JP2001172526A - Yellow pigment, and coating material and resin composition prepared by using same - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a yellow pigment which is nonpolluting, is excellent in heat resistance, has a strong coloring power, and exhibits yellow color with a stronger yellowish tint. SOLUTION: This yellow pigment comprises (A) a composite metal oxide powder which is based basically on Fe, Ti, and Li, has a crystal phase mainly comprising a pseudobrookite structure, and has an average particle size of 0.1-2.0 μm, (B) a cover layer which is formed from an organosilane compound or a polysiloxane derived from an alkoxysilane and covers the surfaces of particles of the metal oxide powder, and (C) 1-30 pts.wt. (based on 100 pts.wt. metal oxide powder) organic yellow pigment attached to the cover layer.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

The present invention relates to a non-polluting,
The present invention relates to a yellow pigment which is excellent in heat resistance, has a large coloring power, and exhibits a more yellowish yellow.

The main use of the yellow pigment according to the present invention is as a colorant for paints and resin compositions.

[0003]

2. Description of the Related Art Conventionally, as an inorganic yellow pigment, graphite (P
bCrO ₄ ) or cadmium yellow (CdS · nZn)
S) and the like are used, but since graphite has harmful metals Pb and Cr, and cadmium yellow contains harmful metal Cd, there is a problem in safety and hygiene. That is, when a yellow paint or a yellow resin composition using these as a yellow pigment is used outdoors, the coating film or the resin molded product is exposed to a harsh environment such as ultraviolet rays or acid rain, thereby reducing the P value.
Since harmful metals such as b, Cr, and Cd are eluted and cause environmental pollution and the like, harmless yellow pigments are required.

[0004] Next, when a yellow pigment is used as a colorant for a paint or a resin composition, it is required not only to have excellent coloring power but also to have excellent heat resistance in the production process.

That is, a paint using a yellow pigment, in particular, a road marking paint (traffic paint) contains two paint compositions.
It is manufactured by heating and melting at a high temperature of 00 to 260 ° C.

A resin composition using a yellow pigment is prepared by heating and kneading a mixture of a thermoplastic resin such as polyethylene, polypropylene, styrene polymer, polyamide, polyolefin, and ABS with a yellow pigment at a high temperature of 200 to 260 ° C. , And then molded.

Conventionally, harmless yellow pigments include inorganic pigments such as goethite (α-FeOOH), composite metal oxide particles having a basic composition of Fe and Ti, Hansa Yellow, and the like.
Organic pigments such as benzidine yellow, pigment yellow and permanent yellow are known.

[0008]

A yellow pigment that is non-polluting, has excellent heat resistance, high coloring power, and exhibits a more yellowish yellow color has been most demanded at present. A yellow pigment satisfying these properties has not yet been obtained.

That is, the known goethite (α-FeO)
OH) has a yellow color and has no problem in terms of color. However, goethite has a crystal structure that changes by heating and dehydration at a temperature of about 230 ° C. or more, so that hematite (α- Fe ₂ O ₃ ), resulting in poor heat resistance. And coloring power is not enough.

Various attempts have been made on the above-mentioned known yellow pigment mainly composed of metal oxide particles having a basic composition of Fe and Ti, for example, pseudo-brookite lattice (pseudobrookite type structure) and titanium dioxide. An inorganic yellow pigment comprising a solid solution of the above (JP-A-50-51128) and a pigment comprising a titanium oxide / iron oxide composite sol (JP-A-8-239223) are known.

[0011] Further, as a metal oxide particle powder comprising Fe and Ti further containing another metal element,
For example, a yellow inorganic pigment comprising metal oxide particles of titanium, iron and molybdenum (JP-A-60-42236), a yellow pigment comprising a mixture of a pseudobrookite-type structure and a rutile-type structure in which Al is dissolved ( JP-A-8-732
No. 24) and heat-resistant inorganic pigment powders made of metal oxide particles with Fe, Ti and other metals (Japanese Patent Application Laid-open No.
221323) is known.

As the composite metal oxide particles of Fe and Ti containing an alkali metal element, a pigment containing a metal oxide having a rutile or polyrutile structure or a metal fluorine compound as a main component (Japanese Patent Publication No. 37-3460), a yellow to flesh-colored pigment obtained by firing a mixture of a specific composition comprising an alkali metal compound, a ferric compound and titanium dioxide (Japanese Patent Publication No. 3-2158).
No. 0) is known.

Further, the present inventor has proposed a yellow pigment exhibiting yellowness excellent in environmental resistance such as acid resistance and alkali resistance as F pigment.
A yellow pigment having a basic composition of e, Ti, and Li and mainly containing a pseudobrookite-type crystal phase has been developed (Japanese Patent Application Laid-Open No. 2000-203845).

However, any of these yellow pigments mainly composed of composite metal oxide particles having a basic composition of Fe and Ti has excellent heat resistance, but has extremely poor coloring power and hue. Insufficient yellowness.

The above-mentioned known organic yellow pigments exhibit a stronger yellowish color and a higher coloring power, but have a heat resistance of at most 200 ° C. and a poor heat resistance.

Accordingly, it is a technical object of the present invention to obtain a yellow pigment which is non-polluting, has excellent heat resistance, has high coloring power, and exhibits a yellowish yellow color.

[0017]

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

That is, the present invention relates to a metal oxide particle powder having a basic composition of Fe, Ti and Li and having a pseudobrookite type crystal phase as a main component and having an average particle diameter of 0.1 to 2.0 μm. The particle surface is coated with an organosilane compound or polysiloxane formed from alkoxysilane, and is composed of a yellow composite metal oxide particle powder having an organic yellow pigment adhered to the coating. It is a yellow pigment characterized by being 1 to 30 parts by weight based on 100 parts by weight of metal oxide particles (Invention 1).

Further, according to the present invention, the metal oxide particles have a particle surface in which aluminum hydroxide,
A yellow pigment characterized by being coated with an intermediate coating comprising at least one selected from an oxide of aluminum, a hydroxide of silicon and an oxide of silicon (Invention 2).

Further, the present invention is a paint characterized in that the yellow pigment according to the present invention 1 or 2 is blended in a paint constituting base material.

Further, the present invention is a resin composition characterized by being colored using the yellow pigment described in the present invention 1 or 2.

The configuration of the present invention will be described in detail as follows.

First, the yellow pigment according to the present invention will be described.

The yellow pigment according to the present invention has a basic composition of core particle powders of Fe, Ti and Li, and has an alkoxy powder on the surface of a metal oxide particle powder mainly composed of a pseudobrookite type crystal phase. The composite metal oxide particles are coated with an organosilane compound or polysiloxane formed from silane and have an organic yellow pigment adhered to the coating.

The basic composition of the core particle powder in the present invention is as follows:
17 to 55 atomic% of Fe, preferably 20 to 48 atomic%
Where Ti is 40 to 62 atomic%, preferably 4 atomic%.
5 to 62 atomic%, and Li is 5 to 22 atomic%.
Preferably, it is in the range of 5 to 20 atomic%. If the composition is out of the above-mentioned range, it is difficult to obtain a yellow pigment having a stronger yellow tint as the object of the present invention.

The core particle powder is composed of a crystal phase mainly composed of a crystal phase having a pseudobrookite structure.

The composition formula of the crystal phase of the pseudobrookite type structure is Fe _2-xy Li _x Ti _y TiO ₅ (0.15 ≦ x ≦ 0.66, 0.2 ≦ y ≦ 0.86), The crystal system is orthorhombic.

The pseudobrookite-type crystal phase present in the core particle powder is preferably 60 to 100%, more preferably 80 to 100% by volume of the total crystal phase calculated from the integrated intensity of the X-ray diffraction pattern. %. 60
%, It is difficult to obtain a yellow pigment having a stronger yellow tint, which is the object of the present invention.

The crystal phases other than the pseudobrookite structure include a rutile structure and a spinel structure.

The crystal phase having a rutile structure has a volume ratio of 20%
And preferably less than 10%. When the content is 20% or more, it is difficult to obtain a yellow pigment having a stronger yellowish color than desired.

Further, a crystal phase having a spinel structure (Li _x T
i _2x-1 Fe _4-3x O ₄ , 0.5 ≦ x ≦ 1.33, solid solution type) is less than 10% by volume, preferably 5% or less. Since the crystal phase having a spinel structure has a brown color, the presence of an excessive amount of the crystal phase having a spinel structure causes a brownish color. Therefore, it is difficult to obtain a yellow pigment having a stronger yellowish color, which is the object of the present invention.

The particle shape of the core particle powder is granular.

The core particle powder has an average particle diameter of 0.1 to
It is 2.0 μm, preferably 0.1 to 1.0 μm.

When the average particle diameter of the core particle powder exceeds 2.0 μm, the obtained yellow pigment also becomes coarse and the coloring power is reduced. When the average particle diameter is less than 0.1 μm, aggregation tends to occur due to an increase in intermolecular force due to finer particles, so that the surface of the core particle powder is uniformly coated with alkoxysilane or polysiloxane, Uniform adhesion treatment with yellow pigment becomes difficult.

The coloring power of the core particle powder is determined by the following method.
, And 70% or more, preferably 80% or more, and the upper limit thereof is about 110%.

The hue of the core particle powder has an L ^* value (brightness) of 4
8 or more, preferably 55 or more, the upper limit is 85, and the a ^* value is +8 to +25, preferably +10 to +22.
Wherein the b ^* value is between +30 and +50, preferably +35
To +50, and is yellow.

The heat resistance of the core particle powder is 600 ° C. or higher.

The core particle powder according to the present invention may comprise, if necessary, at least a part of Fe and Ti of the metal oxide particle powder having a basic composition of Fe, Ti and Li, of Al or Mg.
Alternatively, it may be substituted with any of Al and Mg.

The composition range of the core particle powder substituted with Al or Mg is such that the composition range of Fe, Ti and Li is 1%.
5 to 55 at%, preferably 16 to 45 at%, Ti 25 to 65 at%, preferably 25 to 62 at%, Li
Is 5 to 22 at%, preferably 6 to 21 at%, Al is in the range of 1 to 30 at%, preferably 1 to 20 at% with respect to the total metal, and Mg is with respect to the total metal. In the range of 1 to 20 atomic%, preferably 1 to 15 atomic%, and when substituting with Al and Mg, the total amount is in the range of 1 to 30 atomic%, preferably 1 to 20 atomic% with respect to all metals. It is. When Fe, Ti, and Li are out of the above range,
It is difficult to obtain a yellow pigment having a stronger yellow tint, which is the object of the present invention.

When Al exceeds 30 atomic%, a crystal phase having a hematite, alumina, or rutile type structure is produced as a by-product in addition to the core particle powder, so that a yellow pigment having a more yellowish color can be obtained. It will be difficult.

When Mg exceeds 20 atomic%, a crystal phase having a structure of MgO, hematite and rutile is produced as a by-product in addition to the core particle powder, so that a yellow pigment having a stronger yellowish color can be obtained. It will be difficult.

When the total amount of Al and Mg exceeds 30 atomic%, hematite, alumina, a crystalline phase having a rutile structure and MgO are produced as by-products in addition to the core particle powder, and the yellowishness is stronger than the object of the present invention. It becomes difficult to obtain a yellow pigment.

The core particles that are substituted with Al or Mg is made crystal phase composed mainly of crystalline phases of pseudobrookite type structure, composition formula of the crystal phase _{Fe 2-pqrs Li p Mg q} Al r Ti _s O ₅ (provided that 0.15 <p <0.66, 0.03 <q <0.
60, 0.03 <r <0.90, 0.75 <s <1.9
5).

The core particle powder substituted with Al or Mg has various properties such as hue, average particle diameter, coloring power and heat resistance, as well as the crystal system, lattice constant, type and volume ratio of the existing crystal phase. It is equivalent to a core particle powder not substituted with Al or Mg.

The particle shape and the particle size of the yellow pigment according to the present invention depend on the particle shape and the particle size of the metal oxide particles as the core particles, and are substantially equal to the particle shape and the particle size of the core particles.

That is, the yellow pigment according to the present invention has an average particle size of 0.1 to 2.0 μm, preferably 0.1 to 1.0 μm.
m.

When the average particle size of the yellow pigment exceeds 2.0 μm, the coloring power is reduced as the particle size increases, and the particle size is too large, so that the uniform dispersion in the vehicle or the resin composition may occur. It will be difficult. When the average particle diameter is less than 0.1 μm, the coloring power is reduced due to the finer particles, and the aggregation is likely to occur due to the increase in the intermolecular force due to the finer particles. Becomes difficult to disperse.

The yellow pigment according to the present invention has the same particle shape as the particle shape of the core particle powder.

The desorption rate of the organic yellow pigment of the yellow pigment according to the present invention is preferably 15% or less, more preferably 12% or less. When the desorption rate of the organic yellow pigment exceeds 15%, the desorbed organic yellow pigment may hinder uniform dispersion in a vehicle or a resin composition, and the core of the desorbed portion may be hindered. Since the hue of the particle powder appears on the particle surface of the composite metal oxide particle powder, it is difficult to obtain a uniform hue.

The hue of the yellow pigment according to the present invention has an L ^* value of 25 to 80, preferably 30 to 80 and an a ^* value of -30 to +30, preferably -25 to +25,
b ^* value of +55 to +100, preferably +60 to +10
It is in the range of 0. When each of the L ^* value, the a ^* value, and the b ^* value is out of the above range, a yellow pigment exhibiting a yellow hue with a stronger yellow tint cannot be obtained.

The coloring power of the yellow pigment according to the present invention is preferably 130% or more, more preferably 135% or more, based on the later-described core particles 1, and the upper limit thereof is 170%.

The heat resistance of the yellow pigment according to the present invention is 270.
° C or higher, preferably 275 ° C or higher, more preferably 28 ° C or higher.
0 ° C. or higher, and its upper limit is 350 ° C.

The organosilane compound formed from alkoxysilane in the present invention (hereinafter referred to as "organosilane compound") is an organosilane compound formed from alkoxysilane represented by the following chemical formula 1.

[0054]

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As the alkoxysilane, specifically,
Methyltriethoxysilane, dimethyldiethoxysilane, phenyltriethoxysilane, diphenyldiethoxysilane, dimethyldimethoxysilane, methyltrimethoxysilane, phenyltrimethoxysilane, diphenyldimethoxysilane, isobutyltrimethoxysilane, decyltrimethoxysilane, etc. Can be

In consideration of the desorption rate and adhesion effect of the organic yellow pigment, an organosilane compound formed from methyltriethoxysilane, methyltrimethoxysilane, dimethyldimethoxysilane, isobutyltrimethoxysilane, and phenyltriethoxysilane is preferable. Most preferred are organosilane compounds formed from triethoxysilane and methyltrimethoxysilane.

As the polysiloxane in the present invention, a polysiloxane represented by Chemical Formula 2, a modified polysiloxane represented by Chemical Formula 3, a terminal modified polysiloxane represented by Chemical Formula 4, or a mixture thereof can be used.

[0058]

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[0059]

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[0060]

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In consideration of the desorption rate and adhesion effect of the organic yellow pigment, polysiloxanes having methyl hydrogen siloxane units, polyether-modified polysiloxanes, and carboxylic acid-modified polysiloxanes whose terminals have been modified with carboxylic acids are preferred.

The coating amount of the organosilane compound or polysiloxane is preferably 0.02 to 5.0% by weight in terms of Si with respect to the organosilane compound-coated core particle powder or the polysiloxane-coated core particle powder. , More preferably 0.03 to 4.0% by weight, and even more preferably 0.05 to 3.0% by weight.

When the amount is less than 0.02% by weight, it is difficult to obtain a yellow pigment intended for the present invention.

By coating the organosilane compound or polysiloxane in an amount of 0.02 to 5.0% by weight, 1 to 30 parts by weight of the organic yellow pigment can be adhered to 100 parts by weight of the core particle powder. There is no point in covering above.

The organic yellow pigments of the present invention include Hansa Yellow GR, Hansa Yellow G, Hansa Yellow 3G, Hansa Yellow 5G, Hansa Yellow 10G, Hansa Yellow A, Hansa Yellow RN, Hansa Yellow R, Pigment Yellow L, Benzidine Yellow G, Benzidine Yellow G, Benzidine Yellow GR, Permanent Yellow NCG, Vulcan Fast Yellow 5G, Vulcan Fast Yellow R, Permanent Yellow FGL, Permanent Yellow H10G, Permanent Yellow HR
Hansa Yellow GR, Hansa Yellow G, Hansa Yellow 3
It is preferable to use G, Hansa Yellow R, Pigment Yellow L, Permanent Yellow FGL, Benzidine Yellow, Benzidine Yellow G, Benzidine Yellow GR.

The amount of the organic yellow pigment adhered was determined based on the core particle powder 10
It is 1 to 30 parts by weight with respect to 0 parts by weight.

When the amount is less than 1 part by weight or more than 30 parts by weight, it becomes difficult to obtain a yellow pigment having a stronger yellowish color, which is the object of the present invention. It is more preferably 3 to 30 parts by weight, and still more preferably 5 to 30 parts by weight.

The yellow pigment according to the present invention, if necessary, has a particle surface of the core particle powder which is selected from the group consisting of aluminum hydroxide, aluminum oxide, silicon hydroxide and silicon oxide. Alternatively, it may be coated with two or more kinds of intermediate coatings, and the amount of the organic yellow pigment detached from the particle surface of the composite metal oxide particle powder is further reduced as compared with the case where the coating is not coated with the intermediate coating. Can be.

The amount of the coating with the intermediate coating is 0.01 to 1000 in terms of Al, SiO _2, or the sum of the Al conversion and the SiO ₂ conversion with respect to the core particle powder coated with the intermediate coating.
20% by weight is preferred.

If the amount is less than 0.01% by weight, it is difficult to obtain the effect of reducing the rate of desorption of the organic yellow pigment. 0.01 ~
Since the effect of reducing the desorption rate of the organic yellow pigment is sufficiently obtained with the coating amount of 20% by weight, it is meaningless to cover more than 20% by weight more than necessary.

The yellow pigment according to the present invention coated with the intermediate coating has a particle size, tinting strength and the like which are almost the same as those of the yellow pigment according to the present invention not coated with the intermediate coating.
Has hue and heat resistance. Further, the desorption rate of the organic yellow pigment is improved by coating the intermediate coating, and the desorption rate is preferably 12% or less, more preferably 10% or less.

Next, a paint containing the yellow pigment according to the present invention will be described.

The paint containing the yellow pigment according to the present invention is
The heat-resistant temperature of the coating film is 260 ° C. or higher, preferably 265 ° C. or higher, and the upper limit is 320 ° C.
L ^* value is 30-85, preferably 35-85,
a ^* values of -30 to +30, preferably -25 to +25, and b ^* values of +55 to +100, preferably +60.
~ + 100. And the glossiness of the coating film is 75 to 11
0%, preferably 80 to 110%.

The coating material containing the yellow pigment according to the present invention in which the core particle surface is coated with the intermediate coating has a heat-resistant temperature of the coating film of 265 ° C. or more, preferably 270 ° C. or more, and the upper limit is 320 ° C. The L ^* value of the hue of the coating film is 30 to
85, preferably 35-85, wherein the a ^* value is -30
+30, preferably -25 to +25, and the b ^* value is +55 to +100, preferably +60 to +100. And the glossiness of a coating film is 80 to 115%, preferably 85 to 115%.

Water-based paint containing the yellow pigment according to the present invention
Has a heat resistant temperature of 255 ° C. or more, preferably 260 ° C.
℃ or higher, the upper limit is 320 ℃, the hue of the coating film
Is L ^*Values between 30 and 85, preferably between 35 and 85
And a^*Value is -30 to +30, preferably -25 to +2
5 and b^*Value +55 to +100, preferably +
60 to +100. And the glossiness of the coating film is 75-
It is 115%, preferably 80 to 115%.

The water-based paint containing the yellow pigment according to the present invention, whose particle surface is coated with an intermediate coating, has a heat resistance temperature of the coating film of 260 ° C. or higher, preferably 265 ° C. or higher, and its upper limit is 320 ° C. The hue of the coating film is L ^* value of 3.
0 to 85, preferably 35 to 85, wherein the a ^* value is-
30 to +30, preferably -25 to +25, and b
^* Value is +55 to +100, preferably +60 to +100
It is. And the glossiness of a coating film is 75-115%, preferably 80-115%.

The mixing ratio of the yellow pigment in the paint according to the present invention is 1.0 to 1 with respect to 100 parts by weight of the paint constituting base material.
It can be used in the range of 00 parts by weight, and preferably 2.0 to 100 parts by weight, more preferably 5.0 to 100 parts by weight, in consideration of the handling of the paint.

As the base material for the coating composition, a resin, a solvent, and if necessary, an antifoaming agent, an extender, a drying accelerator, a surfactant, a curing accelerator, an auxiliary agent and the like are blended.

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 and the like which are generally used for solvent-based paints can be used. For water-based paints, commonly used water-soluble alkyd resins, water-soluble melamine resins, water-soluble acrylic resins,
A water-soluble urethane emulsion resin or the like can be used.

As the solvent, toluene, xylene, thinner, butyl acetate, methyl acetate, methyl isobutyl ketone, butyl cellosolve, ethyl cellosolve, butyl alcohol, aliphatic hydrocarbon and the like which are usually used for solvent-based paints are used. Can be used.

As the solvent for water-based paint, water and butyl cellosolve, butyl alcohol and the like usually used in water-based paint can be mixed and used.

As defoaming agents, Nopco 8034 (trade name), SN deformer 477 (trade name), SN deformer 5013 (trade name), SN deformer 247
(Trade name), SN Deformer 382 (Trade name) (all manufactured by San Nopco Co., Ltd.), Anti-Home 0
Commercial products such as No. 8 (trade name) and Emulgen 903 (trade name) (both manufactured by Kao Corporation) can be used.

Next, a resin composition colored using the yellow pigment according to the present invention will be described.

The resin composition colored by using the yellow pigment according to the present invention has a heat resistance temperature of 220 ° C. or higher, preferably 225 ° C. or higher, and a hue having an L ^* value of 30 to 8.
5, preferably 35 to 85, wherein the a ^* value is -30 to
+30, preferably -25 to +25, and the b ^* value is +55 to +100, preferably +60 to +100. The dispersed state by visual observation is 4 or 5, preferably 5, according to the evaluation method described later.

The resin composition colored with the yellow pigment according to the present invention, whose particle surface is coated with an intermediate coating,
The heat-resistant temperature of the resin composition is 225 ° C. or more, preferably 23
At 0 ℃ or higher, hue, L ^* value is 30 to 85, preferably a 35 to 85, a ^* value is -30 30, preferably a -25 to + 25, b ^* value + 55 +10
0, preferably +60 to +100. The dispersed state by visual observation is 4 or 5, preferably 5, according to the evaluation method described later.

The compounding ratio of the yellow pigment in the resin composition according to the present invention is 0.5 to 2 with respect to 100 parts by weight of the resin.
It can be used in the range of 00 parts by weight, and in consideration of handling of the resin composition, preferably 1.0 to 150 parts by weight.
Parts by weight, more preferably 2.5 to 100 parts by weight.

As the constituent base material in the resin composition according to the present invention, a lubricant, a plasticizer, an antioxidant, an ultraviolet absorber, if necessary, together with a yellow pigment and a well-known thermoplastic resin,
Additives such as various stabilizers are blended.

As the resin, natural rubber, synthetic rubber, thermoplastic resin (eg, polyolefin such as polyethylene, polypropylene, polybutene, polyisobutylene, polyvinyl chloride, styrene polymer, polyamide, etc.) can be used.

The amount of the additive may be 50% by weight or less based on the total amount of the yellow pigment and the resin. When the content of the additive exceeds 50% by weight, the moldability decreases.

The resin composition according to the present invention is obtained by thoroughly mixing the resin raw material and the yellow pigment in advance, and then applying a strong shearing action under heating using a kneader or an extruder to form an aggregate of the yellow pigment. After breaking and uniformly dispersing the yellow pigment in the resin composition, the resin composition is molded into a shape suitable for the purpose and used.

Next, a method for producing the yellow pigment according to the present invention will be described.

The core particle powder in the present invention is prepared by mixing a predetermined amount of an Fe compound, a Ti compound, a Li compound, an Al compound or a Mg compound, or an Al compound and a Mg compound as necessary, and then firing the mixture at a temperature of 700 to 1100 ° C. The obtained calcined product can be obtained by pulverizing and, if necessary, performing a washing treatment and a classification.

The Fe compound in the present invention includes
Iron salts such as iron chloride, iron nitrate, iron oxalate, iron sulfate, goethite (α-FeOOH), and akagenite (β-FeOO)
H), hydrous iron oxide such as lipid crocite (γ-FeOOH), hematite (α-Fe ₂ O ₃ ), maghemite (γ-Fe ₂ O ₃ ), magnetite (Fe ₃ O ₄ ), belt ride, etc. Any metallic iron such as iron oxide and iron powder can be used.

The particle size of the Fe compound particles is 0.01 to 2.
Those having a thickness of 0 μm are preferred.

The mixing ratio of the Fe compound particles is 17 to 55.
Atomic%, preferably 20 to 45 atomic%.

When the Al compound and the Mg compound are mixed together, the mixing ratio of the Fe compound is 15 to 55 atomic%, preferably 16 to 45 atomic%.

The Ti compound in the present invention includes:
Titanium dioxide (TiO ₂ ) such as TiO ₂ .nH ₂ O, rutile type or anatase type and non-stoichiometric titanium oxide (TiO _x ) can be used.

The particle size of the Ti compound is 0.01 to 0.8 μm.
m is preferred.

The mixing ratio of the Ti compound is 40 to 62 atomic%, preferably 45 to 60 atomic%.

When the Al compound and the Mg compound are mixed together, the mixing ratio of the Ti compound is 25 to 65 atomic%, preferably 25 to 62 atomic%.

In the present invention, the Li compound includes lithium carbonate, lithium acetate, lithium nitrate, lithium sulfate,
Lithium chloride or the like can be used.

The mixing ratio of the Li compound is 5 to 30 atomic%, preferably 10 to 20 atomic%.

It is to be noted that an oxide of Fe and Ti can be used instead of the Fe compound and the Ti compound.
TiO ₃ (ilmenite), Fe ₂ TiO ₅ (pseudobrookite) or the like can be used. In addition, the Ti
An oxide of Ti and Li can be used instead of the compound and the Li compound, and lithium titanate (Li ₂ Ti
O ₃ ) can be used.

In the present invention, the Al compound includes
Boehmite, gibbsite, Al (OH) ₃ , aluminum nitrate, aluminum chloride and the like can be used.

The particle size of the Al compound is 0.01 to 2.0 μm.
m is preferred.

The mixing ratio of the Al compound is 1 to all metals.
It is preferably from 30 to 30 at%, more preferably from 1 to 20 at%.

The Mg compound in the present invention includes:
Magnesium oxide, magnesium hydroxide, basic magnesium carbonate, magnesium nitrate, magnesium chloride and the like can be used.

The particle size of the Mg compound is 0.01 to 2.0 μm.
m is preferred.

The mixing ratio of the Mg compound was 1 to all metals.
-20 at%, preferably 1-15 at%.

In the present invention, the Al compound and the M
As the g compound, each of the above compounds may be used, or a compound containing both Mg and Al, such as hydrotalcite, may be used.

When both an Al compound and a Mg compound are used, the mixing ratio is preferably from 1 to 30 at%, more preferably from 2 to 28 at%, based on all metals.

In the present invention, the Fe compound, the Ti compound and the Li compound, and if necessary, the Al compound or the Mg compound or the mixture of the Al compound and the Mg compound may be any of a dry method and a wet method. What is necessary is just to carry out with a paddle, a planetary ball mill, a dry ball mill, etc.

The firing temperature in the present invention is 700 to 110.
0 ° C, preferably 800 to 1050 ° C. 1100
If the heating and sintering is performed at a temperature exceeding ℃, the sintering between the particles progresses, and the growth of coarse particles may occur or the pulverization may become difficult. When lithium carbonate is used as a raw material, heating and firing can be performed at a relatively low temperature due to the effect of the flux.

The firing atmosphere is an oxidizing atmosphere such as in air. Under a reducing atmosphere, the iron component is reduced and Fe ²⁺ ions are mixed, so that the hue is undesirably darkened.

The pulverization can be carried out by a conventional method, for example, by a free-type pulverizer, a jet mill, a colloid mill, a sand mill, an edge runner, a grinder or the like.

Note that the washing treatment and the classification may be performed as needed.

The yellow pigment according to the present invention is obtained by mixing the core particle powder with the alkoxysilane or polysiloxane, coating the particle surface of the core particle powder with the alkoxysilane or polysiloxane, and then coating with the alkoxysilane or the polysiloxane. The powder can be obtained by mixing the powdered core particles with an organic yellow pigment.

The core particle powder is coated with the alkoxysilane or polysiloxane by mechanically mixing and stirring the core particle powder and the alkoxysilane or polysiloxane, or by spraying the core particle powder with the alkoxysilane or polysiloxane. May be mixed and stirred. Almost all of the added alkoxysilane or polysiloxane is coated on the particle surface of the core particle powder.

Incidentally, the coated alkoxysilane may be partially coated as an organosilane compound generated from the alkoxysilane, which is generated through a coating step. Even in this case, the subsequent attachment of the organic yellow pigment is not affected.

Mixing and stirring of the core particle powder and the alkoxysilane or polysiloxane or mixing and stirring of the organic yellow pigment and the core particle powder having the particle surface coated with an organosilane compound or polysiloxane formed from the alkoxysilane. As a device for the device, a device capable of applying a shearing force to the powder layer is preferable, and in particular, a device capable of simultaneously performing shearing, spatula and compression, such as a wheel-type kneader, a ball-type kneader, and a blade-type kneader A kneader or a roll-type kneader can be used. In practicing the present invention, a wheel-type kneader can be used more effectively.

Specific examples of the wheel type kneader include edge runners (synonyms for “mix miller”, “Simpson mill”, and “sand mill”), multimul, stots mill, wet pan mill, conner mill, and ring miller. And the like, preferably an edge runner, a multiple, a Stotts mill, a wet pan mill, and a ring muller, and more preferably an edge runner. Examples of the ball-type kneader include a vibration mill and the like. Specific examples of the blade type kneader include a Henschel mixer, a planetary mixer, and a Nauta mixer. Specific examples of the roll-type kneader include an extruder.

The conditions during mixing and stirring are such that the linear load is 19.6 to 1 so that the alkoxysilane or polysiloxane is coated as uniformly as possible on the surface of the core particle powder.
960 N / cm (2-200 kg / cm), preferably 98-1470 N / cm (10-150 kg / cm);
More preferably, 147 to 980 N / cm (15 to 100 N / cm)
Kg / cm), the treatment time is 5 to 120 minutes, preferably 1
The processing conditions may be appropriately adjusted within a range of 0 to 90 minutes. The stirring speed is 2 to 2000 rpm, preferably 5 to 1
The processing conditions may be appropriately adjusted within the range of 000 rpm, more preferably in the range of 10 to 800 rpm.

The addition amount of the alkoxysilane or polysiloxane is 0.15 to 4 parts by weight per 100 parts by weight of the core particle powder.
5 parts by weight are preferred. If less than 0.15 parts by weight,
It is difficult to attach an organic yellow pigment sufficient to obtain a desired yellow pigment. With the addition amount of 0.15 to 45 parts by weight, 1 to 30 parts by weight of the organic yellow pigment can be attached to 100 parts by weight of the core particle powder.
There is no point in adding more than 5 parts by weight more than necessary.

Then, an organic yellow pigment is added to the core particle powder coated with alkoxysilane or polysiloxane, and the mixture is stirred to adhere the organic yellow pigment to the alkoxysilane coating or polysiloxane coating. If necessary,
Drying or heat treatment may be performed.

The organic yellow pigment is preferably added little by little over time, especially over about 5 to 60 minutes.

The conditions during mixing and stirring are such that the line load is 19.6 to 1960 so that the organic yellow pigment is uniformly attached.
N / cm (2-200 Kg / cm), preferably 98-
1470 N / cm (10 to 150 kg / cm), more preferably 147 to 980 N / cm (15 to 100 kg / cm)
cm), the treatment time is 5 to 120 minutes, preferably 10 to 9 minutes.
The processing conditions may be appropriately adjusted within a range of 0 minutes. The stirring speed is 2 to 2000 rpm, preferably 5 to 1000 rpm.
The processing conditions may be appropriately adjusted within the range of rpm, more preferably in the range of 10 to 800 rpm.

The amount of the organic yellow pigment added was 10
It is 1 to 30 parts by weight with respect to 0 parts by weight. If the amount of the organic yellow pigment is out of the above range, the intended yellow pigment cannot be obtained.

The heating temperature in the drying and heating steps is usually preferably from 40 to 200 ° C., and more preferably from 60 to 200 ° C.
50 ° C. The processing time is preferably from 10 minutes to 12 hours, more preferably from 30 minutes to 3 hours.

The alkoxysilane used for coating the obtained yellow pigment is finally coated with an organosilane compound produced from the alkoxysilane through these steps.

If necessary, the core particle powder may be a kind selected from aluminum hydroxide, aluminum oxide, silicon hydroxide and silicon oxide before the alkoxysilane or polysiloxane is attached. Alternatively, it may be coated with two or more kinds of intermediate coatings.

The coating with the intermediate coating is carried out by adding an aluminum compound, a silicon compound or both compounds to a water suspension obtained by dispersing the core particle powder and mixing and stirring, or if necessary, mixing. By adjusting the pH value after stirring, the particle surface of the core particle powder, one or two or more compounds selected from aluminum hydroxide, aluminum oxide, silicon hydroxide and silicon oxide And then filtered, washed with water, dried and pulverized. If necessary, a deaeration / consolidation treatment may be performed.

As the aluminum compound, aluminum salts such as aluminum acetate, aluminum sulfate, aluminum chloride and aluminum nitrate, and alkali aluminates such as sodium aluminate can be used.

As the silicon compound, No. 3 water glass, sodium orthosilicate, sodium metasilicate and the like can be used.

[0134]

DESCRIPTION OF THE PREFERRED EMBODIMENTS A typical embodiment of the present invention is as follows.
It is as follows.

The average particle size of the particles was determined by an electron micrograph (× 2
000) was magnified twice in the vertical and horizontal directions, respectively, and the particle diameter of 350 particles shown in the photograph was measured, and the average value was shown.

The crystal phase of the particles constituting the core particle powder was identified by X-ray diffraction measurement (target Fe, tube voltage 40 kV,
A tube current was 20 mA), and the volume ratio was calculated by calculating the integrated intensity and indicated by the ratio.

The particles Fe, Ti,
The content of each element of Li was indicated by a value measured by an atomic absorption spectrometer and a plasma emission spectrometer SPS4000 (manufactured by Seiko Electronics Co., Ltd.).

The Al amount and the Si amount of the intermediate coating layer coated on the particle surface of the core particle powder and the Si amount contained in the organosilane compound or the polysiloxane formed from the alkoxysilane are each described as “X-ray fluorescence. Analyzer 3
063M type ”(manufactured by Rigaku Denki Kogyo Co., Ltd.)
It was measured in accordance with IS K0119 “General rules for X-ray fluorescence analysis”.

The silicon of the silicon oxide, the hydroxide of silicon, and the silicon contained in the silicon compound formed from the alkoxysilane or the Si contained in the polysiloxane covering the particle surface of the core particle powder, The amount was shown as a value obtained by measuring the amount of Si at each stage after the treatment step, and subtracting the amount of Si measured at the stage before the treatment step from the measured value.

The coating amount of the organic yellow pigment adhering to the core particle powder was measured according to “HORIBA Metal Carbon / Sulfur Analyzer EMIA-2
It was determined by measuring the amount of carbon using "200 type" (manufactured by Horiba, Ltd.).

The desorption rate (%) of the organic yellow pigment adhering to the core particle powder was shown by the value obtained by the following method.
The closer the desorption rate of the organic yellow pigment is to 0%, the smaller the desorption amount of the organic yellow pigment from the surface of the composite metal oxide particle powder is.

3 g of the composite metal oxide particles and 40 ml of ethanol were placed in a 50 ml sedimentation tube, subjected to ultrasonic dispersion for 20 minutes, allowed to stand for 120 minutes, and separated from the composite metal oxide particles at a sedimentation speed. The organic yellow pigment was separated. Next, 40 ml of ethanol was again added to the composite metal oxide particle powder, ultrasonic dispersion was further performed for 20 minutes, and the mixture was allowed to stand for 120 minutes to separate the separated organic yellow pigment and the organic yellow pigment. The composite metal iron oxide particles were dried at 80 ° C. for 1 hour, the amount of the organic yellow pigment was measured, and the value obtained according to the following equation 1 was defined as the desorption rate (%) of the organic yellow pigment.

[0143]

## EQU1 ## Desorption rate (%) of organic yellow pigment = [(Wa-W)
e) / Wa] × 100 Wa: Organic yellow pigment adhesion amount of composite metal oxide particle powder We: Organic yellow pigment adhesion amount of composite metal oxide particle powder after desorption test

The hues of the core particle powder, the organic yellow pigment and the yellow pigment were prepared by kneading 0.5 g of a sample and 0.5 ml of castor oil with a Hoover-type muller to form a paste, and adding 4.5 g of clear lacquer to the paste. Kneaded, made into a coating, and coated on a cast-coated paper using a 150 μm (6 mil) applicator (coating thickness: about 30 μm)
And a multi-light source spectrophotometer (MS)
C-IS-2D, manufactured by Suga Test Instruments Co., Ltd.)
L ^* using spectro-color-Meter
The values, a ^* and b ^* values were measured.

The heat resistance of the core particle powder and the yellow pigment was measured using a thermal analyzer SSC5000 (manufactured by Seiko Instruments Inc.).
Scanning calorimetry (DSC) of the particle powder to be measured using
Of the two inflection points forming the peak shown on the obtained DSC chart, draw tangents on each of the two curves constituting the first inflection point, and correspond to the intersection of the two tangents. The temperature was read and indicated at that temperature.

The coloring power of the core particle powder, the organic yellow pigment, and the yellow pigment was determined by applying each of the primary color enamel and the drawn color enamel prepared according to the following method onto a cast-coated paper using a 150 μm (6 mil) applicator. To prepare a coated piece, and for the coated piece, a multi-source spectrophotometer (MSC-IS-2D, manufactured by Suga Test Instruments Co., Ltd.) M
The L ^* value was measured using the multi-spectro-color-Meter, the difference was indicated by ΔL ^* value, and the value calculated according to the following equation 2 using the ΔLs ^* value of the core particle 1 used as the standard sample was obtained. It was shown as tinting strength (%).

[0147]

[Number 2] tinting strength (%) = 100 + [( ΔLs * value -ΔL ^*
Value) x 10]

Primary color enamel 10 g of the above sample powder, 16 g of amino alkyd resin and 6 g of thinner were blended to obtain 90 g of 3 mmφ glass beads.
Was added to a 140 ml glass bottle, and then mixed and dispersed with a paint shaker for 45 minutes. Then, 50 g of an aminoalkyd resin was added, and the mixture was further dispersed with a paint shaker for 5 minutes to prepare a primary color enamel.

[0149] coatability enamel the primary enamel 12g and Ami rack White (titanium dioxide dispersion amino alkyd resin) were blended with 40 g,
The mixture was mixed and dispersed for 15 minutes using a paint shaker to prepare a primary color enamel.

Each hue of a solvent-based paint and a water-based paint using a yellow pigment was prepared by applying a cold-rolled steel plate (0.8 mm × 70 mm × 150 mm) to each paint prepared according to the formulation described below.
ISG-3141) was applied with a thickness of 150 μm and dried to form a coating film. Using a measurement sample piece, the hue of the resin composition colored with a yellow pigment was:
Using a colored resin plate prepared according to the prescription described later, a multi-source spectrophotometer (MSC-IS-2D, manufactured by Suga Test Instruments Co., Ltd.) Multi-spectro-colou.
Using the r-Meter, the L ^{* of the} sample piece and the plate
The values, a ^* and b ^* values were measured.

The paint viscosity was determined by measuring the paint viscosity at 25 ° C. of each paint prepared by the processing method described below using an E-type viscometer (cone plate viscometer) EMD-R (manufactured by Tokyo Keiki Co., Ltd.). The value at D = 1.92 sec ^-1 was determined.

The glossiness of the coating film was indicated by the glossiness at an incident angle of 20 ° using the “gloss meter UGV-5D” (manufactured by Suga Test Instruments Co., Ltd.). The higher the gloss, the better the dispersibility of the paint containing the yellow pigment.

The heat resistance of the coating film using the yellow pigment was measured by placing the sample for measurement in an electric furnace, heating the electric furnace for 15 minutes at each temperature while changing the temperature of the electric furnace variously. Hue before and after heating (L ^* value, a ^* value, b ^*
Value) is measured using a multi-source spectrophotometer (MSC-IS-2D, manufactured by Suga Test Instruments Co., Ltd.) Multi-spectro-col.
measured using an our-meter, the ΔE ^* value was determined according to the following equation 3 based on the measured value before heating, and the heating temperature was plotted on the horizontal axis and the ΔE ^* value plotted on the vertical axis using a semilogarithmic graph, The temperature at which the ΔE ^* value was exactly 1.5 was defined as the heat-resistant temperature of the coating film.

The heat resistance of the resin composition colored by using a yellow pigment was determined by cutting a colored resin plate prepared by a method described later into a square of 5 cm, subjecting the colored resin plate to hot pressing, and changing the hot pressing temperature variously. Then, a heat treatment was performed for 10 minutes while applying a load of 98 MPa (1 ton / cm ² ) at each temperature, and the hue (L ^* value, a ^* value, b) before and after heating the colored resin plate at each temperature.
^* Value) Multi-spectro-color (MSC-IS-2D, manufactured by Suga Test Instruments Co., Ltd.)
measured using an our-meter, the ΔE ^* value was determined according to the following equation 3 based on the measured value before heating, and the heating temperature was plotted on the horizontal axis and the ΔE ^* value plotted on the vertical axis using a semilogarithmic graph, The temperature at which the ΔE ^* value was exactly 1.5 was defined as the heat-resistant temperature of the resin composition.

[0155]

ΔE ^* value = ((ΔL ^* value) ₂ + (Δa ^* value) ² +
(Δb ^* value) ² ) ^1/2 ΔL ^* value: Difference in L ^* value before and after heat treatment of sample to be compared Δa ^* value: Difference in a ^* value before and after heat treatment of sample to be compared Δb ^* value: Compare Difference of b ^* value before and after heat treatment of sample

<Production of Yellow Pigment> After mixing 4.45 kg of goethite particle powder (average particle diameter 0.98 μm), 12 kg of titanium dioxide (average particle diameter 0.2 μm) and 1.85 kg of lithium carbonate with an edge runner, 900 ° C in air using an electric furnace with a ceramic furnace core tube
, And fired continuously under the condition of a residence time of 1 hour, and the obtained fired product was again pulverized by an edge runner to obtain a powder.

The core particle powder has an average particle size of 1.01.
μm, 20.6 atomic% of Fe, 61.0 atomic% of Ti, and 18.4 atomic% of Li. According to its X-ray diffraction pattern, it is a single crystal phase having a pseudobrookite structure. Was observed.

The obtained powder has a yellow color.
L ^* value of 71.7, a ^* value of 13.2, b ^* value of 48.2
The coloring power was 83% and the heat resistance was 600 ° C. or higher.

11.0 kg of the above-mentioned core particle powder was charged into an edge runner “MPUV-2” (product name, manufactured by Matsumoto Casting Ironworks Co., Ltd.), and methyltriethoxysilane (trade name: TSL8123: manufactured by Toshiba Silicone Co., Ltd.) ) 22
0 g of methyltriethoxysilane solution obtained by mixing and diluting with 200 ml of ethanol is added to the above-mentioned core particle powder in which the agglomeration of the particle powder is released while operating the edge runner, and a line of 392 N / cm (40 Kg / cm) is added. Mixing and agitation were performed under a load for 20 minutes.

Next, the organic yellow pigment A (particle shape: granular,
Average particle diameter 0.03 μm, tinting strength 146%, L ^* value 6
6.1, a ^* value + 39.2, b ^* value +99.5) 825g
Is added over a period of 10 minutes while the edge runner is running, and the mixture is further stirred with a linear load of 392 N / cm (40 Kg / cm) for 20 minutes to deposit an organic yellow pigment on the methyltriethoxysilane coating. Thus, composite metal oxide particles were obtained.

The obtained composite metal oxide particles were subjected to a heat treatment at 105 ° C. for 60 minutes using a drier to volatilize residual water, ethanol and the like. The obtained yellow pigment was a granular particle powder having an average particle size of 1.02 μm. The L ^* value is 65.3, the a ^* value is 17.8, and the b ^* value is 6
9.2, coloring power is 148%, heat resistance is 298 ° C,
The desorption rate of the organic yellow pigment was 7.2%, the adhesion amount of the organic yellow pigment was 6.98% by weight (corresponding to 7.5 parts by weight with respect to 100 parts by weight of the core particle powder), The coating amount of the organosilane compound generated from triethoxysilane was 0.30% by weight in terms of Si. As a result of electron micrograph observation, almost no organic yellow pigment was observed, indicating that almost all of the organic yellow pigment was attached to the organosilane compound coating formed from methyltriethoxysilane.

<Production of Solvent-Based Paint Containing Yellow Pigment> 10 g of the above-mentioned yellow pigment, amino alkyd resin and thinner were blended in the following proportions, added to 90 ml of 3 mmφ glass beads, and added to a 140 ml glass bottle. The mixture was mixed and dispersed for a minute to prepare a mill base.

Yellow pigment 12.2 parts by weight, amino alkyd resin 19.5 parts by weight, (Amirac No. 1026: manufactured by Kansai Paint Co., Ltd.) Thinner 7.3 parts by weight.

Using the above-mentioned mill base, an amino alkyd resin was blended in the following ratio and mixed and dispersed for further 15 minutes with a paint shaker to obtain a solvent-based paint containing a yellow pigment.

39.0 parts by weight of a mill base, 61.0 parts by weight of an amino alkyd resin. (Amilac No. 1026: manufactured by Kansai Paint Co., Ltd.)

The solvent-based paint obtained had a paint viscosity of 2,56.
It was 0 cP.

Next, the solvent-based paint was applied to a cold-rolled steel plate (0.8 mm × 70 mm × 150 mm) (JIS G-
3141) was applied at a thickness of 150 μm and dried to obtain a coating film having a glossiness of 86%, a heat-resistant temperature of the coating film of 294 ° C., a hue of L ^* value of 67.1 and an a ^* value of 17 .8, b ^*
The value was 68.9.

<Production of water-based paint containing yellow pigment> 7.62 g of the above-mentioned yellow pigment and a water-soluble alkyd resin were added to a 140 ml glass bottle together with 90 g of 3 mmφ glass beads at the following ratio, and then the mixture was mixed with a paint shaker.
The mixture was mixed and dispersed for a minute to prepare a mill base.

12.4 parts by weight of a yellow pigment, 9.0 parts by weight of a water-soluble alkyd resin, (trade name: S-118: manufactured by Dainippon Ink and Chemicals, Inc.) 4.8 parts by weight of an antifoaming agent, (trade name) : Nopco 8034: manufactured by San Nopco Ltd.) 4.8 parts by weight of water, 4.1 parts by weight of butyl cellosolve.

Using the above-mentioned mill base, the coating compositions were blended in the following proportions and mixed and dispersed for further 15 minutes with a paint shaker to obtain an aqueous coating.

Mill base 30.4 parts by weight, water-soluble alkyd resin 46.2 parts by weight, (trade name: S-118: manufactured by Dainippon Ink and Chemicals, Inc.) water-soluble melamine resin 12.6 parts by weight, (trade name) : S-695: manufactured by Dainippon Ink and Chemicals, Inc.) 0.1 parts by weight of an antifoaming agent (trade name: Nopco 8034: manufactured by San Nopco Co., Ltd.) 9.1 parts by weight of water, 1.6 parts by weight of butyl cellosolve.

The viscosity of the obtained water-based paint was 1,280.
cP.

Next, the above-mentioned water-based paint was applied to a cold-rolled steel plate (0.8 mm × 70 mm × 150 mm) (JIS G-
3141) was applied at a thickness of 150 μm and dried to obtain a coating film having a gloss of 80%, a heat-resistant temperature of the coating film of 288 ° C., an L ^* value of 66.6, and an a ^* value of 17. .9, b ^*
The value was 68.8.

<Production of Resin Composition> The above yellow pigment 2.5
g and 47.5 g of polyvinyl chloride resin powder 103EP8D (manufactured by Nippon Zeon Co., Ltd.).
The mixture was placed in a ml polybeaker and mixed well with a spatula to obtain a mixed powder.

To the obtained mixed powder, 0.5 g of calcium stearate was added and mixed, and after setting the clearance of a hot roll heated to 160 ° C. to 0.2 mm, the mixed powder was kneaded little by little with a roll. After the kneading was continued until the resin composition was integrated, the resin composition was peeled off from a roll and used as a colored resin plate raw material.

Next, the above resin composition was sandwiched between stainless steel plates whose surfaces were polished, placed in a hot press heated to 180 ° C., and pressed under a pressure of 98 MPa (1 ton / cm ² ) to form a plate having a thickness of 1 mm. Was obtained. The dispersion state of the obtained colored resin plate was 5, the heat resistance temperature of the colored resin plate was 234 ° C., and the hue was L ^* value of 67.
0, the a ^* value was 18.0, and the b ^* value was 68.0.

[0177]

The most important point in the present invention is that the surface of the core particle powder is coated with an organosilane compound or a polysiloxane formed from alkoxysilane, and the coating is coated with an organic yellow pigment. Is the fact that it is non-polluting, has excellent heat resistance, has a high coloring power, and exhibits a yellow color with a stronger yellowish hue.

The reason why the yellow pigment according to the present invention has excellent coloring power is that the organic yellow pigment having excellent coloring power is firmly fixed on the particle surface of the core particle powder through an organosilane compound or a polysiloxane coating. We believe this was due to the compounding.

The reason why the yellow pigment according to the present invention has excellent heat resistance is that the metal oxide particle powder used as the core particle powder is produced by the usual heating and firing method in air, and thus the heat resistance is high. It is considered that by using the metal oxide particle powder as the core particle powder, high heat resistance could be obtained even when an organic yellow pigment having a temperature of at most about 200 ° C. was adhered. I have.

The reason why the yellow pigment according to the present invention has a strong yellow hue is that metal oxide particles having a specific hue are used as the core particles, and that the surface of the core particles has a clear color. It is considered that the organic yellow pigment having a yellow hue is densely and uniformly attached via an alkoxysilane or a polysiloxane.

[0181]

Next, examples and comparative examples will be described.

Core particle powders 1-4: Metal oxide particle powders having a basic composition of Fe, Ti and Li mainly composed of a pseudobrookite type crystal phase having the properties shown in Table 1 were prepared as core particle powders. did.

[0183]

[Table 1]

Core particle powder 5: A slurry containing core particle powder was obtained by using 20 kg of the core particles 1 having been disaggregated and 150 l of water. The pH value of the redispersed slurry containing the obtained core particle powder was adjusted to 10.5 using an aqueous sodium hydroxide solution, and then water was added to the slurry to adjust the slurry concentration to 98 g / l. 150 liters of this slurry
Is heated to 60 ° C., and 1.0 mol
/ L sodium aluminate solution (equivalent to 0.5% by weight in terms of Al with respect to the core particle powder) was added thereto, and the mixture was kept for 30 minutes. Then, the pH value was adjusted to 7.5 using acetic acid.
Was adjusted. After maintaining in this state for 30 minutes, filtration, washing with water, drying, and pulverization were performed to obtain metal oxide particle powder having a particle surface coated with aluminum hydroxide.

The production conditions at this time are shown in Table 2, and various properties of the obtained surface-treated metal oxide particles are shown in Table 3.

Core particles 6 and 7: The core particle powders 2 and 3 were used, and the surface of the particles was coated in the same manner as the core particle powder 5 except that the type and amount of the surface coating were variously changed. A coated core particle powder was obtained.

The production conditions at this time are shown in Table 2, and various properties of the obtained surface-treated metal oxide particles are shown in Table 3.

[0188]

[Table 2]

[0189]

[Table 3]

In the surface treatment step, A of the type of the coating is a hydroxide of aluminum, and S represents an oxide of silicon.

<Production of Yellow Pigment> Examples 1 to 7 and Comparative Examples 1 to 5 First, organic yellow pigments A and B having various properties shown in Table 4 were prepared as organic yellow pigments.

[0192]

[Table 4]

Next, the type and amount of additives in the coating step with alkoxysilane, polysiloxane and silicon compound, the linear load and time of edge runner treatment, the type and amount of organic yellow pigment in the organic yellow pigment attaching step A yellow pigment was obtained in the same manner as in the embodiment of the present invention, except that the line load and the time of the edge runner treatment were variously changed.

Table 5 shows the production conditions and Table 6 shows the properties of the obtained yellow pigment.

[0195]

[Table 5]

[0196]

[Table 6]

<Production of Solvent-Based Coatings> Examples 8 to 14 and Comparative Examples 6 to 10: Solvent-based coatings were obtained in the same manner as in the embodiment of the invention except that the type of the yellow pigment was variously changed. .

Table 7 shows the properties of the obtained solvent-based paint and the properties of the coating film.

[0199]

[Table 7]

<Production of water-based paint> Examples 15 to 21 and Comparative Examples 11 to 15: A water-based paint was obtained in the same manner as in the embodiment of the invention except that the kind of the yellow pigment was changed variously.

Table 8 shows properties of the obtained water-based paint and properties of the coating film.

[0202]

[Table 8]

<Production of Resin Composition> Examples 22 to 28 and Comparative Examples 16 to 20: Resin compositions were obtained in the same manner as in the embodiment of the invention except that the type of the yellow pigment was variously changed. .

Table 9 shows the production conditions and various properties of the obtained resin composition.

[0205]

[Table 9]

[0206]

Industrial Applicability The yellow pigment according to the present invention is suitable as a yellow pigment because it is non-polluting, has excellent heat resistance and coloring power, and has a yellowish yellow color.

The coating composition and the resin composition according to the present invention use a non-polluting yellow pigment having excellent heat resistance and a yellow color having a stronger yellow color. It is suitable as a composition.

──────────────────────────────────────────────────続 き Continued on the front page (51) Int.Cl. ⁷ Identification symbol FI Theme coat ゛ (Reference) C09C 3/06 C09C 3/06 3/12 3/12 C09D 7/12 C09D 7/12 201/00 201 / 00 (72) Inventor Tsutomu Katamoto 1-4, Meiji-Shinkai, Otake City, Hiroshima Pref.

Claims (4)

[Claims] 1. A metal oxide particle powder having a basic composition of Fe, Ti and Li and mainly composed of a crystal phase having a pseudobrookite structure and having an average particle diameter of 0.1 to 2.0 μm has an alkoxy surface. It is composed of a composite metal oxide particle powder coated with an organosilane compound or polysiloxane generated from silane and having an organic yellow pigment adhered to the coating, wherein the amount of the organic yellow pigment adhered is the metal oxide particle powder. 1 to 100 parts by weight
A yellow pigment, which is 0 parts by weight. 2. The metal oxide particles according to claim 1, wherein the surface of the particles is at least one selected from the group consisting of aluminum hydroxide, aluminum oxide, silicon hydroxide and silicon oxide. A yellow pigment characterized by being coated with a coating. 3. A paint comprising the yellow pigment according to claim 1 or 2 incorporated in a paint-constituting base material. 4. A resin composition which is colored using the yellow pigment according to claim 1 or 2.