JPH03139569A - Pigment composition, its preparation, and cosmetic containing the composition - Google Patents

Abstract

PURPOSE:To prepare a pigment compsn. which is stable, has moisture-retentive and antifungal properties, is useful in food, drug, and cosmetic applications, and can offer a wide variety of hues from a limited number of permitted colorants by causing a composite material comprising chitosan and a swellable smectite to adsorb the colorant. CONSTITUTION:A composite material comprising chitosan and a swellable smectite (e.g. sodium montmorillonite) is caused to adsorb a colorant (e.g. tartrazine).

Description

DETAILED DESCRIPTION OF THE INVENTION [Industrial Application Field] The present invention relates to a pigment composition, a method for producing the same, and a cosmetic obtained by blending the pigment composition.

[Conventional technology]

Among pigments, especially for those used as food additives or cosmetic raw materials, harmlessness to the human body is of paramount importance. Traditionally, colorants for this purpose have been pigments in which water-soluble synthetic pigments or natural pigments that are harmless to the human body, such as food pigments, are adsorbed and supported on aluminum hydroxide gel carriers or cellulose carriers. However, there was an inconvenience that a sufficient variety of hues could not be obtained because the types of pigments used were extremely limited.

In response, attempts have been made to focus on the pigment adsorption ability of chitosan, a type of natural multi-IN, and to use it as a pigment carrier to replace aluminum gel and cellulose to obtain new pigments. None have been successful yet.

[Problem to be solved by the invention]

When chitosan, which is a natural polysaccharide, is made to support water-soluble dyes such as synthetic food dyes or natural dyes that have chitosan dyeing properties, a colored gel containing a large amount of paste-like material is obtained, and this gel can be used for filtration, washing, etc. It is so difficult that it is practically impossible to process. Furthermore, even if the colored material is solidified and pulverized, the resulting powder has water-swelling properties and easily becomes sticky. Furthermore, the powder has no oil dispersibility at all. Therefore, there were many problems in obtaining a fine, stable powder with good dispersibility, which is a basic characteristic of a pigment, from colored chitosan gel.

The present invention uses a composite obtained by mixing chitosan with swellable smectite, which is a clay mineral represented by Na-montmorillonite, as a carrier, and supports the chitosan with a synthetic or natural pigment that has dyeing properties. The purpose of this invention is not only to solve the above-mentioned problems and realize a new pigment, but also to apply the thus obtained pigment, which is harmless to the human body, in the field of cosmetics.

[Means for Solving the Problems] In accordance with this object, the present invention provides: (1) A pigment composition characterized in that a pigment is adsorbed onto a complex of chitosan and swellable smectite.

2. A step of mixing an acidic chitosan solution and a swellable smectite aqueous dispersion, a step of adding a solution, suspension, or powder of a chitosan stainable dye to this mixed solution, and a step of filtering the produced 5-filterable colored slurry. 3. A method for producing a pigment composition, characterized by including a step of separating and washing, followed by drying and pulverizing; We provide cosmetics that

[For production]

Chitosan is a deacetylated product of natural chitin, and there are various degrees of deacetylation and degree of polymerization. The dye adsorption ability of chitosan is due to the presence of active amino groups, and the higher the degree of deacetylation, the greater the dye adsorption ability.

Swellable smectite has the property of intercalating various cationic organic substances ranging from low molecular weight to high molecular weight between the aluminosilicate layers forming the clay structure.

A mixed composite of chitosan and swellable smectite has the property of not forming a paste-like substance while retaining the dye adsorption ability unique to chitosan. This characteristic is independent of the degree of polymerization of chitosan.

〔Effect of the invention〕

Therefore, the chitosan of the present invention - swellable smectai -
? A pigment composition using an I-aggregate carrier can obtain a pigment with a different hue from the same pigment than in the case of a carrier that uses conventional metal ions or hydroxyl groups as adsorption points, and is available under limited types of permission. It is possible to significantly expand the range of hues within the range of pigments, b.Chitosan is suitable for fields that require colorants that are harmless to the human body, such as food, medicine, and cosmetics, as it is stable and has appropriate moisturizing, antibacterial, and antifungal properties. It is possible to provide a pigment that has both favorable attributes derived from the following effects.

[Example〕 Next, examples of the present invention will be described.

First, chitosan is dissolved in a dilute acid solution. As the acid, various kinds of inorganic acids and organic acids can be used, and among them, acetic acid and citric acid are preferred. When this acidic chitosan solution and the aqueous dispersion of swellable smectite are mixed, chitosan salt, which is a cationic polymer, is intercalated in the clay structure to form a complex. Swellable smectites are natural or synthetic montmorillonite, beidellite, saponite,
Hectorite etc. can be used, but N
a-montmorillonite is the most practical. The fact that the chitosan solution forms a complex with the swellable smectite is confirmed by the fact that the pasty translucent Na-montmorillonite dispersion increases in white turbidity when mixed with the chitosan solution, or by the fact that the X-ray bottom reflection of the product indicates that it has a clay structure. This can be inferred based on the observation of an increase in interlayer distance.

When an aqueous solution or suspension of the dye is added to this mixed suspension, the dye is adsorbed and supported on the chitosan-smectite complex. As the supported pigment, all synthetic or natural pigments having chitosan dyeability can be used, but for the purpose of the present invention, it is particularly meaningful to use tar pigments and natural pigments for foods, medicines, and cosmetics.

Such coloring agents include Food Yellow No. 4 (Tartrazi).
ne), Yellow No. 5 (SunsetYellow FC)
F), Brilliant Blue
FCF), Red No. 3 (Erythros 1nc), Red No. 201 (LiLhol Rubin B), carminic acid, laccaic acid, calsamine, shikonin, and the like. At this time, it is necessary to adjust the pH of the suspension depending on the solubility and color development of the dye.

To adjust the pH, use acetic acid, citric acid, ammonia water, Na
This can be done by adding an acid or a base, such as an aqueous OH solution. Even with natural pigments and synthetic pigments, the hue is often affected by pH, especially in the case of red colors. Furthermore, in the case of a pigment that does not dissolve on the acidic side, such as calsamine, uniform color development is likely to occur if the acidic suspension is once made weakly basic, then the pigment is added, and then transferred to the acidic side again. After adding the dye, it is effective to continue stirring until the dye is dissolved and evenly adsorbed and the suspension exhibits good color development.

The filterability of the colored suspension is so poor that if smectite does not coexist, the paste-like substance will immediately clog the filter medium, making it impossible to filter. However, when smectite is added in coexistence and the weight ratio of chitosan/smectite is at a predetermined value, the improvement suddenly improves. In many cases, the weight ratio is 1 or less,
That is, if the weight of smectite is equal to or more than the weight of chitosan, the filterability will be sufficiently improved. However, since the dye adsorption capacity per carrier weight decreases as the proportion of chitosan decreases, it goes without saying that there is a natural limit to the amount of smectite added in order to keep the dye loss rate low and increase the coloring density. That is, there is a practical lower limit to the chitosan/smectite weight ratio.

The effect of adding smectite varies greatly depending on the pigment.
In the case of food yellow color No. 4, the amount of Na in chitosan is 115.
- Filterability was significantly improved simply by adding montmorillonite (chitosan/smectite weight ratio: 5), but in the case of Red No. 3 dye, filtration was not possible unless the weight ratio was increased to nearly 1.

If the colored material after filtration and washing is dried with hot air at about 50° C. to solidify it and pulverized, a pigment that can be spread with an oil vehicle such as linseed oil can be obtained.

As a pulverization method, wet ball mill pulverization using an organic solvent such as ethanol yields a pigment powder with better lipophilicity.

The pigment obtained by the present invention is not only made of safe materials, but also has favorable properties derived from chitosan, such as moderate moisturizing properties, antibacterial properties, and antifungal properties. In addition to being used as a coloring agent for foods and medicines, it is particularly suitable as a coloring agent for cosmetics, and is especially useful for makeup products such as foundation, lipstick, pink powder, powder, and nail enamel. In addition, it can be widely applied to colorants in packaging materials, stationery, toys, and other fields where harmlessness to the human body is a concern.

Hereinafter, the pigment composition of the present invention, its manufacturing method, and its application to cosmetics will be explained in more detail with reference to specific examples.

Example 1 20g of chitosan with a degree of deacetylation of 80% and an average molecular weight of 40,000 was dissolved in water with Log acetic acid to give a total amount of 500%.
It was made into m1 chitosan solution. Separately, 4 g of Na-montmorillonite was dispersed in 500 ml of water, and this was mixed with the chitosan solution to form a suspension, which was stirred at 50° C. for 1 hour. Next, a solution prepared by dissolving 11.81 g of food yellow color No. 4 (as pure content) in 300 ml of water was added to the mixed suspension while stirring well. After continuing to stir at 50°C for 1 hour to ripen, the mixture was allowed to stand at room temperature for 1 hour, and the colored suspension could be quickly filtered and washed using filter paper to obtain a cake.

This wet cake was dried with hot air at 50"C and ground in a ball mill to obtain a yellow pigment containing approximately 29% dye ions. This pigment composition can be developed with an oil vehicle such as linseed oil. Ta.

Example 2 In Example 1, the amount of chitosan was 16 g, and the amount of Na-montmorillonite was 8 g. A yellow pigment was obtained which had better filterability and color spreadability than the pigment composition obtained in Example 1 and contained about 23% of dye ions.

Example 3 - In place of 10 g of acetic acid in Example 1, 25 g of citric acid was used. A yellow pigment with properties similar to those of Example 1 was obtained.

Example 4 12 g of chitosan with a degree of deacetylation of 80% and an average molecular weight of 40,000 was dissolved in water with 15 g of acetic acid to give a total of 1500
ml of chitosan solution. Separately, 12 g of Na-montmorillonite was dispersed in 500 ml of water, and this was mixed with the chitosan solution to form a suspension, which was stirred at 50° C. for 1 hour.

Next, a solution of 8.49 g (as pure content) of Food Blue No. 1 dissolved in 200 ml of water was added to the mixed suspension while stirring well.

Thereafter, the same operations as in Example 1, such as aging, filtration, washing, drying, and pulverization, were performed.

A blue pigment containing approximately 25% dye ions was obtained.

This pigment composition exhibited excellent color spreadability in oil vehicles.

Example 5 16 g of chitosan similar to Example 4 was dissolved in water together with 5 g of acetic acid to obtain a chitosan solution having a total volume of 500 ml. Separately,
8 g of Na-montmorillonite was dispersed in 500 ml of water, and this was mixed with the chitosan solution to form a suspension at 50°
The mixture was stirred at C for 1 hour. Next, red dye No. 201 (Li
thol Rubin B) 17.91 g (as pure content) was suspended in 300 ml of water, and this suspension was continuously stirred into the mixed suspension to improve the dispersion state of the colored product, and then mixed with concentrated aqueous ammonia. was gradually added to pH 6,
Adjusted to 5. After further stirring, the product took on a bright red color and was then allowed to stand at room temperature.

The colored suspension can be easily filtered and washed, and the resulting wet cake is dried with hot air at 50°C and then ground in a ball mill to form a dye containing approximately 40% dye ions and can be spread with an oil vehicle. A pigment composition was obtained. This pigment composition is a calcium lake Red No. 202 (Lithol Rub
It had a yellowish red hue that was completely different from the bluish red exhibited by inBCa).

Example 6 12 g of chitosan similar to Example 4 was dissolved in water together with 265 g of acetic acid to obtain a chitosan solution having a total volume of 500 ml. Separately, 12 g of Na-montmorillonite was dispersed in 500 ml of water, which was mixed with the chitosan solution to form a suspension and stirred at 50° C. for 1 hour.

Next, 12 g of carminic acid was dissolved in 100 ml of water, and this solution was added to the mixed suspension while stirring well. Thereafter, the same operations as in Example 1, such as aging, filtration, washing, drying, and pulverization, were performed to obtain a purple pigment. This pigment composition consists of aluminum carmate, which exhibits a red color.
It exhibited a completely different hue from calcium lake.

Example 7 - 12 g of chitosan similar to Example 4 was dissolved in water together with 25 g of citric acid to obtain a chitosan solution having a total volume of 500 ml.

Separately, add 12g of Na-montmorillonite to 500ml of water.
This was mixed with the chitosan solution and stirred at 50°C for 1 hour. After cooling this to room temperature, a dilute NaOH solution was gradually added while stirring well to raise the pH to about 9.1, and 12 g of safflower dye containing red dye calsamine was added.

The dye dissolved and took on a reddish-purple color. A citric acid solution was then added to lower the pH to about 6, producing a reddish colored insolubilized material.

Thereafter, the same operations as in Example 1, such as aging, filtration, washing, drying, and pulverization, were performed to obtain a red pigment. This pigment composition, unlike one in which calsamine is supported on a cellulose carrier, can be developed with an oil vehicle such as linseed oil.

Example 8 Using the pigment obtained in Example 1, an oil-based foundation was prepared according to the following formulation.

Base: Liquid paraffin 24.5% Isopropyl palmitate 15.0% Lanolin alcohol 2.0% Lanolin acetate
3.0% microcrystalline wax 7.0
% Osikelite 8.0% Candelilla wax 0.5% Color material titanium dioxide
15.0% kaolin
10.0% talc
6.0% Pigment of the present invention (Example 1) 9.0% Perfume: Perfume Appropriate amount Production method: Mix the pigments. Separately, the base components are mixed and heated and melted to make them uniform. Add pigment to the melted base. Knead the mixture on a roll mill. After remelting the kneaded material and toning the color, stir slowly to bring bubbles to the surface. Cool while continuing to stir, and cool to 60
Add flavoring at °C, pour into a container and leave to cool to solidify.

Example 9 A lipstick was prepared using the pigment obtained in Example 5 according to the following formulation.

Base: Castor oil 47.0% Isopropyl palmitate 5.0% Lanolin
10.0% Osikelite
7.0% candelilla wax 7
．． 0% carnauba wax 4.0% Coloring agent: Titanium oxide 2.0% Pigment of the present invention (Example 5) 18.0% Fragrance: Fragrance
Appropriate amount manufacturing method: Heat and melt the base raw materials and mix uniformly. Coloring material is added to this, kneaded in a roll mill to uniformly disperse it, then remelted, flavoring added, defoamed, poured into molds, and rapidly cooled to solidify.

Example 1 Using the pigment obtained in Example 7, a solid pink was prepared according to the following formulation.

Talc 30.0% Kaolin
15. ．． 0% Magnesium stearate 2.5% Invention pigment (Example 7)
50.0% Binder: Liquid paraffin
2.5% Fragrance: Fragrance Appropriate amount Manufacturing method: Mix the powder part well and spread. Then, the binder and fragrance are added by spraying in a mixer, mixed uniformly, passed through a sieve, and then compressed and solidified using a press.

Example 11 Using the pigment obtained in Example 7, powder powder was prepared according to the following formulation.

Talc 67.0% Kaolin
7.5% precipitated calcium carbonate
5.0% Magnesium Stearate 5
．． 0% Titanium oxide 0.5% Pigment of the present invention (Example 7) 15.0% Fragrance: Fragrance Appropriate amount Production method: Mix talc and color pigment in a blender. Add the remaining ingredients to this and mix well, then adjust the color, spray the fragrance, and mix evenly. This is passed through a crusher to be ground, and then passed through a sieve for finishing.

Example 12 Using the pigment obtained in Example 5, nail enamel was prepared according to the following formulation.

A: Nitrocellulose 12.5% Isopropanol 3.5% B=Alkyd resin 12.0% Camphor
6.0% Pigment of the present invention (Example 5)
8.0%C: Butyl acetate
23.0% ethyl acetate 9
．． 0% normal butanol 1.0% toluene 25.0% Manufacturing method: 1Ji
1Pour A into a stirrer, mix for 10 minutes, then add B,
After mixing and stirring for 30 minutes, C is added. After further stirring is continued to dissolve the film-forming agent in the evaporated component, the mixture is passed through a sieve and finished.

Comparative Example 24 g of chitosan with a degree of deacetylation of 80% and an average molecular weight of 40,000 was dissolved in water with 10 g of acetic acid, and the total amount was 101.
A 00O chitosan solution was prepared.

Next, 11.81 g of food yellow color No. 4 (as pure content)
was dissolved in 300 ml of water, and 50 ml was added to the above chitosan solution.
When added with thorough stirring in C, a colored insolubilized material in the form of coarse filament aggregates was immediately formed. By continuing stirring for several hours, the product became finely dispersed, and the dye in the solution was absorbed. Exhausted.

This colored product suspension contained a highly viscous paste-like substance that immediately clogged the filter paper and could not be filtered. therefore,
Water was removed by evaporation under reduced pressure, and the resulting solid was immersed in water and washed by decantation to remove water-soluble components. Although the colorant that was dried and ground contained about 30% dye ions, it showed no lipophilic dispersibility and could not be developed with an oil vehicle.

As explained above, the pigment composition using the chitosan smectite composite as a carrier according to the present invention has excellent properties, and furthermore, the pigment composition of the present invention has various applications within the scope of the present invention. , it goes without saying that diversion may take place.

Claims (1)

[Scope of Claims] 1. A pigment composition characterized in that a pigment is adsorbed onto a complex of chitosan and swellable smectite. 2. A step of mixing an acidic chitosan solution and a swellable smectite aqueous dispersion, a step of adding a solution, suspension, or powder of a chitosan stainable dye to this mixed solution, and a step of filtering the produced easily filterable colored slurry. A method for producing a pigment composition, comprising the steps of separating and washing, then drying and pulverizing. 3. A cosmetic comprising a pigment composition obtained by adsorbing a pigment onto a complex of chitosan and swellable smectite.