JPH0625314B2 - Metal complex salt processing Face amount manufacturing method - Google Patents

Description

The present invention relates to an improved method for producing a metal complex salt-processed pigment, which does not change the scent even when a fragrance is coexistently mixed in cosmetics and the like, and has a coloring effect. It is intended to provide a metal complex salt-processed pigment which is also excellent in terms of the aspect.

Conventionally, in the case of a formulation system such as a cosmetic in which an inorganic pigment, in particular, a metal complex salt type and a fragrance coexist, the scent changes with time, and particularly under high temperature and high humidity conditions, the rate of the change also increases. However, the odor was notable, which was a major cause of loss of its commercial value.

Up to now, various methods have been studied in order to prevent such problems, but as a specific example, first, from the pigment side, a method of subjecting the surface to metal soap treatment, a method of performing silicon treatment, Known methods include treatment with amorphous silica, treatment with a sequestering agent, and further treatment with metal soap (JP-A-52-122635), and fine particles with low activity from the perfume side. A method of adsorbing a fragrance on silica or metallic soap powder and blending it, a method of adsorbing it on a porous powder, and the like have been known.

However, among the above methods, when the metal complex salt pigment is subjected to metal soap treatment or amorphous silica treatment, although the number of days until a slight scent change occurs in a normal state is increased, under high temperature and high humidity. It had no effect and the coloring power was lowered. Similarly, the silicone treatment had almost no effect in terms of suppressing fragrance change.

Further, in the case of using the method disclosed in JP-A-52-122635, the surface of the metal complex salt pigment becomes very hydrophilic when only the metal ion sequestering agent treatment is applied to the metal complex salt pigment such as ultramarine blue. However, it is difficult to filter after the treatment, and it is difficult to say that it is advantageous in terms of industrial scale and economy. Furthermore, even when metal soap treatment is performed after treatment with a sequestering agent, dark blue and the like have unstable properties under alkaline conditions, so they decompose and become a partially colored transparent solution, resulting in a pigment. As a result, the actual yield was significantly reduced. Further, the obtained pigment also had a lower cost merit in terms of economical efficiency, for example, the amount of coloring was lower than that of untreated pigment, and about twice the amount of pigment was required to obtain the same color tone.

On the other hand, with respect to the adsorption method based on the studies on the fragrance side as well, the odor was only slightly delayed with time, and almost no effect was observed under the conditions of long-term, high temperature and high humidity.

That is, there are various forms such as alcohols, ketones, aldehydes, esters, ethers, etc. in the fragrance component, and there are many unclear parts in the interaction or reaction between these and the metal complex salt pigment. It was difficult to prevent the odor from changing for all the fragrance ingredients.

Therefore, as a result of intensive studies conducted by the present inventors in view of the above-mentioned present circumstances, a metal oxide obtained by hydrolyzing an organometallic compound after first treating a metal complex salt pigment with a sequestering agent A thin and even coating of the product does not change the scent even when coexisting with a fragrance, and has superior coloring power compared to the metal complex salt pigment before treatment. Heading out, the present invention was completed.

That is, the present invention, as a first step, after the metal complex salt pigment is immersed in an aqueous solution of a sequestering agent, dehydrated and dried to obtain a sequestering agent-treated metal complex salt pigment, and then as a second step, The metal-sequestering agent-treated metal complex salt pigment obtained in the step, (a) a step of dispersing in a hydroalcoholic solution, and adding an organometallic compound thereto for hydrolysis, or (b) an alcohol in which the organometallic compound is dissolved Dispersion in water, hydrolyzed alcohol solution is added to it to decompose, and either one of the hydrolysis steps is selected, and a metal oxide precipitate is formed on the surface of the metal complex salt pigment treated with the sequestering agent. A method for producing a metal complex salt-processed pigment, comprising:
The present invention relates to a method for producing a metal complex salt-processed pigment, characterized in that the hydrous alcohol solution contains 0.1 to 10 V / V% of water.

Hereinafter, the present invention will be described in detail.

First, examples of metal complex salt pigments applicable to the present invention include dark blue, manganese violet, and blue No. 404. Among these, the conventional method is most likely to be adversely affected, and the coloring power by the method of the present invention is high. It is preferable to use dark blue, which has the most remarkable enhancement effect, but is not necessarily limited thereto.

Next, as a metal ion sequestering agent, EDTA and its alkali metal salts such as EDTA-2Na and EDTA-4N are used.
a or the like is used, and the required amount thereof is 0.5 to 10% by weight, preferably 1 to 10% by weight based on the metal complex salt pigment.
A range of 5% by weight applies. Also, in processing,
It is used as an aqueous solution of a sequestering agent having a concentration of about 0.01 to 10%.

Further, as the organometallic compound used in the second-stage treatment, organic silicic acid compounds such as ethyl silicate, aluminum isopropoxide, aluminum monobutylisopropoxide, aluminum aluminum monobutyldiisopropoxide and the like are used. Examples include compounds, titanium tetraisopropoxide, isopropoxytitanium dimethacrylate isostearate, isopropoxytitanium triisostearate, tri-n-butoxytitanium monostearate, and organotitanium compounds such as isopropoxytitanium tris. Further, the method for performing the coating treatment of the metal oxide using these organometallic compounds,
Specifically, it is as follows.

For example, when using an organic silicic acid compound such as ethyl silicate or an organic aluminum compound such as aluminum isopropoxide to perform silica coating or alumina coating, the organic silicic acid compound or the organic aluminum compound is (a) an alcohol. Alcohol solution containing 0.1 to 10 V / V% water relative to the total volume of alcohol and water (hereinafter referred to as "0.1 to 10 V / V% hydrous alcohol solution"), or (b ) 0.1-10V / V%
A method in which the organosilicic acid compound or the organoaluminum compound is hydrolyzed by dissolving in an aqueous alcohol solution and adding a small amount of an acid or an alkali to the solution of (a) or (b) and heating the solution is preferable.

However, when using a metal complex salt pigment that is weak against alkali such as dark blue, it is better to use an acid.

When titanium dioxide coating is performed using an organic titanium compound such as titanium tetraisopropoxide,
A 0.1 to 10 V / V% hydroalcoholic solution is gradually added with a solution of an organotitanium compound previously dissolved in an alcohol such as isopropanol for hydrolysis.

When the hydrolysis is carried out, if the concentration of water present in the hydroalcoholic solution is less than 0.1 V / V%, the amount of water is too small to cause the hydrolysis reaction, and conversely, if it exceeds 10 V / V%, the hydrolysis rate increases. It becomes large, and it becomes difficult to uniformly and densely form a metal oxide film on the surface of the metal complex salt pigment. Therefore,
The preferred concentration range of water in the hydrous alcohol solution is 0.1 to 3
V / V% is good. Here, as a matter of course, the alcohol in the hydroalcoholic solution must be one in which water such as methanol and ethanol can be dissolved.

The coverage of the metal oxide such as silica, alumina and titanium dioxide formed as described above is advantageously in the range of 0.5 to 20% by weight, preferably 1 to 5% by weight based on the metal complex salt pigment. If it is less than 0.5% by weight, the water resistance deteriorated by the treatment with a sequestering agent will not be improved, and if it exceeds 20% by weight, the coloring power will be deteriorated.

Examples will be shown below to further explain the production method of the present invention in detail.

Example 1 99.5 parts of dark blue to 500 parts of 0.1 EDTA-2Na aqueous solution,
It was immersed at room temperature for 12 hours with stirring, dehydrated, and dried in a dryer at 60 ° C. for 2 days. Then, this was dispersed in 500 parts of a methanol solution containing 3% of water, and a solution of 2 parts of titanium tetraisopropoxide dissolved in isopropanol was gradually added thereto. After the completion of the addition, the solvent was distilled off under reduced pressure, followed by drying at 60 ° C. for 22 hours to obtain titanium oxide-coated dark blue.

Examples 2 to 5 0.2% EDTA-each as an aqueous solution of sequestering agent
2Na aqueous solution 500 parts, 0.4% EDTA-2Na aqueous solution 500 parts, 1% EDTA-2Na aqueous solution 500 parts, 2%
Titanium oxide coating was applied to each of the above ion-sequestering agent treated navy blue in the same manner as in Example 1 except that 500 parts of EDTA-2Na aqueous solution was used.

Examples 6 to 10 0.1% EDTA-each as an aqueous solution of sequestering agent
4 Na aqueous solution 500 parts, 0.2% EDTA-4Na aqueous solution 500 parts, 0.4% EDTA-4Na aqueous solution 500 parts, 1
% EDTA-4Na aqueous solution 500 parts, 2% EDTA-4
In the same manner as in Example 1 except that 500 parts of an aqueous Na solution was used, the above-mentioned ion sequestrant treated dark blue was coated with titanium oxide.

Examples 11 to 15 Titanium oxide coating was performed in the same manner as in Example 1 except that 4 parts, 8 parts, 20 parts, 40 parts, and 100 parts of titanium tetraisopropoxide were used as the organometallic compounds.

Example 16 99.5 parts of navy blue was immersed in 500 parts of a 0.1% EDTA-4Na aqueous solution for 12 hours with stirring at room temperature, dehydrated, and dried in a dryer at 60 ° C. for 2 days. Then, this was dispersed in 500 parts of an ethanol solution in which 8 parts of ethyl silicate was dissolved, heated to 60 ° C., and then an ethanol solution containing 3% water (containing 0.001N hydrochloric acid) was gradually added. Was added. After the addition was completed, the solvent was distilled off under reduced pressure at 22 ° C at 22 ° C.
It was dried for a time to obtain (particulate) silicic acid-coated dark blue.

Example 17 99.5 parts of navy blue was immersed in 500 parts of a 0.1% EDTA-2Na aqueous solution for 12 hours with stirring at room temperature, dehydrated, and dried in a dryer at 60 ° C. for 2 days. Then, this was dispersed in 500 parts of an ethanol solution in which 5 parts of aluminum tetraisopropoxide was dissolved, heated to 60 ° C., and then an ethanol solution containing 3% water (containing 0.001 N hydrochloric acid). Added slowly. After the completion of the addition, the solvent was distilled off under reduced pressure, followed by drying at 60 ° C. for 22 hours to obtain aluminum oxide-coated dark blue.

Comparative Example 1 99.5 parts of navy blue was immersed in 500 parts of a 0.1% EDTA-2Na aqueous solution for 12 hours with stirring at room temperature, dehydrated, and dried at 60 ° C. for 2 days in a dryer.

Comparative Example 2 Prussian 100g was dispersed in distilled water or deionized water _{800ml, 10% AlCl 3 · 6H} 2 O solution 100ml
Was also added with 10% sodium hydroxide solution to adjust the pH to 3.
While keeping at 0, added over 20 minutes. After the addition is complete, filter with a Buchner funnel and place in an air oven at 50 ° C for 1 hour.
It was dried at night to obtain a deep blue coating of aluminum hydroxide (about 3%).

Comparative Example 3 100 parts of navy blue was evenly dispersed in 500 parts of purified water, pH was adjusted to 8.3 by adding aqueous ammonia, and 50 parts of 6% sodium disilicate aqueous solution was added to sufficiently stir the pH.
11.3 Then, this mixed solution is heated and kept at 75 ° C.,
Slowly add 5% sulfuric acid to bring the pH to 7.6, and then for another 60 minutes at 75 ° C.
After holding at 50 ° C, 50% sulfuric acid is gradually added to adjust the pH to 6.1. After that, the powder was separated from the mixed solution, washed with water repeatedly until the soluble salt was eliminated, and then dried at 80 ° C. to obtain amorphous silicic acid-coated (about 2%) dark blue.

Comparative Example 4 99.5 parts of navy blue was immersed in 500 parts of a 0.1% EDTA-2Na aqueous solution for 12 hours with stirring at room temperature, dehydrated, and dried in a dryer at 60 ° C. for 2 days. Thereafter, this pigment was coated with amorphous silicic acid in the same manner as in Comparative Example 3.

Next, in order to evaluate the metal complex salt-processed pigments obtained by the method of the present invention obtained as described above, the deep blue-blue processed pigments obtained in Examples 1 to 17 and the deep blue-blue processed pigments obtained in Comparative Examples 1 to 4 were evaluated. Using the pigment and untreated dark blue (Comparative Example 5), changes in scent in the presence of various fragrances were measured. The method was to mix 95 parts of sample pigment and 5 parts of fragrance, and mix this at 40 ° C. for 10
The change in scent after standing for 1 month under 0% RH was evaluated by sensory evaluation by 6 scent panelists. Table of results
Shown in 1.

(Evaluation criteria) 0: No change -1: Slight change -2: Some change -3: Large change

As shown in the results of Table-1, only the sequestering agent treatment,
Alternatively, a processed pigment only coated with a metal oxide has a weak effect of suppressing a change in scent. Further, also in the two-step processing method of the ion-sequestering agent treatment and the metal oxide coating treatment, if the metal oxide coating treatment of the second step is performed in an aqueous system,
It was shown that the effect of suppressing the change of scent was insufficient because a uniform coating was not possible. Therefore, it was revealed that the processed pigment produced by the method of the present invention has a strong inhibitory effect on the change in scent of various types of fragrances.

In addition, the present inventors conducted a test by the following method in order to evaluate the tinting strength of the metal complex salt processed pigment similarly obtained by the method of the present invention.

(Method) Using the dark blue processed pigment obtained in Example 1, the deep blue processed pigment obtained in Comparative Examples 1 to 4 and untreated dark blue (Comparative Example 5), and these and talc in a ratio of 1: 9. After mixing with, the squalane as an oil agent (oil amount: 0%, 4%, 8%,
12%) and press-press on a metal plate, and then measure the color tone with a color difference meter (L value, b value)
did. The results are shown in Table-2.

As is clear from the results shown in Table 2, the dark blue processed pigments obtained by the method of the present invention are lighter (L value) than the various dark blue processed pigments obtained by the method of Comparative Example and untreated dark blue.
It was proved that the colorant was low, the chroma (b value: bluish) was high and the coloring power was excellent. Especially when compared to untreated dark blue, the pigments obtained according to the invention give 1
It has a coloring efficiency of ⅓ and shows that the coloring power of dark blue is enhanced by the method of the present invention.

As described above, the metal complex salt-processed pigment obtained by the method of the present invention is combined with the reduction of the pigment surface activity by the sequestering treatment of the metal ion, and the coating effect of the metal oxide having a low surface activity, and thus various excellent perfumes. It is an excellent pigment that has the effect of suppressing the change of the scent, retains the water resistance without deteriorating, and further enhances the coloring effect of the metal complex salt pigment.

 ─────────────────────────────────────────────────── ─── Continuation of the front page (56) Reference JP-A-52-122635 (JP, A) JP-A-55-115459 (JP, A) JP-A-56-133368 (JP, A) JP-A-53- 115744 (JP, A) JP-B-55-34184 (JP, B2) JP-A-55-125164 (JP, A) JP-A-56-11964 (JP, A) JP-A-58-76461 (JP, A)

Claims (4)

[Claims] 1. As a first step, the metal complex salt pigment is immersed in an aqueous solution of a sequestering agent, dehydrated and dried to obtain a metal complex salt pigment treated with a sequestering agent, and then, as a second step, the above step. The metal-sequestering agent-treated metal complex salt pigment obtained in (a) a step of dispersing in a hydroalcoholic solution and adding an organometallic compound thereto for hydrolysis, or (b) in an alcohol in which an organometallic compound is dissolved And hydrolyzed by adding a hydroalcoholic solution to the surface of the metal complexing agent to cause a metal oxide to precipitate on the surface of the metal complex salt pigment treated with the sequestering agent. A method for producing a metal complex salt-processed pigment, comprising:
A method for producing a metal complex salt-processed pigment, characterized in that the hydrous alcoholic solution contains 0.1 to 10 V / V% of water. 2. The method for producing a metal complex salt processed pigment according to claim 1, wherein the hydrolysis is carried out in the presence of an acid or a base. 3. The method for producing a processed metal complex salt pigment according to claim 1 or 2, wherein the metal complex salt pigment is dark blue. 4. The method for producing a processed metal complex salt pigment according to claim 1 or 2, wherein the coverage of the metal oxide is 0.5 to 20% by weight based on the metal complex salt pigment.