KR101314345B1 - Pearlescent pigment - Google Patents

Abstract

A pearl pigment coated with a colored metal or colored metal oxide on the surface of the flake powder and coated with a colorless metal or colorless metal oxide, the pearl pigment being coated on the surface of the black artificial leather at an average of 0.05 mg / cm 2, and incident light side When the amount of reflected light of the pearl pigment was measured using a spectrometer equipped with an S polarizing plate and a P polarizing plate on the light receiving side at 2 ° field of view, the incident light was incident at 45 ° with respect to the normal direction of the sample surface. And a pearl pigment having an absolute value of a * value and b * value of the powder reflected light received in the normal direction.

Pearl pigment

Description

Pearl pigment {PEARLESCENT PIGMENT}

BRIEF DESCRIPTION OF THE DRAWINGS It is a figure which shows "the measuring method of a * value and b * value of this invention" in this invention.

The present invention relates to a pearl pigment and a method for producing the same.

Various color pigments are used in the fields of paints, plastics, printing inks and cosmetics. In recent years, in order to realize bright color development and designability, the optical interference pearl pigment which coat | covered titanium oxide, iron oxide, etc. on the surface of flaky powder is used.

A general pearl pigment coats colorless metal oxides, such as a titanium oxide, on flaky powder, changes its thickness, and has obtained various interference colors. In order to obtain a clearer interference color, it is known that the materials having different refractive indices may be multilayered. Various methods have been proposed, and multilayered pearl pigments are also commercially available. On the other hand, even in the multi-layered pearl pigment using a colored metal compound such as iron oxide, a vivid interference color can be obtained.However, due to the color effect of the colored metal compound, for example, only a red color is used in the case of using iron oxide. Only pearl pigments of the same color line were present. That is, the multilayered pearl pigment which controls the color of the colored compound used for an inner layer, and obtains interference color freely without being bound to the color of the colored metal compound itself is not known.

For example, Japanese Laid-Open Patent Publication No. Hei 6-100794 proposes a multi-layered pearl pigment in which an iron oxide layer is formed on a plate-like particle and which is coated with an aluminum compound. This relates to a red pigment and its manufacturing method, and only a red pearl pigment is obtained. Further, Japanese Patent Laid-Open Nos. 7-11161 and 8-259840 have proposed multi-layered pearl pigments coated with colorless metal oxides such as titanium oxide on iron oxide-coated plate-like powders, but have different colorless metal oxide species. As described above, only a red pearl pigment is obtained, and it is not described that a pigment of a color other than a red color is obtained.

The present invention is a pearl pigment coated with colored metal or colored metal oxide on the surface of flake powder and coated with a colorless metal or colorless metal oxide, and the pearl pigment is applied to the surface of black artificial leather at an average of 0.05 mg / cm 2. When the amount of reflected light of the pearl pigment was measured using a spectrophotometer equipped with an S polarizing plate on the incident light side and a P polarizing plate on the light receiving side, under the condition of receiving light at 2 ° field of view, the measured sample surface was measured. The pearl pigment which is incident at 45 degrees with respect to the normal direction of and whose absolute values of the a * value and b * value of the powder reflection light (scattered light) which were received in the normal direction is 10 or less.

In addition, in this invention, a * value and b * value represent chromaticity normalized by the International Illumination Commission (1976) (CIE). In addition, the measuring method (refer FIG. 1) of the a * value and b * value of the pearl pigment shown here is called "the measuring method of the a * value and b * value of this invention."

Moreover, this invention provides the pearl pigment which coat | covered colored metal or colored metal oxide with the surface average roughness 10 nm or less, and coated the colorless metal or the colorless metal oxide on the surface of flaky powder.

Moreover, this invention adds the aqueous solution of colored metal oxide precursor to the aqueous dispersion of flaky powder so that the amount of metal ions per 100 g of flaky powder may be 5 * 10 <^-4> -12 * 10 <^-4> mol / min, and then to a liquid mixture. An aqueous alkali solution is added to separate the solid at pH 5-8, and then calcined at 500-1000 ° C. to obtain a pearl pigment. The obtained pearl pigment is suspended in water to add an aqueous solution of a precursor of a colorless metal or a precursor of a colorless metal oxide. Then, an aqueous alkali solution is added to the mixed solution to obtain a pH of 5 to 8, the solids are separated, and there is provided a method for producing a pearl pigment which is calcined at 500 to 1000 ° C.

Moreover, this invention adds the aqueous solution of colored metal oxide precursor to the aqueous dispersion of flaky powder so that the amount of metal ions per 100 g of flaky powder may be 5 * 10 <^-4> -12 * 10 <^-4> mol / min, and then to a liquid mixture. After adding the aqueous alkali solution and separating the solid obtained by pH 5-8, the solid obtained by adding the aqueous solution of a colorless metal precursor or the precursor of a colorless metal oxide to the dispersion liquid of this solid is isolate | separated, and baked at 500-1000 degreeC It is to provide a method for producing a pearl pigment.

The present invention relates to a novel multilayered pearl pigment having various interference colors which suppress scattering color and make use of the properties of colored metal compounds and are not bound by the color tone, and a method for producing the same.

MEANS TO SOLVE THE PROBLEM The present inventors are the pearl pigment which coat | covered the colored metal or the colored metal oxide on the surface of flake powder, and coated the colorless metal or the colorless metal oxide, and the absolute value of the a * value and b * value of the scattered light measured on the specific conditions. The present invention was completed by finding that a pearl pigment having a value of 10 or less has a very vivid color.

The pearl pigment of this invention suppresses scattering color, and shows very vivid coloring.

It is preferable that the flaky powder used by the pearl pigment of this invention is an average particle diameter of 2-200 micrometers, and an average thickness of 0.01-5 micrometers. In view of compounding suitability, the average particle size is more preferably 2 to 20 µm and more preferably 0.05 to 1 µm. Here, an average particle diameter shows the volume average particle diameter (D4; average particle diameter computed by volume fraction). The measurement can be easily measured with a high reproducibility with a laser diffraction particle size distribution meter. The thickness of the flaky particles is the average thickness obtained by measuring the difference from the reference plane with an atomic force microscope and arithmetic average.

Such flake powders include mica, sericite, talc, kaolin, smectite clay mineral, synthetic mica, synthetic sericite, flaky titanium dioxide, flaky silica, flaky aluminum oxide, boron nitride, barium sulfate, flaky titania and silica composite Oxides; and the like. Of these, mica is preferred in terms of surface smoothness.

In the present invention, examples of the colored metal covering the flaky powder include gold and copper, and gold is preferred. Examples of the colored metal oxide include iron oxide, lower titanium oxide, copper oxide, cobalt oxide, chromium oxide, and nickel oxide. Iron oxide is preferable.

In the present invention, the colorless metal further covering the surface of the colored metal or colored metal oxide coated with the flaky powder includes titanium, zirconium, zinc, tin, silicon, aluminum and the like, and titanium is preferable. Examples of the colorless metal oxide include titanium oxide, zinc oxide, aluminum oxide, and the like, and titanium oxide is preferable.

As for the pearl pigment of this invention, when measured according to the "measurement method of a * value or b * value of this invention", the absolute value of the a * value and b * value of powder reflection light (scattered light) is 10 or less, Preferably it is 5 or less.

As the measuring device which can be measured in this way, the GCMS series manufactured by Murakami Color Research Institute can be used.

In addition, although the pearl pigment of this invention coat | covered the surface of flaky powder with a colored metal or colored metal oxide, the surface average roughness of a colored metal or colored metal oxide is 10 nm or less, Preferably it is 5 nm or less. Since colored metal or colored metal oxide has the property of absorbing light of a specific wavelength, when the roughness of the coating surface is large, the scattering color becomes strong, resulting in weak pearl luster. By making roughness of a coating surface small, scattering of light is suppressed and the pigment which has vivid coloring with few scattered light is obtained.

In the present invention, the surface average roughness Ra represents the centerline average roughness, and a range of 2 μm × 2 μm is measured at a scanning rate of 1.0 Hz using an atomic force microscope (manufactured by Digital Instruments, Inc., Nanoscope III). It represents the average value of. In the measurement, the pearl pigment is adhered to the base by removing the solvent by adhering on a smooth base surface in a state dispersed in a solvent such as ethanol, and then measured by atomic force microscope.

In addition, the pearl pigment of the present invention has an optical film thickness of the colored metal or the colored metal oxide coating layer of 15 to 650 nm, more preferably 25 to 650 nm, 250 nm or less, and more preferably 210 nm or less. If the thickness exceeds 650 nm, the absolute thickness of the absorbing layer increases, and the influence of light absorption becomes stronger. Therefore, it is preferable to use a pearl pigment utilizing the intrinsic color of colored metal or colored metal oxide. For example, in iron oxide, when the optical film thickness exceeds 250 nm, it is preferable to set it as a red pearl pigment.

The optical film thickness here refers to the product of the refractive index multiplied by the geometric film thickness of colored metal or colored metal oxide. For example, in the case of iron oxide, the geometric film thickness is 80 nm or less, more preferably 50 nm or less. When the scattered light is sufficiently suppressed, for example, when iron oxide is used as the colored metal oxide, the interference light is gold when the optical film thickness is 120 to 210 nm, and the interference light is silver when it is 60 to 120 nm. The geometric film thickness is measured by SEM.

In the present invention, the surface of the colored metal or colored metal oxide is coated with a colorless metal or a colorless metal oxide to multiply to obtain pigments of various color shades such as gold to green which are not bound by the color peculiar to iron oxide. The optical film thickness of the colorless metal or colorless metal oxide is preferably 180 to 900 nm on average. In the case of titanium oxide, the geometric film thickness is preferably 80 to 360 nm. If the colored scattering color is strong as in the conventional pearl pigments, these interference light cancels the scattering color and cannot be observed with the naked eye. However, since the scattering color is suppressed, the pearl pigment of the present invention is coated colored metal or colored. It can produce gold or green interfering light other than the intrinsic color of metal oxides. The pearl pigment obtained in this way has an interference color with a higher chroma than that coated with one layer.

When the optical film thickness, such as iron oxide, is large, it is advantageous at the time of making a red pigment peculiar to iron oxide, and by suppressing scattering color, it becomes possible to make red with a clearer color than a conventional pigment even if it is red.

And in relation to the refractive index, there can be a higher reflectance when the flaky powder (n _s) and that n _s <n> n ₀ in relation to the non-ferrous metal compound (n) as colorless metal compound (n _0), Can increase saturation. Specifically, a combination of mica (refractive index 1.58), iron oxide (Fe ₂ O ₃ ; refractive index 3.01), and titanium oxide (refractive index 2.5 to 2.7) is more preferable.

The pearl pigment of this invention can be manufactured by selecting the addition rate of the colored metal oxide precursor aqueous solution using a neutralization titration method, for example. Neutralization titration is preferred in order to reduce the surface average roughness of the colored metal or colored metal oxide.

(Manufacturing method 1)

Specifically, the aqueous solution of the colored metal oxide precursor is added to the aqueous dispersion of the flaky powder so that the amount of metal ions per 100 g of the flaky powder is 5 × 10 ^-4 to 12 × 10 ^-4 mol / min, and then alkali to the mixed liquid. The aqueous solution was added to pH 5-8 to separate solids, and then calcined at 500-1000 ° C. to obtain a pearl pigment. The obtained pearl pigment was suspended in water to add an aqueous solution of a precursor of colorless metal or a precursor of colorless metal oxide. Then, an alkali aqueous solution is added to a mixed liquid, pH 5-8 can isolate | separate solid, and can manufacture by baking at 500-1000 degreeC.

That is, first, the flake powder is dispersed in water and stirred well to prepare an aqueous dispersion of the flake powder. It is preferable that the slurry concentration of the dispersion is 1 to 50% by mass so that the metal compound uniformly covers the flaky powder surface.

On the other hand, as a colored metal oxide precursor, ferric nitrate, ferric chloride, ferric sulfate, etc. are mentioned, It is preferable that these aqueous solution concentrations are 20-70 mass%.

The dispersion of the flaky powder is warmed to 50-100 ° C., preferably 70-80 ° C., and acid is added to the dispersion to make it acidic, and again alkaline to maintain the pH of the reaction solution at 2-4, preferably 2.5-3.5. The colored metal oxide precursor aqueous solution is added to the reaction mixture while adjusting to the aqueous solution. In order to realize a smooth coating state with a low surface roughness, the amount of metal ions per 100 g of flaky powder can be added at a rate of 5 × 10 ^-4 to 12 × 10 ^-4 mol / min, preferably 8 It is added to a ^{× 10 -4 ~ 11 × 10 -4} mol / min. When the addition rate is in this range, scattered light is suppressed to obtain a more preferable pigment.

Moreover, as aqueous alkali solution used for pH adjustment, aqueous solution, such as sodium hydroxide, a calcium hydroxide, sodium carbonate, potassium carbonate, sodium hydrogencarbonate, potassium hydrogencarbonate, is mentioned.

After the addition is completed, the mixed solution is aged. Thereafter, an aqueous alkali solution is added and the mixture is brought to pH 5-8 and aged again. Next, the solids are separated and the salts are removed by water washing and dried. Then, it bakes for 30 to 180 minutes at 500-1000 degreeC, Preferably it is 700-800 degreeC.

Next, an aqueous dispersion of flaky powder coated with the obtained colored metal oxide is prepared. It is preferable that the slurry concentration of the dispersion is 1 to 50% by mass to uniformly coat the flaky powder coated with the colored metal oxide with the colorless metal or the colorless metal oxide.

Titanium sulfate, titanium tetrachloride, etc. are mentioned as a colorless metal oxide precursor, It is preferable that these aqueous solution concentrations are 20-60 mass%.

The dispersion of flaky powder coated with colored metal oxide is heated to 50-100 占 폚, preferably 70-80 占 폚, acid is added to acid, and the pH of the reaction mixture is 1-5, preferably 1-3. An aqueous solution of a colorless metal oxide precursor is added while adjusting to an aqueous alkaline solution to maintain the solution.

As the aqueous alkali solution used for the adjustment of pH, the same thing as the above can be used.

After the addition is completed, the mixed solution is aged. Thereafter, an aqueous alkali solution is added and the mixture is brought to pH 5-8 and aged again. Next, the solids are separated and the salts are removed by water washing and dried. Then, the pearl pigment of this invention can be obtained by baking for 30 to 180 minutes at 500-1000 degreeC, Preferably it is 700-800 degreeC.

(Manufacturing Method 2)

In addition, the pearl pigment of this invention can be manufactured by shifting to the process of coat | covering with a colorless metal or a colorless metal oxide, skipping the baking process after coating a colored metal oxide precursor to flaky powder. That is, the aqueous solution of the colored metal oxide precursor is added to the aqueous dispersion of flaky powder like the above-mentioned manufacturing method 1, and then the aqueous alkali solution is added to pH 5-8, the solids are separated, and the salt is removed by water washing. Remove The pearl pigment of the present invention can be obtained by coating the surface of the solid thus obtained with a colorless metal or colorless metal oxide in the same manner as in Production Method 1 and firing.

The pearl pigment of this invention can be used, for example for coloring materials, such as a cosmetics, a paint, a printing ink, plastics, ceramics, and glaze for glass.

(Example)

Example 1

80 g of flaky mica having a particle diameter of 5 to 60 µm is added to 1.2 L of water, sufficiently dispersed, and the temperature is raised to 80 ° C, followed by addition of hydrochloric acid to pH 3. Next, 337 g of the ferric nitrate aqueous solution prepared in advance (17 parts by mass of ferric nitrate: 26 parts by mass of water) was kept at pH 3 using an aqueous solution of sodium hydroxide, while maintaining a ratio of 9x10 ^-4 mol / min of iron ion concentration. Add slowly. After completion of the addition, the pH is adjusted to 5 with an aqueous sodium hydroxide solution. The mixture was filtered, washed with water to remove salts, suction filtered and dried, and then calcined at 700 ° C for 1 hour.

In the obtained pearl pigment, very fine iron oxide particles were uniformly coated on the flaky mica with a geometric film thickness of 20 nm. When the surface roughness of the coating layer was measured, the surface roughness was 3.44 nm.

Subsequently, 80 g of the iron oxide-coated pearl pigment is added to 1.2 L of water to sufficiently disperse, and the temperature is raised to 75 ° C. After raising the temperature, hydrochloric acid is added to bring the pH to 1.6. Thereafter, 240 g of a 40 mass% titanium tetrachloride aqueous solution is added at a rate of 1.4 g / min, and the pH is maintained at 1.6 using a 20 mass% sodium hydroxide aqueous solution. Thereafter, the dispersion is neutralized to pH 7 using a 20 mass% sodium hydroxide aqueous solution. Thereafter, the salt was removed by water washing, suction filtration and dried, and then fired at 700 ° C. for 90 minutes. This obtained the chromaticity titanium oxide / iron oxide coating coloring pearl pigment of high chromaticity.

Example 2

An iron oxide-coated pearl pigment was prepared in the same manner as in Example 1 except that 337 g of an aqueous ferric nitrate solution (17 parts by mass of ferric nitrate: 26 parts by mass of water) was changed to 430 g. In the obtained pigment, very fine iron oxide particles were uniformly coated with a geometrical film thickness of 30 nm on the flaky mica. When the surface roughness of the coating layer was measured, the surface roughness was 4.30 nm.

Next, except for changing the addition amount of the 40 mass% titanium tetrachloride aqueous solution from 240 g to 200 g, it carried out similarly to Example 1, and obtained the titanium oxide / iron oxide coating pearl pigment of the high saturation gold interference.

Example 3

An iron oxide-coated pearl pigment was prepared in the same manner as in Example 1 except that 337 g of an aqueous ferric nitrate solution (17 parts by mass of ferric nitrate: 26 parts by mass of water) was changed to 544 g. In the obtained pigment, very fine iron oxide particles were uniformly coated on the flaky mica with a geometric film thickness of 50 nm. When the surface roughness of the coating layer was measured, the surface roughness was 3.03 nm.

Subsequently, except for changing the addition amount of the 40 mass% titanium tetrachloride aqueous solution from 240 g to 63 g, it carried out similarly to Example 1, and obtained the titanium oxide / iron oxide coating pearl pigment of high saturation red interference.

Example 4

An iron oxide-coated pearl pigment was prepared in the same manner as in Example 1 except that 337 g of an aqueous ferric nitrate solution (17 parts by mass of ferric nitrate: 26 parts by mass of water) was changed to 544 g. In the obtained pigment, very fine iron oxide particles were uniformly coated on the flaky mica with a geometric film thickness of 50 nm. When the surface roughness of the coating layer was measured, the surface roughness was 3.03 nm.

Subsequently, except for changing the addition amount of the 40 mass% titanium tetrachloride aqueous solution from 240 g to 320 g, it carried out similarly to Example 1, and obtained the titanium oxide / iron oxide coated pearl pigment of high saturation red interference.

Example 5

An iron oxide-coated pearl pigment was prepared in the same manner as in Example 1 except that 337 g of an aqueous ferric nitrate solution (17 parts by mass of ferric nitrate: 26 parts by mass of water) was changed to 430 g. In the obtained pigment, very fine iron oxide particles were uniformly coated with a geometrical film thickness of 30 nm on the flaky mica. When the surface roughness of the coating layer was measured, the surface roughness was 4.30 nm.

Subsequently, except for changing the addition amount of the 40 mass% titanium tetrachloride aqueous solution from 240 g to 350 g, it carried out similarly to Example 1, and obtained the high chromaticity green oxide titanium oxide / iron oxide coating pearl pigment.

Example 6

80 g of flake mica having a particle diameter of 5 to 60 µm is added to 1.2 L of water, sufficiently dispersed, and warmed up to 80 ° C, followed by addition of hydrochloric acid to pH 3. Next, 337 g of the ferric nitrate aqueous solution prepared in advance (17 parts by mass of ferric nitrate: 26 parts by mass of water) was kept at pH 3 using an aqueous solution of sodium hydroxide, while maintaining a ratio of 9x10 ^-4 mol / min of iron ion concentration. Add slowly. After completion of the addition, the pH is adjusted to 5 with aqueous sodium hydroxide solution. The slurry-like reactant obtained here was filtered and the salt was removed by water washing. Subsequently, the moisture content of this slurry phase reactant is measured and the said slurry phase reactant is weighed so that it may be 80 g of solid content. Subsequently, water was added thereto, the volume was 1.2 L, sufficiently dispersed, and the temperature was raised to 75 ° C. After raising the temperature, hydrochloric acid is added to bring the pH to 1.6. Hereinafter, the titanium tetrachloride aqueous solution was added like Example 1, and then it baked at 700 degreeC for 90 minutes. This resulted in a high chromatic gold interference titanium oxide / iron oxide coated pearl pigment.

Example 7

An iron oxide-coated pearl pigment was prepared in the same manner as in Example 1 except that 337 g of an aqueous ferric nitrate solution (17 parts by mass of ferric nitrate: 26 parts by mass of water) was changed to 140 g. In the obtained pigment, very fine iron oxide particles were uniformly coated on the flaky mica with a geometric film thickness of 10 nm (optical film thickness of 30 nm). When the surface roughness of the coating layer was measured, the surface roughness was 8.5 nm.

Subsequently, except for changing the addition amount of the 40 mass% titanium tetrachloride aqueous solution from 240 g to 260 g, it carried out similarly to Example 1, and obtained the titanium oxide / iron oxide coating pearl pigment of the high saturation gold interference.

Example 8

An iron oxide-coated pearl pigment was prepared in the same manner as in Example 1 except that 337 g of an aqueous ferric nitrate solution (17 parts by mass of ferric nitrate: 26 parts by mass of water) was changed to 140 g. In the obtained pigment, very fine iron oxide particles were uniformly coated with a geometrical film thickness of 10 nm on the flaky mica. When the surface roughness of the coating layer was measured, the surface roughness was 8.5 nm.

Subsequently, except for changing the addition amount of the 40 mass% titanium tetrachloride aqueous solution from 240 g to 150 g, it carried out similarly to Example 1, and obtained the titanium oxide / iron oxide coating pearl pigment of high saturation red interference.

Example 9

An iron oxide-coated pearl pigment was prepared in the same manner as in Example 1 except that 337 g of an aqueous ferric nitrate solution (17 parts by mass of ferric nitrate: 26 parts by mass of water) was changed to 65 g. In the obtained pigment, very fine iron oxide particles were uniformly coated on the flaky mica with a geometric film thickness of 5 nm (optical film thickness of 15 nm). When the surface roughness of the coating layer was measured, the surface roughness was 3.5 nm.

Next, except for changing the addition amount of the 40 mass% titanium tetrachloride aqueous solution from 240 g to 305 g, it carried out similarly to Example 1, and obtained the titanium oxide / iron oxide coating pearl pigment of the high saturation gold interference.

Example 10

An iron oxide-coated pearl pigment was prepared in the same manner as in Example 1 except that 337 g of an aqueous ferric nitrate solution (17 parts by mass of ferric nitrate: 26 parts by mass of water) was changed to 65 g. In the obtained pigment, very fine iron oxide particles were uniformly coated on the flaky mica with a geometric film thickness of 5 nm (optical film thickness of 30 nm). When the surface roughness of the coating layer was measured, the surface roughness was 3.5 nm.

Subsequently, except for changing the addition amount of the 40 mass% titanium tetrachloride aqueous solution from 240 g to 170 g, it carried out similarly to Example 1, and obtained the titanium oxide / iron oxide coating pearl pigment of high saturation red interference.

Example 11

An iron oxide-coated pearl pigment was prepared in the same manner as in Example 1 except that 337 g of an aqueous ferric nitrate solution (17 parts by mass of ferric nitrate: 26 parts by mass of water) was changed to 65 g. In the obtained pigment, very fine iron oxide particles were uniformly coated with a geometrical film thickness of 5 nm on the flaky mica. When the surface roughness of the coating layer was measured, the surface roughness was 3.5 nm.

Subsequently, except for changing the addition amount of the 40 mass% titanium tetrachloride aqueous solution from 240 g to 251 g, it carried out similarly to Example 1, and obtained the high chromaticity green oxide titanium oxide / iron oxide coating pearl pigment.

Comparative Example 1

120 g of flaky mica having a particle diameter of 5 to 60 µm was added to 820 g of water, and the mixture was heated to 95 ° C. An aqueous solution of 350 g of urea, 170 g of ferrous sulfate, 10 g of ferric nitrate, 7 g of an aqueous 30% nitric acid solution and 308 g of water was added dropwise at a rate of about 25 g / min for 35 minutes. Then, the mixture was stirred for 2 hours, and 205 g of 30% aqueous potassium carbonate solution was added dropwise for about 40 minutes. Thereafter, the salt was removed by water washing, suction filtration and dried, and then calcined at 700 ° C for 1 hour. In the obtained pigment, iron oxide particles having a thickness of about 0.1 μm were slightly roughly coated on the flaky mica with a geometric film thickness of 30 nm. When the surface roughness of the coating layer was measured, the surface roughness was 13.41 nm.

Next, except for changing the addition amount of the 40 mass% titanium tetrachloride aqueous solution from 240 g to 200 g, it carried out similarly to Example 1, and obtained the titanium oxide / iron oxide coating pearl pigment of gold interference.

Test Example

For the pearl pigment obtained in Examples 1 to 5 and Comparative Example 1 and commercially available titanium oxide coated mica (Flamenco Gold, Flamenco Red (above ENGELHARD)), the a * value, the b * value of the powder reflected light, and the geometric film of the coating layer The thickness was measured.

(1) The a * value and b * value of powder reflection light were measured according to the "method of measuring the a * value and b * value of this invention." The spectrophotometer was measured by installing a polarizing plate (polaroid company, model: HN32) in GCMS-4 manufactured by Murakami Color Research Institute. As a light source, a halogen lamp (HLWS7) of Navas Corporation was used. A black artificial leather (Okamoto Co., Model: OK-7) was used, and a powder was uniformly coated using a sponge so as to have an average of 0.05 mg / cm 2 in a 5 cm x 10 cm range, as a measurement sample.

In addition, the measurement of the geometric film thickness was performed by SEM. By measuring the thickness of the flaky powder before coating and the thickness of the pearl pigment after coating, it was set as the geometric film thickness. The optical film thickness was obtained by multiplying the geometric film thickness by the refractive index, the refractive index of iron oxide (Fe ₂ O ₃ ) was 3.0, and the refractive index of titanium oxide was 2.5. The results are shown in Table 1.

(2) In addition, the a * value and the b * value of the powder reflection light were measured by the usual general colorimeter method (measurement angle 45 degrees) which does not use a polarizing plate on the said conditions. In addition, the c * and h values represent the saturation and color angle standardized by the International Commission on Illumination (1976) (CIE). The results are shown in Table 2.

The results of Table 2 show that the pearl pigment of the present invention is free of interference colors without being bound to the color of the vivid colored metal compound itself, which has a larger C * value than that of a comparative example and a commercial product having the same color angle.

Appearance of Coating Sample Iron oxide
Geometric film thickness
[Optical Film Thickness] (nm) Titanium oxide
Geometric film thickness
[Optical Film Thickness] (nm) a * value b * value Example 1 Gold Pearl 20 [60] 140 [350] 7.6 4.5 Example 2 Gold Pearl 30 [90] 130 [325] 6.3 1.3 Example 3 Red Pearl 50 [150] 80 [200] 5.5 0.2 Example 4 Red Pearl 50 [150] 140 [350] 5.0 4.1 Example 5 Green Pearl 30 [90] 220 [550] 8.8 7.4 Example 6 Gold Pearl 20 [60] 140 [350] 3.8 2.4 Example 7 Gold Pearl 10 [30] 160 [400] 3.5 3.0 Example 8 Red Pearl 10 [30] 130 [320] 3.4 2.8 Example 9 Gold Pearl 5 [15] 170 [425] 4.5 3.0 Example 10 Red Pearl 5 [15] 130 [325] 5.0 4.2 Example 11 Green Pearl 5 [15] 160 [400] 6.3 7.2 Comparative Example 1 Gold Pearl 30 [90] 130 [325] 10.8 9.3

*: The commercial item was excluded because it does not contain colored metal in the inner layer.

Appearance of Coating Sample Iron oxide
Geometric film thickness
[Optical film thickness]
(Nm) Titanium oxide
Geometric film thickness
[Optical film thickness]
(Nm) a * value b * value c * value h value Example 1 Gold Pearl 20 [60] 140 [350] -6.5 47.3 48 98 Example 2 Gold Pearl 30 [90] 130 [325] -5.3 48.3 49 96 Example 3 Red Pearl 50 [150] 80 [200] 35.3 -4.1 36 353 Example 4 Red Pearl 50 [150] 140 [350] 25.2 -11.5 28 335 Example 5 Green Pearl 30 [90] 220 [550] -7.9 4.7 9 149 Example 6 Gold Pearl 20 [60] 140 [350] -11.7 43.5 45.1 105 Example 7 Gold Pearl 10 [30] 160 [400] -6.8 49.6 50 98 Example 8 Red Pearl 10 [30] 130 [320] 33.5 -3.9 34 353 Example 9 Gold Pearl 5 [15] 170 [425] -5.6 50.7 51 96 Example 10 Red Pearl 5 [15] 130 [325] 30.2 -13.8 33 335 Example 11 Green Pearl 5 [15] 160 [400] -15.8 9.4 18 148 Comparative Example 1 Gold Pearl 30 [90] 130 [325] -5.9 25.7 26 103 Commercial item 1 Gold Pearl Flamenco gold -6.5 30.1 31 102 Commercial item 2 Red Pearl Flamenco red 17.1 -0.6 17 358

Application example

The application example of the coating material, ink, and plastic which used the pearl pigment obtained by the Example is shown below.

Application Example 1 (Car paint)

A steel sheet on which an intermediate coating film was formed on the electrodeposition coating film was prepared and coated with a color base paint, followed by baking at 140 ° C. for 30 minutes to dry. Next, the base paint containing 5 weight% of the pearl pigment obtained by Example 1 was prepared in the resin liquid which consists of an acrylic resin and a melamine resin, and spray-coated so that it might become 15 micrometers of film thickness on the color-base coating film surface. Then, the acrylic-melamine-based clear coating was spray-coated with Wet-on-Wet so as to have a film thickness of 40 µm again, and baked at 140 ° C for 30 minutes to harden the base coating film and the clear coating film integrally. The coated steel sheet thus obtained had a very vivid and glossy interference color of gold.

Application Example 2 (Ink Composition for Printing)

The components of Table 3 were mixed and kneaded with a sand mill to obtain an ink composition for printing.

When printing was carried out on black paper with a coating film thickness (after drying) of 50 mu m using this printing ink composition, the coating body had a very vivid and glossy interference color of gold.

ingredient Formulation amount (parts by weight) Pearl Pigment of Example 1 12.5 Acrylic resin 25.0 naphtha 30.0 Butyl cellosolve 32.5

Application Example 3 (Plastic Coloring Composition)

The components of Table 4 were mixed with a Henschel mixer, and the resulting mixture was extruded with an extruder to obtain colored pellets. When the pellets were molded into a plate-shaped molded product of 90 × 50 × 2 mm by an extruder, the molded product had a red, very bright glossy interference color.

ingredient Formulation amount (parts by weight) Pearl Pigment of Example 3 2.0 Polyethylene resin 97.5 Dibutylhydroxytoluene (Antioxidant) 0.5

The pearl pigment of this invention can be used for coloring materials, such as a cosmetics, a paint, a printing ink, plastics, ceramics, and glaze for glass.

Claims (16)

The pearl pigment which coated iron oxide on the surface of flaky powder and also coated titanium oxide, The pearl pigment coat | covers iron oxide with the surface average roughness 10 nm or less on the surface of flaky powder, and then pearl coated with titanium oxide It was a pigment, and the pearl pigment was coated on the surface of black artificial leather at an average of 0.05 mg / cm 2, and the C pigment was applied to the C light using a spectrophotometer equipped with an S polarizing plate on the incident light side and a P polarizing plate on the light receiving side. When the reflected light amount of the pearl pigment was measured under a light-receiving condition in ° C, the absolute value of the a * and b * values of the powder-reflected light received in the normal direction was incident at 45 ° with respect to the normal direction of the measurement sample surface. Pearl pigment which is below. delete delete delete The method of claim 1, Pearl pigment with an average optical thickness of iron oxide of 15 to 650 nm. The method of claim 1, A pearl pigment whose optical film thickness of titanium oxide which coat | covers iron oxide surface is 180-900 nm on average. To the aqueous dispersion of the flaky powder, an aqueous solution of the iron oxide precursor was added so that the amount of metal ions per 100 g of the flaky powder was 5 × 10 ^-4 to 12 × 10 ^-4 mol / min, and then an aqueous alkali solution was added to the mixed solution to pH 5 ~. The solid was separated into 8 and calcined at 500 to 1000 ° C. to obtain a pearl pigment. The obtained pearl pigment was suspended in water to add an aqueous solution of a titanium oxide precursor, and then an aqueous alkali solution was added to the mixed solution to pH 5-8. Method for producing a pearl pigment which is calcined at 500 ~ 1000 ℃ after separating the solids. To the aqueous dispersion of the flaky powder, an aqueous solution of the iron oxide precursor was added so that the amount of metal ions per 100 g of the flaky powder was 5 × 10 ^-4 to 12 × 10 ^-4 mol / min, and then an aqueous alkali solution was added to the mixed solution to pH 5 ~. After separating the solid obtained by 8, the solid obtained by adding the aqueous solution of the precursor of a titanium oxide to the dispersion liquid of this solid is isolate | separated, and the method of manufacturing the pearl pigment baked at 500-1000 degreeC. 9. The method according to claim 7 or 8, A method for producing a pearl pigment, wherein the temperature of the mixed liquid is 50 to 100 ° C. when an aqueous solution of an iron oxide precursor is added to an aqueous dispersion of flaky powder. 9. The method according to claim 7 or 8, A method for producing a pearl pigment, wherein the pH of the mixed solution is 2 to 4 when an aqueous solution of an iron oxide precursor is added to an aqueous dispersion of flaky powder. delete The paint containing the pearl pigment of Claim 1. The printing ink containing the pearl pigment of Claim 1. The plastic containing the pearl pigment of Claim 1. Ceramics containing the pearl pigment of Claim 1. The glaze for glass containing the pearl pigment of Claim 1.

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