JP2001181533A - Green pigment, and coating material and resin composition prepared by using same - Google Patents

Abstract

PROBLEM TO BE SOLVED: To obtain a green pigment which is nonpolluting, has a high tinting strength, and is excellent in heat resistance and light resistance, especially ultraviolet resistance. SOLUTION: This green pigment is a composite metal oxide powder which comprises (A) a metal oxide powder essentially containing Fe, Ti, and Li, consisting mainly of a crystal phase of a pseudobrookite structure, and having an average particle size of 0.1-2.0 μm, (B) a covering layer comprising an orgnosiloxane compound formed from an alkoxysilane or comprising a polysiloxane and covering the surface of the metal oxide powder, and (C) an organic blue pigment attached to the covering layer. The amount of the blue pigment attached is 1-30 pts.wt. based on 100 pts.wt. metal oxide powder.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

The present invention relates to a non-polluting,
The present invention relates to a green pigment having excellent heat resistance, high tinting strength, and excellent light resistance, particularly excellent ultraviolet light resistance.

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

[0003]

2. Description of the Related Art Conventionally, chromium oxide, chromium oxide, zinc green, phthalocyanine green and the like have been used as inorganic green pigments. Green inorganic pigments such as chrome green, chromium oxide, and zinc green are toxic because they contain Pb and Cr as their constituent elements, and are problematic in terms of safety and hygiene.
That is, when a green paint or a green resin composition using these as a green 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, resulting in Pb. Since harmful metals such as Cr and Cr elute and cause environmental pollution, harmless green pigments are required.

[0004] On the other hand, phthalocyanine green is harmless, but has poor light resistance, especially ultraviolet light resistance, and a green pigment excellent in ultraviolet light resistance is required.

[0005] Next, when a green pigment is used as a colorant for paints and resin compositions, it is required not only to have excellent coloring power but also to have excellent heat resistance in the manufacturing process. .

That is, a paint using a green pigment may be produced by heating and melting a paint composition at a high temperature of 200 to 260 ° C.

A resin composition using a green pigment is
It is manufactured by heating and kneading a mixture of a thermoplastic resin such as polyethylene, polypropylene, styrene polymer, polyamide, polyolefin, or ABS with a green pigment at a high temperature of 200 to 260 ° C., and then molding.

Conventionally, a technique of combining an inorganic pigment and an organic pigment has been attempted to improve various properties as a pigment. For example, a method of co-precipitating graphite and phthalocyanine blue or an organic pigment is applied to the surface of the inorganic pigment particles. A method of adhering (JP-A-4-132770, JP-A-10-880)
No. 32, etc.) have been proposed.

Further, as an inorganic pigment which is harmless and has excellent heat resistance, a pigment mainly composed of metal oxide particles with a basic composition of Fe and Ti has been proposed.
Inorganic pigment consisting of a solid solution of pseudobrookite lattice (pseudobrookite type structure) and titanium dioxide
No. 51128) and a pigment comprising a titanium oxide / iron oxide composite sol (JP-A-8-239223) are known.

[0010] Further, as a metal oxide particle powder comprising Fe and Ti further containing another metal element,
For example, a yellow inorganic pigment composed of metal oxide particles of titanium, iron, and molybdenum (Japanese Patent Application Laid-Open No. 60-42236), a pigment composed of a mixture of a pseudobrookite structure and a rutile structure dissolved in Al (particularly, Kaihei 8-73224
JP-A-9-22) and a heat-resistant inorganic pigment powder made of metal oxide particles with Fe, Ti and other metals.
No. 1323) is known.

As the metal oxide particles containing 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. −
No. 3460), and a pigment (JP-B-3-21580) obtained by calcining a mixture having a specific composition comprising an alkali metal compound, a ferric compound and titanium dioxide.

The present inventor has developed a pigment having a basic composition of Fe, Ti and Li and having a crystalline phase of a pseudobrookite type structure as a main component (JP-A-2000-2000).
-203845).

[0013]

A green pigment which is non-polluting, has excellent heat resistance, high coloring power, and is excellent in light resistance, particularly in ultraviolet light resistance, has been most demanded at present. However, green pigments satisfying these characteristics have not yet been obtained.

That is, the above-mentioned method of co-precipitating graphite and phthalocyanine blue is toxic because of the use of graphite, and is produced by co-precipitation. Is difficult to say that the storage stability is sufficient when it is made into a paint, and it is not preferable when it is made into a coating film because color floating may occur.

The method described in the above-mentioned Japanese Patent Application Laid-Open No. 4-132770 is a method in which an organic pigment is precipitated in the presence of an inorganic pigment, and the adhesion strength of the organic pigment is hardly sufficient. The method described in the above-mentioned Japanese Patent Application Laid-Open No. 10-88032 is a method of mechanically mixing and grinding an inorganic pigment and an organic pigment, and it is hard to say that the adhesion strength of the organic pigment is sufficient.

Various pigments mainly composed of metal oxide particles having the basic composition of Fe and Ti described above have extremely poor coloring power, and have an insufficient green hue and hue.

[0017] Accordingly, an object of the present invention is to provide a green pigment which is non-polluting, has excellent heat resistance, has high coloring power, and is excellent in light resistance, particularly in ultraviolet light resistance. And

[0018]

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 mainly composed of a crystalline phase having a pseudobrookite structure and having an average particle diameter of 0.1 to 2.0 μm. The particle surface is composed of a composite metal oxide particle powder coated with an organosilane compound or polysiloxane formed from alkoxysilane and having an organic blue pigment adhered to the coating. The green pigment is 1 to 30 parts by weight based on 100 parts by weight of the oxide particles (Invention 1).

Further, according to the present invention, the metal oxide particle powder has a particle surface in which aluminum hydroxide,
A green 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 green pigment described in 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 green pigment according to the present invention 1 or 2.

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

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

The green pigment according to the present invention has a basic composition of core particle powders of Fe, Ti and Li, and has a particle surface of a metal oxide particle powder mainly composed of a pseudobrookite type crystal phase. It is a composite metal oxide particle powder coated with an organosilane compound or polysiloxane formed from alkoxysilane and having an organic blue 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%. When the content is outside the above-mentioned range, it is difficult to obtain the green pigment intended for the present invention because the yellowness of the core particle powder is insufficient.

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
%, The yellowness of the core particle powder is insufficient, so that it is difficult to obtain the green pigment intended for the present invention.

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

The crystal phase of the rutile structure has a volume ratio of 20%
And preferably less than 10%. When the content is 20% or more, the light resistance is reduced, so that it is difficult to obtain a green pigment intended for the present invention.

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 of the spinel structure has a brown color, the presence of an excess of the crystal phase of the spinel structure causes the crystal phase to become brownish, so the yellowness of the core particle powder is reduced, and the green pigment intended for the present invention is obtained. It is difficult.

The particle shape of the core particle powder is granular.

The core particle powder has an average particle diameter of 0.1 to 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 resulting green pigment also becomes coarse,
The coloring power decreases. 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, It becomes difficult to perform a uniform adhesion treatment using a blue pigment.

The coloring power of the core particle powder is determined by the core particles 1 described later.
, 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 light resistance of the core particle powder is 2.0 or less, preferably 1.5 or less in terms of ΔE ^* in the evaluation method described later.

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.
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 atomic%, preferably 6 to 21 atomic%, and Al is 1 to 30 atomic%, preferably
Mg in the range of 1 to 20 atomic%,
-20 atomic%, preferably 1-15 atomic%, and when substituting with Al and Mg, the total amount is 1-30 atomic%, preferably 1-20 atomic%, based on the total metal. When Fe, Ti, and Li are out of the above ranges, it is difficult to obtain the green pigment intended for 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, making it difficult to obtain the green pigment intended for the present invention.

When Mg exceeds 20 atomic%, a crystal phase having a structure of MgO, hematite or rutile is produced as a by-product in addition to the core particle powder, and it is difficult to obtain the green pigment intended in the present invention.

When the total amount of Al and Mg exceeds 30 atomic%, hematite, alumina, a crystal phase having a rutile structure and MgO are produced as by-products in addition to the core particle powder, and the green pigment intended for the present invention is obtained. It becomes difficult.

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, light resistance and heat resistance, as well as the crystal system, lattice constant, type and volume ratio of existing crystal phases. In characteristics, it is equivalent to the core particle powder not substituted by Al or Mg.

The particle shape and particle size of the green pigment according to the present invention depend on the particle shape and particle size of the metal oxide particle powder as the core particle powder, and are substantially equal to the particle shape and particle size of the core particle powder. It is.

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

When the average particle size of the green pigment exceeds 2.0 μm, the coloring power is reduced due to the enlargement of the particles and the particle size is too large, so that the uniform dispersion in the vehicle or the resin composition is caused. Becomes 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 green 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 blue pigment from the green pigment according to the present invention is preferably 15% or less, more preferably 12%.
It is as follows. When the desorption rate of the organic blue pigment is more than 15%, the desorbed organic blue 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 green pigment according to the present invention has an L ^* value of 25 to 80, an a ^* value of -100 to 0, and a b ^* value of -25 to +29. L ^* value, a ^*
When the value and the b ^* value are out of the above ranges, the green pigment intended for the present invention cannot be obtained.

The coloring power of the green pigment according to the present invention is preferably 140% or more, more preferably 150% or more, based on the core particles 1 of Examples described later, and the upper limit is 250%.

The light resistance of the green pigment according to the present invention is 2.0 or less, preferably 1.5 or less in terms of ΔE ^* according to the evaluation method described later.

The heat resistance of the green pigment according to the present invention is 30
0 ° C. or higher, preferably 320 ° C. or higher, more preferably 3 ° C.
It is 50 ° C. or higher, and its upper limit is 500 ° 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 formula (1).

[0057]

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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 blue pigment, organosilane compounds formed from methyltriethoxysilane, methyltrimethoxysilane, dimethyldimethoxysilane, isobutyltrimethoxysilane, and phenyltriethoxysilane are 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.

[0061]

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[0062]

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[0063]

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In consideration of the desorption rate and adhesion effect of the organic blue pigment, a polysiloxane having a methyl hydrogen siloxane unit, a polyether-modified polysiloxane, and a terminal carboxylic acid-modified polysiloxane having a terminal modified with a carboxylic acid 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 greenish pigment intended for the present invention.

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

The organic blue pigment used in the present invention is a phthalocyanine pigment such as metal-free phthalocyanine blue, phthalocyanine blue, fast skiable, and the like. It is preferable to use phthalocyanine blue in consideration of sharpness of hue.

The amount of the organic blue 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 is difficult to obtain the green pigment intended for the present invention. It is more preferably 3 to 30 parts by weight, and still more preferably 5 to 30 parts by weight.

The green pigment according to the present invention may be optionally
The particle surface of the core particle powder is previously coated with one or more intermediate coatings selected from aluminum hydroxide, aluminum oxide, silicon hydroxide and silicon oxide. Alternatively, the desorption of the organic blue pigment from the particle surface of the core particle powder can be further reduced as compared with the case where the organic blue pigment is not coated with the intermediate coating.

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

When the amount is less than 0.01% by weight, it is difficult to obtain the effect of reducing the desorption rate of the organic blue pigment. 0.01 ~
With the coating amount of 20% by weight, the effect of reducing the desorption rate of the organic blue pigment can be sufficiently obtained, so that it is meaningless to cover more than 20% by weight more than necessary.

The green pigment according to the present invention coated with the intermediate coating has almost the same particle size, tinting strength, hue, and the like as the green pigment according to the present invention not coated with the intermediate coating. It has light resistance and heat resistance. The desorption rate of the green 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 green pigment according to the present invention will be described.

Paint containing the green pigment according to the present invention
Has a heat resistance temperature of 280 ° C. or higher, preferably 290 ° C.
℃ or higher, the upper limit is 400 ℃, the hue of the coating
Is L ^*30 to 85, a^*Value is -100 to 0, b^*value
Is −25 to +29, and the light resistance is ΔE^*If the value is 2.
0 or less, preferably 1.5 or less. And of the coating
Gloss is 75-110%, preferably 80-110%
is there.

The coating material containing the green pigment according to the present invention in which the core particle surface is coated with an intermediate coating material has a heat resistance temperature of the coating film of 285 ° C. or more, preferably 295 ° C. or more, and the upper limit is 400 ° C. The hue of the coating film is L ^* value of 3
0 to 85, a ^* value is -100 to 0, b ^* value is -25 to +2
9, and the light fastness is such that the ΔE ^* value is 2.0 or less, preferably 1.5 or less. And the glossiness of the coating film is 80 ~
It is 115%, preferably 85 to 115%.

The water-based paint containing the green pigment according to the present invention has a heat-resistant temperature of the coating film of 275 ° C. or higher, preferably 28 ° C.
At 5 ° C. or higher, the upper limit is 400 ° C., and the hue of the coating film has an L ^* value of 30 to 85, an a ^* value of −100 to 0, and b ^*
The value is −25 to +29, and the light fastness is ΔE ^* value of 2.0 or less, preferably 1.5 or less. And the glossiness of the coating film is 75 to 110%, preferably 80 to 110%.
%.

The water-based paint containing the green pigment according to the present invention, in which the particle surface is coated with an intermediate coating, has a heat resistance temperature of the coating film of 280 ° C. or higher, preferably 290 ° C. or higher.
The upper limit is 400 ° C., and the hue of the coating film has an L ^* value of 30 to 85, an a ^* value of −100 to 0, and a b ^* value of −25 to 25.
+29, and the light resistance is such that the ΔE ^* value is 2.0 or less, preferably 1.5 or less. And the glossiness of the coating film is 8
It is 0 to 115%, preferably 85 to 115%.

The mixing ratio of the green pigment in the paint according to the present invention is 1.0 to 1.0 part by weight based on 100 parts by weight of the paint constituting base material.
It can be used in the range of 100 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 usually 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.

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

As the solvent for the water-based paint, water and butyl cellosolve, butyl alcohol and the like usually used in water-based paints 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, the resin composition colored with the green pigment according to the present invention will be described.

The resin composition colored using the green pigment according to the present invention has a heat resistance temperature of 225 ° C. or higher,
Preferably at 230 ° C. or higher, the hue has an L ^* value of 30 to 8
5. The a ^* value is −100 to 0, the b ^* value is −25 to +29, and the light resistance is ΔE ^* value of 2.0 or less, preferably 1.5 or less. 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 green pigment according to the present invention, whose particle surface is coated with an intermediate coating, has a heat resistance temperature of 230 ° C. or higher, preferably 235 ° C. or higher, and a hue of at least 230 ° C. , L ^* value is 30 to 85, a ^* value is -100 to 0, b ^* value is -25 to +29, and light resistance is ΔE ^* value of 2.0 or less, preferably 1.5 or less. is there. The state of dispersion by visual observation is 4 according to the evaluation method described later.
Or 5, preferably 5.

The mixing ratio of the green 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 green pigment and a known thermoplastic resin are used.
If necessary, additives such as a lubricant, a plasticizer, an antioxidant, an ultraviolet absorber, and various stabilizers are added.

As the resin, natural rubber, synthetic rubber, thermoplastic resin (for example, 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 green pigment and the resin. When the content of the additive exceeds 50% by weight, the moldability decreases.

In the resin composition according to the present invention, the resin raw material and the green pigment are mixed well in advance, and then a strong shearing action is applied under heating using a kneader or an extruder to form the green pigment. After the aggregate is broken and the green pigment is uniformly dispersed in the resin composition, it is molded into a shape suitable for the purpose and used.

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

The core particle powder of 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 if 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 from 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%.

The mixing ratio of the Ti compound when the Al compound and the Mg compound are mixed together 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%.

Incidentally, an oxide of Fe and Ti can be used in place 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.

The Al compound in the present invention 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 was 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.
Mg and Al such as hydrotalcite containing g and Al
May be used.

When both the Al compound and the 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 performed by a conventional method, for example, a free-type pulverizer, a jet mill, a colloid mill, a sand mill, an edge runner, a grinder, or the like.

The washing treatment and the classification may be performed as needed.

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

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

Mixing and stirring of the core particle powder and the alkoxysilane or polysiloxane, and mixing and stirring of the organic blue pigment and the core particle powder coated with an organosilane compound or polysiloxane formed from alkoxysilane on the particle surface. 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”), multi-mul, 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 mixing and stirring conditions 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 blue pigment sufficient to obtain a desired green pigment. With an addition amount of 0.15 to 45 parts by weight, 1 to 30 parts by weight of the organic blue pigment can be attached to 100 parts by weight of the core particle powder,
There is no point in adding more than 45 parts by weight more than necessary.

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

The organic blue 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 linear load is 19.6 to 1960 so that the organic blue 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 blue 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 blue pigment is out of the above range, the desired green pigment cannot be obtained.

The heating temperature in the drying or heating step is usually preferably from 40 to 200 ° C., more preferably from 60 to 1 ° 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 green pigment is finally coated as an organosilane compound generated 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.

[0137]

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
0000) was magnified twice in the vertical and horizontal directions, respectively. 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 constituting the core particle powder, 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.).

Each of the amount of Al and the amount of Si in the intermediate coating layer coated on the particle surface of the core particle powder and the amount of Si contained in the organosilane compound or polysiloxane formed from the alkoxysilane are referred to as “fluorescent X-rays”. 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”.

[0142] Each Si of Si contained in the silicon compound or silicon contained in the polysiloxane which is formed from silicon oxide, silicon hydroxide and alkoxysilane coating 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 blue pigment adhering to the core particle powder was measured using a 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 blue pigment adhering to the core particle powder was shown by a value obtained by the following method.
The closer the desorption rate of the organic blue pigment is to 0%, the smaller the desorption amount of the organic blue 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 blue 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 then the mixture was allowed to stand for 120 minutes to separate the separated organic blue pigment from the composite metal oxide particle powder. The composite metal oxide particle powder was dried at 80 ° C. for 1 hour, the amount of the organic blue pigment was measured, and the value obtained according to the following equation 1 was defined as the desorption rate (%) of the organic blue pigment.

[0146]

## EQU1 ## Desorption rate (%) of organic blue pigment = [(Wa-W)
e) / Wa] × 100 Wa: Amount of organic blue pigment attached to composite metal oxide particle powder We: Amount of organic blue pigment attached to composite metal oxide particle powder after desorption test

The hues of the core particle powder, the organic blue pigment and the green pigment were kneaded with 0.5 g of a sample and 0.5 ml of castor oil using a Hoover type muller to form a paste, and 4.5 g of clear lacquer was added 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)
m), and the multi-light source spectrometer (MSC-IS-2D, manufactured by Suga Test Instruments Co., Ltd.)
L ^* value, a ^* value, and b ^* value were measured using ti-spectro-color-Meter.

The heat resistance of the core particle powder, the organic blue pigment and the green pigment was determined by performing differential scanning calorimetry (DSC) on the particle powder to be measured using a thermal analyzer SSC5000 (manufactured by Seiko Instruments Inc.). Of the two inflection points forming the peak shown on the DSC chart, a tangent was drawn for each of the two curves constituting the first inflection point, and the temperature corresponding to the intersection of the two tangents was read. At that temperature.

The coloring power of the core particle powder, the organic blue pigment, and the green 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 obtain a coated piece, and the coated piece is subjected to a multiple light source spectrometer (MSC-IS-2D, manufactured by Suga Test Instruments Co., Ltd.).
Multi-spectro-color-Meter
Is used to measure the L ^* value, and the difference is indicated by ΔL ^* value. Using the ΔLs ^* value of the core particle 1 of the example used as a standard sample, the value calculated according to the following equation 2 is used as the coloring power (% ).

[0150]

[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.

[0152] 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.

The light fastness of the core particle powder, the organic blue pigment and the green pigment is determined by applying the primary color enamel obtained above to a cold-rolled steel plate (0.8 mm × 70 mm × 150 mm) (JIS G
-3141) with a thickness of 150 μm and drying to form a coating film, and half of the measurement sample piece obtained was covered with a metallic foil.
UV-W13 (manufactured by Iwasaki Electric Co., Ltd.) was used to continuously irradiate UV rays at an irradiation intensity of 100 mW / cm ² for 6 hours, and then covered with a metal foil to expose the UV-irradiated portion and the UV-irradiated portion. Hue (L
^* Value, a ^* value, and b ^* value), and the light resistance was determined by the ΔE ^* value calculated according to the following equation 3 based on the measurement value of the portion that was not irradiated with ultraviolet light by covering with a metal foil. Indicated.

[0154]

ΔE ^* value = ((ΔL ^* value) ² + (Δa ^* value) ² +
(Δb ^* value) ² ) ^1/2 ΔL ^* value: Difference in L ^* value of the sample to be compared with / without UV irradiation Δa ^* value: Difference in a ^* value of the sample with / without UV irradiation Δb ^* value: Compare Difference of b ^* value of sample with and without UV irradiation

Each hue of a solvent-based paint and a water-based paint using a green 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.
(JIS G-3141) with a thickness of 150 μm,
Using a test sample piece obtained by drying to form a coating film, the hue of the resin composition colored using a green pigment was determined using a colored resin plate prepared according to the formulation described below. About the sample piece and the plate, a multi-source spectrometer (MSC-IS-2D, manufactured by Suga Test Instruments Co., Ltd.) Multi-spectro-colou
The L ^* value, a ^* value, and b ^* value were measured using r-Meter.

Regarding the paint viscosity, the paint viscosity at 25 ° C. of each paint prepared by the processing method described below was measured using an E-type viscometer (cone plate viscometer) EMD-R (manufactured by Tokyo Keiki Co., Ltd.). Speed 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.) on the sample for measurement. The higher the gloss, the better the dispersibility of the paint containing the green pigment.

The light fastness of a coating film obtained from a solvent-based paint and a water-based paint using a green pigment was determined by using an eye super UV tester in which half of the above-mentioned measurement sample pieces prepared for measuring hue were mostly made of metal foil. UV irradiation intensity 100 using SUV-W13 (manufactured by Iwasaki Electric Co., Ltd.)
After continuous irradiation for 6 hours at mW / cm ² , the hue (L ^* value, a ^* value, b ^* value) of the part not irradiated with ultraviolet rays and the part irradiated with ultraviolet rays by covering with a metal foil were measured respectively. Then, the light resistance was indicated by a ΔE ^* value calculated according to the above equation 3 based on a measured value of a portion which was not irradiated with ultraviolet rays by covering with a metal foil.

The heat resistance of the coating film using the green pigment was measured by placing the above-mentioned test piece prepared for measuring the hue in an electric furnace, changing the temperature of the electric furnace variously, and setting the temperature to 1 at each temperature.
Heat treatment is performed for 5 minutes, and the hue (L ^* value, a ^* value, b ^* value) before and after heating at each temperature of the coated plate is measured, and the ΔE ^* value is calculated according to the following equation 4 based on the measured value before heating. The heating temperature was plotted on the horizontal axis and the ΔE ^* value was plotted on the vertical axis using a semilogarithmic graph, and the temperature at which the ΔE ^* value was exactly 1.5 was taken as the heat-resistant temperature of the coating film.

The light resistance of the resin composition using the green pigment was determined by covering half of the colored resin plate prepared for measuring hue with a metal foil,
Using a tester SUV-W13 (manufactured by Iwasaki Electric Co., Ltd.), continuously irradiate with ultraviolet light at an irradiation intensity of 100 mW / cm ² for 2 hours, and then cover with a metal foil, a part that was not irradiated with ultraviolet light and a part that was irradiated with ultraviolet light (L ^* value, a ^* value, b ^* value) were measured, and ΔE calculated according to the above equation 3 based on the measurement value of the portion which was not irradiated with ultraviolet rays by covering with a metal foil.
^* Light resistance was indicated by the value.

The heat resistance of a resin composition colored with a green pigment was determined by cutting a colored resin plate prepared by the method described later into a square of 5 cm, applying a hot press to the colored resin plate, and changing the hot press temperature variously. Then, 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 ^.
Measured value), obtains a Delta] E ^* values according to the following equation (4) based on the measurement value before heating, the heating temperature on the horizontal axis using a semilogarithmic graph, plotting the Delta] E ^* value on the vertical axis, Delta] E ^* value Is exactly 1.5 when the heat resistance temperature of the resin composition was determined.

[0162]

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

The dispersibility of the green pigment in the resin composition was evaluated on a five-point scale by visually determining the number of undispersed agglomerated particles on the surface of the colored resin plate prepared by the method described below. 5 indicates that the dispersion state is the best.

[0164] 5: not observed undispersed material, 4: 1 or more than 5 per 1 cm ^2, 3: 5 or more than 10 per 1 cm ^2, 2: 1 cm 10 or more than 50 per ^2, 1: 50 or more per 1 cm ² .

<Production of green pigment> 4.45 kg of goethite particle powder (average particle size 0.98 μm), 12 kg of titanium dioxide (average particle size 0.2 μm), and lithium carbonate 1.
After mixing 85 kg with an edge runner, continuous heating and firing were performed in air at 900 ° C. for 1 hour using an electric furnace having a ceramic furnace core tube, and the obtained fired product was edged again. It was pulverized with a runner to obtain a powder.

The above-mentioned core particle powder has an average particle diameter of 0.96.
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 is 83% and the light fastness is 1.4 in ΔE ^* value.
3. The heat resistance was 600 ° C. or higher.

20 kg of the above-mentioned core particle powder are brought into contact with 150 liters of pure water using a stirrer in order to disperse agglomeration, and further passed through "TK pipeline homomixer" (manufactured by Tokushu Kika Kogyo Co., Ltd.) three times. A slurry containing the core particle powder was obtained.

Next, the slurry containing the core particle powder was transferred to a horizontal sand grinder “Mighty Mill MHG-1.
5L "(manufactured by Inoue Manufacturing Co., Ltd.)
The dispersion was passed five times at 000 rpm to obtain a dispersion slurry containing the core particle powder.

325 mesh of the obtained dispersion slurry
The sieve residue at (opening 44 μm) was 0%. The dispersion slurry was separated by filtration and washed with water to obtain a core particle powder cake. After drying the cake of the core particle powder at 120 ° C., 11.0 kg of the dry powder was added to an edge runner “MPUV”.
-2 type "(made by Matsumoto Casting Iron Works)
Mixing and stirring was performed at 94 N / cm (30 Kg / cm) for 30 minutes to loosen aggregation of particles.

Next, 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. The stirring speed at this time was 22 rpm.

Next, an organic blue pigment A (type: phthalocyanine blue, particle shape: granular, average particle size 0.06 μm)
m, coloring power 262%, L ^* value 5.2, a ^* value +9.7, b
^* Value -21.8, light resistance ΔE ^* value 5.65, heat resistance 288
° C) 825 g while operating the edge runner.
Over a period of about 392 N / cm (40 Kg / c
m) The mixture was stirred for 20 minutes at a linear load to deposit the organic blue pigment A on the methyltriethoxysilane coating, and then subjected to a heat treatment at 105 ° C. for 60 minutes using a drier to obtain a composite metal oxide. Particle powder was obtained.

The resulting green pigment has an average particle size of 0.1.
It was a granular particle powder of 97 μm. L ^* value is 39.9,
The a ^* value is -20.4, the b ^* value is -0.5, the coloring power is 153%, the light fastness is 1.36 in ΔE ^* value, and the heat resistance is 40.
At 2 ° C., the desorption rate of the organic blue pigment was 6.5%, and the adhesion amount of the organic blue pigment A was 4.58% by weight in terms of C (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 methyltriethoxysilane was 0.30% by weight in terms of Si. As a result of electron micrograph observation, almost no organic blue pigment A was observed, indicating that almost all of the organic blue pigment A had adhered to the organosilane compound coating generated from methyltriethoxysilane.

<Production of solvent-based paint containing green pigment> 90 g of 3 mmφ glass beads were prepared by blending 10 g of the above green pigment, amino alkyd resin and thinner in the following proportions.
Was added to a 140 ml glass bottle, and then mixed and dispersed with a paint shaker for 90 minutes to produce a mill base.

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

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 green 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 viscosity of the solvent-based paint obtained was 2,81.
It was 6 cP.

Next, the solvent-based paint was applied to a cold-rolled steel plate (0.8 mm × 70 mm × 150 mm) (JIS G-
3141) is applied at a thickness of 150 μm and dried to obtain a glossiness of 85%, and a heat resistance temperature of the coating film of 350 ° C.
The light fastness was 1.26 in ΔE ^* value and the hue was 4 ^* in L ^* value.
2.1, a ^* value was -20.6, b ^* value was -0.3.

<Production of water-based paint containing green pigment> The above-mentioned green pigment (7.62 g) and a water-soluble alkyd resin or the like were mixed in the following ratio together with 90 g of 3 mmφ glass beads to 140 m.
Then, the mixture was dispersed in a paint shaker for 90 minutes to prepare a mill base.

Green pigment: 12.4 parts by weight, water-soluble alkyd resin: 9.0 parts by weight, (trade name: S-118: manufactured by Dainippon Ink and Chemicals, Inc.) defoamer: 4.8 parts by weight, (product Name: Nopco 8034: manufactured by San Nopco Co.) 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 with a paint shaker for further 15 minutes 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 water-based paint obtained had a paint viscosity of 1,456.
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 glossiness of 81% and a heat-resistant temperature of the coating film of 345 ° C.
The light fastness is 1.31 in ΔE ^* value, and the hue is 4 ^* in L ^* value.
1.8, the a ^* value was -20.4, and the b ^* value was -0.6.

<Production of Resin Composition>
5 g and 47.5 g of polyvinyl chloride resin powder 103EP8D (manufactured by Zeon Corporation) were weighed,
The mixture was placed in a 0 ml poly beaker 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. 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 had been polished, placed in a hot press heated to 180 ° C., and pressed under a pressure of 98 MPa (1 ton / cm ² ) to obtain 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 239 ° C., the light resistance was 1.41 in ΔE ^* value, the hue was 41.9 in L ^* value, and the a ^* value was −1.9. 20.
1, the b ^* value was -0.7.

[0189]

The most important point in the present invention is that the surface of the core particle powder is coated with an organosilane compound or polysiloxane formed from alkoxysilane, and an organic blue pigment is adhered to the coating. The fact is that pigments are non-polluting, have excellent heat resistance, high coloring power, and exhibit a green hue.

The reason why the green pigment according to the present invention is excellent in coloring power is that an organic blue pigment having excellent coloring power is firmly immobilized on the particle surface of the core particle powder through an organosilane compound or polysiloxane coating. I think that it was possible to combine.

The reason why the green pigment according to the present invention is excellent in heat resistance is that the metal oxide particle powder used as the core particle powder is produced by a usual heating and firing method in air, and thus the heat resistance is high. It is considered that the metal oxide particle powder is used as the core particle powder.

The reason why a pigment exhibiting a green color can be obtained in the present invention is based on the same principle that a blue transparent film is superimposed on a yellow film to exhibit a green color. Is considered to be green by coating with the metal oxide particles powder exhibiting the following.

[0193]

Next, examples and comparative examples will be described.

Core particle powders 1-4: Table 1 as core particle powder
A metal oxide particle powder having a basic composition of Fe, Ti, and Li mainly composed of a crystal phase having a pseudobrookite structure having the following characteristics was prepared.

[0195]

[Table 1]

Core particle powder 5: A slurry containing core particle powder was obtained by using 20 kg of the core particles 1 whose coagulation was loosened and 150 l of water. After adjusting the pH value of the redispersed slurry containing the obtained core particle powder to 10.5 using an aqueous sodium hydroxide solution, water was added to the slurry to adjust the slurry concentration to 98 g / l. 150 liters of this slurry was heated to 60 ° C., and 1.0 mol /
Then, 2722 ml of sodium aluminate solution (corresponding to 0.5% by weight in terms of Al with respect to the core particle powder) of 1 l was added, and the mixture was kept for 30 minutes.
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 particles were coated in the same manner as the core particle powder 5 except that the core particle powders 2 and 3 were used and 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.

[0200]

[Table 2]

[0201]

[Table 3]

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

<Production of Green Pigment> Examples 1 to 7 and Comparative Examples 1 to 6 First, organic blue pigments A and B having various properties shown in Table 4 were prepared as organic blue pigments.

[0204]

[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 blue pigment in the organic blue pigment attaching step A green pigment was obtained in the same manner as in the embodiment of the invention, except that the line load and the time of the edge runner treatment were variously changed.

The production conditions at this time are shown in Table 5, and various properties of the obtained green pigment are shown in Table 6.

[0207]

[Table 5]

[0208]

[Table 6]

<Manufacture of Solvent-Based Coatings> Examples 8 to 14 and Comparative Examples 7 to 11: Solvent-based coatings were obtained in the same manner as in the embodiment of the present invention except that the type of the green pigment was variously changed. Was.

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

[0211]

[Table 7]

<Production of Water-based Paint> Examples 15 to 21 and Comparative Examples 12 to 16: Water-based paints were obtained in the same manner as in the embodiment of the invention except that the type of the green pigment was changed variously.

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

[0214]

[Table 8]

<Production of Resin Composition> Examples 22 to 28 and Comparative Examples 17 to 21: A resin composition was obtained in the same manner as in the embodiment of the invention except that the type of the green pigment was changed in various ways. Was.

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

[0219]

[Table 9]

[0218]

The green pigment according to the present invention is pollution-free, has excellent heat resistance, and has a large coloring power.
In addition, since it has excellent light resistance, particularly excellent ultraviolet light resistance, it is suitable as a colorant for paints and resin compositions.

The paint and the resin composition according to the present invention use a green pigment which is non-polluting, has excellent heat resistance, has a higher coloring power, and is excellent in light resistance, especially in ultraviolet light resistance. Therefore, it is suitable as a green paint and a resin composition in consideration of environmental pollution.

──────────────────────────────────────────────────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 pseudobrookite-type crystal phase and having an average particle diameter of 0.1 to 2.0 μm, wherein the particle surface is an alkoxysilane. Consisting of a composite metal oxide particle powder coated with an organosilane compound or polysiloxane formed from and having an organic blue pigment adhered to the coating, wherein the amount of the organic blue pigment adhered is 100%. A green pigment which is 1 to 30 parts by weight based on 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 green pigment characterized by being coated with a coating. 3. A paint characterized in that the green pigment according to claim 1 or 2 is blended in a paint-constituting base material. 4. A resin composition which is colored using the green pigment according to claim 1 or 2.