use, it may melt and lose its shape. On the other hand, although synthetic detergent solids have excellent foaming properties in hard water and PH, synthetic detergents generally have a large ability to remove fat from the skin, causing skin damage. In addition, synthetic detergent solids generally have poor clumps when molded into solids, resulting in low workability during production. Furthermore, the aqueous solution of synthetic detergents usually does not gel, and if a molded product is left in a soap box after use, it will melt and disintegrate, causing problems such as loss of shape. The present inventor conducted screening research using various synthetic detergents as a base in order to obtain a solid synthetic detergent that has improved all of the properties required of a solid detergent, and as a result, discovered that N-(N'-acylglycyl )
It was discovered that glycine salt has good foaming power, moderate water solubility, little irritation to the skin, and gives a refreshing feel after washing, leading to the completion of the present invention. . That is, the present invention uses the general formula RCONHCH ₂ CONHCH ₂ COOM (wherein, RCO represents a saturated or unsaturated fatty acid residue having 6 to 22 carbon atoms, and M represents an alkali metal atom, an ammonium group, or an alkanolamine cation residue. The present invention provides a solid detergent characterized by having at least one type of N-(N'-acylglycyl)glycine salt represented by N-(N'-acylglycyl)glycine salt represented by the following formula (representing a cationic residue of a basic amino acid) as a base. N- used as a base for the solid detergent of the present invention
Examples of the acyl group represented by RCO in the above general formula of the (N'-acylglycyl)glycine salt include hexanoic acid, caprylic acid, capric acid, lauric acid, myristic acid, palmitic acid, stearic acid, erucic acid, isostearic acid, oleic acid,
Examples include saturated or unsaturated fatty acid residues having 6 to 22 carbon atoms, such as linoleic acid, isooleic acid, coconut oil fatty acid, beef tallow fatty acid, hydrogenated beef tallow fatty acid, and bran oil fatty acid. In addition, N-(N'-acylglycyl)glycine salts include alkali metal salts such as sodium, potassium and lithium, ammonium salts, monoethanolamine, diethanolamine, triethanolamine, monoisopropanolamine,
Preferred are alkanolamine salts in which the alkyl group has 2 to 3 carbon atoms, such as diisopropanolamine and triisopropanolamine, and basic amino acid salts, such as lysine, ornithine, and arginine. These N-(N'-acylglycyl)glycine salts used as a base for the solid detergent of the present invention may be used singly or in an appropriate combination of two or more. In addition, the properties of the product required as a solid detergent,
Adjuvants may be appropriately added to the solid detergent of the present invention according to usage preferences and the need to improve production efficiency in kneading, extrusion, molding, etc. Adjuvants include dyes, fragrances, and the following: The adjuvants may be used alone or in combination of two or more. However, if the total content of adjuvants in the solid detergent is N
-(N'-acylglycyl)glycine salt shall not be exceeded. (1) Plasticizer: An additive that adjusts the hardness of the product and the workability of mixing, extrusion, and molding, and is used in the range of 0 to 30% by weight per solid detergent. a) Lauryl alcohol, myristyl alcohol, cetyl alcohol, stearyl alcohol, oleyl alcohol, patyl alcohol,
Higher alcohols such as long-chain α,β-glycols. b) Higher fatty acids such as lauric acid, myristic acid, palmitic acid, stearic acid, 12-hydroxystearic acid. c) aspartic acid,
Acidic amino acids such as glutamic acid, basic amino acids such as lysine, ornithine, and arginine, and their salts. d) Iminodiacetic acid, iminodipropionic acid, iminodibutyric acid and their salts. e)N
-Long chain acyliminodiacetic acid, N-long chain acyliminodipropionic acid, N-long chain acyl-3:
Alkali metal salts or alkaline earth metal salts of N-long chain acylimino dibasic acids such as 3'-iminodibutyric acid. f) Beeswax, wood wax, spermaceti wax, bran wax, montan wax, carnaupal wax, stearyl stearate, palmityl palmitate, octyldodecyl myristate, isopropyl myristate, isopropyl palmitate, stearyl 2-ethylhexanoate, etc. Chain esters. g) Hydrocarbons such as solid paraffin, liquid paraffin, microcrystalline wax, and squalane. h) Ethylene glycol, polyethylene glycol, propylene glycol, polypropylene glycol, polyoxyethylene polyoxypropylene copolymer,
Glycols and polyhydric alcohols such as glycerin and sorbitol. i) Lanolin and derivatives. j) Lipids and their derivatives such as lecithin, hydrogenated lecithin, and cholesterol. k) Polyvinylpyrrolidone, polypynylmethyl ether, polyacrylates, polyalkylene oxides. 1) Polyhydric alcohols or their alkylene oxide derivatives and higher fatty acid esters of sugars (glycerin as polyhydric alcohols,
(alkylene glycol, polyalkylene glycol, sorbitol, sorbitan, pentaerythritol, etc.; sugars such as sucrose and glucose)
m) Polyoxyalkylene ethers such as higher alcohols, alkylamines, higher fatty acids, alkylmercaptans, and alkylphenols.
n) Acid amides of higher fatty acids such as stearic acid and amides and ammonia or organic amines. (2) Viscosity modifier: This additive is used to adjust the feel of foam when rubbed by hand during use, and is blended in an amount of 0 to 25% by weight per solid detergent. a) Water-soluble cellulose derivatives such as sodium carboxymethylcellulose, hydroxymethylcellulose, hydroxyethylcellulose, and hydroxypropylcellulose. b) Caseins such as milk casein. c) Gelatin.
d) Sodium alginate, propylene glycol alginate, carrageenan. e) Quaternary ammonium salts such as distearyldimethylammonium chloride, stearyltrimethylammonium chloride, myristyldimethylbenzylammonium chloride, and cationized cellulose. (3) Other surfactants: These are general anionic surfactants, amphoteric surfactants, and nonionic surfactants, which are used to adjust cleaning performance and dirt dispersibility. is suitable. These are blended in an amount of 0 to 40% by weight per solid detergent. a) Fatty acid soap. b) Higher alcohol sulfate ester salt. c) Polyoxyethylene higher alcohol sulfate salt. d) Higher alcohol phosphate esters and salts thereof. e) Polyoxyethylene higher alcohol phosphate ester and its salt. f) Polyoxyethylene higher fatty acid ethyl phosphate and its salts. g) Alcohol ester salts of sulfonated higher fatty acids. h) Sulfosuccinate salt of higher alcohol. i) Isethionic acid higher alcohol ester salt. j) Acyl taurine salt. k) α-Sulfo higher alcohol ester salt. l) Condensates of higher fatty acids and alkylolamines, such as lauric acid diethanolamide, stearic acid diethanolamide, lauric acid monoethanolamide, and stearic acid monoethanolamide, and ethylene oxide adducts thereof. m) Polyoxyethylene higher fatty acid monoethanolamide phosphate ester salt.
n) N-long chain acylamino acid salts such as N-long chain acyl sarcosine salts, N-long chain acyl-N-alkyl-β-alanine salts, N-long chain acyl glutamates and N-long chain acylaspartates; N-acyl peptide. o) 2-Alkyl-N-carboxymethyl-N-hydroxyethylimidazoliniumpetaine, alkylpropylpetaine. p) lauryl aminopropionate. q) Higher alkylminodiacetates such as laurylminodiacetate. r) Higher alkyldimethylpetaine, higher alkyldihydroxyethylpetaine. s) N-alkyloyl-
N'-(2-hydroxyethyl)-N'-carboxymethylethylenediamine salt, N-alkyloyl-N-(2-hydroxyethyl)-N',N'-
Amine amide compounds such as biscarpoxymethylethylene diamine salts. (4) Bulking agents a) Anhydrous silicic acid, magnesium silicate, colloidal magnesium aluminum silicate. b)
Magnesium oxide, zinc oxide. c) Metal soaps such as aluminum stearate, calcium stearate, magnesium stearate, zinc stearate. d) pareissillo starch;
Starches and their derivatives, such as wheat starch, rice starch, corn starch, and dextrins. e) Inorganic salts such as sodium chloride and potassium chloride. (5) Moisturizing agent a) 2-pyrrolidone-5-carboxylic acid and its salt. b) Hydrolyzed protein. c) N-acetylglycine salt. d) Lactate. (6) Other auxiliaries a) PH regulators for organic carboxylic acids such as malic acid and citric acid. b) Heavy metal ion scavengers such as EDTA. c) Fungicides such as 3,4,4'-trichlorocarbanilide, 2,4,4'-trichloro-2'-hydroxydiphenyl ether, undecylenic acid, zinc undecylenate, and undecylenic acid ethanolamide. d) Vitamin E. e) Medicinal plant powders such as comfrey and aloe. f) Ulcer therapeutic agents such as allantoin and glycyl phosphate. To produce the solid detergent of the present invention, N-(N'-
A mechanical kneading method for soap production may be employed, in which an appropriate amount of water is added to the acylglycylglycine salt alone or in combination with an auxiliary agent, and the mixture is kneaded with rolls, extruded, and molded by stamping. The amount of water to be added varies depending on the type and amount of the N-(N'-acylglycyl)glycine salt and the adjuvant used in combination.
It is usually 20% by weight or less per solid detergent, preferably 8 to 15% by weight. The solid detergent of the present invention thus produced has the following excellent performance. (1) Demonstrates good foaming power in both hard and soft water, giving the skin a refreshing feel after use without irritating the skin. (2) It dissolves appropriately during use, hardly melts or crumbles even when stored wet with water after use, and has particularly good shape retention properties. (3) Even if it is stored on a smooth surface such as a tile, a stainless steel plate, or inside a soap box after use, it has almost no property of firmly adhering. The present invention will be explained in more detail below using experimental examples and examples. Experimental Example 1 66.5 g (0.52 mol) of N-glycylglycine and 40.6 g (1,01 mol) of sodium hydroxide were dissolved in a mixed solvent of 567 ml of tetrahydrofuran and 567 ml of water and kept at 20°C to 30°C. 91.6 g (0.42 mol) of coconut oil fatty acid chloride was added to this solution under stirring.
was added dropwise over 2 hours. After further aging at the same temperature for 1 hour, concentrated hydrochloric acid was added to adjust the pH to 1, and the precipitated solid was collected and dried, yielding 116.6 g of N-(N'-coconut oil fatty acid acylglycyl)glycine. . The yield of this product was 91.0%, and the free fatty acid content was less than 10.0%. When this product was analyzed by infrared spectroscopy, it was confirmed that it had been acylated based on the occurrence of absorption due to the amide group at 1640 cm ^-1 in the infrared absorption spectrum and the disappearance of absorption due to the -COCl group at 1800 cm ^-1 . Ta. Experimental Example 2 1% of N-(N'-coconut oil fatty acid acylglycyl)glycine (produced in Experimental Example 1), N-(N'-beef tallow fatty acid acyl)glycylglycine, and a (1:1) mixture thereof An aqueous solution was prepared, and the pH was adjusted to 7.0 with sodium hydroxide and used as a sample. N-mixed fatty acyl-L-sodium glutamate (trade name Amisoft GS-11, manufactured by Ajinomoto Co., Inc.) whose pH was adjusted in the same way using this sample and hydrochloric acid.
Two drops of the aqueous solution were placed on a closed batch test bandage made by Torii Pharmaceutical Co., Ltd., and 20 healthy men aged 25 to 40 were tested.
The adhesive was applied to the back of the neck for 24 hours, and 2 hours after the adhesive was removed, the condition of the skin was evaluated for skin irritation according to the following criteria. Evaluation criteria for ΓSkin irritation - No reaction ± Slightly discernible erythema + erythema Erythema + edema Erythema + edema + blisters The skin irritation results are shown in Table 1.

[Table] From this result, N-
It was found that sodium (N'-acylglycyl)glycine causes only mild irritation to the skin. Example 1 880g of sodium N-(N'-coconut oil fatty acid acylglycyl)glycine and 120g of water were mixed, thoroughly kneaded using a small roll, and extruded into a rod shape using an experimental soap extruder with a mouth temperature maintained at 45°C. The detergent was molded into a solid detergent measuring 50 mm x 35 mm x 10 mm and weighing approximately 20 g using a foot-operated molding machine. Comparative Example 1 Sodium N-mixed fatty acid acyl-L-glutamate (trade name Amisoft GS-11, manufactured by Ajinomoto Co., Inc.)
880 g and 120 g of water were mixed and molded in the same manner as in Example 1 to obtain a solid detergent. The solid detergents of Example 1 and Comparative Example 1 were evaluated for foamability, meltability, and adhesion by hand washing tests. The results are shown in Table 2.

[Table] Each test method is as follows. (1) Foaming property 10 people (5 men, 5 women) conducted a hand washing test with warm water at approximately 40℃, and if the foaming of the solid detergent was the same as that of the sample of Comparative Example 1, The evaluation score was 0, +1 for better, and -1 for worse, and the following judgment was made according to the total score of the 10 evaluations. −10−−6……× − 5~0……△ 1~5……○ 6~10……◎ (2) Dissolution test Water was placed in a plastic soap box measuring 62 mm long x 45 mm wide x 20 mm wide. Pour 5ml into it, 50mm x 35mm x 10
A solid detergent molded to a size of 20 g and weighing approximately 20 g was immersed in the bath, and after being left for 24 hours, the way the solid detergent crumbled was observed. The evaluation method is one that completely retains its original form,
Items that have almost kept their original shape are rated ○, items that are slightly collapsed are rated △, and items that are completely collapsed are rated ×.
The measurement was performed three times for each sample, and the evaluation was based on the average of the measurements. (3) Adhesion Wet the surface of the solid detergent with water, place a polyethylene adhesive terminal on top of it, and observe how the adhesive terminal separates from the solid detergent after 24 hours. As for the evaluation method, those that were easy to separate from the sample of Comparative Example 1, those that were the same, and those that were difficult to separate were marked as ×. The measurement was performed three times for each sample, and the evaluation was based on the average. Example 2 A solid detergent having the following formulation was prepared in the same manner as in Example 1, and evaluated according to Example 1. In addition, Examples 3 to 6 below were similarly prepared and evaluated in detail. ●N-(N'-Tallow fatty acid acylglycyl) sodium glycine 850g ●Water 130 ●Glycerin 20 Example 3 ●N-(N'-lauroylglycyl)glycine sodium 800g ●Lauric acid diethanolamide 50 ●Glycerin 30 ●Water 120 Example 4 ●N-(N'-stearoylglycyl)glycine potassium 800g ●Coconut oil fatty acid diethanolamide 50 ●Glycerin 30 ●Water 120 Example 5 ●N-(N'-decanoylglycyl)glycine sodium 450g ●N- Sodium mixed fatty acid acylglutamate
350 (Product name Amisoft GS-11, manufactured by Ajinomoto Co., Inc.) ●Cetyl alcohol 80 ●Water 120 Example 6 ●N-(N'-hardened beef tallow fatty acid acylglycyl) glycine triethanolamine 350g ●N-(N'-coconut) Oil fatty acid acylglycyl) sodium glycine 350 ●Stearyl alcohol 100 ●Dextrin 130 ●Water 70 The solid detergents of Examples 2 to 6 all foamed,
It had excellent performance in both dissolution and adhesion.

Claims (1)

[Claims] 1 General formula RCONHCH ₂ CONHCH ₂ COOM [In the formula, RCO represents a saturated or unsaturated fatty acid residue having 6 to 22 carbon atoms, and M represents an alkali metal atom, an ammonium group, or an alkanolamine. Represents a cationic residue or a cationic residue of a basic amino acid. ] A solid detergent characterized by having at least one type of N-(N'-acylglycyl)glycine salt as a base.