JPH07304997A - Organic/inorganic composite pigment and production thereof - Google Patents

Abstract

PURPOSE:To obtain the pigment excellent in saturation and hiding power and resistant to bleeding caused by water or ethanol. CONSTITUTION:A white inorganic pigment having a refractive index of 2 or above and an average particle diameter of 0.01-60, desirably 0.1-60mum, is firmly coated with calcium carbonate and C. I. Pigment Red 202.

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 saturation and high hiding power, which hardly causes bleeding in water or sweat.

[0002]

2. Description of the Related Art Conventionally, when a colored pigment or dye is used as a colorant for various products, an inorganic white pigment having a hiding power is also used together to maintain the appearance of the product. In addition, it is known to disintegrate and disperse the agglomerates of colorants and inorganic white pigments using an atomizer, roll mill, sand mill or the like for the purpose of stabilizing the color developability and hiding power during compounding.

However, in these conventional techniques, since the cohesive force varies depending on the type of pigment or dye, sufficient dispersion stability cannot be obtained, and as a result, re-aggregation of particles tends to occur, resulting in good color development. However, it has a drawback that it is difficult to stably obtain the hiding power.

As a technique for improving such drawbacks of the prior art, (1) after adding finely pulverized flaky substrate to a dye made into an aqueous solution by a chemical method, the dye is precipitated on the surface of substrate particles,
A method of obtaining a pigment having good color developability by depositing (JP-A-62-91565). (2) A method of obtaining a colored mica pigment by depositing and coating a pigment on the surface of a substrate particle in an aqueous system (JP-A-63-63)
243168). (3) Flake-like substrate particles and pigments obtained by stirring pigments and / or dye particles on flake-like substrate particles such as mica, mica, sericite, kaolin and the like coated with metal oxide by a predetermined high speed stirring without using a liquid medium. A method of forming an ordered mixture with particles of a dye or a dye to obtain a flaky composite pigment having excellent saturation and dispersibility and excellent adhesion stability of the pigment or the dye (JP-A-5-214257). (4) 4- (o-sulfo-p on the surface of the inorganic or organic powder
-Tolylazo) -3-hydroxy-2-naphthoate is attached to obtain a highly saturated composite pigment (Japanese Patent Laid-Open No. 4-292).
664 publication). Etc. have been proposed.

[0005]

[Problems to be Solved by the Invention] However,
In the techniques (1) and (2), it is difficult to obtain a satisfactory color because the fine particles and the dispersion of the pigment or the dye are not yet sufficient.
Furthermore, pigments or dyes that did not adhere to the surface of the substrate particles in the treatment process or were weakly adhered were separated and dropped during the filtration process or washing process, and the expected color development was found for the amount of pigment or dye used. You may not get it.

Further, in the technique (3), since the particles are fixed by physical means such as impact force, compression force and shearing force, not all the pigments and dyes are necessarily fixed stably and uniformly on the surface of the substrate. . Furthermore, as a result of crushing the substrate by high-speed stirring, the particle size distribution width of the substrate is widened, which does not have a good effect on the high saturation.

Furthermore, since a flaky material having a low refractive index is used as the substrate, the obtained composite pigment has high transparency and is affected by the background color, so that it is difficult to achieve high saturation. Therefore, the use as a coloring agent is greatly limited particularly in the fields 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, the refractive index is 1.
51-1.52 polyethylene powder and nylon powder are used as substrates, and 4- (o-
Sulfo-p-tolylazo) -3-hydroxy-2-naphthoate (monosodium salt of "resole rubin B",
Since only the calcium salt "Resor-rubin BCA") is attached, these complexes cause bleeding in water, sweat and ethanol, and the attached dye or lake easily desorbs from the substrate. Has the drawback that it is dyed on the skin, and further, the saturation decreases with time.

[0009] Therefore, it is an object of the present invention to solve the above-mentioned problems of the prior art, and to provide a pigment having both high saturation and high hiding power, which hardly causes bleeding, and a method for producing the pigment.

[0010]

In order to solve the above-mentioned problems, the present inventors have conducted extensive studies on changes in saturation and hiding power when an organic pigment and a high-refractive-index inorganic white pigment are combined. In the case where 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, it is much more than when the high-refractive-index inorganic white pigment is mixed with Red No. 202. The inventors have found that the present invention has high saturation and high hiding power, and that bleeding is unlikely to occur with respect to water, sweat and ethanol, resulting in completion of the present invention.

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

Further, there is provided a method for producing an organic-inorganic composite pigment having high chroma and high hiding power, which is obtained by strongly coating an inorganic white pigment with calcium carbonate and Red No. 202 of the present invention.

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

The method for producing an organic-inorganic composite pigment in which the high-refractive-index inorganic white pigment of the present invention is strongly coated with calcium carbonate and Red No. 202 includes (1) Red No. 201 and / or Red 202 No. 201 in a lower alcohol and (2) Red No. 201 and / or Red No. 202
No. 201 and / or Red No. 202 on the surface of the inorganic white pigment by adding an alkali carbonate or a solution thereof to the lower alcohol solution. A step of depositing (4) a lower alcohol solution of calcium chloride is added to the lower alcohol solution to generate and deposit calcium carbonate on the surface of the inorganic white pigment, and at the same time, red No. 201 and / Alternatively, the step of making red No. 202 laked or re-laked and fixing the red No. 202 to the surface of the inorganic white pigment is essential.

The steps (1) and (2) may be carried out before or after or at the same time, but red No. 201 and /
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.

Lower alcohols for dissolving Red No. 201 and / or Red No. 202 and dispersing the inorganic white pigment are 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.

When the lower alcohol has a high water content, the inorganic white pigment is strongly aggregated when the alkali agent is added in the step (3), and the organic-inorganic composite pigment in a non-uniform coating state is formed. The water content is 5%
It is desirable to use less than lower alcohols.

Next, red No. 201 and / or red No. 202 is dissolved, and an alkali carbonate or a solution thereof is added to a lower alcohol solution in which an inorganic white pigment is dispersed, and red No. 201 and / or red No. 202 is made inorganic. Deposit on the surface of the white pigment. Na ₂ CO ₃ as the alkali carbonate,
K ₂ CO ₃ , Li ₂ CO _{3 as it} is, or an aqueous solution,
It can be suitably used as a lower alcohol solution or a hydrous lower alcohol solution, and the concentration thereof is not particularly limited, but red 2
Since it is necessary to introduce an amount sufficient to deposit No. 01 and / or Red No. 202 on the surface of the inorganic white pigment, it is desirable to use it as a solution having a concentration as high as possible from the viewpoint of work efficiency.

Next, in the step (4), calcium carbonate is produced and deposited on the surface of the inorganic white pigment by calcium chloride, and red 2 is deposited on the surface of the inorganic white pigment.
No. 01 and / or Red No. 202 is raked or re-laked and firmly fixed in the form of Red No. 202. As calcium chloride, any form of anhydrous salt, dihydrate and hexahydrate can be preferably used. As a solvent for dissolving calcium chloride, lower alcohols such as methanol, ethanol and isopropanol can be used, but the water content is 0.
It is preferable to use a lower alcohol of less than 5% because the dissolution rate of calcium chloride is faster. Although the concentration to be used is not particularly limited, it is advantageous to use a solution having a concentration as high as possible from the viewpoint of work efficiency.

With calcium chloride, calcium carbonate is produced and deposited on the surface of the inorganic white pigment, and red color 2
After the No. 01 and / or Red No. 202 is laked or re-laked, it is preferable to age the reaction at a temperature not higher than the boiling point of the solvent used, preferably near room temperature. The reaction aging time may vary depending on the aging temperature, but if it is less than 3 hours, it may not be possible to obtain a bluish red color which is the original color of Red No. 202, and even if it is aged for 5 hours or more. It is desirable to ripen for 3 to 5 hours since there is substantially no change in color tone.

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, centrifugation, decantation and the like 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 kinds of these can be used.

When the finally obtained inorganic white pigment is coated with calcium carbonate and Red No. 202, the organic-inorganic composite pigment is preferably dried at a temperature of 60 ° C. or lower. When it is dried at a temperature over 60 ° C., a color shift phenomenon in which the color tint of Red No. 202 shifts to a bluish color is more likely to occur. The drying time depends on the solvent used for washing, but usually 4 to 30 hours is sufficient.

The inorganic white pigment to be coated preferably has a refractive index of 2 or more. When a material having a refractive index of less than 2 is used, the transparency becomes strong, the form of the base is easily visible, and the color tone of the undertone of the base is affected, so that a pigment with high saturation 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), rutile type oxidation. Titanium (refractive index 2.
75) or a mixture or a mixture of two or more kinds of these can be preferably used.

The shape of the inorganic white pigment is not particularly limited, but the average particle diameter is preferably in the range of 0.01 to 60 μm. If the average particle size is less than 0.01 μm, the hiding power of the pigment is lowered, and it is difficult to obtain an optically sufficient pigment dispersion state, and it is 0.1 μm or more particularly for applications requiring hiding power. Things are desirable. If it exceeds 60 μm, not only a sufficient coloring power cannot be obtained, but also a particle feeling can be felt, which is not preferable.

The amount of Red No. 202 coated on the inorganic white pigment can be selected according to the desired tint. If the amount of Red No. 202 adhered to the surface of the inorganic white pigment is increased, the reddish organic color is increased. -Inorganic composite pigment can be obtained. However, if the weight ratio of the inorganic white pigment to Red No. 202 exceeds 1: 1, the red color does not substantially darken. Therefore, it is preferable to appropriately select within this range.

When the diffraction pattern of the thus obtained organic-inorganic composite pigment was examined with an X-ray diffractometer, the peaks of the inorganic white pigment and calcium carbonate were confirmed, and red 20
It is presumed that Red No. 202 is fixed to the surface of the inorganic pigment by coating No. 2 with calcium carbonate or that Red No. 202 is fixed to the surface of the inorganic pigment in a state of being mixed with calcium carbonate. 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.

Example 1. 200 g of 95% ethanol was weighed into a glass container, and 2 g of Red No. 202 (manufactured by Daito Kasei) was added with stirring to completely dissolve it. 8 g of titanium oxide A-100 (manufactured by Ishihara Sangyo Co., Ltd.) was added to this solution, and stirring was continued for 30 minutes using a homomixer to uniformly disperse the mixture.
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. Then, the reaction was aged at room temperature for 4 hours. After completion of aging, the supernatant was removed by decantation, and then 9
The process of adding 200 g of 5% ethanol, stirring and filtering was repeated 3 times. The obtained organic-inorganic composite pigment is 50 ° C.
It was dried for 12 hours and pulverized to obtain an organic-inorganic composite pigment in which calcium carbonate and Red No. 202 were firmly adhered to the surface of titanium oxide.

Example 2. In a glass container, 200 g of 95% ethanol was weighed, and 2 g of Red No. 202 (manufactured by Daito Kasei) and 1 g of Red No. 201 (manufactured by Konami Kasei) were charged with stirring to completely dissolve them. Titanium oxide CR-5 was added to this solution.
0 g (made by Ishihara Sangyo) and 7.5 g of zirconium oxide (made by Tosoh) were charged, and 8000 rp using a disper.
At m, stirring was continued for 30 minutes to uniformly disperse. Separately purified water 8
An alkaline solution in which 13.4 g of potassium carbonate was dissolved 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. Furthermore, a solution prepared by dissolving calcium chloride / hexahydrate in 100 g of 95% ethanol was added over 60 minutes. Then, the reaction was aged at room temperature for 5 hours. After completion of aging, the supernatant was removed by decantation, 200 g of 95% ethanol was added, and the mixture was stirred.
The process of filtering was repeated 3 times. The obtained organic-inorganic composite pigment is dried at 50 ° C. for 10 hours and pulverized to give calcium carbonate and red 2 on the surfaces of titanium oxide and zirconium oxide.
An organic-inorganic composite pigment firmly adhered to No. 02 was obtained.

Example 3. 200 g of 95% ethanol was weighed in a glass container, and red No. 202 (manufactured by Konami Kasei) 0.5
g was added with stirring to completely dissolve it. To this solution, 9 g of titanium oxide A-100 (manufactured by Ishihara Sangyo) and 1 g of zinc oxide (manufactured by Sakai Chemical Co., Ltd.) were charged, and 90 using a disper.
Stirring was continued at 00 rpm for 30 minutes to uniformly disperse. 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 prepared by dissolving 80 g of anhydrous calcium chloride in 100 g of 95% ethanol was added over 60 minutes. Then, the reaction was aged at room temperature for 4 hours. After completion of aging, the supernatant was removed by decantation, 200 g of 95% ethanol was added, and the steps of stirring and filtering were repeated 3 times. The obtained organic-inorganic composite pigment was dried at 30 ° C. for 24 hours and pulverized to give calcium carbonate and red 202 on the surfaces of titanium oxide and zinc oxide.
To obtain an organic-inorganic composite pigment in which No. 1 and No. 3 are firmly fixed.

Comparative Example 1. Titanium oxide A-100 (made by Ishihara Sangyo) 8 g, calcium carbonate (Wako Pure Chemical Industries) 4 g 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. Titanium oxide CR-50 (made by Ishihara Sangyo) 7.5 g, zirconium oxide (made by Tosoh) 2 g, calcium carbonate 5 g, and red No. 202 (made by Daito Kasei) 2 g
And 1 g of Red No. 201 (manufactured by Konami Kasei) were uniformly mixed using a ball mill to obtain a mixed pigment of Red No. 202-Red No. 201-calcium carbonate-titanium oxide-zirconium oxide.

Comparative Example 3. Titanium oxide A-100 (manufactured by Ishihara Sangyo) 9 g, zinc oxide (manufactured by Sakai Chemical Industry) 1 g, calcium carbonate 5 g, and red No. 202 (manufactured by Kinomi Kasei) were uniformly mixed using a Henschel mixer, and red 202 Issue-
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.

(Preparation Method of Evaluation Sample) 1.0 g of the 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 disposable polyethylene cup having a capacity of 50 ml, and 10 g of transparent nail enamel lacquer is placed therein.
Was added and stirred until uniform. After the nail enamel lacquer volatilized during stirring was replenished and stirred, it was coated on a hiding rate test paper (manufactured by Japan Test Panel Industry Co., Ltd.) for 10 mi.
A film was formed using a doctor blade of 1 to obtain an evaluation sample.

(Evaluation Method of Saturation) The white portion of the evaluation sample formed as a film on the hiding ratio test paper was replaced with a spectrophotometer CM-1 manufactured by Minolta.
000 is used to measure the spectrum and L-a-b
The value was calculated.

(Evaluation Method of Concealment Power) Concealment Ratio The difference in the spectral spectrum between the white part and the black part of the test paper at 400 to 700 nm where the film is not formed is set to 100, and the white part and the black part where the film is formed are 400 to 700 nm. The concealment ratio was calculated by converting the difference in the spectral spectrum in 1 to the percentage.

The above results are summarized in Table 1.

[0039]

[Table 1]

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

1. Dissolution test in water After adding 6 g of pigment to 100 g of purified water and stirring with a magnetic stirrer for 1 hour, No. It filtered with the filter paper of 5c, and measured the light transmittance in 505 nm of the filtrate using a spectrophotometer.

2. Dissolution test for 95% ethanol: 1.5 g of pigment was added to 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 filter membrane (MF-PTFE, 0.5 μm), and the light transmittance of the filtrate at 505 nm 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 pigments of the present invention are excellent in saturation and hiding power, and have very little elution of the dye with respect to water or ethanol. there were.

[0046]

Industrial Applicability According to the present invention and the production method of the present invention, it is possible to obtain an organic-inorganic composite pigment which is excellent in saturation and hiding power and which hardly causes bleeding in water or ethanol.

Claims (6)

[Claims] 1. A refractive index of 2 or more and an average particle diameter of 0.01 to
An organic-inorganic composite pigment obtained by coating an inorganic white pigment of 60 μm with Red No. 202 and calcium carbonate. 2. A refractive index of 2 or more and an average particle diameter of 0.1 to 6
An organic-inorganic composite pigment obtained by coating an inorganic white pigment having a size of 0 μm with Red No. 202 and calcium carbonate. 3. (1) Red No. 201 and / or Red 20
Step of dissolving No. 2 in lower alcohol and (2) Red 20
Red No. 201 on the surface of the inorganic white pigment by adding an alkali carbonate or a solution thereof to the lower alcohol solution in which the inorganic white pigment is dispersed in a lower alcohol solution in which No. 1 and / or Red No. 202 is dissolved. And / or (4) adding a lower alcohol solution of calcium chloride to the lower alcohol solution to generate and deposit calcium carbonate on the surface of the inorganic white pigment, and at the same time, deposit on the surface of the inorganic white pigment. The organic-inorganic composite according to claim 1 or 2, characterized in that the red No. 201 and / or the red No. 202 thus formed are laked or re-laked to fix the Red No. 202 on the surface of the inorganic white pigment. Method for producing pigment. 4. The organic-inorganic according to claim 1, wherein the inorganic white pigment is selected from one kind or a combination of two or more kinds of zinc oxide, zirconium oxide, titanium oxide (anatase type) and titanium oxide (rutile type). Composite pigment. 5. The inorganic white pigment is selected from a composite of two or more kinds of zinc oxide, zirconium oxide, titanium oxide (anatase type), and titanium oxide (rutile type).
The organic-inorganic composite pigment according to item 1. 6. The method for producing an organic-inorganic white pigment according to claim 2, wherein the alkali carbonate is selected from one or more of sodium carbonate, potassium carbonate and lithium carbonate.