JP3286463B2 - Organic-inorganic composite pigment and method for producing the same - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a novel organic-inorganic composite pigment having high color saturation and high concealing property and hardly causing bleeding with water or sweat.

[0002]

2. Description of the Related Art Conventionally, when a colored pigment or dye is used as a coloring agent for various products, the appearance of the product is kept beautiful by using an inorganic white pigment having a hiding power. It is also known that, for the purpose of stabilizing the coloring and hiding power at the time of blending, the aggregation of the colorant and the inorganic white pigment is broken up and dispersed using an atomizer, a roll mill, a sand mill or the like.

However, in these prior arts, since the cohesive force differs depending on the type of pigment or dye, sufficient dispersion stability cannot be obtained, and as a result, the particles are liable to re-agglomerate and have good color development. However, it is difficult to stably obtain the hiding power.

[0004] Techniques for improving such disadvantages of the prior art include: (1) adding a finely ground flaky substrate to a dye which has been made aqueous by a chemical method, and then precipitating the dye on the surface of the substrate particles;
A method of obtaining a pigment having good coloring properties by depositing it (JP-A-62-91565). (2) A method of obtaining a colored mica pigment by precipitating and coating a pigment on the surface of a substrate particle in an aqueous system (Japanese Patent Application Laid-Open No.
243168). (3) The flaky substrate particles and the pigments are formed on the flaky substrate particles of metal oxide-coated mica, mica, sericite, kaolin, etc. by stirring the pigment and / or dye particles at a predetermined high speed without using a liquid medium. A method in which an ordered mixture is formed with the pigment and the dye particles to obtain a flaky composite pigment which is excellent in chroma, dispersibility and adhesion stability of pigments and dyes (JP-A-5-214257). (4) 4- (o-sulfo-p) is added to the surface of the inorganic or organic powder.
-Tolylazo) -3-hydroxy-2-naphthoic acid salt to obtain a high-chroma composite pigment (JP-A-4-292)
664). Etc. have been proposed.

[0005]

[Problems to be solved by the invention]
According to the techniques (1) and (2), since the fine particles and the dispersion of the pigment and the dye are not sufficient, it is difficult to obtain a satisfactory color.
Furthermore, pigments and dyes that did not adhere to the substrate particle surface or were weakly adhered in the treatment step were separated and dropped off in the filtration step or the washing step, and the expected coloring property with respect to the used amount of the pigment or dye used. May not be obtained.

In the technique (3), all of the pigments and dyes are not necessarily fixed stably and uniformly to the substrate surface because they are fixed by physical means such as impact force, compression force, and shear force. . In addition, as a result of the substrate being pulverized by the high-speed stirring, the width of the particle size distribution of the substrate is widened, which does not have a favorable effect on high chroma.

Furthermore, since a flaky substance having a low refractive index is used as a substrate, the resulting composite pigment has high transparency, is affected by the undercolor, and is unlikely to have high saturation. Therefore, the use as a coloring agent is greatly limited particularly in the field of cosmetics and paints.

In the technique (4), in the embodiment, in addition to silica having a refractive index of 1.47 to 1.52, a refractive index of 1.47 to 1.52 is used.
Polyethylene powder and nylon powder of 51 to 1.52 are used as substrates, and 4- (o-
Sulfo-p-tolylazo) -3-hydroxy-2-naphthoate (monosodium salt “Risolrubin B”;
Since only calcium salt “Risol-rubin BCA”) is deposited, these complexes cause bleeding in water, sweat, and ethanol, and the attached dye or lake is easily desorbed from the substrate. Has the drawback of dyeing the skin, and further has the drawback that the chroma decreases over time.

Accordingly, an object of the present invention is to solve the above-mentioned problems of the prior art, and to provide a pigment which has both high chroma and high hiding power and which does not easily cause bleeding, and a method for producing the pigment.

[0010]

Means for Solving the Problems In order to solve the above-mentioned problems, the present inventors have conducted intensive studies on changes in chroma and hiding power when an organic pigment and a high refractive index inorganic white pigment are combined. When calcium carbonate and Red No. 202 are uniformly and firmly adhered to the surface of the high refractive index inorganic white pigment to form a composite, much more than simply mixing the high refractive index inorganic white pigment and Red No. 202 The present inventors have found that they exhibit high chroma and high hiding power and hardly cause bleeding in water, sweat, and ethanol, and have completed the present invention.

That is, the present invention provides a high chroma which is obtained by strongly coating an inorganic white pigment having a refractive index of 2 or more and an average particle size of 0.01 to 60 μm, preferably 0.1 to 60 μm with calcium carbonate and Red No. 202. And an organic-inorganic composite pigment exhibiting high hiding power.

Also, the present invention provides a method for producing an organic-inorganic composite pigment exhibiting high chroma and high hiding power, wherein the inorganic white pigment is firmly coated with calcium carbonate and Red No. 202.

Hereinafter, the present invention and the method for producing the organic-inorganic composite pigment of the present invention will be described in detail.

The method for producing an organic-inorganic composite pigment in which the high refractive index inorganic white pigment of the present invention is firmly coated with calcium carbonate and Red No. 202 is as follows: (1) Red No. 201 and / or Red 202 (2) Red No. 201 and / or Red 202
And (3) adding an alkali carbonate or a solution thereof to the lower alcohol solution to form red 201 and / or red 202 on the surface of the inorganic white pigment. And (4) adding a lower alcohol solution of calcium chloride to the lower alcohol solution to form and deposit calcium carbonate on the surface of the inorganic white pigment, and to deposit red carbonate No. 201 and / or Or a step of making red No. 202 lake or re-rake and fixing red No. 202 on the surface of the inorganic white pigment.

Although the steps (1) and (2) may be performed before or after or simultaneously, red No. 201 and / or
Alternatively, in order to confirm the dissolved state of Red No. 202 and the dispersed state of the inorganic white pigment, it is preferable to follow the above procedure.

The lower alcohol which dissolves Red No. 201 and / or Red No. 202 and disperses an inorganic white pigment is methanol, ethanol, isopropyl alcohol, n-propyl alcohol, isobutanol, sec.
-Butanol, tert-butanol, n-butanol and the like can be used alone or in combination of two or more.

If these lower alcohols have a large water content, the inorganic white pigments are strongly agglomerated when an alkali agent is added in the step (3), and the organic-inorganic composite pigments in a non-uniform coating state are not coagulated. Water content is 5%
It is desirable to use less than less lower alcohols.

Next, an alkali carbonate or a solution thereof is added to a lower alcohol solution in which red # 201 and / or red # 202 are dissolved and an inorganic white pigment is dispersed, and red # 201 and / or red # 202 are converted to an inorganic white pigment. Deposit on the surface of the white pigment. Na ₂ CO ₃ as an alkali carbonate,
K ₂ CO ₃ and Li ₂ CO _{3 as} they are, or an aqueous solution,
It can be suitably used as a lower alcohol solution or a hydrated lower alcohol solution, and its concentration is not particularly limited.
It is necessary to introduce an amount sufficient to cause No. 01 and / or Red No. 202 to be deposited on the surface of the inorganic white pigment. Therefore, from the viewpoint of working efficiency, it is desirable to use the solution as highly concentrated as possible.

Next, in the step (4), calcium carbonate is generated and deposited on the surface of the inorganic white pigment by calcium chloride, and the red color 2 deposited on the surface of the inorganic white pigment.
No. 01 and / or Red No. 202 is laked or re-raked and firmly fixed in the form of Red No. 202. As calcium chloride, any form of anhydrous salt, dihydrate, and hexahydrate can be suitably used. As a solvent for dissolving calcium chloride, lower alcohols such as methanol, ethanol, and isopropanol can be used.
It is preferable to use a lower alcohol of less than 5% because the dissolution rate of calcium chloride is higher. The concentration to be used is not particularly limited, but it is more advantageous to use a solution with as high a concentration as possible from the viewpoint of working efficiency.

With calcium chloride, calcium carbonate is formed and deposited on the surface of the inorganic white pigment.
After the lake No. 01 and / or the red No. 202 are laked or re-laken, it is preferable to carry out the ripening of the reaction at a temperature lower than the boiling point of the solvent used, preferably around room temperature. The reaction ripening time varies slightly depending on the ripening temperature, but if it is less than 3 hours, a bluish red color, which is the original color of Red No. 202, may not be obtained. Since substantially no change in color is observed, it is desirable to carry out aging for 3 to 5 hours.

After completion of the reaction aging, the obtained organic-inorganic composite pigment is filtered and washed. As a method for filtering the organic-inorganic composite pigment, known methods such as pressure filtration, vacuum filtration, natural filtration, centrifugal separation, and decantation can be used. As a solvent used for washing the obtained organic-inorganic composite pigment, water, lower alcohol, or a mixture of two or more of these can be used.

When drying the organic-inorganic composite pigment obtained by coating the finally obtained inorganic white pigment with calcium carbonate and Red No. 202, it is desirable to dry at a temperature of 60 ° C. or less. Drying at a temperature exceeding 60 ° C. tends to cause a color shift phenomenon in which the original color of Red No. 202 is further shifted to a bluish hue. The drying time depends on the solvent used for washing, but usually about 4 to 30 hours is sufficient.

The inorganic white pigment to be coated preferably has a refractive index of 2 or more. When the one having a refractive index of less than 2 is used, the transparency becomes strong, the shape of the undercoat is easily seen, and the undertone of the undercoat is influenced by the undertone, so that a pigment with high chroma and high hiding power cannot be obtained. Such inorganic white pigments having a refractive index of 2 or more include zinc oxide (refractive index: 2.0), zirconium oxide (refractive index: 2.4), anatase-type titanium oxide (refractive index: 2.5), and rutile-type oxide. Titanium (refractive index 2.
75) or a mixture or composite of two or more of these.

There are no particular restrictions on the shape of the inorganic white pigment, but it is desirable that the average particle size is in the range of 0.01 to 60 μm. When the average particle size is less than 0.01 μm, the hiding power of the pigment is reduced, and it is difficult to obtain an optically sufficient dispersion state of the pigment, and particularly 0.1 μm or more for applications requiring the hiding power. Things are desirable. If it exceeds 60 μm, not only a sufficient coloring power cannot be obtained, but also a grainy feeling can be felt, which is not preferable.

The amount of Red No. 202 to be coated on the inorganic white pigment can be selected according to the desired tint. If the amount of Red No. 202 fixed on the surface of the inorganic white pigment is increased, the red organic color becomes darker. -An inorganic composite pigment is obtained, but if the weight ratio of the inorganic white pigment to Red No. 202 exceeds 1: 1, the red color will not be substantially increased. Therefore, it is desirable to appropriately select within this range.

When the diffraction pattern of the thus obtained organic-inorganic composite pigment was examined by an X-ray diffractometer, peaks of an inorganic white pigment and calcium carbonate were confirmed.
It is presumed that Red No. 202 is fixed to the surface of the inorganic pigment in a form in which No. 2 is coated with calcium carbonate, or that Red No. 202 is fixed to the surface of the inorganic pigment in a state where Red No. 202 and calcium carbonate are combined. The exact structure is unknown.

[0027]

Examples and Comparative Examples Hereinafter, the present invention will be described in more detail with reference to Examples and Comparative Examples.

Embodiment 1 FIG. 200 g of 95% ethanol was weighed into a glass container, and 2 g of Red No. 202 (manufactured by Daito Kasei) was charged with stirring to completely dissolve. 8 g of titanium oxide A-100 (manufactured by Ishihara Sangyo) was added to this solution, and the mixture was uniformly dispersed by stirring with a homomixer for 30 minutes.
Separately, an alkaline solution in which 13.4 g of sodium carbonate was dissolved in 40 g of purified water was prepared, and slowly poured into an ethanol solution of Red No. 202 in which titanium oxide was dispersed over 30 minutes. Further, a solution prepared by dissolving 80 g of anhydrous calcium chloride in 100 g of 99.5% ethanol was added over 60 minutes. Thereafter, the reaction was aged at room temperature for 4 hours. After the ripening was completed, the supernatant was removed by decantation, and then 9
The steps of adding 200 g of 5% ethanol, stirring and filtering were repeated three times. The obtained organic-inorganic composite pigment was heated at 50 ° C.
For 12 hours, and pulverized to obtain an organic-inorganic composite pigment in which calcium carbonate and Red No. 202 were firmly fixed on the surface of titanium oxide.

Embodiment 2 FIG. 200 g of 95% ethanol was weighed into a glass container, and 2 g of Red No. 202 (manufactured by Daito Kasei) and 1 g of Red No. 201 (manufactured by Kishi Kasei) were charged with stirring and completely dissolved. Titanium oxide CR-5 was added to this solution.
0 (manufactured by Ishihara Sangyo) and 2 g of zirconium oxide (manufactured by Tosoh), and 8000 rpm using a disper.
The mixture was stirred at m for 30 minutes to be uniformly dispersed. Separate purified water 8
An alkaline solution prepared by dissolving 13.4 g of potassium carbonate in 0 g was prepared and slowly poured into an ethanol solution of Red No. 202 and Red No. 201 in which titanium oxide and zirconium oxide were dispersed over 30 minutes. Further, a solution obtained by dissolving calcium chloride hexahydrate in 100 g of 95% ethanol was added over 60 minutes. Thereafter, the reaction was aged at room temperature for 5 hours. After completion of aging, the supernatant was removed by decantation, and 200 g of 95% ethanol was added.
The filtration step was repeated three times. The obtained organic-inorganic composite pigment was dried at 50 ° C. for 10 hours and pulverized, and calcium carbonate and red color 2 were applied to the surface of titanium oxide and zirconium oxide.
No. 02 was firmly fixed to obtain an organic-inorganic composite pigment.

Embodiment 3 FIG. In a glass container, 200 g of 95% ethanol was weighed, and red No. 202 (manufactured by Kishi Kasei) 0.5
g was added with stirring and completely dissolved. 9 g of titanium oxide A-100 (manufactured by Ishihara Sangyo) and 1 g of zinc oxide (manufactured by Sakai Chemical Co., Ltd.) were added to the solution, and 90 g was added using a disper.
Stirring was continued at 00 rpm for 30 minutes for uniform dispersion. Separately, an alkaline solution prepared by dissolving 13.4 g of lithium carbonate in 40 g of purified water was prepared, and slowly poured into an ethanol solution of Red No. 202 and Red No. 201 in which titanium oxide and zinc oxide were dispersed over 30 minutes. Further, a solution obtained by dissolving 80 g of anhydrous calcium chloride in 100 g of 95% ethanol was added over 60 minutes. Thereafter, the reaction was aged at room temperature for 4 hours. After the ripening was completed, the supernatant was removed by decantation, and the steps of adding 200 g of 95% ethanol, stirring and filtering were repeated three times. The obtained organic-inorganic composite pigment was dried at 30 ° C. for 24 hours and pulverized, and calcium carbonate and red 202
And an organic-inorganic composite pigment to which the compound was firmly fixed.

Comparative Example 1 8 g of titanium oxide A-100 (manufactured by Ishihara Sangyo), 4 g of calcium carbonate (Wako Pure Chemical Industries) and red 2
No. 02 (manufactured by Daito Kasei) was uniformly mixed with a Henschel mixer to obtain a red No. 202-calcium carbonate-titanium oxide mixed pigment.

Comparative Example 2 7.5 g of titanium oxide CR-50 (manufactured by Ishihara Sangyo), 2 g of zirconium oxide (manufactured by Tosoh), 5 g of calcium carbonate, and 2 g of Red No. 202 (manufactured by Daito Kasei)
And 1 g of Red No. 201 (manufactured by Kishi Kasei) were uniformly mixed using a ball mill to obtain a red 202-red 201-calcium carbonate-titanium oxide-zirconium oxide mixed pigment.

Comparative Example 3 9 g of titanium oxide A-100 (manufactured by Ishihara Sangyo), 1 g of zinc oxide (manufactured by Sakai Chemical), 5 g of calcium carbonate, and 0.5 g of Red No. 202 (manufactured by Kishi Kasei) are uniformly mixed using a Henschel mixer to obtain red 202 No.-
A calcium carbonate-titanium oxide-zinc oxide mixed pigment was obtained.

The saturation and hiding power of the organic-inorganic composite pigments of Examples 1 to 3 and the organic-inorganic mixed pigments of Comparative Examples 1 to 3 were evaluated.

(Method of adjusting evaluation sample) 1.0 g of a pigment was precisely weighed and kneaded 150 times with 1.5 g of castor oil using a Hoover Mahler. 0.5 g of the kneaded sample is weighed into a 50 ml polyethylene disposable cup, and 10 g of transparent nail enamel lacquer is placed therein.
And stirred until uniform. After replenishing the nail enamel lacquer volatilized during stirring and stirring, 10 mi was placed on a concealing rate test paper (manufactured by Nippon Test Panel Industries Co., Ltd.).
The film was formed using a 1 doctor blade to obtain an evaluation sample.

(Saturation Evaluation Method) The white portion of the evaluation sample formed on the opacity test paper was subjected to a Minolta spectral colorimeter CM-1.
000, and the spectrum was measured.
Values were calculated.

(Evaluation method of concealing power) The difference between the spectral spectrum of the white part and the black part of the concealing rate test paper at 400-700 nm where the film was not formed was taken as 100, and the white part and the black part of the film were formed at 400-700 nm. Was converted to a percentage to determine a hiding ratio.

The above results are summarized in Table 1.

[0039]

[Table 1]

The bleeding of the organic-inorganic composite pigments of Examples 1 to 3 and the organic-inorganic mixed pigment of Comparative Examples 1 to 3 was evaluated by the following evaluation method.

1. Dissolution test in water 6 g of pigment was put in 100 g of purified water, stirred for 1 hour with a magnetic stirrer. The solution was filtered through filter paper 5c, and the light transmittance of the filtrate at 505 nm was measured using a spectrophotometer.

2. Dissolution test for 95% ethanol 1.5 g of pigment was placed in 100 g of 95% ethanol, stirred for 1 hour with a magnetic stirrer, treated with a centrifuge at 3000 rpm for 30 minutes, and then treated with Teflon. The supernatant was filtered through a filtration membrane (MF-PTFE, 0.5 μm), and the light transmittance at 505 nm of the filtrate was measured using a spectrophotometer.

The results of the dissolution test of the organic-inorganic composite pigment in water and ethanol are shown in Table 2.

[0044]

[Table 2]

As is clear from the results shown in Tables 1 and 2, the organic-inorganic composite pigment of the present invention has excellent chroma and hiding power, and has very little elution of the dye to water or ethanol. there were.

[0046]

According to the present invention and the production method of the present invention, an organic-inorganic composite pigment having excellent chroma and hiding power and hardly causing bleeding in water or ethanol can be obtained.

────────────────────────────────────────────────── ─── Continued on the front page (51) Int.Cl. ⁷ Identification code FI // A61K 7/02 A61K 7/02 P 7/027 7/027 7/031 7/031 7/032 7/032 7/043 7/043 (56) References JP-A-7-267824 (JP, A) JP-A-5-214257 (JP, A) JP-A-3-153765 (JP, A) JP-A-2-34669 (JP, A) A) JP-A-62-169716 (JP, A) JP-A-62-101662 (JP, A) JP-A-61-286309 (JP, A) JP-A-61-268763 (JP, A) JP-A-4 JP-A-227666 (JP, A) JP-A-58-21455 (JP, A) JP-A-56-106964 (JP, A) JP-A-55-13714 (JP, A) JP-A-52-148632 (JP, A) JP-A-48-56833 (JP, A) JP-A-1-157908 (JP, A) JP-A-1-294611 (JP, A) JP-A-7-216256 (JP, A) JP-A-7-216 13 3211 (JP, A) JP-A-2-51419 (JP, A) (58) Fields investigated (Int. Cl. ⁷ , DB name) C09C 1/00-3/12 A61K ⁷ /00-7/047 C09B 67/02

Claims (6)

(57) [Claims] Claims: 1. A refractive index of 2 or more and an average particle diameter of 0.01 to 0.01.
An organic-inorganic composite pigment obtained by coating an inorganic white pigment having a thickness of 60 μm with Red No. 202 and calcium carbonate. 2. A refractive index of 2 or more and an average particle size of 0.1 to 6.
An organic-inorganic composite pigment obtained by coating an inorganic white pigment having a thickness of 0 μm with Red No. 202 and calcium carbonate. (1) Red No. 201 and / or Red 202
And (2) red 201
(3) dispersing an inorganic white pigment in a lower alcohol solution in which No. 2 and / or Red No. 202 are dissolved; and (3) adding an alkali carbonate or a solution thereof to the lower alcohol solution to form a red 201 and a red 201 on the surface of the inorganic white pigment. / Or red 2
No. 02 and (4) a lower alcohol solution of calcium chloride is added to the lower alcohol solution to form and deposit calcium carbonate on the surface of the inorganic white pigment, and a red 201 deposited on the surface of the inorganic white pigment. No. and / or the red No. 202 is laked or re laking, the refractive index of 2 or more, characterized in that the surface of the inorganic white pigment and a step of fixing the red No. 202 and an average particle
An inorganic white pigment having a diameter of 0.01 to
And a method for producing an organic-inorganic composite pigment coated with calcium carbonate . 4. The organic-inorganic composition according to claim 1, wherein the inorganic white pigment is selected from one or a combination of two or more of zinc oxide, zirconium oxide, titanium oxide (anatase type), and titanium oxide (rutile type). Composite pigment. 5. The inorganic white pigment is selected from two or more compounds of zinc oxide, zirconium oxide, titanium oxide (anatase type) and titanium oxide (rutile type).
2. The organic-inorganic composite pigment described in 1. above. 6. The method for producing an organic-inorganic white pigment according to claim 3 , wherein the alkali carbonate is selected from one or more of sodium carbonate, potassium carbonate and lithium carbonate.