JP3384426B2 - Inorganic colored particle powder, method for producing the same, and water-based paint using the inorganic colored particle powder - Google Patents

Description

Detailed Description of the Invention

[0001]

FIELD OF THE INVENTION The present invention relates to an inorganic colored particle powder excellent in easy dispersibility, uniform dispersibility and dispersion stability, which is particularly suitable as an inorganic colored particle for a water-based coating as well as a solvent-based coating. The present invention relates to a production method and a water-based paint using the inorganic colored particle powder.

[0002]

2. Description of the Related Art Inorganic colored particles, which are oxides, are stable in air and have various colors depending on the difference in crystal structure and the presence or absence of crystal water. It is used by being dispersed.

In recent years, there is an ever-increasing demand for higher performance and higher quality of coating films obtained by coating a coating material on a substrate and drying it. To satisfy these requirements, the sharpness of the color tone in the coating film must be met. It is strongly required to improve the properties of the inorganic colored particles, which are said to have the greatest effect on the various properties such as the improvement of the coloring power, hiding power and glossiness. That is, it is necessary that the dispersibility of the inorganic colored particles in the vehicle, particularly the easy dispersibility, the uniform dispersibility, and the dispersion stability are excellent.

This fact is described on page 15 of "Latest Pigment Dispersion Technology" (1993) published by the Technical Information Institute.
The pigment is never used by itself, it is always dispersed in a resin called a binder, a solvent, etc., but in order to obtain a clear color tone, high coloring power and other properties, these fine pigments are used. The pigment particles must be easily dispersible in the binder and, at the same time, be uniformly dispersed. However, the finer the particles, the more unstable it becomes, so it is important how stable dispersibility can be maintained. From the various viewpoints, the following properties are required as the properties required for the pigment and “...
Can be classified. Although the dispersibility is classified as having an influence on the physical properties, it is also greatly related to and affects various properties such as optical properties, chemical properties and special functions. That is, to improve the dispersibility of the pigment and to disperse it uniformly,
Not only the improvement of the sharpness of color tone, the coloring power, the hiding power, and the glossiness of a coating film, but also the various robustness which is a chemical property and the workability are also improved. "..." is as described.

[0005] Paints include solvent-based paints containing an organic solvent as a main solvent and water-based paints containing water as a main solvent, depending on the type of solvent. In recent years, however, the air is less polluted, and resources and energy are saved. Moreover, water-based paints are regarded as promising from the viewpoint of safety and hygiene, such as low risk of fire.

However, since the dispersion mechanism of the inorganic colored particles in the water-based paint is different from that of the conventional solvent-based paint, it is necessary to sufficiently disperse the inorganic colored particles in the vehicle by the same dispersion technique as the solvent-based paint. I can't. That is, in the case of a water-based paint, a water-based resin (color-developing agent) is used. In this water-based resin, while the solvent-based resin (color-developing agent) exists in a spread state in a dissolved state, it is mainly emulsion-polymerized particles or Since it exists in the state of particles such as colloidal particles, first, by what means the inorganic colored particles are dispersed in the vehicle, and how much time is required, that is, the easy dispersibility and dispersion of the inorganic colored particles. Uniformity becomes a problem, and then it is easy to re-aggregate due to the interaction between the dispersed inorganic colored particles and the water-based resin particles.
Dispersion stability becomes a problem.

Therefore, not only in solvent-based paints, but especially in water-based paints, those having excellent dispersibility, dispersion uniformity and dispersion stability so that the inorganic colored particles sufficiently exhibit their original functions as inorganic colored particles. Is strongly required.

Conventionally, in order to improve the dispersibility of the inorganic colored particles in the vehicle, the particle surfaces of the inorganic colored particles have been coated with various inorganic compounds or organic compounds,
For example, a method of depositing an organopolysiloxane on the surface of inorganic colored particles (Japanese Patent Publication No. 41-9890, Japanese Patent Publication No. 56-43264, Japanese Patent Publication No. 58-13099, Japanese Patent Publication No. 1-54379, Japanese Patent Publication No. 1-54379). Fairness 3-177
Japanese Patent No. 64, Japanese Patent Publication No. 5-4129, Japanese Patent Publication No. 5-8
6820, JP 47-33127, JP 59-15455, JP 60-31576, JP 61-127767, JP 62-
87237, JP-A-63-27419, JP-A-63-113082, JP-A-63-1390.
15, JP-A-63-165461, JP-A-63-168346, and JP-A-63-202671.
Japanese Patent Laid-Open No. 1-282368, Japanese Patent Laid-Open No. 2-2
No. 12561, No. 3-163172, No. 4-68041, No. 5-111631, No. 5-214264, No. 5-33.
No. 9518) or a method of depositing a silane coupling agent on the surface of inorganic colored particles (Japanese Patent Application Laid-Open No. 55-9496).
No. 8) has been tried.

Further, Japanese Unexamined Patent Publication (Kokai) No. 62-187772 discloses that polyester-modified polysiloxane is used by adding it to a coating material because it has an action of lowering tackiness and improving lubricity. ing.

[0010]

Inorganic colored particles having excellent dispersibility, dispersion uniformity, and dispersion stability are currently most demanded not only in solvent-based paints but also in water-based paints. Inorganic colored particles have not yet been obtained.

That is, the inorganic colored particles having the known organopolysiloxane or silane coupling agent deposited on the surface of the particles are easily dispersible in the vehicle and have uniform dispersion, as shown in Comparative Examples below. It is hard to say that neither the dispersion stability nor the dispersion stability is sufficient.

Also, when the polyester-modified polysiloxane disclosed in the above-mentioned Japanese Patent Laid-Open No. 62-187772 is added to the coating material, the dispersibility of the inorganic colored particles in the vehicle is similarly shown in the comparative example. Is insufficient in easy dispersibility, dispersion uniformity, and dispersion stability.

Therefore, it is a technical object of the present invention to obtain an inorganic colored particle powder having excellent dispersibility, dispersion uniformity and dispersion stability, not only in solvent-based paints but also in water-based paints.

[0014]

The above technical problems can be achieved by the present invention as described below.

That is, according to the present invention, the surface of the particles is coated with squaric acid, and further, the surface of the deposited square acid is
Polyether-modified polysiloxane shown in Chemical formula 4, Chemical formula 5
1 selected from the polyester-modified polysiloxane represented by the formula 1 and the aralkyl-modified polysiloxane represented by the formula 6
Inorganic colored particle powder consisting of inorganic colored particles coated with one or more specific modified polysiloxane, and a water suspension containing the inorganic colored particles and squaric acid are mixed, filtered, and dried. The method for producing an inorganic colored particle powder, which comprises mixing the inorganic colored particles coated with squaric acid obtained by 1. and the characteristically modified polysiloxane at a temperature of 80 ° C. or higher, and a water-based paint composition for the inorganic colored particle powder. It is a water-based coating compounded in a base material.

[Chemical 4]

[Chemical 5]

[Chemical 6]

The structure of the present invention will be described in detail below.

First, the inorganic colored particle powder according to the present invention will be described.

The inorganic colored particles in the present invention are particles having a large coloring power and giving a color to a coating film or a molded product when kneaded with a color-developing agent.

Specifically, zinc white (ZnO), lead white (2
PbCO ₃ · Pb (OH) ₂ ), basic lead sulfate (3Pb
SO ₄ · PbO to 2PbSO ₄ · PbO), lead sulfate (P
bSO ₄ ), lithopone (ZnS + BaSO ₄ ), zinc sulfide (ZnS), titanium oxide (TiO ₂ ), white colored particles such as antimony oxide (Sb ₂ O ₃ ), carbon black (C), graphite (C), iron black. ( FeO x · Fe ₂ O ₃ (0
<X ≦ 1)) black colored particles such as yellow lead (PbCr
O ₄ ), zinc yellow (ZnCrO ₄ ), barium chromate (BaCrO ₄ ), cadmium yellow (CdS), yellow iron oxide hydroxide (FeOOH.nH ₂ O), ocher (Fe ₂
O ₃ · SiO ₂ · Al ₂ O ₃ ), titanium yellow (TiO ₂ ·
NiO.Sb ₂ O ₃ ) and lead cyanamide (Pb (C
N) ₂ ), yellow colored particles such as calcium leadate (Ca ₂ PbO ₄ ), reddish yellow lead (PbCrO ₄ · PbO), chrome vermilion (PbCrO ₄ · PbMoO ₄ · PbSO)
₄ ) orange colored particles such as brown iron oxide (γ-Fe)
₂ O ₃ ), amber (Fe ₂ O ₃ + MnO ₂ + Mn ₃ O
₄ ) such as brown colored particles, red iron oxide (α-Fe ₂ O ₃ ),
Reedan (Pb ₃ O ₄ ), silver vermilion (HgS), cadmium red (CdS + CdSe), cadmium mercury red (CdS + HgS), antimony vermilion (2Sb ₂ S ₃ · S)
b ₂ O ₃ or Sb ₂ S ₃ · Sb ₂ O ₃ ) or other red colored particles, cobalt purple (Co ₃ (PO ₄ ) ₂ , Co ₃ (P
_{O 4) 2 · 8H 2 O} ), cobalt violet _(Co 3 _{(As
O 4) 2, Co 3 (} AsO 4) 2 · 8H 2 O), manganese violet _{(Mn 2 (PO 4) 3} , (NH 4) 2 Mn (P 2 O
₇ ) ₂ ) Purple colored particles such as ultramarine blue (3NaAl.SiO)
₄・ Na ₂ S ₂ , 2 (Na ₂ O ・ Al ₂ O ₃・ 2SiO
₂ ) ・ Na ₂ S ₂ ), dark blue (Fe ₄ [Fe (CN) ₆ ]]
₃・ nH ₂ O), cobalt blue (CoO ・ nAl ₂ O)
₃ ), Cerulean Blue (CoO ・ nSnO ₂・ mGg)
Blue colored particles such as O (n = 1.5 to 3.5, m = 2 to 6)), chrome green (dark blue + yellow lead), zinc green (zinc yellow + dark blue), chromium oxide (Cr ₂ O _3). ), Viridian (Cr ₂ O (OH) ₄ ), emerald green (C
Examples include green colored particles such as u (CH ₃ CO ₂ ) ₂ .3CuO (AsO ₂ ) ₂ ) and cobalt green (CoO.ZnO.MgO).

Of the above-mentioned inorganic colored particles, zinc white, lead white,
Titanium oxide, antimony oxide, iron black, yellow lead, zinc yellow, cadmium yellow, yellow hydrous iron oxide, titanium yellow, chrome vermillion, brown iron oxide, red iron oxide, cadmium red, cadmium mercury red, cobalt blue,
The object of the present invention can be effectively achieved by using chromium green, chromium oxide or the like as the inorganic colored particles, and in particular, iron oxide such as iron black, red iron oxide, brown iron oxide or yellow iron oxide hydroxide, oxidation When titanium, yellow lead, chromium oxide or the like is used as the inorganic colored particles, the object of the present invention can be achieved more effectively.

Therefore, the present invention does not include extender pigment particles which have a small coloring power and become transparent or translucent when kneaded with a color-developing agent. The extender pigment is specifically B
Examples thereof include sulfates, silicates, oxides, hydroxides and carbonates of a, Ca, Al, Si and Mg.

Iron oxide such as red iron oxide (α-Fe ₂ O ₃ ) particles, iron black ( FeO x · Fe ₂ O ₃ (0 <x ≦ 1)) particles, and brown iron oxide (γ-Fe ₂ O ₃ ) particles System particles, goethite (α-FeOOH) particles, agenite (β-Fe
OOH) particles, lepidocrocite (γ-FeOOH) particles, and other yellow iron oxide hydroxide particles have a cubic, octahedral, or spherical granular shape, needle-shaped particles, spindle-shaped particles, plate-shaped particles. Or the like.

The particle size of the iron oxide-based particles and the yellow iron oxide hydroxide-based particles is an average particle diameter of 0.01 to 1 in the case of granular particles.
It is 0 μm, and is 0.1 to 0.1 when the coloring power and the hiding power are taken into consideration.
0.5 μm is preferable. In the case of needle-shaped particles or spindle-shaped particles, the major axis diameter is 0.1 to 20 μm and the axial ratio (major axis diameter: minor axis diameter) is 2: 1 to 20: 1. Considering coloring power and hiding power. For example, particles having a major axis diameter of 0.1 to 1.0 μm and an axial ratio (major axis diameter: minor axis diameter) of 3: 1 to 10: 1 are preferable. In the case of plate-like particles, the average particle size (plate surface diameter) is 0.01 to 20.0.
μm, thickness 0.005 to 2.0 μm, and taking the coloring power and glitter into consideration, the average particle diameter (plate surface diameter) is 0.1 to 1
Particles having a thickness of 0.0 μm and a thickness of 0.01 to 1.0 μm are preferable.

As the above-mentioned inorganic colored particles other than iron oxide particles and yellow iron oxide hydroxide particles, those commercially available as colored particles can be used, and the particle size thereof is
Considering the colorability, it is usually 0.01 to 10 μm, preferably 0.05 to 1.0 μm, and more preferably 0.1 to 10 μm.
Those having a thickness of about 0.5 μm can be used.

As squaric acid in the present invention, commercially available 3,4-dihydroxy-3-cyclobutene-1,2-
Zion (manufactured by Tokyo Chemical Industry Co., Ltd.) can be used.

The amount of squaric acid deposited on the particle surface of the inorganic colored particle powder according to the present invention is preferably 0.01 to 10% by weight based on C based on the inorganic colored particles. 0.0
When it is less than 1% by weight, it becomes difficult to obtain the inorganic colored particle powder having excellent dispersibility which is the object of the present invention.
Even if the amount exceeds 10% by weight, the inorganic colored particle powder having a higher dispersibility, which is the object of the present invention, can be obtained, but the effect is in a saturated state and it is meaningless to add more than necessary.

The modified polysiloxane deposited on the surface of the inorganic colored particles according to the present invention is a polyether modified polysiloxane represented by Chemical formula 7, a polyester modified polysiloxane represented by Chemical formula 8 and an aralkyl represented by Chemical formula 9. One or more selected from modified polysiloxanes (referred to as specific modified polysiloxane).

The polyether-modified polysiloxane has a molecular weight in the range of 350 to 500,000, preferably 1.
000 to 100,000, more preferably 2
It is in the range of 000 to 50,000.

The polyester-modified polysiloxane has a molecular weight in the range of 400 to 500,000, preferably 1.
000 to 100,000, more preferably 2
It is in the range of 000 to 50,000.

The molecular weight of the aralkyl-modified polysiloxane is in the range of 350 to 500,000, preferably 1.
000 to 100,000, more preferably 2
It is in the range of 000 to 50,000.

[0031]

[Chemical 7]

[0032]

[Chemical 8]

[0033]

[Chemical 9]

The amount of the specific modified polysiloxane deposited on the particle surface of the inorganic colored particle powder according to the present invention is C
It is preferably 0.01 to 10% by weight based on the inorganic colored particles. If the amount is less than 0.01% by weight, it becomes difficult to obtain the inorganic colored particle powder having excellent dispersibility, which is the object of the present invention. Even when the amount exceeds 10% by weight, the inorganic colored particle powder excellent in dispersibility which is the object of the present invention can be obtained, but the effect is in a saturated state and it is meaningless to add more than necessary.

The ratio of the amount of the modified polysiloxane deposited on the particle surface of the inorganic colored particle powder according to the present invention to the amount of the squaric acid deposited is 1: 1000 to 1000: 1.
Is preferred. It is more preferably 1: 100 to 100: 1.

The shape and particle size of the inorganic colored particle powder according to the present invention are almost the same as those characteristics of the inorganic colored particles described above.

Dispersibility in the case where an inorganic colored particle powder according to the present invention, in which squaric acid is adhered to the surface of a particle and the specific modified polysiloxane is adhered to the surface of the adhered square acid, is used in a solvent-based paint. In case of red iron oxide particles, dispersion time is 4
The coating film has a gloss of 85% or more in 5 minutes and a dispersion time of 90.
The coating film has a gloss of 90% or more and a gloss reduction rate of 5% or less, and in the case of yellow iron oxide hydroxide particles, the coating film has a gloss of 85% or more at a dispersion time of 45 minutes and a coating at a dispersion time of 90 minutes. When the gloss of the film is 90% or more and the reduction rate of the gloss is 5% or less, and in the case of iron black particles, the dispersion time is 45
In the case of brown iron oxide particles, the gloss of the coating film is 85% or more, the gloss of the coating film is 90% or more at a dispersion time of 90 minutes, and the reduction rate of the gloss is 5% or less.
The coating film has a gloss of 80% or more at 90 minutes, the coating film has a gloss of 85% or more at a dispersion time of 90 minutes, and the gloss reduction rate is 5% or less.

Inorganic coloring other than iron oxide-based particles and yellow iron oxide hydroxide-based particles, in which squaric acid is adhered to the surface of particles according to the present invention, and the specific modified polysiloxane is adhered to the surface of the adhered square acid. When the particle powder is used in a solvent-based paint, the dispersibility is such that the coating film has a gloss of 80 at a dispersion time of 45 minutes.
% Or more, the coating film has a gloss of 83% at a dispersion time of 90 minutes.
As described above, the reduction rate of gloss is 10% or less.

The dispersibility of an inorganic colored particle powder according to the present invention, in which a square acid is adhered to the surface of a particle and the specific modified polysiloxane is adhered to the surface of the adhered square acid, is used in an aqueous paint. , For red iron oxide particles, dispersion time 45
The coating film has a gloss of 80% or more at a dispersion time of 90 minutes, the coating film has a gloss of 85% or more at a dispersion time of 90 minutes, and the reduction rate of the gloss is 5% or less. Film gloss is 80% or more, dispersion time 9
The gloss of the coating film at 0 minutes is 85% or more, the reduction rate of the gloss is 5% or less, and in the case of iron black particles, the coating film has a gloss of 80% or more at a dispersion time of 45 minutes and a coating film at a dispersion time of 90 minutes. The gloss is 85% or more, and the gloss reduction rate is 5
%, And in the case of brown iron oxide particles, the coating film has a gloss of 80% or more at a dispersion time of 45 minutes, a coating film has a gloss of 85% or more at a dispersion time of 90 minutes, and a reduction rate of the gloss is 5%.
% Or less.

Inorganic coloring other than iron oxide-based particles or yellow iron oxide hydroxide-based particles in which squaric acid is adhered to the surface of particles according to the present invention and the specific modified polysiloxane is adhered to the surface of the adhered square acid. The dispersibility when the particle powder is used in the water-based paint is such that the gloss of the coating film at the dispersion time of 45 minutes is 82%.
As described above, the gloss of the coating film at the dispersion time of 90 minutes is 85% or more, and the reduction rate of the gloss is 8% or less.

The blending ratio of the inorganic colored particle powder in the present invention to the coating material is 10 to 100 parts by weight of the coating material base material.
It can be used in the range of 90 parts by weight. Considering the handling of the paint, the upper limit value is 60 parts by weight, and more preferably 50 parts by weight.

The paint-constituting base material in the present invention contains a resin, a solvent, and if necessary, extender pigment particles, a drying accelerator, a surfactant, a curing accelerator, an auxiliary agent and the like.

The mixing ratio of the resin and the solvent in the coating material according to the present invention is preferably 50 to 5000 parts by weight, more preferably 100 to 2000 parts by weight, with respect to 100 parts by weight of the resin. If it is less than 50 parts by weight, the viscosity of the vehicle becomes too high, and it becomes difficult to uniformly mix and disperse. 5000
If the amount is more than parts by weight, the amount of the solvent composition in the coating material becomes too large, and the dispersion share to the particles is not applied during mixing and dispersion, which is not preferable.

As the resin, an acrylic resin, an alkyd resin, a polyester resin, a polyurethane resin, an epoxy resin, a phenol resin, a melamine resin, an amino resin or the like which is usually used for a solvent type paint can be used. For water-based paint, water-soluble alkyd resin, water-soluble acrylic resin, water-soluble urethane resin, which are usually used,
Water-soluble epoxy resin, water-soluble melamine resin, acrylic emulsion resin, acrylic / styrene emulsion resin, urethane emulsion resin, epoxy emulsion resin, vinyl acetate emulsion resin and the like can be used.

As the solvent, it is possible to use toluene, xylene, butyl acetate, methyl acetate, methyl isobutyl ketone, butyl cellosolve, ethyl cellosolve, butyl alcohol, aliphatic hydrocarbon and the like which are commonly used for solvent-based paints.

For water-based paints, butyl cellosolve, butyl alcohol and the like which are commonly used can be used.

As the defoaming agent, Nopco 8034 (trade name), SN deformer 477 (trade name), SN deformer 5013 (trade name), SN deformer 247
(Brand name), SN Deformer 382 (Brand name) (all above are manufactured by San Nopco Ltd.), Anti Home 08
Commercial products such as (trade name) and Emulgen 903 (trade name) (all of which are manufactured by Kao Corporation) can be used.

Next, a method for producing the inorganic colored particle powder according to the present invention as described above will be described.

Squaric acid is in a powder state, and even if it is used by directly adding it to the water to be adhered, it can be dissolved in water beforehand to have a solution concentration of 0.1 to 50 g / l, preferably 0. Although it may be used in an amount of 0.5 to 10 g / l, the latter method is preferable.

The process for depositing squaric acid in the present invention is as follows.
After mixing the aqueous suspension containing the inorganic colored particles and squaric acid, the mixture may be filtered and dried.

The inorganic colored particles and squaric acid may be added to water in any order, or they may be added simultaneously.

The addition amount of squaric acid is 0.01 to 30.0%, preferably 0.02 to 25.
It is 0%. If it is less than 0.01%, it will be difficult to obtain the inorganic colored particle powder having a better dispersibility than the object of the present invention. Even when the content exceeds 30.0%, the inorganic colored particle powder having excellent dispersibility, which is the object of the present invention, can be obtained, but the effect is in a saturated state and it is meaningless to add more than necessary.

It is essential that the time for mixing the water suspension is such that the inorganic colored particles and the squaric acid are sufficiently mixed and stirred, and at least 5 minutes, preferably 10 minutes or more.

It is essential that the specific modified polysiloxane in the present invention is modified with one or more selected from polyether, polyester and aralkyl, and the known polydimethylsiloxane and methylphenylpolysiloxane described above are essential. Depending on the organopolysiloxane and silane coupling agent such as methylhydrogenene polysiloxane, dimethylpolysiloxycyclolide, alkoxypolysiloxane, amino group-end modified polysiloxane, etc., as shown in Comparative Examples below, the dispersion targeted by the present invention can be obtained. Inorganic colored particle powder having excellent properties cannot be obtained.

Commercially available products can be used as the specific modified polysiloxane in the present invention. As polyether modified polysiloxane, BYK-320, BYK
-325, BYK-080 (trade name) (manufactured by BYK Chemie Co., Ltd.), as polyester modified polysiloxane, BYK-310 (trade name) (manufactured by BYK Chemie Co., Ltd.), and as aralkyl modified polysiloxane , BYK-322 (trade name) (Big Chemie Co., Ltd.)
Manufactured), all of which are in a solution state, and may be used by adding them to the inorganic colored particles as they are.

The addition amount of the specific modified polysiloxane is preferably 0.05 to 20.0% with respect to the inorganic colored particles.
If it is less than 0.05%, it will be difficult to obtain the inorganic colored particle powder having excellent dispersibility, which is the object of the present invention. Two
Even when it exceeds 0.0%, the inorganic colored particle powder excellent in dispersibility which is the object of the present invention can be obtained, but the effect is in a saturated state and it is meaningless to add more than necessary.

The inorganic colored particles and the specific modified polysiloxane in the present invention are mixed at a temperature of 80 ° C. or higher.
If the temperature is lower than 80 ° C., the modified polysiloxane has a very high viscosity, and it becomes difficult to uniformly deposit the inorganic colored particles on the particle surface, and the inorganic colored particle powder aimed at by the present invention cannot be obtained.

As a device for mixing, a high speed agitate mixer which is usually used in mixing the inorganic colored particles and the surface treatment agent, specifically, a Henschel mixer, a speed mixer, a ball cutter, a power mixer, a hybrid is used. A mixer or the like may be used, and a Henschel mixer is preferably used in consideration of uniform deposition of the specific modified polysiloxane.

It is important to sufficiently mix the inorganic colored particles and the specific modified polysiloxane in the high speed agitator, and the stirring time is at least 5 minutes or more, preferably 10 minutes or more.

When the inorganic colored particles are mixed with the modified polysiloxane, it is preferably heated in advance at 80 ° C. or higher to reduce the water content, and particularly adjusted to 0.2% by weight or less. When the amount of water in the inorganic colored particles is large, the water that is liquid-crosslinked between the particles strengthens the aggregation of the particles, which makes it difficult to uniformly adhere the particles to each other.

[0061]

The most important point in the present invention is that the surface of the particles is coated with squaric acid, and the surface of the deposited square acid is coated with the specific modified polysiloxane. It is a point that excellent dispersibility, dispersion uniformity and dispersion stability are exhibited not only in water-based paints but also in water-based paints.

The reason why the inorganic colored particle powder coated with the specific modified polysiloxane exhibits excellent easy dispersibility, dispersion uniformity and dispersion stability, particularly in an aqueous coating composition, is as follows. I think so.

In the solvent-based paint, the resin is spread and adsorbed on the surface of the inorganic colored particles, and when the adsorbed resin brings the inorganic colored particles close to each other, a large exchange repulsive force is exerted, so-called steric hindrance occurs, and the inorganic colored The particles are prevented from approaching each other and the inorganic colored particles are stably present in the paint.

However, in the water-based paint, as described above, since the resin does not spread and exists in a particle state, it is difficult to exhibit the steric hindrance effect seen in the inorganic colored particles in the solvent-based paint. Dispersion of colored particles becomes difficult.

It is generally known that the larger the absolute value of the zeta potential of the suspended particles in the paint, the better the dispersion suitability of the suspended particles due to electrostatic repulsion. The inorganic colored particle powder to which the specific modified polysiloxane is adhered to is, when the zeta potential is measured in a water-based paint, as shown in the later-described examples, −25 to −5.
Since the absolute value is high at about 5 mV, particularly -30 to -55 mV, the surface of the particles is easily negatively charged in the water-based paint, and the electric repulsion between the particles is large. . Moreover, since the molecular chains of polyether, polyester, aralkyl, etc. are spread and adsorbed on the particle surface, the synergistic effect of the large electric repulsion and steric hindrance effect makes it easy to loosen the aggregation, and the primary particles It becomes possible to disperse even to a state close to, and as a result, excellent dispersibility and dispersion uniformity are obtained.

After the particles are once dispersed in a state close to that of the primary particles, the electrical repulsion can maintain the dispersed state for a long time, resulting in excellent dispersion stability.

[0067]

EXAMPLES Next, the present invention will be described with reference to Examples and Comparative Examples.

The average particle size of the particles in the following Examples and Comparative Examples is the average value of the numerical values measured from electron micrographs.

The shape of the particles was observed with a transmission electron microscope and a scanning electron microscope.

The specific surface area value is shown by the value measured by the BET method.

The amount of the modified polysiloxane and the square acid deposited was determined by "Horiba Metal Carbon / Sulfur Analyzer EMIA-220".
0 ”(manufactured by Horiba Ltd.) was used to measure the carbon content.

The dispersibility was indicated by a value obtained by measuring the glossiness (gloss) of the coating film using a digital gloss meter UGV-5D (manufactured by Suga Test Instruments Co., Ltd.) at an incident angle of 20 °. The higher the gloss value, the better the dispersibility.

As for easy dispersibility, the coating composition obtained by mixing the following predetermined components in a predetermined ratio and dispersing the mill base for 45 minutes was used as a cold rolled steel plate (0.8 mm × 70 mm × 150 m).
m) (JIS G 3141) with a thickness of 150 μm and dried to show the glossiness of the coating film produced.

The dispersion uniformity is obtained by blending the following predetermined composition in a predetermined ratio and dispersing the mill base for 90 minutes (the dispersion is saturated at this point). Steel plate (0.8 mm x 70 mm x 150 mm) (J
IS G 3141) was applied to a thickness of 150 μm and dried, and the glossiness of the coating film produced was measured.

The dispersion stability is determined by blending the following predetermined components in a predetermined ratio and dispersing the mill base for 90 minutes. Further, in the case of a solvent type paint, a thinner is added to the solvent type paint at 40%. %, In the case of water-based paint, 40% of water is added to the water-based paint to dilute the paint, and the diluted paint obtained is a cold rolled steel plate (0.8 mm x 70 mm x 150 mm).
(JIS G 3141) with a thickness of 150 μm,
The gloss of the dried coating film was measured, and the difference between the gloss before and after the dilution and the gloss before the dilution was shown. In the case of the present invention, the smaller the absolute value of the difference, the better the dispersion stability.

The storage stability of the water-based paint was determined by blending the following predetermined components in a predetermined ratio and dispersing the mill base for 90 minutes, leaving the paint for 1 day, and then cold-rolling the steel sheet (0. 8 mm x 70 mm x 150 mm) (JIS G
3141) was applied and dried to a thickness of 150 μm, and the glossiness of the coating film produced was measured.

The value of the zeta potential of the inorganic colored particle powder in the water-based paint is obtained by blending the following predetermined composition in a predetermined ratio,
The paint obtained by dispersing the mill base for 90 minutes is pure water 1
0.5g was added to 00g, and ultrasonic disperser C-10 was used.
(Ultrasonic Industry Co., Ltd.) using a suspension obtained by dispersing for 1 minute, using a zeta potentiometer MODEL-501 (P
The value was measured by EN-KEM).

<Production of Iron Oxide Particles> Examples 1-6, Comparative Examples 1-14;

Example 1 Squaric acid 3,4-dihydroxy-3-cyclobutene-
30 g of 1,2-dione (manufactured by Tokyo Chemical Industry Co., Ltd.) was previously added to 5 l of pure water, and water was added to a squaric acid solution to make 25 l, which was well stirred with a stirrer. The concentration of squaric acid at this time was 1.2 g / l.

An average particle size of 0.25 in the above square acid solution
After gradually adding 3 kg of granular red iron oxide (α-Fe ₂ O ₃ ) particles having a particle diameter of 30 μm and mixing and stirring with a homomixer for 30 minutes,
Squaric acid was applied to the particle surface of the red iron oxide particles by filtration, drying and pulverization.

The red iron oxide particles thus obtained had a square acid deposition amount of 0.41% by weight in terms of C.

2.5 kg of red iron oxide particles whose surface was coated with squaric acid were charged into a Henschel mixer (10 l) which had been heated to 110 ° C. in advance, and the mixture was operated and mixed at 1200 rpm for 10 minutes to remove water. The water content of the red iron oxide particles was removed to 0.07% by weight.

The above Henschel mixer is heated to 100 ° C.
While maintaining the polyether modified polysiloxane BYK
-080 (trade name) (manufactured by Big Chemie) 50 g
(Active ingredient 100%) (corresponding to 2.0% by weight with respect to the red iron oxide particles) was added at an addition rate of 2.5 g / min over 20 minutes, followed by mixing for 20 minutes to obtain particles of the red iron oxide particles. The surface was coated with a polyether modified polysiloxane.

Then, while cooling with a Henschel mixer, the mixture was cooled to room temperature to obtain a red iron oxide powder having the surface of the particle coated with the polyether-modified polysiloxane.

In the obtained red iron oxide powder, the polyether-modified polysiloxane coating amount was 1.10% in terms of C.

Table 1 shows various conditions at this time.

Examples 2 to 6 The type and amount of iron oxide-based particles or iron oxide hydroxide-based particles, the temperature of heat treatment, the type and amount of squaric acid, the type and amount of modified polysiloxane treatment, and the mixing temperature were variously changed. A treated iron oxide-based particle powder or hydrous iron oxide-based particle powder was obtained in the same manner as in Example 1 except that the treatment was performed.

Table 1 shows various conditions at this time.

Comparative Examples 1 to 5 For comparison, untreated iron oxide particles or hydrous iron oxide particles were prepared. Table 2 shows various characteristics of these iron oxide-based particles or hydrous iron oxide-based particles.

Comparative Example 6 Granular red iron oxide (α-Fe having an average particle size of 0.25 μm)
2.5 kg of ₂ O ₃ ) particles were charged into a Henschel mixer (10 l) which had been preheated to 85 ° C., and the rotation speed was 120.
The water content was removed by operating and mixing at 0 rpm for 10 minutes to adjust the water content of the red iron oxide particles to 0.11% by weight.

While maintaining the Henschel mixer at a temperature of 90 ° C., a polyether-modified polysiloxane BYK-0
80 (trade name) (manufactured by Big Chemie Co., Ltd.) 0.125 g
(Active ingredient 100%) (0.005 for red iron oxide particles)
Corresponds to% by weight. ) Was added and mixed for 20 minutes to deposit the polyether-modified polysiloxane on the particle surface of the red iron oxide particles.

Next, while cooling with a Henschel mixer, the mixture was cooled to room temperature to obtain a red iron oxide powder having the surface of the particle coated with the polyether-modified polysiloxane.

In the obtained red iron oxide powder, the amount of the polyether-modified polysiloxane deposited was 0.003% by weight in terms of C.

Table 2 shows various conditions at this time.

Comparative Examples 7 to 13 Except that the type and amount of the iron oxide-based particles or the iron oxide hydroxide-based particles, the temperature of the heat treatment, the presence or absence of the modified polysiloxane treatment, the type, the amount, and the mixing temperature were variously changed. In the same manner as in Comparative Example 6, treated iron oxide-based particle powder or hydrous iron oxide-based particle powder was obtained.

Table 2 shows various conditions at this time.

Comparative Example 14 Same as Example 1 except that the type and amount of iron oxide-based particles or hydrous iron oxide-containing particles, the presence or absence of heat treatment, the amount of squaric acid, and the presence or absence of modified polysiloxane treatment were variously changed. Thus, treated iron oxide-based particle powder or hydrous iron oxide-based particle powder was obtained.

Table 2 shows various conditions at this time.

[0099]

[Table 1]

[0100]

[Table 2]

[0101] <Production of solvent-based paint containing iron oxide-based powder> Examples 7-12, Comparative Examples 15-28;

Example 7 10 g of the inorganic colored particle powder obtained in Example 1 was mixed in a 140 ml mayonnaise container, the coating composition was blended in the following proportions, and mixed with 90 g of 3 mmφ glass beads in a paint shaker for 45 minutes or 90 minutes. Then, a mill base was produced.

[0103]   12.2 parts by weight of iron oxide-based particle powder obtained in Example 1   Amino alkyd resin 19.5 parts by weight     (Amilak No 1026: Kansai Paint Co., Ltd.)   Thinner 7.3 parts by weight

Using the above mill base, the coating composition was blended in the following proportions, and further mixed and dispersed for 15 minutes on a paint shaker to obtain a solvent-based coating.

[0105]   Mill base 39.0 parts by weight   Amino alkyd resin 61.0 parts by weight     (Amilak No 1026: Kansai Paint Co., Ltd.)

For comparison, the same procedure as in Example 7 was carried out except that the polyether-modified polysiloxane BYK-080 was added to the solvent-based paint during the production of the solvent-based paint without depositing on the particle surfaces of the red iron oxide particles. A paint was produced (corresponding to the method described in JP-A-62-187772). The dispersion time of a coating film produced using this paint was 45.
The glossiness at the minute was 77%, the glossiness at the dispersing time of 90 minutes was 83%, and the decrease rate of the glossiness was -10%.

Examples 8 to 12 and Comparative Examples 15 to 28 Solvent-based paints were produced in the same manner as in Example 7 except that the type of iron oxide particles or iron oxide hydroxide particles was changed.

Table 3 shows various properties of the obtained solvent-based paint.

[0109]

[Table 3]

[0110] <Manufacture of water-based paint containing iron oxide-based particle powder> Examples 13-18, Comparative Examples 29-42;

Example 13 In a 140 ml glass container, 7.62 g of the inorganic colored particle powder obtained in Example 1 was used, and the coating composition was blended in the following proportions together with 90 g of 3 mmφ glass beads in a paint shaker for 45 minutes or 90 minutes. It was mixed and dispersed to prepare a mill base.

[0112]   12.4 parts by weight of iron oxide-based particle powder obtained in Example   Water-soluble alkyd resin 9.0 parts by weight     (Product name: S-118: manufactured by Dainippon Ink and Chemicals, Inc.)   Defoaming agent 0.1 part by weight     (Product name: Nopco 8034: manufactured by San Nopco Ltd.)   Water 4.8 parts by weight   Butyl cellosolve 4.1 parts by weight

Using the above mill base, the coating composition was blended in the following proportions and further mixed and dispersed for 15 minutes with a pain shaker to obtain a water-soluble coating.

[0114]   Mill base 30.4 parts by weight   Water-soluble alkyd resin 46.2 parts by weight     (Product name: S-118: manufactured by Dainippon Ink and Chemicals, Inc.)   Water-soluble melamine resin 12.6 parts by weight     (Product name: S-695: manufactured by Dainippon Ink and Chemicals, Inc.)   Defoaming agent 0.1 part by weight     (Product name: Nopco 8034: manufactured by San Nopco Ltd.)   Water 9.1 parts by weight   Butyl cellosolve 1.6 parts by weight

For comparison, a paint was prepared in the same manner as in Example 13 except that the polyether-modified polysiloxane BYK-080 was added to the paint during the production of the water-based paint without depositing on the particle surfaces of the red iron oxide particles. (Corresponding to the method described in Japanese Unexamined Patent Publication (Kokai) No. 62-187772). The dispersion time of the coating film produced using this coating material is 45
The glossiness at 68 minutes was 68%, the glossiness at a dispersion time of 90 minutes was 74%, and the reduction rate of glossiness was -13%.

Examples 14 to 18 and Comparative Examples 29 to 42 Aqueous paints obtained in the same manner as in Example 13 were produced except that the type of iron oxide particles or hydrous iron oxide particles was changed.

Table 4 shows various properties of the obtained water-based paint.

[0118]

[Table 4]

[0119] <Production of inorganic colored particle powder other than iron oxide type> Examples 19-24, Comparative Examples 43-56;

Example 19 Squaric acid 3,4-dihydroxy-3-cyclobutene-
30 g of 1,2-dione (manufactured by Tokyo Chemical Industry Co., Ltd.) was previously added to 5 l of pure water, and water was added to a squaric acid solution to make 25 l, which was well stirred with a stirrer. The concentration of squaric acid at this time was 1.2 g / l.

An average particle size of 0.27 was added to the above squaric acid solution.
3 kg of particulate titanium oxide particles having a size of 3 μm were gradually added, and after mixing and stirring for 30 minutes with a homomixer, filtration, drying and pulverization were performed to apply squaric acid to the particle surface of the titanium oxide particles.

The obtained titanium oxide particles had a square acid deposition amount of 0.40% by weight in terms of C.

2.5 kg of titanium oxide particles, the surface of which was coated with squaric acid, were put into a Henschel mixer (10 l) preheated to 90 ° C., and the mixture was operated and mixed at a rotation speed of 1200 rpm for 10 minutes to obtain a water content. Was removed to adjust the water content of the titanium oxide particles to 0.08% by weight.

While maintaining the temperature of the Henschel mixer at 85 ° C., polyether modified polysiloxane BYK-
080 (trade name) (manufactured by Big Chemie) 125 g
(Active ingredient 100%) 2 at the addition rate of 6.25 g / min
The mixture was added over 0 minutes and then mixed for 20 minutes to deposit the polyether-modified polysiloxane on the particle surfaces of the titanium oxide particles.

Then, the mixture was cooled to room temperature while mixing with a Henschel mixer to obtain a titanium oxide particle powder having a polyether-modified polysiloxane deposited on the particle surface.

The resulting titanium oxide particle powder had a polyether-modified polysiloxane coating amount of 2.56% in terms of C.

Table 5 shows various conditions at this time.

Examples 20 to 24 Examples except that the type and amount of inorganic colored particles, the temperature of heat treatment, the type and amount of squaric acid, the type and amount of modified polysiloxane treatment, and the mixing temperature were variously changed. 19
In the same manner as described above, a treated inorganic colored particle powder was obtained.

Table 5 shows various conditions at this time.

Comparative Examples 43 to 47 For comparison, untreated inorganic colored particles were prepared. Table 6 shows the characteristics of these inorganic colored particles.

Comparative Example 48 2.5 kg of granular titanium oxide particles having an average particle size of 0.27 μm
Henschel mixer (1
The water content of the titanium oxide particles was adjusted to 0.13% by weight.

While maintaining the Henschel mixer at a temperature of 80 ° C., a polyether-modified polysiloxane BYK-0
80 (trade name) (manufactured by Big Chemie Co., Ltd.) 0.125 g
(Active ingredient 100%) (0.000 for titanium oxide particles)
This corresponds to 5% by weight. ) Was added at an addition rate of 2.5 g / min, followed by mixing for 20 minutes to deposit the polyether-modified polysiloxane on the particle surface of the titanium oxide particles.

Then, the mixture was cooled to room temperature while mixing with a Henschel mixer to obtain titanium oxide particles having polyether modified polysiloxane deposited on the surface of the particles.

The obtained titanium oxide particle powder had a coating amount of polyether-modified polysiloxane of 0.003% by weight.

Comparative Examples 49 to 55 A treated inorganic material was prepared in the same manner as Comparative Example 48 except that the type and amount of the inorganic colored particles, the temperature of the heat treatment, the type and amount of the modified polysiloxane, and the mixing temperature were variously changed. A colored particle powder was obtained.

Table 6 shows various conditions at this time.

Comparative Example 56 Same as Example 19 except that the type and amount of inorganic colored particles, presence or absence of heat treatment, amount of squaric acid, type and amount of modified polysiloxane treatment, and mixing temperature were variously changed. To obtain a treated inorganic colored particle powder.

[0138]

[Table 5]

[0139]

[Table 6]

<Manufacture of Solvent-based Paints Containing Colored Particle Powders Other Than Iron Oxide> Examples 25-30, Comparative Examples 57-70;

Example 25 10 g of the titanium oxide particle powder obtained in Example 19 was used in a 140 ml mayonnaise container, the coating composition was blended in the following proportions, and mixed with 90 g of 3 mmφ glass beads in a paint shaker for 45 minutes or 90 minutes. Then, a mill base was produced.

[0142]   12.2 parts by weight of titanium oxide particle powder obtained in Example 19   Amino alkyd resin 19.5 parts by weight     (Amilak No 1026: Kansai Paint Co., Ltd.)   Thinner 7.3 parts by weight

Using the above-mentioned mill base, the coating composition was blended in the following proportions and further mixed and dispersed for 15 minutes with a paint shaker to obtain a solvent-based coating.

[0144]   Mill base 39.0 parts by weight   Amino alkyd resin 61.0 parts by weight       (Amilak No 1026: Kansai Paint Co., Ltd.)

For comparison, the same procedure as in Example 25 was carried out except that the polyether-modified polysiloxane BYK-080 was added to the hematite particles during the production of the solvent-based paint without depositing on the particle surfaces of the hematite particles. A paint was produced (corresponding to the method described in JP-A-62-187772). A coating film produced using this paint has a glossiness of 76% and a dispersion time of 45 minutes when the dispersion time is 45 minutes. At 90 minutes, the glossiness was 78%, and the glossiness reduction rate was -12%.

Examples 26 to 30 and Comparative Examples 57 to 70 Solvent-based paints were produced in the same manner as in Example 25 except that the kind of the inorganic colored particle powder was variously changed.

Table 7 shows various properties of the obtained solvent-based coating material.

[0148]

[Table 7]

[0149] <Manufacture of water-based paint containing colored particle powder other than iron oxide> Examples 31-36, Comparative Examples 71-84;

Example 31 7.62 g of the titanium oxide particle powder obtained in Example 19 was used in a 140 ml glass container and the coating composition was blended in the following proportions together with 90 g of 3 mmφ glass beads in a paint shaker for 45 minutes or 90 minutes. It was mixed and dispersed to prepare a mill base.

[0151]   12.4 parts by weight of titanium oxide particle powder obtained in Example 19   Water-soluble alkyd resin 9.0 parts by weight     (Product name: S-118: manufactured by Dainippon Ink and Chemicals, Inc.)   Defoaming agent 0.1 part by weight     (Product name: Nopco 8034: manufactured by San Nopco Ltd.)   Water 4.8 parts by weight   Butyl cellosolve 4.1 parts by weight

Using the above mill base, the coating composition was blended in the following proportions and further mixed and dispersed with a pain shaker for 15 minutes to obtain a water-soluble coating.

[0153]   Mill base 30.4 parts by weight   Water-soluble alkyd resin 46.2 parts by weight     (Product name: S-118: manufactured by Dainippon Ink and Chemicals, Inc.)   Water-soluble melamine resin 12.6 parts by weight     (Product name: S-695: manufactured by Dainippon Ink and Chemicals, Inc.)   Defoaming agent 0.1 part by weight       (Product name: Nopco 8034: manufactured by San Nopco Ltd.)   Water 9.1 parts by weight   Butyl cellosolve 1.6 parts by weight

For comparison, the same procedure as in Example 31 was carried out except that polyether-modified polysiloxane BYK-080 was added to the water-based paint during the production thereof without depositing on the surface of the titanium oxide particles. A paint was produced (corresponding to the method described in JP-A-62-187772). A coating film produced by using this paint has a glossiness of 64% and a dispersion time of 45 minutes when the dispersion time is 45 minutes. At 90 minutes, the glossiness was 73% and the glossiness reduction rate was -14%.

Examples 32 to 36, Comparative Examples 71 to 84 Water-based paints obtained in the same manner as in Example 31 were manufactured except that the kind of the inorganic colored particle powder was variously changed.

Table 8 shows various properties of the obtained water-based paint.

[0157]

[Table 8]

[0158]

INDUSTRIAL APPLICABILITY As described in the above-mentioned Examples, the inorganic colored particle powder according to the present invention is an inorganic coloring material excellent in easy dispersibility, dispersion uniformity, and dispersion stability in paints, especially in water-based paints. Since it is a particle powder, it is suitable as an inorganic colored particle powder for paints.

Further, in the water-based paint according to the present invention, the paint constituent base material, especially the inorganic colored particle powder blended in the water-based paint constituent base material is excellent in easy dispersibility, dispersion uniformity and dispersion stability. Due to this, it has excellent storage stability.

─────────────────────────────────────────────────── ─── Continuation of front page (56) Reference JP-A-6-166829 (JP, A) (58) Fields investigated (Int.Cl. ⁷ , DB name) C09C 1/00-3/12 C09D 4 / 00-201/10

Claims (3)

(57) [Claims] 1. A surface of the particle is coated with squaric acid, and the surface of the deposited square acid is further modified with a polyether modified polysiloxane represented by Chemical formula 1, a polyester modified polysiloxane represented by Chemical formula 2, and An inorganic colored particle powder comprising inorganic colored particles coated with one or more specific modified polysiloxanes selected from the aralkyl modified polysiloxanes shown in Chemical formula 3. [Chemical 1] [Chemical 2] [Chemical 3] 2. A water suspension containing inorganic colored particles and squaric acid is mixed, filtered, and dried to deposit squaric acid on the particle surface of the inorganic colored particles. The inorganic color particles that have been deposited and the specific modified polysiloxane according to claim 1 are mixed at a temperature of 80 ° C. or higher to deposit the specific modified polysiloxane on the surface of the deposited square acid. The method for producing the inorganic colored particle powder according to claim 1. 3. A water-based paint, characterized in that the inorganic colored particle powder according to claim 1 is blended in a water-based paint constituent base material.