JPS6149349B2 - - Google Patents

Description

[Detailed description of the invention]

This invention relates to a method for producing a new red colored pigment with excellent color effects by adsorbing complex salts (hereinafter referred to as complexes) obtained by reacting rhodamine B, a cationic dye, with an anionic dye on clay minerals. be. Specifically, an ionic complex obtained by reacting rhodamine B, which has unparalleled properties in terms of coloring power and light resistance, with a type of acid dye permitted for cosmetics, is adsorbed onto clay minerals. It is a red colored pigment. Conventionally, there are colored pigments of Rhodamine B and cationic dyes adsorbed solely on clay minerals. (Tokuko Akira
48-32178, Japanese Unexamined Patent Publication No. 135117/1983) These dyes have a staining property (to the skin) and do not have bright colors or a wide color gamut, which poses problems in use. Furthermore, rhodamine B lakes are not approved for cosmetic use in Japan. In addition, although it can be used as a dye, since it is a cationic dye, it has a high tendency to stain the skin, which severely limits its use in cosmetics, especially make-up cosmetics, and the excellent properties of Rhodamine B cannot be fully utilized. Not yet. In order to solve these drawbacks, as a result of intensive research, we have developed a method that allows the reaction between dyes to occur without using surfactants or adding other additives to adjust the color tone. That is, by generating complexes through ionic reactions and adsorbing them to clay minerals, we have discovered a new method for producing colored pigments that do not stain the skin and have bright colors and a wide color gamut. By changing the type of acid dye used in this plex formation and its reaction ratio (i.e., the amount of complex added), or by changing the concentration of the pigment to be adsorbed, it is possible to obtain a color ranging from a bluish red to a yellowish red. A wide range of color tone adjustment is also possible. Therefore, the present invention is also effective in solving the shortage of prohibited pigments due to their teratogenicity, mutagenicity, etc., which will be increasingly regulated in the future. The reaction between the acidic dye _and rhodamine B according to ^the present invention is _D1 - _SO3Na + _D2 =N( _C2H5 ) _12C- = _D1-
SO ₃ (C ₂ H ₅ ) ₂ N=D ₂ (D ₁ and D ₂ represent the matrix of the dye.) The specific conductivity method shows that the reaction proceeds as described above in an aqueous solution and forms a complex. and demonstrated by capillary method. Furthermore, in this case, according to the specific conductivity method, Rhodamine B has a 1:1 complex with an acidic dye having one sulfon group (see Figure 1).
In addition to the 1:1 type, the acidic dye having 2 types is the 1:2 type.
It has been found that type complexes are also generated (see Figure 2). Furthermore, X-ray diffraction (Table 1) was performed on the pigment containing the generated complexes, and changes in the interplanar spacing were compared.
% Rhodamine B and 10% Lysol Rubin B (to which clay mineral (bentonite) is added) has a diameter of 16.12 Å, and 10% Rhodamine B (17.66 Å) and 10% Lysol Rubin B (14.72 Å). It was found that the results were different from those obtained by adsorbing clay minerals alone.

[Table] Moreover, 10% Rhodamine B and 10% Lysol Rubin B are added to clay minerals without forming complexes.
When adsorbed at the same time (17.66 Å) (20% adsorbed pigment for clay minerals, composition ratio is the same as 20% complex content), complexes are formed between the layers of clay minerals because they have different interplanar spacings. It was demonstrated that it was adsorbed in the form of Tuxus. Therefore, it can be said that the characteristic of vivid pigments is that they contain this complex. Next, the production method of the present invention will be explained. When an aqueous dye solution containing equimolar amounts of Rhodamine B and an acid dye is prepared in advance and the two are mixed, a reaction immediately occurs according to the reaction mechanism described above, and a complex is precipitated. Clay minerals are gradually added to this mixture, and stirring is continued until it swells uniformly. After that, it is treated with chlorides such as Ca, Ba, A, etc., and after further stirring at 50℃ for 1 hour (30 minutes is also possible). If left standing, non-swellable pigments will precipitate. The desired pigment is obtained through the process of filtration, washing with hot water, drying, and pulverization.Other drying and pulverization methods such as spray drying and freeze drying can also be used to obtain the desired pigment. It was possible to obtain pigments. The clay mineral used in the present invention can be montmorillonite, hectorite, kaolin, hallosite, illite, etc., which have cation exchange ability, but in particular, the synthetic product Laponite CP (manufactured by Laporte, UK) has a structure Although the composition is natural hectorite, it does not contain the impurities found in natural clay, and is itself a white powder, so it can be said to have an excellent constitution. On the other hand, acidic dyes that serve as counter ions for Rhodamine B include Lake Red C, Acid Red, which has a sulfon group in its structure, and
Sunset Yellow FCF, Orange, Lysol Rubin B, Newcoccin, Amaranth, Tartrazine, Fast Acids Magenta, Quinoline Yellow WS, Violamine R, Ponceau 3R,
Ponceau R, Ponceau SX, Fastrez S,
Orange, Polar Yellow 5G, Naphthol Yellow S, Methanyl Yellow, Fast Light Yellow 30, etc., and valent and valent metal salts are possible as metal ions, but pigments treated with A ions cause dullness. Preferably, Ca and Ba salts give better results. Next, the following experiment was carried out regarding the color tone and coloring power of the red colored pigment obtained in the present invention. A complex-containing substance (i.e., 20% pigment) obtained by reacting a 10% aqueous dye solution of Rhodamine B and Lake Red C is adsorbed on Laponite CP, and a certain amount of castor oil is added to a certain amount of the red pigment to be produced. , furthermore, titanium oxide is added to the pigment by 1, 2,
Add 3 to 4 times the amount and knead with a Huber muller. This was applied to a certain coating film on a hiding rate test paper using a doctor blade, and then measured using a spectrophotometer (Hitachi
607 Color Analyzer) and calculate the value.
It was converted to the HVC Munsell display system and plotted on a chromaticity diagram. (See Figure 3). At the same time, Rhodamine B and Lake Red C were separately adsorbed onto Laponite CP, and the resulting pigments were mixed during kneading and compared with the color tone of the monochromatic mixture. As a result, the chroma of the monochromatic mixture rapidly decreased as the dilution rate of titanium increased. I'm going down. That is, while the color becomes dull, complex-containing substances are diluted in the direction of increasing bluish color saturation (in the direction of less change in color saturation). That is, since the saturation does not decrease due to dilution, the result is a clear difference in tone from a monochromatic mixture. Next, regarding the coloring power, the obtained HVC is calculated using Godlove's concentration formula S = √16 ² + ² (V
= 10-V (equivalent to darkness) and compared based on its saturation value (S). The larger the S value, the greater the coloring power.

[Table] From this, it was found that the complex-containing material had a larger S value than the monochromatic mixture, and the reduction rate of the S value was smaller, so it was found that the complex-containing material had a greater coloring power than the monochromatic mixture. Next, the following experiment was conducted regarding the bleedability of the present invention. Adsorb Rhodamine B and Lakered C complex to Laponite CP,
1 g of the pigment treated with Ba and Ca salts was diluted to 100 g with H ₂ O, and after stirring for 1 hour, the supernatant liquid was filtered, and its absorbance was measured with a spectrophotometer (Hitachi EPS-3T model). In comparison with lake (see Figure 4), the absorbance (ε) is shown in Table 3. It was demonstrated that the pigment of the present invention exhibits no bleeding into water compared to commercially available Rhodamine B and A lakes.

[Table] Next, examples will be shown, and examples of application to cosmetics will also be given and explained. Example 1 Rhodamine B 1.2%, dye aqueous solution 1000 ml and Lysol Rubine B 0.4% dye aqueous solution 2000 ml were reacted to form a complex.
After adding 100g of CP and dispersing it uniformly,
Add 100 ml of 0.2N barium chloride, stir at 50°C for 60 minutes, and then undergo the steps of filtration, washing with hot water, drying, and pulverization to form a pigment. The resulting pigment was blended into a lipstick. (Lipstick formulation example) Carnauba wax 16.0% Ozokerite 16.0 Lanolin 24.0 Liquid paraffin 24.0 Butyl stearate 10.0 The above pigments 6.0 Titanium oxide 4.0 Fragrance Appropriate amount Antioxidant Example 2 1000 ml of Rhodamine B1.2% dye aqueous solution and Sunset Yellow FCF0. Laponite was reacted with 1000ml of 8% dye aqueous solution to form a complex.
CP was dispersed and made into a pigment in the same manner as in Example 1, and then blended into an oil-based foundation.

[Table] Other uses include skin cosmetics such as oil-based white powder, solid white powder, nail enamel, body paint, and blusher, and hair cosmetics such as hair dye. It can also be fully used in fields such as paint and printing ink.

[Brief explanation of the drawing]

(Figure 1), Rhodamine B, Lysolrubin B
A drawing showing the change in specific conductivity when 0.5 mmol aqueous dye solutions of each were mixed at a constant ratio. (The vertical axis represents the specific conductivity, and the horizontal axis represents the dye molar ratio.)
(Fig.) A drawing showing the change in specific conductivity when 0.5 mmol aqueous dye solutions of Rhodamine B and Sunset Yellow-FCF were mixed at a constant ratio. (The vertical axis represents the specific conductivity, and the horizontal axis represents the dye molar ratio.) (Figure 3)
Complex-containing pigment obtained by adding castor oil to a complex-containing pigment obtained from Rhodamine B and Lake Red C, and then adding titanium oxide in the direction of the arrow at 1, 2, 3, and 4 times the amount of titanium oxide. and a drawing showing a change in color tone of a monochromatic mixture. (The vertical axis H represents hue, and the horizontal axis C represents saturation.) (Figure 4)
Add 1 g of A lake of commercially available Rhodamine B, A-treated product, Ca-treated product, and Ba-treated product of the pigment of the present invention to 99% water.
The graph shows the bleedability into water measured using a spectrophotometer (Hitachi EPS model) after dissolving the solution in g and stirring for 1 hour.

Claims (1)

[Claims] 1 Rhodamine B, a cationic dye for clay minerals
A method for producing a red colored pigment, characterized in that it is obtained by adsorbing a complex obtained by reacting with an anionic dye.