JPH07100774B2 - Black pigment composition - Google Patents

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a black pigment composition. More specifically, the present invention relates to a new black pigment composition having excellent color tone and other pigment characteristics, which is useful for various molded articles, paints, cosmetics and the like.

[0002]

2. Description of the Related Art Conventionally, pigments having various color tones and characteristics have been used in various fields. For these pigments, the types are divided into inorganic pigments and organic pigments, generally water, inorganic reagents, organic solvents, oils,
Insolubility in synthetic resins and plasticizers and good dispersibility are important requirements. In addition, the properties and performance required from the use side include color, rheology, light resistance,
Properties such as solvent and vehicle are mentioned, and in addition to these, when used for cosmetics in particular, the problem of safety to the body is added.

[0003] As the black pigment of the conventional pigments in need of such requirement, Fe ₃ O ₄ as a black oxide is an inorganic _{(FeO, Fe 2 O 3)} , include carbon black, Pig. Black 1 (Aniline Blac
k) etc. are known. Of these, most of those used for cosmetics are iron oxide and carbon black. Among the black pigments for cosmetics, carbon black is excellent in light resistance and color (brightness). In other words, carbon black is indispensable for producing long-lasting and attractive black color.

[0004] However, in recent years, it has been pointed out harmful to the body of the carbon black. This is because it is inevitable that benzpyrene, which has been pointed out to be carcinogenic, is mixed in the production process of carbon black. For this reason, black pigments using titanium nitride (TiN) fine particles have been experimentally produced as an alternative to carbon black, but there are problems such as the inability to develop an attractive black color and economical problems in manufacturing. is there. For this reason, it has been strongly desired to realize a black pigment for cosmetics or the like having a clear black color and excellent characteristics with good economic efficiency. The present invention has been made in view of such circumstances, and an object thereof is to solve the drawbacks of the conventional black pigments and to provide a new black pigment composition as described above.

[0005]

[Means for Solving the Problems] In order to solve the above-mentioned problems, the present invention makes iron nitrite fine particles having a particle size of 6 to 20 nanometers into a non-aqueous or aqueous dispersion medium by a surfactant. A black pigment composition comprising a dispersed colloid . Further, the present invention uses the composition as a cosmetic pigment, further adds an antioxidant, an inorganic or organic pigment or dye, and further, a colloid in which iron nitride fine particles are dispersed is an iron nitride magnetic fluid. Is also one of its aspects.

Namely, the present invention except for the shortcomings of conventional black pigment, there is provided a color, rheology, light fastness, a black pigment composition comprising a dispersion mixture of new iron nitride particles having excellent safety and the like. The background and premise of the present invention is the establishment of an iron nitride magnetic fluid manufacturing technique by the inventor of the present invention.

In this method, a metal carbonyl such as iron carbonyl and a surfactant are dissolved in a nonpolar organic solvent such as kerosene, and a nitrogen-containing compound such as ammonia gas is introduced into the solution and heated, Generates metal nitride fine particles such as iron nitride in the solution, and at the same time, by the action of the surfactant, the metal nitride fine particles are dispersed in a non-aqueous solvent,
This is a method for obtaining a metal nitride fine particle colloid or a metal nitride magnetic fluid. The surfactant molecule is adsorbed on the surface of the metal nitride fine particles with its lipophilic group facing outside. As a result, the metal nitride fine particles are dispersed in kerosene. The coating layer of such surfactant molecules What if sticking in magnetostatic force of the fine particles itself prevents the agglomeration, to serve as a molecular spacer. Therefore, the fine particles do not come closer than a certain distance, and the distance is almost determined by the structure and molecular weight of the surfactant. In this way, since the nucleation and growth of particles takes place in solution, Ri characterized der that the uniformity of the particle size is very good, the particle size is 6 to
It can be arbitrarily changed within the range of 20 nanometers.

[0008] As a result of the inventors' earnest research,
Among the above metal nitride colloid, has a property of colors colloidal iron nitride was excellent as a black pigment, by controlling the size of the iron nitride particles in particle size range of 6 to 20 nanometers
It was clarified that if the colloid is used and the type of the dispersion medium and the surfactant at that time are appropriately selected, the rheology, light resistance and solvent / vehicle properties required in terms of pigment usage are significantly improved. Also, because of the fine particle size
Because you are, hue as the pigment, gloss, uniformity, coatability
It is excellent in various performances and becomes extremely high quality.
It was Furthermore, from the viewpoint of safety to the body, it was confirmed that the residue such as unreacted iron carbonyl can be suppressed by performing sufficient heat treatment. The present invention has been completed based on the findings obtained as a result of the above research.

[0009] The following describes in detail the pigment compositions of the present invention. First, the method for producing the composition of the present invention will be described. The pigment composition has a particle size of 6 to 20 nanometers.
The iron nitride fine particles are used to disperse using a surfactant and a dispersion medium selected according to the purpose of use of the pigment composition and its application.In that case, it is directly connected to the synthetic reaction of the iron nitride fine particles as described above. The composition may be manufactured. That is, for example, as a cosmetic composition, iron carbonyl (Fe (CO) ₅ ) as a raw material of iron nitride fine particles is dissolved in olive oil or the like as a dispersion medium, and an ethylene oxide / propylene oxide block copolymer or the like is added as a surfactant. Stir. Of course, other than olive oil as this dispersion medium, purity, skin irritation, skin respiration, stability of microscopic substances,
Any substance may be used as long as it is excellent in terms of chemical stability, and the temperature at the time of synthesis (about 150
Any material may be used as long as it becomes a liquid at (° C or higher). For example, animal and vegetable oils include castor oil, coconut oil, squalane in addition to olive oil, mineral oils include liquid paraffin, petrolatum, solid paraffin, and synthetic oils such as synthetic polyether. To be In this case, the nonionic surfactant (nonionic) is preferable as the surfactant, and in addition to the ethylene oxide / propylene oxide block copolymer, polyoxyethylene type and polyhydric alcohol ester type represented by sorbitan higher fatty acid ester Any of the above surfactants may be used. The synthesis is performed according to the gas phase liquid phase reaction method described above. After completion of the synthesis, a nitrogen-containing compound typified by unreacted NH ₃ gas is removed by heat treatment in an inert gas (eg Ar gas), and unreacted Fe (CO)
By confirming that ₅ does not remain, it can be used as it is as a black pigment for eye makeup cosmetics and temporary hair dyes. In this case, it is also effective to add an antioxidant after the completion of the synthesis, especially for the purpose of preventing autoxidation of oils and fats in the air. As an antioxidant, B
HA (butylhydroxyanisole), BHT (butylhydroxytoluene), gallic acid esters, NDGA
Any of (nordihydroguaiaretic acid), thiodipropionic acid and its esters, tocopherol and the like may be used.

Further, it is also possible to manufacture the water-soluble iron black pigment nitride. The manufacturing method of this is as follows. By adding an amphipathic solvent (eg, acetone) to the iron nitride colloid and shaking it, the iron nitride fine particles aggregate and precipitate. This is washed with water and dispersed in water or a water-soluble alcohol such as glycerin or a water-soluble polymer. When dispersed in water, an ionic surfactant is added. For example, as the anionic surfactant, higher fatty acid soap such as sodium laurate, higher alcohol sulfate ester salt such as sodium oil oleyl alcohol, sulfonate such as monoalkylsulfosuccinate and higher alcohol phosphate ester, Cationic surfactants include quaternary ammonium salts such as alkyltrimethylammonium chloride, and amphoteric surfactants include carboxylic acid type and imidazoline derivatives. As a water-soluble polymer, what is required is that it is highly safe for the body, that it is tasteless, colorless and odorless as much as possible, and that it is not decomposed by heat, light, microorganisms, etc. Also, for example, quince seed gum, xateine gum and the like as natural products, cellulose derivatives such as methylcellulose, alginic acid-based such as propylene glycol alginate and the like as semi-synthetic products, polyvinyl alcohol and the like as synthetic products. The vinyl type and the like are listed, and the inorganic substances include bentonite and the like.

[0011] Hereinafter, Examples, further detailed explanation about the present invention.

EXAMPLES Example 1 Fe (CO) ₅ 130 g, ethylene oxide / propylene oxide block copolymer HO (CH ₂ CH ₂ O) m
(CH ₃ CHCH ₂ O) n (CH ₂ CH ₂ O) m′H,
15 g of (m + n + m'≉20, n≅15) was dissolved in 60 g of olive oil, and heated and reacted by the gas phase liquid phase method while flowing NH ₃ gas at 300 cc / min. The reaction was carried out at 90 ° C. for 2 hours and then at 190 ° C. for 2 hours, and this cycle was repeated 5 times. After completion of the reaction, while flowing Ar gas at 500 cc / min,
Heat treatment was performed at about 195 ° C. for 1 hour. As a result, a Fe ₃ N fine particle colloid having a diameter of about 80 Å was obtained by observation with an electron microscope. As a result of analysis by MS and GC-MS,
Fe (CO) ₅ and Fe ₂ (CO) are contained in this colloid.
₉ , Fe ₃ (CO) ₁₂ and NH ₃ were not detected, and condensed polycyclic aromatic compounds represented by benzpyrene were not detected. The iron nitride fine particle colloidal solution obtained by this method has a clear black color, and in an experiment applied to cotton, paper and skin, it has excellent coloring power and hiding power,
In the case of cotton and paper, its clear black color was retained for more than one year, and when applied to skin, it was not washed off with water.

[0012] In the same manner as in Example 1, was prepared iron particle colloidal nitride. By volume ratio, 50 parts of acetone to 50 parts of this colloid
By adding and shaking, fine particles of iron nitride were aggregated and a precipitate was obtained. After filtering this, it was washed with acetone and then with hot water. When about 10 g of this precipitate was dispersed in about 50 g of polyvinyl alcohol which was liquid at room temperature, a good iron nitride fine particle colloid was obtained. In addition, about 30 g of dialkyldimethylammonium chloride is added to 30 g of water.
Good iron nitride fine particle colloids were also obtained when the precipitate was dispersed in an aqueous solution in which 0 g was dissolved. When these water-soluble iron nitride fine particle colloids were applied to the skin,
I was able to easily wash it off with soap for face washing (higher fatty acid soap) and water.

[0013] in water dispersion medium and iron particle colloidal about 10g nitride prepared in Example 3 Example 2, good colloidal solution was bluish black was added ultramarine blue about 0.5g is obtained Was given. Example 4 About 5Og of the medicinal scarlet (Red No. 501) was dissolved in 5g of the iron nitride fine particle colloid prepared in Example 1, and a good colloidal solution having a slightly reddish black color was obtained.

[0014]

As described in detail above, according to the present invention, the following excellent effects are realized. (1) A black pigment having an extremely dark brightness is obtained, and when this is used as a cosmetic product, an attractive black color can be exhibited. (2) Inorganic pigments such as titanium oxide, iron oxide or ultramarine blue or medicinal scarlet (red 5
It is easy to change the color tone to blackish brown or bluish black by mixing tar dyes such as No. 01) and Alizurin purple SS (purple No. 201). (3) By selecting an appropriate organic solvent as the dispersion medium, it becomes stable with respect to water and has a property of being hard to drop by water. (4) By selecting water, water-soluble alcohol (such as glycerin) or water-soluble polymer as the dispersion medium, it is possible to easily wash off with water. (5) There is no change in color, viscosity, and chemical properties compared to the time of manufacture even after being exposed to the air for over 1 year. (6) It has excellent coloring power and hiding power against skin and is safe for the body. (7) Raw materials are inexpensive and mass production is possible. Due to these characteristics, a new pigment composition useful as, for example, a black pigment for eye makeup cosmetics, a black pigment for temporary hair dyes, a black pigment for printing inks, a paint, a black pigment for crayons, etc. is provided. It

Claims (6)

[Claims] 1. A black pigment composition comprising a colloid in which fine particles of iron nitride having a particle size of 6 to 20 nanometers are dispersed in a non-aqueous or aqueous dispersion medium with a surfactant. 2. The composition according to claim 1, wherein the colloid in which the iron nitride fine particles are dispersed is an iron nitride magnetic fluid. 3. The composition according to claim 1, wherein the dispersion medium is a non-aqueous solvent, a water-soluble polymer, water or water-soluble alcohols. 4. The method according to claim 1, wherein an antioxidant is mixed.
2 or 3 compositions. 5. The composition according to claim 1, 2, 3 or 4, which is mixed with an inorganic or organic pigment or dye. 6. A pigment composition for cosmetics according to claim 1, 2, 3, 4 or 5.