JPH04320457A - Pigment composition, its production and cosmetic containing the same - Google Patents

Abstract

PURPOSE:To provide a safe and stable pigment composition, a process for its production and a useful cosmetic containing the same. CONSTITUTION:A pigment composition which can develop various hues and excels in the prevention of release of colorant is obtained by allowing a chitosan/swellable smectite composite material to adsorb a colorant and performing crosslinking by the action of a polyfunctional reagent reactive with chitosan. A process for producing such a pigment composition and a cosmetic containing such a pigment composition can be accomplished by this invention. A safe and stable colorant which can develop a markedly extensive range of hues can be provided by using limited kinds of approved colors.

Description

[Detailed description of the invention]

0001

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a pigment composition with excellent safety and an expanded range of hues, a method for producing the same, and a cosmetic containing the pigment composition.

0002

BACKGROUND OF THE INVENTION 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, this method has the inconvenience of not being able to obtain a sufficient variety of hues because the types of pigments used are very limited.

[0003] In response, attention has been focused on the pigment adsorption ability of chitosan, a type of natural polysaccharide, and attempts have been made to obtain new pigments by using chitosan as a pigment carrier to replace aluminum gel and cellulose. Ta.

[0004] The present inventor first intended to effectively develop the dye adsorption ability of chitosan by using a complex of chitosan and swelling smectite, which is a type of clay mineral, as a dye carrier. We proposed a pigment composition with excellent stability and rich color tone, a method for producing the same, and a method for utilizing such a pigment composition (Japanese Patent Application No. 1-2773).
No. 99).

[0005]

[Problem to be solved by the invention] When chitosan, which is a natural polysaccharide, is supported with a water-soluble dye such as a synthetic food dye or a natural dye that has chitosan dyeing properties, a colored gel containing a large amount of paste-like material can be obtained. This colored gel is difficult to process, such as filtration and washing, to the extent that it is practically impossible. Furthermore, even if the colored material is solidified and pulverized, the resulting powder has water-swelling properties and easily becomes sticky.

[0006] Furthermore, the above-mentioned powder has no oil dispersibility at all, so in order to obtain a fine, stable powder with good dispersibility, which is the basic property required of a pigment, from colored chitosan gel, many steps are required. There was a problem.

[0007] Regarding these problems, as mentioned above, the present inventor proposed an invention in Japanese Patent Application No. 1-277399, in which chitosan is mixed with swellable smectite, which is a clay mineral represented by Na-montmorillonite, in water. Most of these problems have been solved by using a layered composite obtained by reaction as a carrier.

On the other hand, dyes adsorbed on a carrier tend to be liberated when they come into contact with solutions or solvents that have solubility in the dye, and when used as a colorant, migration (
Since this causes undesirable phenomena such as color transfer (color transfer) or bleeding (color bleeding), it has been desired to improve the elution resistance of dyes adsorbed on carriers.

[0009] In the present invention, at the same time as or after adsorbing the dye onto a complex of chitosan and swellable smectite, the adsorbed dye is cross-linked using a polyfunctional reagent having chitosan reactivity. The purpose is to prevent elution and provide a more useful pigment composition. Furthermore, it is an object of the present invention to provide a method for producing such a pigment composition, and also to provide a useful cosmetic material obtained by incorporating the pigment composition.

0010

[Means for Solving the Problems] In order to achieve the above-mentioned objects, the pigment composition of the present invention not only adsorbs a pigment to a complex of chitosan and swellable smectite, but also has chitosan reactivity. It is characterized by being crosslinked by the action of a polyfunctional reagent.

[0011] Furthermore, the method for producing the pigment composition of the present invention includes:
A mixing step of mixing an acidic chitosan solution and a swellable smectite aqueous dispersion, and adding a chitosan stainable dye and a crosslinking agent that has chitosan reactivity and acts in an aqueous solvent to the mixed solution obtained in this mixing step. A method for producing a pigment composition comprising an addition step and a finishing step of filtering and washing the easily filterable colored slurry produced in the addition step, followed by drying and pulverizing, A mixing step of mixing with a swellable smectite aqueous dispersion, a first addition step of adding a chitosan staining dye to the mixture obtained in this mixing step, and an easily filterable colored slurry produced in this first addition step. A replacement step of filtering and washing and replacing water with a non-aqueous solvent, and a second addition step of adding a crosslinking agent that has chitosan reactivity and acts in a non-aqueous solvent to the non-aqueous slurry obtained in this replacement step. and a finishing step of drying and pulverizing the colored solids after separating them from the solvent that has passed through the second addition step.

Furthermore, cosmetics containing the novel pigment composition of the present invention are prepared by adsorbing a pigment onto a complex of chitosan and swellable smectite, and by allowing a polyfunctional reagent having chitosan reactivity to act on the complex. It is characterized by containing a pigment composition obtained by crosslinking treatment.

[0013] In the method for producing a pigment composition as described above, the chitosan stainable pigment added to the mixture of the chitosan acidic solution and the swellable smectite aqueous dispersion is in a solution or suspension state at the time of addition. Or it may be in any form of powder. In addition, when adding a chitosan stainable dye and a crosslinking agent that has chitosan reactivity and acts in an aqueous solvent to the mixed solution of the chitosan acidic solution and the swellable smectite aqueous dispersion, the chitosan dye dye and a crosslinking agent may be added simultaneously, or both may be added sequentially.

[0014] Chitosan is first dissolved in a dilute acid solution to obtain an acidic chitosan solution. As the acid, various inorganic or organic acids can be used. If crosslinking treatment is not performed during the manufacturing process of the pigment composition, it is preferable to use an organic acid such as acetic acid or citric acid as the acid solution. In this case, it is not preferable to use an organic acid depending on the type of crosslinking agent, and it is preferable to use an inorganic acid such as hydrochloric acid as the acid solution.

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 composite. Natural or synthetic montmorillonite, beidellite, saponite, hectorite, etc. can be used as the swelling smectite, but Na-montmorillonite, which is a purified natural product, is the most practical. Furthermore, the formation of a complex between chitosan and the swellable smectite is evidenced by the observation of an increase in the distance between the clay structure layers in the X-ray bottom reflection of the product.

When an aqueous solution or suspension of a dye is added to this mixed suspension, the dye is adsorbed and supported on the chitosan-smectite complex. The supported pigment may be any synthetic or natural pigment that can be dyed with chitosan, but for the purposes of the present invention, it is particularly meaningful to use tar pigments and natural pigments for food, medicine, and cosmetics. .

[0017] Such coloring agents include Food Yellow No. 4 (Ta
rtrazine), Yellow No. 5 (Sunset Ye
low FCF), blue No. 1 (Brilliant
Blue FCF), Red No. 3 (Erythro
sine), Red No. 201 (Lithol Rubi
n B), carminic acid, laccaic acid, calsamine,
Examples include shikonin. When adding a dye, it is necessary to adjust the pH of the suspension depending on the solubility and color development of the dye.

Examples of polyfunctional reagents having chitosan reactivity and used as crosslinking agents include glutaraldehyde, dicarboxylic acid esters, dicarboxylic acid halides, organic diisocyanates, and epihalohydrin. Also,
The most suitable solvent for each crosslinking agent is selected, but for the glutaraldehyde crosslinking agent, an aqueous solution,
Adipic acid di-p-nitrophenyl ester and di-N-
For dicarboxylic acid esters such as hydroxysuccinimide ester, dicarboxylic acid halides such as adipic acid chloride, and amide solvents such as dimethylformamide and dimethylacetamide for the epichlorohydrin crosslinking agent, hexamethylene diisocyanate and 4 ,4'
For organic diisocyanate crosslinking agents such as diphenylmethane diisocyanate, in addition to the above-mentioned amide solvents, alcohols such as ethanol and isopropyl alcohol, and ketone solvents such as acetone and methyl ethyl ketone are suitable. The crosslinking reaction performed using these crosslinking agents is
The process is completed within one to several hours at a temperature range from room temperature to about 70°C.

[0019] When the crosslinking agent acts in an aqueous medium such as glutaraldehyde, the crosslinking treatment can be carried out simultaneously with the adsorption of the dye or after the adsorption of the dye. In the former case, the elution resistance of the product is higher. When the crosslinking agent acts in a non-aqueous solvent, the colored material is once filtered out and washed with water, and then the water is replaced with the non-aqueous solvent to carry out the cross-linking treatment. After the reaction, the colored solids are separated, washed with the same solvent to remove unreacted crosslinking agent, further washed with water, and then dried.
Smash.

[0020]

[Action] Chitosan is a deacetylated product of natural chitin, and there are various degrees of deacetylation and 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 to high-molecular weight molecules between the aluminosilicate layers forming the clay structure.

[0021] Therefore, the mixed composite of chitosan and swellable smectite has the property of not forming a paste-like substance while retaining the dye adsorption ability peculiar to chitosan. This characteristic is independent of the degree of polymerization of chitosan.

On the other hand, chitosan is crosslinked with a polyfunctional reagent such as glutaraldehyde, dicarboxylic acid ester, dicarboxylic acid halide, organic diisocyanate, or epihalohydrin, and this treatment can suppress swelling.

[0023] Since the property of suppressing swelling developed by such cross-linked chitosan is maintained even in a composite of chitosan and swellable smectite, the above-mentioned composite may be By crosslinking the dye, the elution resistance of the dye is significantly improved.

[0024]

EXAMPLES Next, the pigment composition of the present invention, its manufacturing method, and the application of the pigment composition to cosmetics will be described with reference to various specific examples and preferred examples.

(Specific Example 1) 5 g of chitosan with a degree of deacetylation of 80% and an average molecular weight of 40,000 was mixed with 0.05N-H
It was dissolved in 400 ml of Cl to obtain a chitosan solution. Separately, 1 g of Na-montmorillonite was dispersed in 100 ml of water, and this was gradually mixed with the chitosan solution at a temperature of 50°C, stirred for 1 hour, and then cooled to 5°C to prepare a chitosan-montmorillonite mixed solution. Red No. 201 (Li
2.4 g of thol Rubin B) was suspended in water and added to the chitosan-montmorillonite mixture together with 4 g of a 25% aqueous glutaraldehyde solution as a polyfunctional reagent which is a crosslinking agent having chitosan reactivity. Adjust the pH to 6.5 using ammonia water and
The mixture was stirred for 20 hours to obtain an easily filterable yellowish-red colored substance. After filtering and washing with water, it was dried and ground to obtain a pigment. The elution concentration of the pigment in 1% saline was about 1/20 of that of the pigment without crosslinking treatment.

(Specific Example 2) A chitosan solution prepared in the same manner as in Specific Example 1 and a Na-montmorillonite suspension were gradually mixed at a temperature of 50°C, stirred for 1 hour, and then cooled to room temperature to form a chitosan-montmorillonite mixed solution. was prepared. Separately, 2.4 g of red dye No. 201 was suspended in water, and the suspended red dye No. 201 was added to the mixture, stirred at room temperature for 2 hours, and then adjusted to pH 6 using aqueous ammonia.
．． Adjusted to 5. After further stirring for 1 hour, the mixture was cooled to 5° C., and 4 g of the above 25% glutaraldehyde aqueous solution was added and stirred for 20 hours to obtain an easily filterable yellowish red colored product. Then, it was filtered, washed with water, dried, and ground to make a pigment. The elution concentration of the pigment in 1% saline was about 1/10 of that of the pigment without crosslinking treatment.

(Specific Example 3) 5 g of chitosan having a degree of deacetylation of 80% and an average molecular weight of 40,000 was dissolved in 400 ml of 0.25% acetic acid aqueous solution to prepare a chitosan solution. Separately, 1 g of Na-montmorillonite was dispersed in 100 ml of water, and the Na-montmorillonite dispersed in this water was gradually mixed with the chitosan solution at a temperature of 50°C, stirred for 1 hour, and then cooled to room temperature to complete the chitosan-montmorillonite mixture. A liquid was prepared. Separately, red dye No. 201: 2.4
g was suspended in water, and the red dye No. 201 suspended in this water was added to the mixture and stirred at room temperature for 2 hours.The pH was adjusted to 6.5 using aqueous ammonia, and further 1.
After stirring for a period of time, an easily filterable yellowish-red colored product was obtained. After filtering and washing with water, water was completely replaced with acetone. Into this, hexamethylene diisocyanate as a polyfunctional reagent which is a crosslinking agent having a chitosan reaction: 2
After stirring for 2 hours, unreacted crosslinking agent was washed away with acetone, further washed with water, filtered, dried and ground to obtain a pigment. The elution concentration of the pigment in 1% saline was about half that of the pigment without crosslinking treatment.

(Specific Example 4) Using the pigment obtained in Specific Example 3, a lipstick was prepared according to the following formulation. Base: Castor oil
47.0%
isopropyl palmitate
5.0% Lanolin 1
0.0% Ozokerite
7.0
% Candelilla Row
7.0%
carnauba wax
4.0% color material:
titanium oxide
2.0% Pigment of the present invention (Specific Example 3) 18.0%
Fragrance: Synthetic fragrance
Appropriate amount manufacturing method:
Heat and melt the base raw materials and mix them uniformly. Add coloring agents to this mixture, knead it with a roll mill to disperse it evenly, remelt it, add fragrance, defoam, and then
It was poured into a mold and rapidly cooled to solidify. This cosmetic did not show any migration or bleeding, and had good makeup retention.

[0029]

Effects of the Invention: A pigment composition in which pigments are adsorbed using the chitosan-swellable smectite complex of the present invention as a carrier and which is cross-linked to chitosan has the following properties. It is possible to obtain a pigment with a different hue than when using a carrier with adsorption points of
The range of hues can be significantly expanded using a limited range of permitted pigments; b. Particularly as a coloring agent for cosmetics.
It is possible to provide pigments that are stable and also have favorable attributes derived from chitosan, such as moderate moisture retention, antibacterial, and antifungal properties. This provides effects such as being able to provide an excellent coloring agent that is harmless to the human body.

Claims (7)

[Claims] 1. A pigment composition characterized in that a pigment is adsorbed to a complex of chitosan and swellable smectite, and the complex is crosslinked by the action of a polyfunctional reagent having chitosan reactivity. 2. The polyfunctional reagent includes glutaraldehyde, dicarboxylic acid ester, dicarboxylic acid halide,
The pigment composition according to claim 1, which is at least one selected from organic diisocyanates, epihalohydrins, and the like. 3. A mixing step of mixing an acidic chitosan solution and a swellable smectite aqueous dispersion, and a crosslinking agent that has a chitosan dye and a chitosan reactivity in the mixture obtained in this mixing step and acts in an aqueous solvent. A method for producing a pigment composition, comprising an addition step of adding an agent and a finishing step of filtering and washing the easily filterable colored slurry produced in this addition step, followed by drying and pulverizing. 4. The production of the pigment composition according to claim 3, wherein in the addition step, the chitosan dyeing dye and the crosslinking agent are added to the mixed solution either simultaneously or sequentially. Method. 5. A mixing step of mixing an acidic chitosan solution and a swellable smectite aqueous dispersion, a first addition step of adding a chitosan staining dye to the mixed solution obtained in this mixing step, and a first addition step of adding a chitosan stainable pigment to the mixed solution obtained in this mixing step. A replacement step in which the generated easily filterable colored slurry is filtered and washed, and water is replaced with a non-aqueous solvent.The non-aqueous slurry obtained in this replacement step has chitosan reactivity and acts in the non-aqueous solvent. A method for producing a facial composition, comprising a second addition step of adding a crosslinking agent, and a finishing step of separating colored solids from the solvent that has passed through the second addition step, followed by drying and pulverizing. 6. The chitosan stainable pigment added to the mixed solution obtained in the mixing step is in the form of a solution, suspension, or powder. A method for producing a pigment composition. 7. It is characterized by containing a pigment composition obtained by adsorbing a pigment onto a complex of chitosan and swellable smectite and crosslinking it by applying a polyfunctional reagent having chitosan reactivity. Cosmetics.