JP2543205B2 - Pigment composition, method for producing the same, and cosmetic composition containing the pigment composition - Google Patents

Description

TECHNICAL 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 the pigments, the harmlessness to the human body is of utmost importance particularly for those used for food additives and cosmetic raw materials. Conventionally, as a colorant for such purpose, a pigment in which a water-soluble synthetic pigment or a natural pigment which is harmless to the human body, such as an edible pigment, is adsorbed and carried on an aluminum hydroxide gel carrier or a cellulosic carrier has been used. However, there is an inconvenience that a sufficient variety of hues cannot be obtained because the types of base dyes are very limited.

On the other hand, attention has been paid to the dye-adsorbing ability of chitosan, which is one of the natural polysaccharides, and attempts have been made to obtain new pigments by using it as a dye carrier that replaces aluminum gel and cellulosics, but has not yet been made. Nothing has been successful.

[Problems to be Solved by the Invention]

When a natural polysaccharide such as chitosan is loaded with a water-soluble dye such as an edible synthetic dye or a natural dye having chitosan dyeing property, a colored gel containing a large amount of a pasty substance is obtained. It is so difficult that it is practically impossible to process. Even if the colored product is solidified and pulverized, the powder obtained has a swelling property in water and easily becomes a sticky state. Also, the powder has no oil dispersibility. Therefore, there are many problems in obtaining a stable powdery substance having a fine dispersibility and good basic properties as a pigment from the colored chitosan gel.

The present invention uses a complex obtained by mixing swelling smectite, which is a clay mineral typified by Na-montmorillonite, with chitosan as a carrier, and carrying a synthetic or natural pigment having dyeing property on chitosan. The object of the present invention is not only to solve the above-mentioned problems and to realize a new pigment, but also to apply the thus obtained human-harmless pigment to the cosmetics field.

[Means for solving the problem]

In addition to this object, the present invention is: 1. A pigment composition characterized in that a dye is adsorbed on a complex of chitosan and swelling smectite.

2 The step of mixing the chitosan acidic solution and the swelling smectite aqueous dispersion, the step of adding the solution or suspension or powder of the chitosan dyeing dye to this mixed solution, and filtering the produced easily filterable colored slurry. A method for producing a pigment composition, comprising the steps of separate, washing, drying and pulverizing, and 3. containing a pigment composition obtained by adsorbing a dye on a complex of chitosan and swelling smectite. To provide cosmetics.

[Work]

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

The swellable smectite has a property of intercalating by intercalating various kinds of cationic organic substances ranging from low molecular weight to high molecular weight between aluminosilicate layers forming a clay structure.

The mixed complex of chitosan and swelling smectite has the property that it does not form a paste while retaining the dye adsorption ability specific to chitosan. This property is independent of the degree of polymerization of chitosan.

〔The invention's effect〕

Therefore, the pigment composition carrying the chitosan-swellable smectite complex of the present invention can: a From the same dye, obtain a pigment having a hue different from that of a carrier having an adsorption point of a conventional metal ion or hydroxyl group. The range of hues can be remarkably widened with a limited range of permitted dyes. B It is stable and suitable for fields requiring foods, pharmaceuticals, cosmetics, etc. It is possible to provide a pigment having preferable attributes derived from chitosan such as moisturizing property, antibacterial property, and antifungal property, and the like.

〔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 of these, acetic acid and citric acid are preferable. When this acidic chitosan solution and an aqueous dispersion of swelling smectite are mixed, a chitosan salt which is a cationic polymer is intercalated in the clay structure to form a complex. As the swelling smectite, natural or synthetic montmorillonite, beidellite, saponite, hectorite, etc. can be used, but Na-montmorillonite obtained by purifying natural products is the most practical. The fact that the chitosan solution forms a complex with the swelling smectite means that the pasty translucent Na-montmorillonite dispersion increases the white turbidity due to mixing with the chitosan solution or the clay structure from the X-ray bottom reflection of the product. It can be inferred from the fact that an increase in interlayer distance is observed.

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 dye to be carried, all synthetic or natural dyes having a chitosan dyeing property can be targeted, but for the purpose of the present invention, tar dyes for foods, pharmaceuticals, cosmetics and natural dyes are particularly significant.

Food coloring yellow 4 (Tartrazine),
Yellow No. 5 (Sunset Yellow FCF), Blue No. 1 (Brillia)
nt Blue FCF), Red No. 3 (Erythrosine), Red 201
No. (Lithol Rubin B), carminic acid, ratukainic acid, calsamine, shikonin and the like. At this time, it is necessary to adjust the pH of the suspension according to the color development of the solubility of the dye. The pH can be adjusted by adding an acid or a base such as acetic acid, citric acid or aqueous ammonia, and an aqueous NaOH solution. Even in natural or synthetic pigments, the hue is often affected by pH, especially in the reddish color. In the case of a dye that does not dissolve on the acidic side, such as carsamine, uniform coloring is likely to occur if the acidic suspension is once made weakly basic, the dye is added, and then the dye is transferred to the acidic side again. After the addition of the dye, it is effective to continue stirring until the dye is dissolved and adsorbed uniformly and the suspension shows a good color development state.

The filterability of the colored suspension is so poor that if the smectite does not coexist, the pasty material immediately clogs the filter medium, making it impossible to filter. When smectite coexists and is added so that the chitosan / smectite weight ratio becomes a predetermined value, it suddenly improves. In many cases, if the weight ratio is 1 or less, that is, if the weight of smectite is equal to or more than that of chitosan, the filterability is sufficiently improved. However, since the dye adsorption capacity per carrier weight decreases as the proportion of chitosan decreases, it goes without saying that the smectite addition amount naturally has a limit in order to suppress the dye loss rate and increase the coloring density. That is,
There will be a practical lower limit to the chitosan / smectite weight ratio.

The effect of adding smectite varies greatly depending on the dye, and in the case of food yellow No. 4 dye, 1/5 the amount of Na of chitosan
The filterability was remarkably improved only by adding montmorillonite (chitosan / smectite weight ratio of 5), but in the case of Red No. 3 dye, filtration was not possible unless the weight ratio was increased to nearly 1.

The filtered and washed colored product is dried with warm air of about 50 ° C. to be solidified and finely pulverized to obtain a pigment that can be spread with an oil vehicle such as linseed oil.

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

The pigment obtained in the present invention has not only the fact that it is formed only from a safe material, but also suitable properties such as moisturizing property, antibacterial property and antifungal property derived from chitosan. It can be used as a colorant for foods and pharmaceuticals, and is particularly suitable as a colorant for cosmetics,
Above all, it is useful for makeup products such as foundations, lipsticks, blushers, whitewashes and nail enamel. In addition, it can be widely applied to colorants in fields where harmlessness to the human body is a problem, such as packaging materials, stationery and toys.

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

Example 1 Chitosan 20 having a degree of deacetylation of 80% and an average molecular weight of 40,000
g was dissolved in water together with 10 g of acetic acid to obtain a total amount of 500 ml 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.
The mixture was stirred at 0 ° C for 1 hour. Next, edible yellow color No. 4 11.81g
A solution of (as pure content) dissolved in 300 ml of water was added to the mixed suspension while stirring well. After further stirring for 1 hour at 50 ° C. and aging, the mixture was allowed to stand at room temperature for 1 hour, whereby the colored suspension was quickly filtered and washed using a filter paper to obtain a cake.

The wet cake was dried with hot air at 50 ° C. and then pulverized with a ball mill to obtain a yellow pigment containing about 29% of dye ions. The pigment composition could be developed with an oil vehicle such as linseed oil.

-Example 2-The amount of chitosan in Example 1 was 16 g, and the amount of Na-montmorillonite was 8 g. The filterability and color-developing property are better than those of the pigment composition obtained in Example 1, and the dye ion content is about 23%.
A yellow pigment containing was obtained.

-Example 3-In place of 10 g of acetic acid in Example 1, 25 g of citric acid was used. A yellow pigment having the same properties as in Example 1 was obtained.

-Example 4-Chitosan 12 having a deacetylation degree of 80% and an average molecular weight of 40,000
g was dissolved in water together with 15 g of acetic acid to obtain a total amount of 500 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.
The mixture was stirred at 50 ° C for 1 hour. Next, food blue No. 1 pigment 8.49g
A solution of (as pure content) dissolved in 200 ml of water was added to the mixed suspension while stirring well.

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

A blue pigment containing approximately 25% of dye ions was obtained.
This pigment composition showed excellent color development with an oil vehicle.

Example 5 16 g of chitosan similar to that of Example 4 was dissolved in water together with 5 g of acetic acid to prepare 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, which was stirred at 50 ° C. for 1 hour. Next, Red No. 201 dye (Lithol Rubin B) 17.9
1 g (as pure content) was suspended in 300 ml of water, and the suspension was continuously stirred in the mixed suspension to improve the dispersion state of the colored product, and then concentrated ammonia water was gradually added thereto. pH 6.
Adjusted to 5. After further stirring, the product began to show a clear red color, and then the mixture was allowed to stand at room temperature.

The colored suspension can be easily filtered and washed, and the obtained wet cake is dried with warm air at 50 ° C and then pulverized with a ball mill.
A pigment composition was obtained which contained about 40% of dye ions and which could be developed with an oil vehicle. This pigment composition had a yellowish red hue which was completely different from the bluish red exhibited by the calcium lake Red No. 202 (Lithol Rubin BCa).

-Example 6- 12 g of chitosan similar to Example 4 was melt | dissolved in water with 2.5 g of acetic acid, and it was set as the chitosan solution of a total amount of 500 ml. Separately, Na-
12 g of 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, 12 g of carminic acid was dissolved in 100 ml of water, and this solution was added to the above mixed suspension while stirring well. Thereafter, the same aging, filtration, washing, drying and crushing operations as in Example 1 were carried out to obtain a purple pigment. This pigment composition exhibited a hue completely different from that of the aluminum-calcium carminate lake which exhibited a red color.

-Example 7- 12 g of chitosan similar to that of Example 4 was dissolved in water together with 25 g of citric acid to prepare a chitosan solution having a total amount of 500 ml. Separately, Na
-Disperse 12 g of montmorillonite in 500 ml of water,
The suspension was mixed with the chitosan solution and stirred at 50 ° C. for 1 hour. After cooling this to room temperature, dilute NaOH solution was gradually added while stirring well to raise the pH to about 9.1, and 12 g of safflower pigment containing the red pigment carsamine was added.
The dye dissolved to give a magenta color. A citric acid solution was then added to reduce the pH to about 6 and a reddish colored insoluble product was formed.

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

-Example 8-Using the pigment obtained in Example 1, an oily 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% Ozokelite 8.0% Candelilla wax 0.5% Coloring agent: Titanium oxide 15.0% Kaolin 10.0% Talc 6.0% Pigment of the present invention ( Example 1) 9.0% Fragrance: Fragrance Suitable amount Manufacturing method: A pigment is mixed. Separately, the base components are mixed and heated to melt to homogeneity. Add the pigment to the melted base. Knead the mixture on a roll mill. The kneaded product is redissolved, toned, and then gently stirred to allow the bubbles to float. Cool while continuing to stir, add perfume at 60 ° C, pour into a container and let cool to solidify.

-Example 9-Using the pigment obtained in Example 5, a lipstick was prepared according to the following formulation.

Base: castor oil 47.0% isopropyl palmitate 5.0% lanolin 10.0% ozokerite 7.0% candelilla wax 7.0% carnauba wax 4.0% colorant: titanium oxide 2.0% pigment of the present invention (Example 5) 18.0% fragrance: fragrance suitable amount production method: Heat and melt the base material and mix evenly. A colorant is added to this, and the mixture is kneaded with a roll mill to uniformly disperse, then remelted to add a fragrance, defoamed, poured into a mold, and rapidly cooled to solidify.

-Example 10- Using the pigment obtained in Example 7, a solid blusher was prepared according to the following formulation.

Talc 30.0% Kaolin 15.0% Magnesium stearate 2.5% Pigment of the present invention (Example 7) 50.0% Binder: Liquid paraffin 2.5% Fragrance: Fragrance Suitable amount Manufacturing method: The powder part is mixed well to develop the color. The binder and perfume are then sprayed on in a mixer, mixed evenly, passed through a sieve and then pressed and hardened using a press.

-Example 11- Using the pigment obtained in Example 7, a powder screen 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% Perfume: Perfume suitable amount Manufacturing method: Talc and a color pigment are mixed with a blender. The rest of the ingredients are added to this and mixed well, then toned and sprayed with a fragrance to mix evenly. This is crushed through a crusher and then finished through a sieve.

-Example 12-Using the pigment obtained in Example 5, a 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: In a stirrer Add A, mix for 10 minutes, then add B,
After mixing and stirring for 30 minutes, C is added. After further stirring, the film-forming agent is dissolved in the vaporized components, and the product is passed through a sieve to finish.

-Comparative Example- Detoxification degree 80%, average molecular weight 40,000 Chitosan 24
g was dissolved in water together with 10 g of acetic acid to prepare a total 1000 ml of chitosan solution. Next, 11.81 g (as pure content) of Food Yellow No. 4 dye was dissolved in 300 ml of water, and the solution was added to the above chitosan solution to give 5
If it was added at 0 ° C. with good stirring, a coarse filament aggregate-like colored insoluble product was immediately formed. By continuing stirring for several hours, the product became finely dispersed and the dye in the solution was exhausted.

This colored product suspension contained a highly viscous paste and the filter paper was immediately clogged and could not be filtered. Therefore, water was removed by evaporation under reduced pressure, and the obtained solid matter was immersed in water and washed by decantation to remove water-soluble components. The colorant crushed after drying contains about 30% of dye ions
Although it was contained, it showed no lipophilic dispersibility and could not be developed by the oil vehicle.

As explained above, the pigment composition using the chitosan-smectite composite according to the present invention as a carrier has excellent properties, and further, in each of the above-mentioned Examples, there are various types as long as they are within the range of the constitution of the present invention. Needless to say, application and diversion can be performed.

Claims (3)

(57) [Claims] 1. A pigment composition comprising a composite of chitosan and swelling smectite adsorbing a dye. 2. A step of mixing an acidic chitosan solution with an aqueous dispersion of swelling smectite, a step of adding a solution or suspension or powder of a chitosan-dyeing dye to this mixed solution, and A method for producing a pigment composition, which comprises the steps of filtering and washing a colored slurry, then drying and pulverizing. 3. A cosmetic composition comprising a pigment composition obtained by adsorbing a dye on a complex of chitosan and swelling smectite.