JPH02166187A - Liquid composition - Google Patents

Abstract

PURPOSE:To suppress crystallization of a crystalline compd. at low temp. and to improve solubility and stability at low temp. by compounding one or more carboxylate amphoteric surface active agents in a liq. compsn. prepared by dissolving a crystalline compd. in a solvent. CONSTITUTION:A liq. compsn. prepd. by dissolving a crystalline compd. such as an 8-30C alkyl group-contg. fatty acids (or their salts), aliph. alcohols and fatty acid deriv. (e.g. glycerol monopalmitate) in a non-aq. solvent pref. contg. 5% or less water (e.g. ethyl alcohol/water=99.5/0.5) is compounded with one or more carboxylate amphoteric surface active agents of, e.g. the formula R<1> NHCH2CH2COOH or formula I (wherein R<1-4> are each a 1-30C hydrocarbon group) and, if necessary, a nonionic surface active agent with an HLB value of 10 or larger (e.g. sorbitan monolaurate).

Description

DETAILED DESCRIPTION OF THE INVENTION The present invention is characterized in that a crystalline compound such as a fatty acid having an alkyl group having 8 to 30 carbon atoms, a salt thereof, an aliphatic alcohol, or a fatty acid derivative is dissolved in water or an organic solvent. More specifically, it relates to a liquid composition that has excellent low-temperature stability and that prevents crystallization of the above-mentioned crystalline compound as much as possible at low temperatures.

Transparent liquid cosmetics that are made by dissolving crystalline compounds such as fatty acids and their salts, aliphatic alcohols, and fatty acid derivatives having an alkyl group of 8 to 30 carbon atoms in water or organic solvents have been widely used for a long time. It is known that when these crystalline compounds are blended into liquid products and dissolved, there is a limit to the amount that can be blended, as crystalline compounds generally have a specific solubility in each type of solvent, and the solubility is temperature dependent, even if a crystalline compound is completely dissolved at room temperature.

If the temperature is lowered, the solution may become cloudy or crystals may precipitate. Furthermore, in order to prevent cloudiness and crystal precipitation at low temperatures, one crystalline compound is blended under conditions below its solubility; however, in this case as well, the third component blended at the same time causes a coprecipitation phenomenon, causing the solution to deteriorate. It may cause clouding or crystal precipitation.

In particular, for transparent liquid products, it is a fatal problem that the solution becomes cloudy or crystals precipitate at low temperatures, as described above, due to the chemical structure of the substances used. There is also a concern that the effectiveness of the product may be reduced if the active ingredient is

Despite these current conditions, in terms of commercial value, liquid products such as cosmetics and skin preparations are not stable under storage conditions ranging from a low temperature of about -5°C in winter to a high temperature of 40°C or above 40°C in midsummer. It is necessary to demonstrate quality.

Conventionally, as a method of suppressing crystallization or precipitation of crystals in a liquid system, a copolymer of ethylene and carboxylic acid vinyl ester has been used in fuel oil, as described in JP-A-58-129.
No. 096 and No. 62-84186. Also used as a low-temperature stabilizer for fatty acids and their derivatives.
(The use of nonionic surfactants with an HLB value of 10 or less is disclosed in Japanese Patent Application Laid-open No. 31-1,5815, such as polyvinylpyrrolidone, etc., in order to suppress crystal precipitation in gel compositions of poorly soluble pharmaceuticals. The use of Therefore, it has been desired to develop a liquid composition with high solubility of crystalline compounds even at low temperatures.

The present invention has been made in view of the above circumstances, and provides a liquid composition containing a crystalline compound with excellent low-temperature stability, with almost no clouding or crystal precipitation of the crystalline compound observed even when stored at low temperatures for a long period of time. The purpose is to provide

In order to achieve the above object, the present inventors have made extensive studies and found that at least one carboxylic acid type amphoteric surfactant is a fatty acid having an alkyl group having 8 to 30 carbon atoms, or a salt thereof. When blended into a liquid composition in which crystalline compounds such as aliphatic alcohols and fatty acid derivatives are dissolved, it suppresses the crystallization of these crystalline compounds at low temperatures and exhibits excellent effects of improving solubility and low-temperature stability. , it is possible to obtain a liquid composition with excellent low-temperature stability, with almost no clouding of the solution or precipitation of crystals even when stored for a long period of time at a low temperature of about -5°C, and in addition to the above-mentioned amphoteric surfactants. It was discovered that the above effects can be more effectively exhibited by adding a nonionic surfactant having an HLB value of 10 or less, and the present invention was completed based on this finding.

The following two inventions will be explained in more detail.

As described above, the liquid composition of the present invention contains a carboxylic acid type amphoteric surfactant as a crystallization inhibitor for a crystalline compound.

Here, the carboxylic acid type amphoteric surfactant used in the present invention has at least one cationic functional group and one or more anionic functional group in the molecule, for example, the following general formula (
1) or (IN).

[1] R'NHCH20H, C0OH7 amino acid type R+ (However, in formula 1, R", R", R", and R' are each a hydrocarbon group having 1 to 30 carbon atoms. The same applies hereinafter) Specifically, acid type amphoteric surfactants include:
Lauryldimethylaminoacetic acid betaine, coconut oil fatty acid amidopropyldimethylaminoacetic acid betaine, 2-alkyl-N-carboxymethyl-N-hydroxyethylimidazolinium betaine, N-lauryl β-alanine, N
, N,N-trimethylaminopropionic acid, N-hydroxyethyl-N,N-dimethylaminopropionic acid.

N-lauryl-N,N-dimethylaminopropionic acid,
N-myristyl-N, N-dimethylaminopropionic acid, N-stearyl-N, N-dimethylaminopropionic acid, N-lauryl-N, N-dihydroxyethylaminoacetic acid, N-ocdyl-N, N-dimethylaminoacetic acid, N
-Palmityl-N, N-dimethylaminoacetic acid, N-
Stearyl-N,N-dimethylaminoacetic acid, 1- (2
-carboxyethyl)pyridinium betaine, 1-(2
-carboxyethyl)-α-picolinium betaine and the like.

The composition of the present invention may contain one or more of the above-mentioned carboxylic acid type amphoteric surfactants, and the amount of the carboxylic acid type amphoteric surfactants to be blended is determined.

It can be adjusted as appropriate depending on the amount of crystalline compound mixed, etc., but 1
0.001 to 10% (weight%, same below) of the entire composition
, particularly preferably 0.01 to 5%.

The composition of the present invention preferably contains a nonionic surfactant having an HLB value of 10 or less together with the carboxylic acid type amphoteric surfactant.

Here, specific examples of nonionic surfactants include sorbitan fatty acid ester, polyoxyethylene sorbitan fatty acid ester, polyoxyethylene sorbitan fatty acid ester, polyoxyethylene hydrogenated castor oil, polyoxyethylene hydrogenated castor oil fatty acid ester, and polyoxyethylene sorbitan fatty acid ester. Examples include glycerin fatty acid ester, N-long chain acyl-glutamic acid higher alcohol diester, and N-long chain acyl-L-glutamic acid polyoxyethylene higher alcohol ether diester. The HLB value of these nonionic surfactants can be adjusted by adjusting the number of moles of ethylene oxide or propylene oxide added and the carbon chain length of the lipophilic group. If used, the low-temperature stability of a composition may not be improved, so it is desirable that the HLB value of the nonionic surfactant is 10 or less.

The amount of nonionic surfactant to be added is usually 0.1 to 1.
The content is about 10%, but 0.5 to 5% is particularly suitable.

The liquid composition of the present invention is a composition in which a crystalline compound is dissolved in a solvent, and the above-mentioned carboxylic acid type amphoteric surfactant, more preferably, a nonionic surfactant having an HLB value of 10 or less is blended therein. and thereby, as mentioned above, crystalline compounds, especially fatty acids and salts thereof having an alkyl group having 8 to 30 carbon atoms.

The crystallization of aliphatic alcohols and fatty acid derivatives at low temperatures can be prevented as much as possible, and the above-mentioned fatty acids include 1, for example, octanoic acid, nonanoic acid, decanoic acid,
undecanoic acid, dodecanoic acid.

Examples include tetradecanoic acid, pentadecanoic acid, hexadecanoic acid, heptadecanoic acid, octadecanoic acid, nonadecanoic acid, eicosanoic acid, heneicosanoic acid, tocosanoic acid, tricosanoic acid, tetracosanoic acid, pentacosanoic acid, and the like. Examples of the salts include alkali metal salts, ammonium salts, and organic amine salts.

Further, specific examples of the aliphatic alcohol include decanol, undecanol, dodecanol, tridecanol, tetradecanol, pentadecanol, hexadecanol, heptadecanol, octadecanol, nonadecanol, and eicosanol.

Heneicosanol, docosanol, tricosanol,
Examples include tetracosanol and pentacosanol.

Further, as the fatty acid derivative, the above-mentioned fatty acid or aliphatic alcohol derivatives are suitable, such as the following (a) to (a).
(2) crystalline compounds.

(a) Glycerin ester represented by the following formula (however, R
is a fatty acid residue having an alkyl group having 8 to 30 carbon atoms. Same below. ) (b) Ester RCOOR' represented by the following formula (However, R' is a monovalent or divalent alcohol residue such as methanol or ethanol, a polyoxyethylene residue, a sorbitan residue, or a simi sugar residue. ) (c) Amide represented by the following formula (wherein R' and R'' are each a hydrogen atom or an organic group) (d) Dibasic acid represented by the following formula and its salt MOOCR
COOM (However, M is an alkali metal atom, an alkaline earth metal atom, ammonium or an organic amine.) (e) Sterol ester represented by the following formula (g) Phosphatidic acid represented by the following formula (h) Phosphatidic acid represented by the following formula The sphingolipid shown (to) the phospholipid glue shown by the following formula H, C-00-'' \ / (where, X represents a choline residue, an ethanolamine residue, a serine residue, or an inositol residue, When is a choline residue, it becomes phosphatidylcholine, when it is an ethanolamine residue, it becomes phosphatidylethanolamine, when it is a serine residue, it becomes phosphatidylserine, and when it is inositol, it becomes phosphatidylinositol.) ■ ( (However, Y represents a sugar residue, a phosphoric acid residue, or an amine base residue such as choline or ethanolamine.) (S) An ester represented by the following formula R, -0-R' (However, Ra is an aliphatic alcohol residue having an alkyl group having 8 to 30 carbon atoms (the same applies hereinafter), and R' is a fatty acid residue (preferably having a chain length of C2 to C24);
Represents a residue of an organic acid such as succinic acid, citric acid, fumaric acid, lactic acid, pyruvic acid, malic acid, or oxaloacetic acid; or a residue of an inorganic acid such as phosphoric acid. Ether R, -〇-R71 (However, RJl is a monohydric alcohol residue (preferably C2
~C24 chain length); glycerin, polyglycerin, ethylene glycol, propylene glycol,
Residues of polyhydric alcohols such as butanediol; or residues of sugars such as glucose, ribose, galactose, arabinose, mannose, xylose, sorbyl, mannitol. ) In addition to the above compounds, crystalline compounds include vitamins such as biotin, riboflavin, ascorbic acid, and dianocobalamin, amino acids such as glutamic acid, lysine, and cysteine, glutathione, quinones, and tetrabutylammonium perchlorate. It is also possible to use an electrolyte or the like.

As the crystalline compound, one or more of the above compounds can be used, but among them, fatty acids or polyhydric alcohol derivatives of aliphatic alcohols, especially glycerin fatty acid esters, sorbitol fatty acid esters, sucrose fatty acid esters is suitable.

Furthermore, the amount of the crystalline compound blended is not particularly limited, but
0.01 to 50%, especially 1 to 5% of the total composition is preferred.

The solvent used in the liquid composition of the present invention is not particularly limited, and any of water and organic solvents can be used as long as the carboxylic acid type amphoteric surfactant and the crystalline compound can be dissolved in the solvent. The organic solvent may be a hydrophilic solvent or a lipophilic solvent, but a non-aqueous solvent having a water content of 5% or less can be particularly preferably used. A specific example of such a non-aqueous solvent is methyl alcohol.

Propyl alcohol, isopropyl alcohol.

Examples include n-paraffin, benzene, hexane, and chloroform. Among these, when the composition of the present invention is used as a cosmetic, it is preferable to use ethyl alcohol, which is highly safe.

The liquid composition of the present invention may contain arbitrary components other than the above-mentioned components depending on the purpose of its use.

For example, polyhydric alcohols, other surfactants.

Fats and oils, vitamins, hormones, and vasodilators.

Contains medicinal ingredients such as amino acids, anti-inflammatory agents, skin function hexagonal agents, and keratin improvers to produce hair products such as hair restorers, hair tonics, hair liquids, hair lotions, and hair sprays, various pharmaceuticals, and cosmetics. In addition to being used as external skin preparations such as hair dyes and nail polishes, it can also be used as pigment raw materials, paraffin, and petroleum products2.
It can be widely applied to industrial products such as paints and fuel oil by blending it with lime and the like.

In the liquid composition of the present invention, the carboxylic acid type amphoteric surfactant suppresses the crystallization of the crystalline compound at low temperatures and exhibits an excellent solubility improvement effect and low temperature stability improvement effect. −
Even when stored for a long period of time at a low temperature of about 5°C, there is almost no clouding of the solution or precipitation of crystals, and it has excellent low-temperature stability. Therefore, it can be widely used as hair preparations, cosmetics, pharmaceuticals, nail preparations, and even industrial products.

Next, the effects of the present invention will be specifically illustrated by experimental examples.

[Experiment example]

Samples having the component compositions shown in Tables 1 to 3 were prepared, and the number of days of stabilization and low temperature stability were evaluated using the following methods, and the effect of suppressing crystallization was investigated.

The results are also listed in Tables 1-3.

<Evaluation method for stabilization days and low temperature stability> Approximately 50 g of the test sample was placed in a transparent glass bottle, stored in a constant temperature room at -5°C, and the number of days in which it was kept for 1 day from the day the crystals precipitated was defined as the stabilization days. did. Note that the results are expressed as the average number of days of the three measurement results rounded off.

In addition, low-temperature stability is defined as Δ for stabilization days of 28 days or more from 0.14 days to 27 days, and X for stabilization days of 13 days or less.
It was evaluated as

From the results in Tables 1 to 3, it is clear that the sample containing the carboxylic acid type amphoteric surfactant and the crystalline compound according to the present invention has excellent low temperature stability. Along with crystalline compounds.

It was confirmed that samples containing a nonionic surfactant with an HLB value of 10 or less were able to maintain good low-temperature stability.

EXAMPLES The present invention will be specifically explained below with reference to examples, but the present invention is not limited to the following examples.

[Example 1] Hair growth agent pentadecanoic acid glyceride 3% acetic acid dffi-
a-Tocopherol 0.1 Sorbitan monolaurate 4 Pyridoxine caprilate 0.1 Safflower oil 0.2 Succinic acid
0.2 assembly extraction paste 0
．． 1 biotin 0.001N
-Lauryl-N,N-dimethyl 0.1 Hinokitiol aminopropionate 0.05 Fragrance 0.399.5
% ethanol balance 100.0% [Example 2]
Hairspray <g yet> 1-hexacosene 1% amphoteric polymer*
1.0 Carbon dioxide gas PG Nitrogen gas meter [Example 3] Hairstylus sulfocalcic acid heavy lead stearate myristyl aloe ECW 100.0% 1.0% 0,5 0.5 Citric acid 0.32-menthol 0.1 Sorbitan monooleate 0.8 fragrance
0.5 ethanol Remaining total 100.0% I N-methacroylethyl, N,N-, dimethylammonium, α-N-methylcarboxybetaine, alkyl methacrylate copolymer (diluent for filling) Above stock solution 35% POE (5)
Hardened castor oil fragrance Ethyl alcohol Total: 3.0 0.5 Remaining: 100.0% The compositions of Examples 1 to 3 were all excellent in low-temperature stability and exhibited a crystallization inhibiting effect.

Applicant: Laion Co., Ltd. Agent: Patent Attorney Takashi Kojima

Claims (1)

[Scope of Claims] 1. A liquid composition formed by dissolving a crystalline compound in a solvent, which is characterized in that it contains at least one carboxylic acid type amphoteric surfactant. 2. The composition according to claim 1, which contains a nonionic surfactant having an HLB value of 10 or more.