JP2000281932A - Silky nacreous pigment and coating composition, cosmetic, ink, and plastic containing same - Google Patents

Abstract

PROBLEM TO BE SOLVED: To obtain a pigment which, like natural pearl, has a silky delicate luster (silkiness) by coating with a metal oxide synthetic fluorophlogopite particles having a specified mean particle diameter, a specified particle diameter standard deviation, and a specified particle thickness in laser diffraction particle size distribution measurement. SOLUTION: The synthetic fluorophlogopite particles have a mean particle diameter of 3-10 μm, a particle diameter standard deviation of 1.70 or below, and a particle thickness of below 0.2 μm. The mica as the starting material can be obtained by a melt synthesis process, namely, a process comprising mixing silicon oxide with aluminum oxide, magnesium oxide, a silicofluoride, and a fluoride, melting the mixture by heating to about 1,500 deg.C, and crystallizing the melt by cooling. Particles having the specified shape can be obtained by finely powdering the easily peelable synthetic mica crystal lumps. The metal oxide is exemplified by an oxide of titanium, zirconium, iron, chromium, or vanadium, desirably, rutile titanium dioxide.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a silky glossy pigment which exhibits a silky feeling using a specific synthetic fluorophlogopite as a substrate, and a coating composition, a cosmetic, an ink and a plastic containing the pigment.

[0002]

2. Description of the Related Art Pall gloss pigments using synthetic mica or natural mica as a substrate are used in many fields as pigments exhibiting a pal-like design feeling.

[0003]

SUMMARY OF THE INVENTION However, the conventional
The luster pigment blended paint had a strong shine and a grainy (glittery luster), but it was dense like a natural pearl, with a silky depth and calm overall No brilliant (silky feeling) could be exhibited.

[0004] Such a silky feeling expresses a luxurious feeling and is therefore strongly demanded as a paint for high-grade products.

The present invention has been made in view of such a point, and an object of the present invention is to provide a silky glossy pigment exhibiting a dense shine (silky feeling) like silk like a natural pearl. And

[0006]

Means for Solving the Problems To achieve the above object, the present inventors have made intensive studies and found that the average particle diameter in laser diffraction type particle size distribution measurement is 3 to 10 microns and the standard deviation is 1 μm. .70 or less, and found that a silky feeling is exhibited by coating the metal oxide on the synthetic fluorophlogopite particles having a particle thickness of less than 0.2 micron,
The present invention has been reached.

That is, according to the present invention, there is provided a compound having an average particle diameter of 3 to 10 microns, a standard deviation of 1.70 or less, and a particle thickness of less than 0.2 micron in a laser diffraction particle size distribution measurement. It is characterized in that a metal oxide is coated on the fluorophlogopite particles to give a silky feeling.

[0008] The silky glossy pigment of the present invention which exhibits a silky feeling (brightness like silk) is defined as a natural pearl (like silk) by visually evaluating the coating film of a coated plate prepared by coating. Pigment that emits a (deep) calm shine.

Specifically, it means a pigment which has no glittering gloss (particle feeling) but has a silky luster and shines (density) as a whole.

[0010] In short, the present invention provides a synthetic fluorophlogopite particle having a smaller standard deviation of particle diameter of 1.70 or less than ever before, and a metal oxide coated on a synthetic fluorophlogopite particle having a small particle diameter and a small thickness. The gist of the present invention is to obtain a pigment which emits a radiance such as silk, which has been impossible to obtain conventionally.

[0011]

Next, embodiments of the present invention will be described.

The raw synthetic fluorophlogopite of the present invention can be obtained by a melt synthesis method. That is, it is obtained by mixing silicon oxide, aluminum oxide, magnesium oxide, silicon fluoride and fluoride, heating and melting at about 1500 ° C., and then cooling and crystallizing.

The synthetic fluorophlogopite powder of the present invention comprises a laser
The average particle size, standard deviation, and particle thickness in the diffraction type particle size distribution measurement need to be in specific ranges. In addition, the particle size distribution measurement (measurement of standard deviation) was performed by a semilogarithmic distribution using a logarithmic scale having the same particle size as usual.

The raw material used in the present invention must be synthetic fluorophlogopite powder in synthetic mica. When natural muscovite or synthetic tetrafluorosilicic mica is used, as is apparent from the comparative example, a luster pigment giving a luster like silk cannot be obtained.

The synthetic fluorophlogopite powder of the present invention must have an average particle size of 3 to 10 microns and a standard deviation of 1.70 or less. Heretofore, no pearl luster pigment has been produced at all using mica powder having a very small standard deviation of 1.70 or less.

If the average particle size is less than 3 microns, the color becomes whitish and the luster (silky feeling) like silk is not obtained. When the standard deviation value is larger than 1.70, the overall brightness does not become high, and the feeling of denseness is not obtained.

When the thickness of the mica particles exceeds 0.2 microns, the luster is not as silky.

Fine particles in such a specific range can be obtained by pulverizing a synthetic mica crystal mass which is easily peeled.

In order to obtain a synthetic mica crystal mass which is easy to exfoliate,
When melt-synthesizing the synthetic mica, it is preferable to add at least 1% or more of synthetic mica fine powder to the synthetic mica melt to coagulate and crystallize.

Such a synthetic mica crystal lump is crushed into pieces by a usual crusher, further pulverized using a hammer mill, roll mill, ball mill, or the like, and classified into a desired particle size.
The raw material mica particles of the present invention having the above standard deviation and the above size are used.

In order to reduce the standard deviation to 1.70 or less,
It is necessary to cut both small particles and large particles with respect to the median diameter. As a cutting method, wet classification is preferable.

Examples of the wet classification method include natural sedimentation classification, hydroseparator, spiral classification, drum classification, jet sizer, classifying sizer, liquid cyclone classification, sieve classification, arc screen, and the like.
It is more preferable to combine these.

In order to coat the synthetic fluorophlogopite powder with a metal oxide, a known method such as a hydrolysis method of titanium salt or a sputtering method may be used.

For example, a method of coating titanium oxide is to suspend synthetic mica powder in a dilute aqueous solution of titanic acid,
The mixture was heated to 0 to 100 ° C. to hydrolyze the titanium salt to precipitate hydrated titanium oxide particles on the synthetic mica powder.
It can be manufactured by firing at a high temperature of 00 to 1000 ° C.

The metal oxide to be used includes, for example, oxides of titanium, zirconium, iron, chromium and vanadium.

The metal oxide, preferably titanium dioxide, is preferably rutile with a rutile agent such as tin chloride.

The silky glossy pigment of the present invention can be mixed with various paints to form a coating composition, or kneaded with various plastics to give a plastic exhibiting a unique silky feeling, in the same manner as a conventional pearly glossy pigment. It can be used as a coloring agent for cosmetics or the like, or as a coloring agent for ink.

Next, the present invention will be further described with reference to examples and comparative examples, but the present invention is not limited to these examples. In the examples, the laser diffraction particle size distribution was measured using a laser diffractometer (LA-500) manufactured by Horiba, Ltd. The particle size distribution at this time is a semi-log normal distribution having a logarithm of the particle size as usual. The average particle diameter is a median diameter, and the standard deviation is a value of a standard deviation of a lognormal distribution. In the examples, "parts" representing quantities represent "parts by weight".

Example 1 In a laser diffraction particle size distribution, the average particle diameter was 7.2.
30 g of synthetic fluorophlogopite particles having a micron diameter of 1.64 and a particle thickness of 0.15 micron and 400 milliliters of water were placed in a 1-liter glass container and stirred.

Next, a titanyl sulfate solution (Ti
(O ₂ = 80 g / l) 250 ml and 0.5 g of stannous chloride are added and heated rapidly to 100 ° C.
The reaction was continued for one hour.

After completion of the reaction, the mixture was filtered, washed with water, and dried at 110 ° C. The obtained powder is fired at 800 ° C. for 1 hour,
A silky glossy pigment of the invention was obtained.

About 10% by weight of the silky glossy pigment of the present invention is mixed with a thermosetting acrylic melamine resin (a mixture of Acrydic 47-712 and Super Beckamine G821-60 in a weight ratio of 7: 3, manufactured by Dainippon Ink). , Black enamel (Superlac F-47, Nippon Paint Co., Ltd.) is sprayed on an undercoated steel sheet, and wet-on-wet thermosetting acrylic melamine resin (Acrytic 44-179 and Super Beckamine L117-6, manufactured by Dainippon Ink and Chemicals, Inc.)
The mixture was sprayed and baked at 140 ° C. for 18 minutes.

The obtained coating film had a silvery, dense and silky feeling.

Example 2 In the laser diffraction type particle size distribution, the average particle size was 7.0.
30 g of synthetic fluorophlogopite particles having a micron diameter of 1.58 and a standard thickness of 1.55 μm and a particle thickness of 0.15 μm, and 400 ml of water were placed in a 1-liter glass container and stirred.

Next, a titanyl sulfate solution (Ti
(O ₂ = 80 g / l) 400 ml and stannous chloride 0.5 g were added, and heated rapidly to 100 ° C.
The reaction was continued for one hour.

After completion of the reaction, the mixture was filtered, washed with water, and dried at 110 ° C. The obtained powder is fired at 800 ° C. for 1 hour,
A silky glossy pigment of the invention was obtained.

Using this silky glossy pigment, a coated plate was prepared in the same manner as in Example 1, and the coating film was visually evaluated.

The coating film was gold-colored and had a dense and silky feeling.

Example 3 In the laser diffraction type particle size distribution, the average particle size was 7.0.
30 g of synthetic fluorophlogopite particles having a micron diameter of 1.58 and a standard thickness of 1.55 μm and a particle thickness of 0.15 μm, and 400 ml of water were placed in a 1-liter glass container and stirred.

Next, a titanyl sulfate solution (Ti
(O ₂ = 80 g / l) 560 ml and 0.8 g of stannous chloride were added, and the mixture was rapidly heated to 100 ° C.
The reaction was continued for one hour.

After completion of the reaction, the mixture was filtered, washed with water, and dried at 110 ° C. The obtained powder is fired at 800 ° C. for 1 hour,
A silky glossy pigment of the invention was obtained.

Using this silky glossy pigment, a coated plate was prepared in the same manner as in Example 1, and the coating film was visually evaluated.

The coating film was blue with a dense feeling and a silky feeling.

Example 4 In the laser diffraction type particle size distribution, the average particle size was 4.3.
30 g of synthetic fluorophlogopite particles having a micron diameter of 1.59 and a particle thickness of 0.15 micron, and 400 ml of water were placed in a 1-liter glass container and stirred.

Next, a titanyl sulfate solution (Ti
(O ₂ = 80 g / l) 380 ml and 0.6 g of stannous chloride were added, and heated rapidly to 100 ° C.
The reaction was continued for one hour.

After completion of the reaction, the mixture was filtered, washed with water, and dried at 110 ° C. The obtained powder is fired at 800 ° C. for 1 hour,
A silky glossy pigment of the invention was obtained.

Using this silky glossy pigment, a coated plate was prepared in the same manner as in Example 1, and the coating film was visually evaluated.

The coating film had a silvery, dense and silky feeling.

Example 5 In the laser diffraction type particle size distribution, the average particle size was 7.0.
30 g of synthetic fluorophlogopite particles having a thickness of 0.10 micron and a standard deviation of 1.50 and a particle thickness of 0.10 micron, and 400 ml of water were placed in a 1-liter glass container and stirred.

Next, a titanyl sulfate solution (Ti
(O ₂ = 80 g / l) 300 ml and 0.5 g of stannous chloride were added, and heated rapidly to 100 ° C.
The reaction was continued for one hour.

After the completion of the reaction, the mixture was filtered, washed with water, and dried at 110 ° C. The obtained powder is fired at 800 ° C. for 1 hour,
A silky glossy pigment of the invention was obtained.

Using this silky glossy pigment, a coated plate was prepared in the same manner as in Example 1, and the coating film was visually evaluated.

The coating film had a silvery, dense and silky feeling.

Comparative Example 1 The average particle diameter in the laser diffraction particle size distribution was 7.5.
30 g of synthetic fluorophlogopite particles having a particle diameter of 0.15 micron and a standard deviation of 1.74 microns and 400 ml of water were placed in a 1-liter glass container and stirred.

Next, a titanyl sulfate solution (Ti
(O ₂ = 80 g / l) 250 ml and 0.5 g of stannous chloride are added and heated rapidly to 100 ° C.
The reaction was continued for one hour.

After the completion of the reaction, the mixture was filtered, washed with water, and dried at 110 ° C. The obtained powder was fired at 800 ° C. for 1 hour to obtain a pigment.

A coated plate was prepared using this pigment in the same manner as in Example 1, and the coating film was visually evaluated.

The coating film had a silvery color, lacked a dense feeling and had no silky feeling.

Comparative Example 2 The average particle diameter in the laser diffraction particle size distribution was 7.5.
30 g of synthetic fluorophlogopite particles having a micron diameter of 1.79 and a particle thickness of 0.15 micron and 400 ml of water were placed in a 1-liter glass container and stirred.

Next, a titanyl sulfate solution (Ti
(O ₂ = 80 g / l) 400 ml and stannous chloride 0.5 g were added, and heated rapidly to 100 ° C.
The reaction was continued for one hour.

After completion of the reaction, the mixture was filtered, washed with water, and dried at 110 ° C. The obtained powder was fired at 800 ° C. for 1 hour to obtain a pigment.

Using this pigment, a coated plate was prepared in the same manner as in Example 1, and the coating film was visually evaluated.

The coating film was gold-colored, lacked a dense feeling, and had no silky feeling.

Comparative Example 3 The average particle diameter in the laser diffraction particle size distribution was 7.5.
30 g of synthetic fluorophlogopite particles having a micron diameter and a standard deviation of 1.58 and a particle thickness of 0.20 micron, and 400 ml of water were placed in a 1-liter glass container and stirred.

Next, a titanyl sulfate solution (Ti
(O ₂ = 80 g / l) 250 ml and 0.5 g of stannous chloride are added and heated rapidly to 100 ° C.
The reaction was continued for one hour.

After completion of the reaction, the mixture was filtered, washed with water, and dried at 110 ° C. The obtained powder was fired at 800 ° C. for 1 hour to obtain a pigment.

Using this pigment, a coated plate was prepared in the same manner as in Example 1, and the coating film was visually evaluated.

The coating film had a silvery color, a low gloss, and no gloss like silk.

Comparative Example 4 In the laser diffraction type particle size distribution, the average particle size was 12 μm, the standard deviation was 1.58, and the particle thickness was 0.1 μm.
30 g of synthetic fluorophlogopite particles of 10 microns and water 4
00 ml was stirred in a 1-liter glass container.

Next, a titanyl sulfate solution (Ti
(O ₂ = 80 g / l) 200 ml and 0.5 g of stannous chloride were added and heated rapidly to 100 ° C.
The reaction was continued for one hour.

After completion of the reaction, the mixture was filtered, washed with water, and dried at 110 ° C. The obtained powder was fired at 800 ° C. for 1 hour to obtain a pigment.

A coated plate was prepared using this pigment in the same manner as in Example 1, and the coating film was visually evaluated.

The coating film was silver-colored, had a grainy feeling, and had no silky feeling.

Comparative Example 5 In the laser diffraction type particle size distribution, the average particle size was 2.0
30 g of synthetic fluorophlogopite particles having a micron diameter of 1.58 and a particle thickness of 0.10 micron and 400 ml of water were placed in a 1-liter glass container and stirred.

Next, a titanyl sulfate solution (Ti
(O ₂ = 80 g / l) 550 ml and 0.8 g of stannous chloride are added, and the mixture is rapidly heated to 100 ° C.
The reaction was continued for one hour.

After the completion of the reaction, the mixture was filtered, washed with water, and dried at 110 ° C. The obtained powder is fired at 800 ° C. for 1 hour,
A silky glossy pigment of the invention was obtained.

Using this silky glossy pigment, a coated plate was prepared in the same manner as in Example 1, and the coating film was visually evaluated.

The coating film was silvery, whitish and not shiny like silk.

Comparative Example 6 The average particle diameter in the laser diffraction particle size distribution was 7.5.
Micron, having a standard deviation of 1.58 and a particle thickness of 0.15 micron
0 g and 400 ml of water were placed in a 1 liter glass container and stirred.

Next, a titanyl sulfate solution (Ti
(O ₂ = 80 g / l) 250 ml and 0.5 g of stannous chloride are added and heated rapidly to 100 ° C.
The reaction was continued for one hour.

After the completion of the reaction, the mixture was filtered, washed with water, and dried at 110 ° C. The obtained powder was fired at 800 ° C. for 1 hour to obtain a pigment.

A coated plate was prepared using this pigment in the same manner as in Example 1, and the coating film was visually evaluated.

The coating film was silver-colored and had no luster like silk.

Comparative Example 7 The average particle diameter in a laser diffraction particle size distribution was 4.6.
30 g of natural muscovite particles having a standard deviation of 1.56 microns and a particle thickness of 0.15 microns, and water 40
And 0 ml were stirred in a 1 liter glass container.

Next, a titanyl sulfate solution (Ti
(O ₂ = 80 g / l) 380 ml and 0.6 g of stannous chloride were added, and heated rapidly to 100 ° C.
The reaction was continued for one hour.

After completion of the reaction, the mixture was filtered, washed with water, and dried at 110 ° C. The obtained powder was fired at 800 ° C. for 1 hour to obtain a pigment.

A coated plate was prepared using this pigment in the same manner as in Example 1, and the coating film was visually evaluated.

The coating film was silver-colored, yellowish and not glossy like silk.

Table 1 shows the evaluation results of the mica particles, the average particle diameter, the standard deviation, the average thickness and the obtained pigment used in Examples 1 to 5 and Comparative Examples 1 to 7. is there.

[0090]

[Table 1] In the table, ○ means having a silky feeling.

As is evident from the results in Table 1 above, by using a synthetic fluorophlogopite mica powder having a standard deviation smaller than ever before and a certain fixed value or less and having a smaller average particle diameter and average thickness than the conventional one, A silky glossy pigment that exhibits a silky shine that cannot be expressed with a pearlescent pigment is obtained.

Example 6: Plastics 4 parts of the silky glossy pigment of the present invention obtained in Example 1 were mixed with about 100 parts of vinyl chloride resin, 40 parts of dioctyl phthalate and 3 parts of zinc stearate and heated to 165 ° C. The mixture was treated with the kneading two rolls for 3 minutes to form a sheet having a thickness of 0.5 mm.

In this manner, a beautiful vinyl chloride sheet having a translucent reflected light with a silver color and a silky feeling was obtained.

Example 7: Cosmetic (lipstick) A lipstick was produced from the following composition by a conventional method.

Pigment obtained in Example 1 15 parts Red No. 226 1 part Fragrance 0.5 part Lipstick base material 83.5 parts However, the following lipstick base materials were used in combination.

[0096] Beeswax 15 parts Cetyl alcohol 3 parts Lanolin 15 parts Castor oil 62 parts Liquid paraffin 5 parts The lipstick produced in this way exhibited a bright gold-colored glossy gloss with high hiding power.

Example 8: Cosmetic (solid eyeshadow) 30 parts of pigment obtained in Example 1 20 parts of synthetic mica 20 parts of talc 35 parts of titanium oxide 5 parts of liquid paraffin 6 parts of methylpolysiloxane 2 parts of sorbitan sesquiolate 2 parts of the above After mixing the powder of the formulation with a blender, a liquid in which a binder was uniformly dissolved was added, mixed, and then pulverized with a pulverizer to obtain a product by compression molding. This product had a silky feeling and was excellent in finish.

Example 9: Ink 15 parts of the pigment obtained in Example 1 was added to 100 parts of the gravure ink medium, and mixed well to prepare a gravure pearl ink.

The printing paper printed with this ink had a silky feeling and a high-grade silver color.

[0100]

As described above, according to the present invention, it is possible to obtain a pigment exhibiting a silky feeling, which has never been obtained with a conventional pearl luster pigment, and it is possible to express an unprecedented sense of quality. It is extremely useful as a pigment for use.

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Claims (6)

[Claims] 1. An average particle diameter of 3 to 10 microns and a standard deviation of 1.70 in a laser diffraction particle size distribution measurement.
A silky glossy pigment comprising: a metal oxide coated on synthetic fluorophlogopite particles having a particle thickness of less than 0.2 micron to exhibit a silky feeling. 2. The method according to claim 1, wherein the metal oxide is titanium dioxide.
The pigment according to claim 1, wherein the titanium dioxide is rutile. 3. A coating composition comprising the silky glossy pigment according to claim 1 or 2. 4. A cosmetic comprising the silky glossy pigment according to claim 1 or 2. 5. An ink containing the silky glossy pigment according to claim 1 or 2. 6. A plastic comprising the silky glossy pigment according to claim 1 or 2 incorporated therein.