JPH04154716A - Cleaner for body - Google Patents

Abstract

PURPOSE:To obtain a cleaner for body having heat and chemical stabilities and extremely low irritation to the skin and eyes, comprising a maltitol hydroxyaliphatic ether. CONSTITUTION:A cleaner for body containing 0.1-10wt.% compound shown by the formula (A is residue after removal of n X OH groups from maltitol; R<1> and R<2> are H or 1-20C alkyl; (n) is 1 or 2). The compound shown by the formula has stability and safety both of which are not shown in conventional nonionic surfactants, and when the compound is mixed with another surfactant, the compound shows irritation reducing action on the skin and eyes. The compound shown by the formula is stable to heat and will not evolve formaldehyde, etc. The cleaner may be optionally mixed with generally usable various components (e.g. powder component, oil component, humectant, antioxidant, antiseptic and perfume) besides the compound shown by the formula as an essential component and is used as soap, skin cleaner, hair cleaner, hand cleaner, dentifrice, etc.

Description

[Detailed Description of the Invention] [Industrial Application Field] The present invention provides a body cleansing agent that is chemically stable and has extremely low irritation to the skin and eyes by incorporating maltitol hydroxy aliphatic ether. Regarding.

[Prior art 1] Cleaning agents are used for the purpose of removing dirt adhering to the surface or inside of objects, and are used for 1) body use, 2) clothing and textile products, 3) other dishes, bathtubs, etc. Broadly divided into cleaning and other uses.

Conventionally, nonionic surfactants have been used in many cleaning agents.

Commonly used nonionic surfactants include polyoxyethylene sorbitan fatty acid ester, polyoxyethylene glycol fatty acid ester, polyoxyethylene alkyl ether, and alkyl glucoside.

[Problem to be solved by the invention 1] Are the surfactants contained in these detergents agents that exhibit the cleaning power and foaming power that are the inherent properties of detergents, or do they have any effect on the skin? Are known. Cleaners that come into direct contact with the skin are required to be mildly irritating to the skin and eyes.

In addition, among nonionic surfactants, nonionic surfactants containing low molecular weight oxyethylene chains, etc., which are the most widely used, have the advantage of having a wide HLB range and being able to be adjusted arbitrarily. On the other hand, they generally undergo oxidation over time and generate low-molecular-weight aldehydes and organic acids, causing odor and skin irritation, as well as causing a decrease in pH.

In view of the above circumstances, the inventors of the present invention have conducted extensive studies and found that by incorporating maltitol hydroxy aliphatic ether into cleaning agents, the problems associated with conventionally used nonionic surfactants can be avoided. The present inventors have discovered that, when used in combination with other surfactants, they have the effect of reducing irritation to the skin and eyes, leading to the completion of the present invention.

[Means for Solving the Problems] That is, the present invention has the following general formula (1)% formula% (wherein A is a residue obtained by removing n hydroxyl groups from maltitol, and R1 and R2 are both hydrogen Atom, carbon number 1
~20 alkyl groups or branched alkyl groups, where n represents 1 or 2. ) is a body cleansing agent characterized by containing maltitol hydroxy aliphatic ether represented by:

The structure of the present invention will be explained in detail below.

In the above general formula (I), specific examples of C1 to C20 alkyl groups and branched alkyl groups other than hydrogen atoms for R1 and R2 include methyl group, ethyl group, isopropyl group, pentyl group, hexyl group, Examples include heptyl group, octyl group, lauryl group, myristyl group, palmityl group, stearyl group, 2-ethylhexyl group, and isostearyl group.

In the above general formula (I), the residue A is maltitol, which is a hydrophilic group, and R1 and R2 are hydrophobic groups. Therefore, the total number of carbon atoms in R1 and R2 is preferably 10 to 20.

If the total number of carbon atoms in R1 and R2 is outside the range of 10 to 20, the balance between hydrophilicity and hydrophobicity will be lost and the range of use as an activator will be narrowed. Furthermore, in general formula (1), when n is 3 or more, the product becomes wax and is difficult to use as an activator.

The maltitol hydroxy aliphatic ether used in the present invention can be prepared, for example, by the method of Hase et al.
(No.). That is, maltitol can be mixed with dimethylformamide, dimethyl sulfoxide,
General formula (II) is dissolved in a non-aqueous solvent such as dioxane, dimethylacetamide, N-methylpyrrolidone, N-acedelmorpholine, N-methylsuccinimide, etc.
: (wherein R1 and R2 are the same as the formula (1) above) is added, and in the presence of a catalyst, 50
It is obtained by stirring and reacting at ~130'C.

At this time, the compound represented by the general formula (II) may be used alone or 2
More than one species may be used in combination.

The above-mentioned catalysts include mineral acids such as sulfuric acid, alkalis such as lithium hydroxide, sodium hydroxide, potassium hydroxide, sodium alcoholades such as sodium methylate and sodium ethylate, and amines such as N-methylbenzylamine. etc.

The molar ratio of maltitol and the compound represented by general formula (II) used in this reaction is, for example, 1:1 to 3:1, more preferably 2:1 when monoether is to be obtained as the main product. ~3:1. If there is too little maltitol, impurities such as triether are likely to occur, and if it is too much, a large amount of maltitol will remain and cause problems in subsequent purification.

When the compound represented by general formula (II) is completely consumed, acetic acid, hydrochloric acid, sulfuric acid,
An acid such as phosphoric acid, an alkali such as lithium hydroxide, sodium hydroxide, potassium hydroxide, etc. are added, and the reaction solvent is distilled off under reduced pressure.

The reaction product thus obtained has the general formula (I)
In addition to the maltitol hydroxy aliphatic ether represented by, salts during neutralization, maltitol, maltitol aliphatic ethers with three or more alkyl groups or branched alkyl groups, etc. coexist. Therefore, for example, when removing maltitol and salt, it is necessary to extract it with a solvent that does not dissolve maltitol such as methyl alcohol, ethyl alcohol, butyl alcohol, or isopropyl alcohol, or to partition it between water containing a large amount of salt and methyl ethyl ketone or n-butanol. It can be purified by separating the organic solvent layer.

In addition, when removing maltitol and salt and maltitol aliphatic ether bonded with three or more alkyl groups or branched alkyl groups, the reaction product is suspended in water or a mixture of water and alcohol, and hyperporous polymer (For example, high porous resin manufactured by Mitsubishi Chemical Industries, Ltd.), octadecyl silica, etc., are first passed through a reverse phase distribution column with water, and then a mixture of water and an alcohol such as methanol, ethanol, or a polar organic solvent such as acetonitrile. Pass the liquid through the
Purification can be achieved by fractionating this liquid.

The maltitol aliphatic ether synthesized as described above is
It may be used after distilling off the extraction solvent or purifying with a column, or it may be used as it is.

In addition, the body cleansing agent in the present invention is intended to remove dirt from the human body, and specifically includes the following, but the present invention is not limited to these. isn't it.

There are toilet soaps, skin cleansers, hair cleansers, hand cleaners, toothpaste, etc.

Maltitol hydroxy aliphatic ether can be blended in any amount in the body cleansing agent of the present invention, but it is 0.01 to 30% by weight (hereinafter abbreviated as %), preferably 0.1 to 10% of the total amount of the cleansing agent. There is.

In addition to the above-mentioned essential components, the detergent of the present invention may contain various components commonly used in detergents, if necessary, within a range that does not impair the effects of the invention. For example, powdered ingredients such as scrubs, avocado oil, macadamia nut oil, corn oil, olive oil, rapeseed oil, evening primrose oil, castor oil, sunflower oil, tea seed oil, rice bran oil, jojoba oil, cacao butter, coconut oil, squalene. , squalane, tallow, Japanese wax, beeswax, candelilla wax, carnauba wax, spermaceti, lanolin, silicone oil, liquid paraffin,
Ceresin, petrolatum, polyoxyethylene (8 mol) oleyl alcohol ether, oils such as glyceryl monooleate, caprylic alcohol, lauryl alcohol,
Higher alcohols such as myristyl alcohol, cetyl alcohol, cholesterol, and phytosterols, higher fatty acids such as capric acid, lauric acid, myristic acid, palmitic acid, stearic acid, behenic acid, lanolin fatty acids, linoleic acid, and linuric acid, polyethylene glycol, glycerin, Sorbitol, xylitol, maltitol,
Mucopolysaccharides, hyaluronic acid, chondroitin sulfate, humectants such as chitosan, methylcellulose, ethylcellulose,
Thickeners such as gum arabic, polyvinyl alcohol, montmorillonite, laponite, organic solvents such as ethanol, 1,3-butylene glycol, butylated hydroxytoluene, tocopherol, antioxidants such as phytic acid, benzoic acid, salicylic acid, sorbic acid, Antibacterial preservatives such as dehydroacetic acid, paraoxybenzoic acid alkyl esters (ethylparaben, butylparaben, etc.), hexachlorophene,
Glycine, alanine, valine, leucine, serine, threonine, phenylalanine, tyrosine, aspartic acid, asparagine, glutamine, taurine, arginine,
Amino acids such as histidine and their alkali metal salts and hydrochlorides, acylsarcosinates (e.g. sodium lauroylcosinate), organic acids such as glutathione, citric acid, malic acid, tartaric acid, lactic acid, vitamin A and its derivatives, vitamin B6 hydrochloride , vitamin B6 tripalmitate, vitamin B6 dioctanoate, vitamin B2 and its derivatives, vitamin B12, vitamin B15 and its derivatives, ascorbic acid, ascorbic acid sulfate (salt), ascorbic acid phosphate (
salt), vitamin C such as ascorbyl dipalmitate, α-tocopherol, β-tocopherol, 7-docopherol, vitamin E such as vitamin E acetate, vitamin E nicotinate, vitamin D, vitamin H1
Vitamins such as pantothenic acid and pantethine, nicotinamide, benzyl nicotinate, 7-oryzanol, tranexamic acid, epsilon caproic acid, allantoin, glycyrrhizic acid (salt), glycyrrhetinic acid and its derivatives, hinokitiol, mucidin, bisabolol, eucarib Toll, thymol, inositol, saponins (saponin, carrot saponin, hetyl ether, ethinyl estradiol, cephalanthine, placenta extract, etc.), staghorn, clara, kola shimane, oreshji, sage, yarrow, mallow, nematode, Japanese japonica, thyme, fir tree, spruce, birch, horsetail, loofah, horse chestnut, saxifrage, aljiki,
Natural extracts of lily, mugwort, peony, aloe, gardenia, Spanish mackerel, etc. extracted with organic solvents, alcohol, polyhydric alcohol, water, aqueous alcohol, etc., pigments, sorbitan monolaurate, sorbitan monopalmitate, sorbitan sesquioleate, trio Sorbitan oleate, polyoxyethylene sorbitan monolaurate, polyoxyethylene sorbitan monostearate, polyethylene glycol monooleate, polyoxyethylene alkyl ether, glycol diester, lauroyl jetanolamide, fatty acid isopropanolamide,
Nonionic surfactants such as alkylated polysaccharides, alkyl glucosides, sugar esters, cationic surfactants such as stearyltrimethylammonium chloride, benzalkonium chloride, laurylamine oxide, sodium palmitate, sodium laurate, sodium lauryl sulfate, lauryl Anionic surfactants such as potassium sulfate, alkyl sulfate triethanolamine ether, funnel oil, linear dodecylbenzene sulfate, polyoxyethylene hydrogenated castor oil maleic acid, hydroxyether carboxylic acid, acyl methyl taurine, amphoteric surfactants, fragrances,
Purified water etc. can be blended.

[Example] Next, the present invention will be explained in more detail with reference to Examples.

Note that the present invention is not limited to this. The blending amount is in weight%.

The maltitol hydroxy aliphatic ether of the present invention exhibits stability and safety that are not found in conventional nonionic surfactants, and when used in combination with other surfactants, exhibits the effect of reducing irritation to the skin and eyes. For this purpose, we conducted hydrolysis tests, measured the amount of formalin generated, and conducted practical use tests.

(Hydrolysis test) A 1% aqueous solution of maltitol hydroxymyristyl ether was heated at 900C for 5 hours, but all samples were stable with almost no hydrolysis observed.

On the other hand, with commercially available sucrose laurate and polyethylene glycol (PEG) laurate, the first
As shown in the table, under the same conditions, approximately 20% and 2%, respectively.
Decomposition of the ester group was observed.

The above-mentioned hydrolysis reaction was measured by taking a certain amount of the cooled aqueous solution, extracting it with ethyl ether, and determining it from the gas chromatogram of the extract.

(Measurement of Formalin Generation Amount) Maltitol hydroxylauryl ether was left on an 8000 container for 100 hours, and then 5 g of each sample was collected. Then 500 ml of water and 3 ml of diluted phosphoric acid.
1 was added and distilled, and when the distilled volume reached 190 ml, the distillation was stopped and water was added to make 200 ml, which was used as a test solution.

To 10 ml of this test solution was added 5 ml of acetylacetone, shaken, and heated in a 600 C water bath for 10 minutes. After cooling, the absorbance at the maximum absorption wavelength around 420 nm was measured, and as shown in Table 1, no aldehyde was observed.

On the other hand, when polyethylene glycol laurate was similarly treated and evaluated, the presence of aldehyde was observed as shown in Table 1.

In addition, as shown in Table 1, the presence of aldehyde was not observed in sucrose lauric acid ester even when treated in the same manner.

(Actual use test) A cleaning agent with the formulation shown in Example 1 and a cleaning agent with the formulation shown in Comparative Example 1.2 were each prepared by a conventional method, and were administered to a panel of 50 housewives in each group using protective gloves and hand cream. After prohibiting the use of the product, an actual use test was conducted for 60 days in winter.

After 60 days, a replica of the skin was taken using a silicone resin replica method to examine the surface morphology of the skin on the palm of the hand and examined under a microscope (
Observation was made at a magnification of 17 times. That is, the state of rough skin was evaluated based on the criteria shown in Table 2 from the state of skin marks and the state of peeling of the stratum corneum. The results are shown in Table-3.

Example 1 Polyoxyethylene (3 mol) 15
．． 0 Sodium lauryl sulfate Maltitol Hydroxy 5.0 Lauryl ether Coconut oil fatty acid diethanol 5,0 Luamite ethanol 2.0 Fragrance Appropriate amount Pigment
Appropriate amount of purified water
Remaining Comparative Example 1.2 Table 2 Judgment was made based on the score based on the following criteria.

○: The percentage of panels that scored 3.4 and 5 was 75.
% or more △: The percentage of panels rated 3.4 and 5 is 25
% or more and less than 75%×: The percentage of panels rated 3.4 and 5 is 25
Less than % Table 3 Actual use test results From the above, the cleaning agent of the present invention does not undergo oxidation over time, does not generate low molecular weight aldehydes or organic acids, and does not cause odor or skin irritation. It does not have the problem of causing a decrease in pH.

In addition, practical tests have shown that the cleaning agent containing maltitol hydroxy aliphatic ether of the present invention not only has stability and safety not found in cleaning agents containing conventional nonionic surfactants. It was found that when used in combination with other surfactants, it works to reduce skin irritation.

Example 2 Liquid detergent A liquid detergent was produced by a conventional method according to the following recipe.

Polyoxyethylene (3 mol) lauryl 15.
0 Ether sodium sulfate maltitol hydroxymyristyl 20.0 Ether distearyl dimethyl ammonium 2.0 Chloride fragrance Appropriate amount of purified water
Remaining Example 3 Body Soap A body soap was manufactured by a conventional method according to the following recipe.

Polyoxyethylene (3 mol) 15
．． 0 Sodium lauryl sulfate maltitol hydroxy 5.0 Stearyl ether polyoxyethylene (15 mol) 2.0 Lauryl ether laurylamide provil 5.0 Betaine ethanol 2.0 Fragrance Appropriate amount Pigment
Appropriate amount of purified water
Remaining Example 4 Kneaded Toothpaste A kneaded toothpaste was manufactured by a conventional method according to the following recipe.

Magnesium Carbonate 40.0 Maltitol Hydroxy 1.0 Decyl Ether Glycerin 40.0 Sweetener Appropriate Flavoring
Appropriate amount of pigment
Appropriate amount of preservative
The detergents obtained in appropriate amounts from Examples 2 to 4 were chemically stable and exhibited extremely low irritation to the skin and eyes.

〔Effect of the invention〕

The body cleanser of the present invention is extremely non-irritating to the skin and eyes. In addition, it is stable against heat and does not generate polmaldehyde.

Claims (1)

[Claims] (1) A body cleanser characterized by containing a maltitol hydroxy aliphatic ether represented by the following general formula (I). ▲There are mathematical formulas, chemical formulas, tables, etc.▼ (I) (However, in the formula, A is the residue obtained by removing n hydroxyl groups from maltitol, R^1 and R^2 are both hydrogen atoms, and have 1 to 1 carbon atoms. 20 alkyl groups or branched alkyl groups, where n represents 1 or 2.)