JP2002161221A - Fine green pigment and paint and resin composition using the fine green pigment - Google Patents

Abstract

(57) [Problem] To provide the present invention, without containing a harmful element,
A fine green pigment having improved chemical resistance such as acid resistance and alkali resistance, and improved heat resistance, and a paint and resin having excellent transparency by using the fine green pigment. A fine green pigment from which a composition can be obtained is provided. SOLUTION: A fine green pigment is an average in which an organic blue pigment is attached to an organosilane compound or a polysiloxane formed from alkoxysilane on the particle surface of an iron oxide-containing fine particle powder and the coating is coated. It consists of fine green composite iron oxide hydroxide fine particles having a major axis diameter of 0.005 μm or more and less than 0.1 μm, and the adhesion amount of the organic blue pigment is 5 to 30 parts by weight based on 100 parts by weight of the iron oxide hydroxide fine particles. It is.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

The present invention relates to a fine green pigment having improved chemical resistance such as acid resistance and alkali resistance without containing harmful elements, and improved heat resistance. By using the fine green pigment, a fine green pigment capable of obtaining a paint and a resin composition having excellent transparency is provided.

[0002]

2. Description of the Related Art At present, inorganic pigments such as chrome green, chromium oxide and zinc green, and organic pigments such as phthalocyanine green are known as green pigments, and widely used as coloring pigments for resins, paints, printing inks and the like. It is used.

[0003] Inorganic pigments such as chrome green, chromium oxide, and zinc green generally have excellent light fastness, but have low coloring power and poor chemical resistance such as acids and alkalis. It is known to be expensive.

Further, chromium green, chromium oxide and zinc green are toxic because they contain lead and chromium as their constituent elements, and are therefore alternative green from the viewpoint of hygiene, safety and environmental pollution prevention. Pigments are in great demand.

On the other hand, organic green pigments such as phthalocyanine green have a large coloring power and a clear hue, but are known to have a problem in weather resistance such as floating of bronze when exposed to the outdoors.

[0006] A resin composition using a thermoplastic resin such as polyethylene, polypropylene, polyolefin, styrene polymer, polyamide, ABS, etc. is usually processed at a high temperature of 200 ° C. or higher. The green pigment must have heat resistance.

Therefore, there is a strong demand for a harmless green pigment having excellent chemical resistance and coloring power and excellent heat resistance.

[0008] Among the green pigments, the particle diameter is 0.1 μm.
It is known that particles composed of particles having a particle size of less than m can exhibit transparency because they can form a coating film that is transparent to light in the visible light region when formed into a coating film.

The fine green pigment having a particle diameter of less than 0.1 μm is a fine particle and has a large specific surface area.
Generally, heat resistance tends to decrease, and from this point, improvement in heat resistance of the pigment itself is strongly demanded.

Further, since the particles are fine particles, the surface energy of the powder is high, and the particles are apt to agglomerate. Therefore, the dispersibility in the vehicle or the resin composition is poor. It is difficult to exhibit sufficient transparency when the resin composition is used.

Therefore, there is a strong demand for improving the dispersibility of fine green pigments in vehicles and resin compositions.

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

[0013]

A fine green pigment which does not contain a harmful element, has excellent chemical resistance and improved heat resistance has been most demanded at present, but has not yet been obtained. Absent.

That is, the above-mentioned method of coprecipitating graphite and phthalocyanine blue is toxic due to the use of graphite, and the pigment obtained is co-precipitated. 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 Japanese Patent Application Laid-Open No. 4-132770 is a method of precipitating an organic pigment in the presence of an inorganic pigment, and it is difficult to say that the adhesion strength of the organic pigment is sufficient. The method described in the above-mentioned JP-A-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.

Accordingly, an object of the present invention is to provide a fine green pigment which is harmless, has excellent chemical resistance such as acid resistance and alkali resistance, and has improved heat resistance.

[0017]

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

That is, according to the present invention, an average major axis diameter in which the particle surface of the iron oxide hydroxide fine particles is coated with an organosilane compound or polysiloxane formed from alkoxysilane and an organic blue pigment is attached to the coating. It is made of fine green composite iron oxide hydroxide fine particles having a particle size of 0.005 μm or more and less than 0.1 μm, and the adhesion amount of the organic blue pigment is 5 to 30 parts by weight based on 100 parts by weight of the iron oxide hydroxide fine particles. (A present invention 1).

The present invention also relates to the present invention, wherein the particle surface of the iron oxide-containing fine particle powder of the present invention has at least one kind selected from aluminum hydroxide, aluminum oxide, silicon hydroxide and silicon oxide in advance. The present invention is a fine green pigment which is characterized by being coated with an intermediate coating consisting of (the present invention 2).

Further, the present invention is a paint characterized in that the fine green pigment of the present invention 1 or 2 is blended in a paint constituting base material.

The present invention is also a resin composition characterized by being colored using the fine green pigment of the present invention 1 or 2.

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

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

In the fine green pigment according to the present invention, an organosilane compound or polysiloxane formed from alkoxysilane is coated on the particle surface of iron oxide hydroxide fine particles, which is a core particle powder, and the coating is coated on the surface. It is composed of fine green composite iron oxide hydroxide fine particles having an average major axis diameter of 0.005 μm or more and less than 0.1 μm to which an organic blue pigment is attached.

The shape of the particles of the iron oxide fine particles in the present invention is acicular or rectangular parallelepiped. Here "needle"
The term “shape” means not only a needle-like shape, but also a spindle shape and a rice grain shape.

The iron oxide-containing fine iron oxide particles in the present invention are goethite (α-FeOOH) particles and lepidocrocite (γ-FeOOH) particles. In consideration of the heat resistance of the obtained green pigment, hydrous iron oxide fine particles obtained by subjecting hydrous iron oxide fine particles to heat treatment are preferable,
Specifically, the surface of the hydrous iron oxide particles is treated with an aluminum compound, and the surface of the hydrous iron oxide particles contains aluminum and iron. Iron oxide hydroxide fine particles having a composite hydrated oxide layer, and iron oxide hydroxide fine particles obtained by combining these heat treatments are preferred.

The aluminum content of the fine iron oxide powder obtained by treating the surface of the fine iron oxide particles with an aluminum compound is 0.1% in terms of Al relative to the fine iron oxide powder.
1 to 20.0% by weight, and the aluminum content of the iron oxide hydroxide fine particles containing aluminum inside the iron oxide hydroxide fine particles is A with respect to the iron oxide hydroxide fine particles.
It is 0.05 to 50% by weight in terms of 1. Further, the aluminum content in the composite hydrated oxide layer adhered to the particle surface of the iron oxide hydrate fine particle powder having a composite hydrated oxide layer composed of aluminum and iron on the surface of the iron oxide hydrate fine particles,
0.1 to 10 in terms of Al relative to hydrous iron oxide fine particle powder
%, And the iron content is 0.1 to 30% by weight in terms of Fe with respect to the iron oxide hydroxide fine particle powder.

The average major axis diameter of the iron oxide hydroxide fine particles according to the present invention is not less than 0.005 μm and less than 0.1 μm.

When the average major axis diameter is less than 0.005 μm, aggregation tends to occur due to the fineness of the particles. It becomes difficult to perform a uniform adhesion treatment using a blue pigment. The average major axis diameter is 0.
If it is 1 μm or more, the resulting fine green pigment is not preferable because the particles become coarse and the hiding power increases.

Considering the uniform coating treatment with the alkoxysilane or polysiloxane and the uniform adhesion treatment with the organic blue pigment on the particle surface of the fine particles of hydrous iron oxide, and the hiding power of the fine green pigment obtained, the average length is considered. The shaft diameter is preferably from 0.008 to 0.096 μm, more preferably from 0.01 to 0.092 μm.

The iron oxide hydroxide fine particles according to the present invention are:
The average minor axis diameter is preferably 0.0025 μm or more and less than 0.05 μm, more preferably 0.004 to 0.048 μm.
m, more preferably 0.005 to 0.046 μm
m. Axial ratio (ratio of average major axis diameter to average minor axis diameter)
(Hereinafter referred to as “axial ratio”) is preferably 20 or less, more preferably 15 or less, further preferably 10 or less, and the lower limit is 2. The BET specific surface area value is 50
To 300 m ² / g, more preferably 70 to ² m ² / g.
80 m ² / g, more preferably, 80~250m ² / g
It is. The geometric standard deviation of the major axis diameter is preferably 1.8 or less, more preferably 1.7 or less, and the lower limit is 1.0.
It is one.

When the average minor axis diameter is less than 0.0025 μm, the particles are liable to be agglomerated due to the fineness of the particles. It becomes difficult to perform a uniform adhesion treatment using a blue pigment. Those having an average minor axis diameter of 0.05 μm or more are difficult to obtain industrially.

If the BET specific surface area value is less than 50 m ² / g, the iron oxide hydroxide particles are coarse, and the resulting fine green pigment also becomes coarse particles to increase the hiding power, which is not preferable. . BET specific surface area value of 300 m ² /
When the amount exceeds g, it is easy to cause agglomeration due to the refinement of the particles, so that it is difficult to uniformly coat the surfaces of the particles of the iron oxide-containing fine particles with alkoxysilane or polysiloxane and to uniformly adhere the particles with the organic blue pigment. Become.

If the geometric standard deviation value of the major axis diameter exceeds 1.80, uniform dispersion is hindered by the existing coarse particles, so that the alkoxysilane or polysiloxane on the surface of the iron oxide hydroxide fine particles is not effective. It is difficult to perform a uniform coating treatment with the organic blue pigment and a uniform adhesion treatment with the organic blue pigment. The lower limit of the geometric standard deviation is 1.01, and 1.0
Those less than 1 are difficult to obtain industrially.

When the axial ratio is more than 20, entanglement between the particles increases, and uniform coating treatment with alkoxysilane or polysiloxane and uniform adhesion with an organic blue pigment are applied to the surface of the fine particles of the iron oxide hydroxide. Processing becomes difficult.

The hue of the iron oxide hydroxide particles according to the present invention has an L ^* value of 40 to 80, an a ^* value of -57.7 ≦ a ^* value ≦ + 57.7 (a value ≠ 0), and a b ^* value of 0 <b ^* value ≦ + 1
00 and h value are in the range of 0 <h value <120 °. If the L ^* value, a ^* value, b ^* value, and h value are outside the above ranges, it becomes difficult to obtain the green pigment intended for the present invention.

The hiding power of the iron oxide hydroxide fine particles according to the present invention is preferably less than 600 cm ² / g, more preferably 500 cm ² / g or less. Concealment power is 600cm
When it is ² / g or more, the hiding power is too high, and therefore, a fine green pigment obtained by using this as a core particle also has a high hiding power, which is not preferable.

The chemical resistance of the fine particles of iron oxide hydroxide according to the present invention is evaluated by the evaluation method described below. The acid resistance is preferably such that the ΔE ^* value is 3.0 or less, more preferably 2.5 or less, and the alkali resistance is ΔE ^* value is preferably 3.0 or less,
More preferably, it is 2.5 or less. If the ΔE ^* value of the acid resistance and the alkali resistance exceeds 3.0, it is difficult to obtain a fine green pigment excellent in chemical resistance, which is the object of the present invention.

The iron oxide hydroxide fine particles according to the present invention are:
It preferably has a heat resistance of 180 ° C. or higher, more preferably 185 ° C. or higher. In consideration of the heat resistance of the obtained fine green pigment, iron oxide hydroxide fine particles powder obtained by subjecting iron oxide hydroxide particles to heat treatment are preferable, and iron oxide hydroxide particles obtained by treating an aluminum compound on the surface of iron oxide hydroxide particles are preferred. In this case, the heat resistant temperature is about 240 ° C., and in the case of the iron oxide hydroxide fine particles containing aluminum inside the iron oxide hydroxide fine particles, the heat resistance temperature is about 245 ° C. The temperature is about 250 ° C. in the case of an iron oxide hydroxide fine particle powder having a composite hydrated oxide layer composed of

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

[0041]

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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 adhesion effect and desorption rate of the organic blue pigment, an organosilane compound formed from methyltriethoxysilane, methyltrimethoxysilane, dimethyldimethoxysilane, isobutyltrimethoxysilane, and phenyltriethoxysilane is preferable. Organosilane compounds formed from triethoxysilane, methyltrimethoxysilane and phenyltriethoxysilane are more preferred.

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.

[0045]

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[0046]

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[0047]

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In consideration of the adhesion effect and the desorption rate 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 the polysiloxane is 0.02 to 5.0% by weight in terms of Si, based on the weight of the organosilane compound-coated hydrous iron oxide particles or the polysiloxane-coated hydrous iron oxide particles. Is preferably 0.03 to 4.0% by weight, and still more preferably 0.05 to 3.0% by weight.
It is.

When the amount is less than 0.02% by weight, it is difficult to attach 5 parts by weight or more of the organic blue pigment to 100 parts by weight of the iron oxide hydroxide fine powder.

If it exceeds 5.0% by weight, the organic blue pigment is added in an amount of 5 to 100 parts by weight of the fine iron oxide hydroxide powder.
Since 30 parts by weight can be adhered, there is no point in coating more than necessary.

The organic blue pigments in the present invention are phthalocyanine pigments such as metal-free phthalocyanine blue, phthalocyanine blue (copper phthalocyanine), fast sky blue (sulfonated copper phthalocyanine) and alkali blue, and the fine green pigment obtained is In consideration of the hue, it is preferable to use phthalocyanine blue.

In particular, when light resistance is taken into consideration, low chlorinated copper phthalocyanine and NC-type (non-crystal)
copper phthalocyanine or NC type low chlorinated copper phthalocyanine is preferred.

The adhesion amount of the organic blue pigment is 5 to 30 parts by weight based on 100 parts by weight of the iron oxide hydroxide fine powder.

When the amount is less than 5 parts by weight or more than 30 parts by weight, it is difficult to obtain a fine green pigment intended for the present invention. More preferably, it is 7.5 to 25 parts by weight.

The particle shape and particle size of the fine green pigment according to the present invention greatly depend on the particle shape and particle size of the iron oxide hydroxide fine particles which are the core particles, and have a particle morphology similar to the core particles. I have.

That is, the fine green pigment according to the present invention is:
The average major axis diameter is 0.005 μm or more and less than 0.1 μm, preferably 0.008 to 0.096 μm, and more preferably 0.01 to 0.092 μm.

The average major axis diameter of the fine green pigment is 0.1 μm.
In the case of m or more, the particle size is large, so that the hiding power is high, and the coating film or the resin composition obtained using the fine green pigment does not have sufficient transparency. If the average major axis diameter is less than 0.005 μm, the particles are likely to be agglomerated due to the refinement of the particles, so that it is difficult to disperse the particles in a vehicle or a resin composition.

The shape of the fine green pigment according to the present invention is
Needle-like or rectangular parallelepiped.

The axial ratio of the fine green pigment according to the present invention is 2
It is preferably 0 or less, more preferably 2 to 15, and still more preferably 2 to 10. When the axial ratio exceeds 20, the entanglement of the particles increases, and the dispersibility in the vehicle or the resin composition may deteriorate or the viscosity may increase.

The average minor axis diameter of the fine green pigment according to the present invention is preferably not less than 0.0025 μm and less than 0.05 μm, more preferably 0.004 to 0.048 μm, and further preferably 0.1 to 0.048 μm. 005 to 0.046 μm. When the particle size is less than 0.0025 μm, the particles are liable to aggregate due to the fineness of the particles, and it is difficult to disperse the particles in a vehicle or a resin composition. Those having an average minor axis diameter of 0.05 μm or more are difficult to obtain industrially.

The geometric standard deviation of the particle size of the fine green pigment according to the present invention is preferably 1.8 or less.
If it exceeds 1.8, uniform dispersion in the vehicle or the resin composition becomes difficult due to the coarse particles present.
In consideration of uniform dispersion in a vehicle or a resin composition, it is preferably 1.7 or less. In consideration of industrial productivity, the lower limit of the geometric standard deviation of the particle diameter of the fine green pigment is 1.01, and those having a particle diameter of less than 1.01 are difficult to obtain industrially.

BET ratio of fine green pigment according to the present invention
Surface area value is 50-300m²/ G is preferred, more preferred
Or 70-280m²/ G, even more preferably 80
~ 250m²/ G. BET specific surface area value is 50m²
/ G, the green pigment is coarse,
The covering power is high, and it is obtained using the fine green pigment.
The coating film and the resin composition do not have sufficient transparency. BET
Specific surface area value is 300m ²/ G, the particle size
Since aggregation tends to occur due to miniaturization, it is difficult to
Dispersibility in the fat composition is reduced.

The fine green pigment according to the present invention preferably has an organic blue pigment desorption rate of 15% or less, more preferably 12% or less. When the desorption rate of the organic blue pigment exceeds 15%, the desorbed organic blue pigment may hinder uniform dispersion in a vehicle or a resin composition, and the desorbed portion may contain water. Since the hue of the iron oxide fine particle powder appears on the particle surface, 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 ≦ a ^* value <0, a b ^* value of -100 ≦ b ^* value ≦ + 100 and an h value. Is 120 ° ≦ h
The value is in the range of ≦ 240 °.

The heat resistance of the fine green pigment according to the present invention is improved by about +10 to + 40 ° C. with respect to the heat resistance of the iron oxide hydroxide fine particles which are the core particles, preferably by 21%.
The temperature is 0 ° C or higher, more preferably 215 ° C or higher.

The coloring power of the fine green pigment according to the present invention is preferably 115% or more, more preferably 120% or more, by an evaluation method described later.

The hiding power of the fine green pigment according to the present invention is preferably less than 600 cm ² / g, more preferably 500 cm ² / g or less. The hiding power is 600 cm ² /
In the case of g or more, the hiding power is too high, so that a coating film or a resin composition obtained using the fine green pigment does not have sufficient transparency.

The chemical resistance of the fine green pigment according to the present invention is evaluated by the evaluation method described below. The acid resistance is preferably such that the ΔE ^* value is 1.5 or less, more preferably 1.3 or less, and the alkali resistance is The value of ΔE ^* is preferably 1.5 or less, more preferably 1.3 or less.

The fine green pigment according to the present invention may be prepared, if necessary, by pre-adhering the surface of the fine particles of iron oxide hydroxide.
Aluminum hydroxide, aluminum oxide, silicon hydroxide and silicon oxide may be coated with an intermediate coating of at least one selected from the group consisting of:
Compared with the case where the particles are not coated with the intermediate coating, the desorption of the organic blue pigment from the particle surfaces of the iron oxide-containing fine particles can be further reduced, and the heat resistance is slightly improved.

The amount of coating by the intermediate coating is expressed in terms of Al, based on the weight of the fine iron oxide hydroxide particles coated with the intermediate coating.
iO ₂ terms or terms of Al quantity and 0.01 to 20 wt% in total of SiO ₂ equivalent amount is preferred.

If the amount is less than 0.01% by weight, the effect of reducing the desorption rate of the organic blue pigment cannot be obtained. 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 fine green pigment according to the present invention coated with the intermediate coating has a particle size and a geometry substantially equal to those of the fine green pigment according to the present invention not coated with the intermediate coating. It has standard deviation value, BET specific surface area value, hue, coloring power, hiding power and chemical 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 1% or less.
0% or less. In addition, the heat resistance is +5 to a fine green pigment using core particle powder that has not been subjected to heat treatment.
About + 30 ° C.

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

The coating composition containing the fine green pigment according to the present invention has a storage stability ΔE ^* value of preferably 1.5 or less, more preferably 1.3 or less. When formed into a coating film, the glossiness is 75 to 110%, preferably 80 to 11%.
0%, the heat-resistant temperature of the coating film is 220 ° C. or higher, preferably 225 ° C. or higher, and the acid resistance of the chemical resistance is preferably 12% or less in ΔG value, more preferably 10% or less. The alkalinity is preferably 12% or less in ΔG value,
More preferably, it is 10% or less, and the hue has an L ^* value of 25.
~ 85, a ^* value is -100≤a ^* value <0, b ^* value is -1
00 ≦ b ^* value ≦ + 100 and h value is 120 ° ≦ h value ≦ 2
40 °, the transparency of the coating film is 0.05μ linear absorption coefficient
It is preferably at most m- ¹ .

The paint according to the present invention containing a fine green pigment whose particle surface is coated with an intermediate coating material has a storage stability ΔE ^* value of preferably 1.5 or less, more preferably 1.3 or less. It is. When coated, gloss is 80
To 115%, preferably 85 to 115%, the heat-resistant temperature of the coating film is 230 ° C or more, preferably 235 ° C or more, and the acid resistance among the chemical resistances is preferably 12% or less in ΔG value. It is preferably 10% or less, and the alkali resistance is preferably 12% or less in ΔG value, more preferably 1% or less.
0% or less, and the hue has an L ^* value of 25 to 85, an a ^* value of −100 ≦ a ^* value <0, and a b ^* value of −100 ≦ b ^* value ≦ +
The 100 and h values are preferably 120 ° ≦ h value ≦ 240 °, and the transparency of the coating film is preferably such that the linear absorption coefficient is 0.05 μm ⁻¹ or less.

The fine green pigment according to the present invention is compounded.
Water-based paints have a storage stability of ΔE^*1.5 or less is preferred
And more preferably 1.3 or less. Place to make a coating
In this case, the glossiness is 70 to 110%, preferably 75 to 1
10%, and the heat-resistant temperature of the coating film is preferably 220 ° C or more.
Or 225 ° C or higher, and the acid resistance of the chemical resistance is ΔG
The value is preferably 12% or less, more preferably 10% or less.
The alkali resistance is preferably 12% or less in ΔG value.
And more preferably 10% or less, and the hue is L ^*value
25-85, a^*Value is -100 ≦ a^*Value <0, b^*value
-100 ≦ b^*Value ≤ +100 and h value is 120 ° ≤ h value
≦ 240 °, and the transparency of the coating film was determined to have a linear absorption coefficient of 0.0
5 μm^-1The following is preferred.

The surface of the particles according to the present invention is covered by an intermediate coating.
A water-based paint blended with a fine green pigment coated with
The storage stability is preferably 1.5 or less in ΔE, more preferably
Or 1.3 or less. When coated, the gloss is 75
To 115%, preferably 80 to 115%,
The heat-resistant temperature is 230 ° C or more, preferably 235 ° C or more.
Therefore, acid resistance of chemical resistance is less than 12% in ΔG value.
Preferably 10% or less,
The resilience is preferably 12% or less in ΔG value, more preferably
10% or less, and the hue is L^*Value 25-85, a^*value
Is -100 ≦ a ^*Value <0, b^*Value is -100 ≦ b^*Value ≤
+100 and h value are 120 ° ≦ h value ≦ 240 °,
Regarding the transparency of the coating film, the linear absorption coefficient is 0.05 μm^-1Below
Preferably.

The compounding ratio of the fine green pigment in the paint according to the present invention can be used in the range of 0.5 to 100 parts by weight with respect to 100 parts by weight of the base material constituting the paint. Considering this, preferably 1.0 to 8
0 parts by weight, more preferably 1.0 to 50 parts by weight.

As the base material for the coating material, an antifoaming agent, an extender, a fine green pigment, a resin, and a solvent, if necessary.
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 using the fine green pigment according to the present invention will be described.

The dispersion state of the resin composition colored by using the fine green pigment according to the present invention is 4 or 5, preferably 5, according to the evaluation method described below, and the heat resistance temperature of the resin composition is as follows. 210 ° C. or higher, preferably 215 ° C. or higher, and the hue has an L ^* value of 25 to 85 and an a ^* value of −10.
0 ≦ a ^* value <0, b ^* value is −100 ≦ b ^* value ≦ + 100
And the h value is 120 ° ≦ h value ≦ 240 °, and the transparency of the coating film is preferably a linear absorption coefficient of 0.05 μm ⁻¹ or less.

The resin composition according to the present invention, which has been colored using a fine green pigment whose surface is coated with an intermediate coating, has a dispersion state by visual observation of 4 or 5, preferably 5 by the evaluation method described later. And the heat resistance temperature of the resin composition is 215 ° C. or higher, preferably 220 ° C. or higher, and the hue of the resin composition is an L ^* value of 25 to 85 and an a ^* value of -100 ≦ a ^* value
0, b ^* value is −100 ≦ b ^* value ≦ + 100 and h value is 1
It is preferable that 20 ° ≦ h value ≦ 240 ° and the transparency of the coating film has a linear absorption coefficient of 0.05 μm ⁻¹ or less.

The mixing ratio of the fine green pigment in the resin composition according to the present invention can be used in the range of 0.01 to 50 parts by weight based on 100 parts by weight of the resin. Is considered, preferably 0.
It is 0.5 to 45 parts by weight, more preferably 0.1 to 40 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, various stabilizers and the like are used together with a fine green pigment and a well-known thermoplastic resin, if necessary. Is 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 of the fine green 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 prepared by thoroughly mixing a resin raw material and a fine green pigment in advance and then applying a strong shearing action under heating using a kneader or an extruder to obtain a fine green pigment. After agglomerates of the pigments are broken and the fine green pigments are uniformly dispersed in the resin composition, the pigments are molded into a desired shape and used.

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

The fine green pigment according to the present invention is obtained by mixing fine powder of iron oxide hydroxide and alkoxysilane or polysiloxane, coating the surface of the fine powder of iron oxide hydroxide with alkoxysilane or polysiloxane,
It can be obtained by mixing an organic blue pigment with an iron oxide hydroxide fine particle powder coated with an alkoxysilane or polysiloxane.

The coating of the iron oxide hydroxide fine particles with the alkoxysilane or polysiloxane can be performed by mechanically mixing and stirring the iron oxide hydroxide fine particles and the alkoxysilane or polysiloxane, or by adding the alkoxysilane or polysiloxane to the iron oxide hydroxide fine particles. May be mechanically mixed and stirred while spraying. Almost all of the added alkoxysilane or polysiloxane is coated on the particle surface of the iron oxide hydroxide fine particle powder.

The coated alkoxysilane may be partly 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 fine particles of the iron oxide hydroxide and the alkoxysilane or polysiloxane, and the mixing of the organic blue pigment with the fine particles of the iron oxide hydroxide coated with an organosilane compound or polysiloxane formed from alkoxysilane on the particle surface. As equipment for mixing and stirring,
A device capable of applying a shearing force to the powder layer is preferred. In particular, a device capable of simultaneously performing shearing, spatula and compression, such as a wheel-type kneader, a ball-type kneader, a blade-type kneader, and a roll-type kneader Machine 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 conditions during the mixing and stirring are such that a linear load is set to 1 so that the alkoxysilane or polysiloxane is coated as uniformly as possible on the particle surfaces of the iron oxide hydroxide fine powder.
9.6 to 1960 N / cm (2 to 200 kg / cm),
Preferably 98 to 1470 N / cm (10 to 150 Kg
/ Cm), more preferably 147 to 980 N / cm (1
The processing conditions may be appropriately adjusted within the range of 5 to 120 minutes, preferably 10 to 90 minutes. The stirring speed is 2 to 2000 rpm, preferably 5 to 1000 rpm, more preferably 10 to 800 rpm.
The processing conditions may be appropriately adjusted within the range of rpm.

The addition amount of the alkoxysilane or polysiloxane is preferably from 0.15 to 45 parts by weight based on 100 parts by weight of the iron oxide hydroxide fine powder. When the amount is less than 0.15 parts by weight, it is difficult to attach an organic blue pigment sufficient to obtain a desired fine green pigment. 0.
With an addition amount of 15 to 45 parts by weight, 5 to 30 parts by weight of the organic blue pigment can be adhered to 100 parts by weight of the iron oxide-containing fine powder particles. Absent.

Next, an organic blue pigment is added to the iron oxide-containing fine 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 the mixing and stirring were such that the linear load was 19.6 to 1960 so that the organic blue pigment was 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 addition amount of the organic blue pigment is 5 to 30 parts by weight based on 100 parts by weight of the iron oxide hydroxide fine particle powder. If the amount of the organic blue pigment is out of the above range, the desired fine green pigment cannot be obtained.

The heating temperature in the drying and heating steps is usually preferably from 40 to 150 ° C., and more preferably from 60 to 150 ° C.
20 ° 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 fine green pigment is finally coated with an organosilane compound generated from the alkoxysilane through these steps.

If necessary, the fine particles of iron oxide hydroxide may be mixed with an aluminum hydroxide, an aluminum oxide, a silicon hydroxide and a silicon oxide before mixing and stirring with an alkoxysilane or polysiloxane. It may be coated with at least one selected intermediate coating.

The coating with the intermediate coating may be carried out by adding an aluminum compound, a silicon compound or both compounds to an aqueous suspension obtained by dispersing the fine powder of iron oxide hydroxide and mixing and stirring, or if necessary. After mixing and stirring
By adjusting the H value, the surface of the particles of the above-mentioned iron oxide hydroxide fine particles is coated with at least one selected from the group consisting of 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.

Examples of the aluminum compound include aluminum salts such as aluminum acetate, aluminum sulfate, aluminum chloride and aluminum nitrate, and alkali aluminates such as sodium aluminate.

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

[0111]

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

The average major axis diameter and the average minor axis diameter of the particles were 350 mm in the electron micrograph (× 30000), each of which was magnified 4 times in the vertical and horizontal directions, respectively. The minor axis diameter was measured, and the average value was shown.

The axial ratio was shown by the ratio between the average major axis diameter and the average minor axis diameter.

The particle size distribution of the major axis diameter of the particles was shown by a value obtained by the following method.

That is, the value obtained by measuring the major axis diameter of the particles shown in the above enlarged photograph is calculated from the actual major axis diameter and the number of the particles calculated from the measured values, and the logarithmic normal On the probability paper, the horizontal axis represents the major axis diameter, and the vertical axis represents the percentage of the cumulative number of particles (under the integrated screen) belonging to each of the predetermined major axis diameter sections. Then, the value of the major axis diameter corresponding to 50% and 84.13% of the number of particles is read from this graph, and the geometric standard deviation value = the major axis diameter at 84.13% under the integrated screen / 50 under the integrated screen. %
The values calculated in accordance with the major axis diameter (geometric mean diameter) are shown. The closer the geometric standard deviation value is to 1, the better the particle size distribution of the major axis diameter of the particles.

The specific surface area was indicated by a value measured by the BET method.

The amount of Al present inside the particles or on the surface of the iron oxide hydroxide fine powder and the iron oxide hydroxide fine powder,
i amount, Al amount contained in the composite hydrate of aluminum and iron adhered to the particle surface of the iron oxide hydroxide fine particle powder, and Si amount contained in the organosilane compound or polysiloxane, respectively. Is "Fluorescent X
Ray analyzer 3063M "(manufactured by Rigaku Corporation)
And measured according to JIS K0119 “General rules for X-ray fluorescence analysis”.

The Si content of the oxide of silicon, the hydroxide of silicon, and the Si contained in the organosilane compound or the Si contained in the polysiloxane covering the particle surface of the iron oxide hydroxide fine powder is as follows. The amount of Si was measured at each stage after the treatment step, and the value was obtained by subtracting the amount of Si measured at the stage before the treatment step from the measured value.

The amount of Fe in the composite hydrated oxide layer composed of aluminum and iron adhered to the particle surfaces of the fine particles of hydrous iron oxide was determined by the following method. The value was calculated according to Equation 1 from the weight ratio of the amount and the Al weight% in the composite hydrated oxide layer obtained by the fluorescent X-ray analysis.

That is, 0.25 g of the iron oxide hydroxide fine powder was weighed into a 100 ml Erlenmeyer flask, and ion-exchanged water 3
3.3 ml was added, and the mixture was stirred for 20 minutes using a magnetic stirrer in a water bath heated to 60 ° C.
A dispersion suspension was obtained. Then, 16.7 m of 12N hydrochloric acid was added.
l, and further stirred for 20 minutes. From the outermost surface of the composite hydrated oxide composed of aluminum and iron adhered to the particle surface of the hydrated iron oxide fine particles, The part where the composition was substantially uniform up to the central part of the distance to the surface was acid-dissolved (confirmed based on many experimental results). This acid-dissolved suspension was subjected to suction filtration using a 0.1 μm membrane filter, and the amount of Al (ppm) and the amount of Fe (ppm) in the obtained filtrate were measured using an induction plasma emission spectrometer SPS4000 (Seiko). (Manufactured by Denshi Kogyo Co., Ltd.).

[0121]

## EQU1 ## Fe weight% = Al weight% / weight ratio of Al to Fe

The amount of the organic blue pigment adhering to the green composite iron oxide hydroxide fine particles was determined by measuring the amount of carbon using a “HORIBA Metal Carbon / Sulfur Analyzer EMIA-2200” (manufactured by HORIBA, Ltd.). I asked by doing.

The desorption rate (%) of the organic blue pigment adhering to the green composite hydrous iron oxide fine particles was shown by the 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 green composite iron oxide hydroxide fine particle powder is.

3 g of the green composite iron oxide hydroxide fine particles and 40 ml of ethanol were placed in a 50 ml sedimentation tube, subjected to ultrasonic dispersion for 20 minutes, and allowed to stand for 120 minutes. The separated organic blue pigment was separated. Next, 40 ml of ethanol was again added to the green composite iron oxide hydroxide fine particles, ultrasonic dispersion was further performed for 20 minutes, and the mixture was allowed to stand for 120 minutes to separate the separated green blue iron oxide hydroxide fine powder and the organic blue pigment. . The green composite hydrous iron oxide fine particles were dried at 80 ° C. for 1 hour, the amount of the organic blue pigment was measured, and the value determined according to the following equation 2 was defined as the desorption rate (%) of the organic blue pigment.

[0125]

## EQU2 ## Desorption rate of organic blue pigment (%) = {(Wa-W
e) / Wa} × 100 Wa: Adhesion amount of organic blue pigment on green composite iron oxide hydroxide fine particles powder We: Organic blue pigment adhesion amount on green composite iron oxide hydroxide fine particles powder after desorption test

The hue of the iron oxide hydroxide fine powder, the organic blue pigment and the green composite iron oxide hydroxide fine powder was 0.5 g for the sample.
And 0.5 ml of castor oil by kneading with a Hoover type muller to form a paste.
g, kneading and coating to make 15
A coated piece (coating thickness: about 30 μm) was prepared using a 0 μm (6 mil) applicator, and the coated piece was subjected to a multi-source spectrophotometer (MSC-IS-2D, manufactured by Suga Test Instruments Co., Ltd.). Multi-spectro-col
L ^* value, a ^* value, and b ^* value were measured using our-Meter.

The h value can be determined according to the following equation 3 using the a ^* value and the b ^* value obtained by the above measurement.

[0128]

H = tan ⁻¹ (b ^* / a ^* ) (when a ^* > 0, b ^* ≦ 0) h = 180 + tan ⁻¹ (b ^* / a ^* ) (when a ^* <0) h = 360 + tan ^-1 (b ^* / a ^* ) (when a ^* > 0, b ^* <0)

The heat resistance of the iron oxide hydroxide fine particles, the organic blue pigment and the green composite iron oxide hydroxide fine particles was measured by using a thermal analyzer SSC5000 (manufactured by Seiko Denshi Kogyo KK) using a differential scanning calorimeter. DSC) to obtain the first inflection point among the two inflection points forming the peak shown on the obtained DSC chart.
A tangent was drawn for each of the three curves, and the temperature corresponding to the intersection of both tangents was read and indicated as the temperature.

[0130] The coloring power of the green composite oxide-containing iron oxide fine particles powder was determined by placing each of the primary color enamel and the drawn color enamel prepared according to the method described below on a cast-coated paper sheet.
Using a 6 μm (approx.) applicator, a coated piece is prepared, and the coated piece is subjected to a multi-source spectrophotometer (MSC-IS-2D, manufactured by Suga Test Instruments Co., Ltd.).
The L ^* value was measured using a ti-spectro-color-Meter, the difference was indicated by ΔL ^* value, and the value calculated according to the following equation 4 using the ΔLs ^* value of chrome green used as a standard sample. It was shown as tinting strength (%).

[0131]

## EQU4 ## Coloring power (%) = 100 + {(ΔLs ^* −Δ
L ^* ) × 10}

Preparation of primary color enamel: 10 g of the above sample powder
And 16 g of aminoalkyd resin and 6 g of thinner were added to a 140 ml glass bottle together with 90 g of 3 mmφ glass beads, and then mixed with a paint shaker.
After mixing and dispersing for 5 minutes, 50 g of amino alkyd resin was added, and further dispersed for 5 minutes with a paint shaker.
A primary color enamel was prepared.

Preparation of Decorative Enamel: Primary Color Enamel 1
2 g and 40 g of Amirac White (titanium dioxide-dispersed amino alkyd resin) were blended and mixed and dispersed for 15 minutes with a paint shaker to prepare a colored enamel.

The hiding power of the fine particles of the iron oxide hydroxide, the organic blue pigment and the green fine particles of the iron oxide hydroxide were determined by using the primary color enamel obtained above in accordance with JIS K 5101.
The value was obtained according to the cryptometer method of 8.2.

The acid resistance of the iron oxide-containing fine particles and the green composite iron oxide-containing particles was soaked in 10 g of the sample powder for 10 minutes in 5% sulfuric acid, then the sample was taken out of the aqueous sulfuric acid solution, washed with water, and dried. Then, a coating film was prepared in the same manner as described above, and the L ^* value, a ^* value, and b ^* value were measured for color, and indicated by the color difference ΔE ^* value calculated according to the following equation (5). Δ
The smaller the E ^* value, the better the acid resistance.

The alkali resistance of the iron oxide-containing fine particles and the green composite iron oxide-containing fine particles was determined as follows.
% Of immersion for 15 minutes in an aqueous sodium hydroxide solution, then the sample is dried after washing with water taken out from the aqueous sodium hydroxide solution, to prepare a coating film in a manner similar to that described above, L ^* value, the a ^* and b ^* values The color difference Δ measured by the color measurement and calculated according to the following Equation 5
Indicated by E ^* value. The smaller the ΔE ^* value, the better the alkali resistance.

[0137]

(Equation 5)^*Value = ((ΔL^*)²+ (Δa^*)²+
(Δb^*)²)^1/2  ΔL^*Value: L before and after acid or alkali immersion treatment of sample powder
^*Value difference Δa^*Value: a before and after acid or alkali immersion treatment of sample powder
^*Value difference Δb^*Value: b before and after acid or alkali immersion treatment of sample powder
^*Value difference

The hue of each coating film of a solvent-based paint and a water-based paint obtained by using a fine green pigment was 150 μm on a clear base film prepared by applying a paint prepared by a processing method described later.
(6 mil) thickness, and dried to form a coating film, the coated sample for measurement was used as a multi-light source spectrophotometer (MSC-IS-2D,
Suga Test Machine Co., Ltd.) Multi-spectro-
JIS Z 872 using a color-meter
The measurement was performed according to the conditions specified in Section 9.

The hue of the resin composition was determined by measuring the color of a resin plate prepared by the method described below with a multi-source spectrophotometer (MSC).
-IS-2D, manufactured by Suga Test Instruments Co., Ltd.) Multi-s
JI using a vector-spectro-color-meter
It was measured according to SZ8729.

The glossiness of the coating film was indicated by a glossiness at an incident angle of 60 ° using a “gloss meter UGV-5D” (manufactured by Suga Test Instruments Co., Ltd.) for the above-mentioned measuring piece. The higher the gloss, the better the dispersibility of the paint containing the fine green pigment.

The transparency of each of the solvent-based paint and the water-based paint obtained using the fine green pigment was determined by applying the paint prepared by the treatment method described later to a clear base film having a thickness of 100 μm and a thickness of 150 μm (6 mil). The transparency of the resin composition of the coating film obtained by coating with a thickness of was measured using a “self-recording photoelectric spectrophotometer UV-2100” (manufactured by Shimadzu Corporation) for a resin plate having a composition described below. The measured light transmittance was represented by a linear absorption coefficient defined by the following equation (6). The smaller the linear absorption coefficient, the higher the transmittance of light and the higher the transparency.

[0142]

The linear absorption coefficient (μm ⁻¹ ) = ln (1 / t) / FT t: light transmittance at λ = 900 nm (−) FT: thickness of coating film or resin plate (μm) used for measurement )

Solvents obtained using fine green pigments
The heat resistance of each paint film and water-based paint film is determined by the treatment method described later.
Therefore, apply the prepared paint to a transparent glass plate (0.8 mm (thick)).
X 70mm (width) x 150mm (length))
(6 mils) and place the plate in an electric furnace
The temperature of the electric furnace was changed variously to 15
Heat treatment at each temperature of the coated plate
Hue (L^*Value, a ^*Value, b^*Value) with the standard white plate.
And a multi-source spectrophotometer (MSC-IS-2D,
Suga Test Machine Co., Ltd.) Multi-spectro-
JIS Z 872 using a color-meter
Each measurement was performed according to the conditions specified in Section 9. Before heat treatment
ΔE expressed by the above equation 5 based on the colorimetric value of^*Find the value,
Using a semilogarithmic graph, the horizontal axis represents the heating temperature, and the vertical axis represents ΔE.^*
Plot the values and^*When the value is exactly 1.5
Was taken as the heat-resistant temperature of the coating film.

The heat resistance of the resin composition is determined by the treatment method described later.
Cut the resin plate prepared in 5 cm square,
The hot press temperature in various ways.
98MPa in degree (1 ton / cm²) Load
Heat treatment for 10 minutes while maintaining the temperature of the resin plate.
Hue before and after heat treatment (L^*Value, a^*Value, b^*value)
Of each color and measure
ΔE represented by the notation 5 ^*And using a semilogarithmic graph
The horizontal axis is the heating temperature, and the vertical axis is ΔE^*Plot the values and
^*The temperature at which the value is exactly 1.5 is the temperature of the resin composition.
The heat resistant temperature was set.

[0145] The storage stability of the paint was determined by applying the paint prepared by the treatment method described below to a clear base film of 150 µm.
(6 mils) applied and dried to produce L
^* Value, a ^* value and b ^* value,
The L ^* value, a ^* value, and b ^* value of the coating film produced by applying the paint obtained by standing for a week on a clear base film and drying are measured, and the ΔE ^* value obtained according to the following equation 7 is obtained. Indicated.

[0146]

Equation 7 ΔE^*Value = ((ΔL^*)²+ (Δa^*)²+
(Δb^*)²)^1/2  ΔL^*Value: L before and after standing of the coating film to be compared^*Value difference Δa^*Value: a before and after standing of the coating film to be compared^*Value difference Δb^*Value: b before and after standing of the coating film to be compared^*Value difference

The acid resistance of the coating film is determined by preparing a coated plate in the same manner as in the evaluation of heat resistance and measuring the glossiness. Next, a 5% by weight aqueous solution of sulfuric acid is placed in a 1000 ml beaker, the coated plate is hung with a thread, dipped to a depth of about 120 mm, and left at 25 ° C. for 24 hours.

Next, the coated plate is taken out from the aqueous sulfuric acid solution, gently washed with running water, and the water is shaken off. Then, the gloss of the central portion of the coated plate is measured. The change in gloss (ΔG value) before and after immersion in the aqueous sulfuric acid solution was measured, and the acid resistance was evaluated based on the magnitude of the change. The smaller the ΔG value, the better the acid resistance.

The alkali resistance of the coating film is determined by preparing a coated plate in the same manner as in the evaluation of heat resistance and measuring the glossiness. Next, a 1% aqueous solution of caustic soda is put into a 1000 ml beaker, the coated plate is hung with a thread, immersed to a depth of about 120 mm, and left still at 25 ° C. for 24 hours.

Next, the coated plate is taken out of the aqueous solution of caustic soda, gently washed with running water, and the water is shaken off. Then, the gloss of the central portion of the coated plate is measured. The change in gloss (ΔG value) before and after immersion in the aqueous sulfuric acid solution was measured, and the magnitude of the change was evaluated for alkali resistance. The smaller the ΔG value, the better the alkali resistance.

The paint viscosity at 25 ° C. of the 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.). The value at the speed D = 1.92 sec ^-1 was determined.

The dispersibility of the fine green pigment in the resin composition was determined by visual observation of the number of undispersed agglomerated particles on the surface of the colored resin plate obtained by the following method. evaluated. 5 indicates that the dispersion state is the best.

[0153] 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: 1cm ² per 50 or more.

<Production of Fine Green Pigment> Goethite fine particle powder (particle shape: acicular, average major axis diameter 0.0710 μm)
m, average minor axis diameter 0.0081 μm, axial ratio 8.8, geometric standard deviation 1.38, BET specific surface area 159.8 m ² /
g, aluminum content 0.83% by weight, L ^* value 5
1.6, a ^* value 31.4, b ^* value 61.7, h value 63.
0 °, hiding power 152 cm ² / g, heat resistance 245 ° C.) 1
1.0 kg is put into an edge runner “MPUV-2 type” (product name, manufactured by Matsumoto Casting Ironworks Co., Ltd.), and 220 g of methyltriethoxysilane (trade name: TSL8123: manufactured by Toshiba Silicone Co., Ltd.) is added with 200 ml of ethanol. A methyltriethoxysilane solution obtained by mixing and diluting is added to the above goethite fine-particle powder while operating an edge runner, and then 392 N / cm (40 kg / cm).
The mixture was stirred for 20 minutes with a linear load of. The stirring speed at this time was 22 rpm.

Next, an organic blue pigment A (type: copper phthalocyanine blue, particle shape: granular, average major axis diameter 0.06 μm)
m, hiding power 240 cm ² / g, L ^* value 17.7, a ^* value 9.7, b ^* value-23.9, h value 292.5 °) 110
0 g was added over 10 minutes while operating the edge runner, and further mixed and stirred at a linear load of 392 N / cm (40 Kg / cm) for 20 minutes, so that the organic blue pigment A was coated on the methyltriethoxysilane coating. After the adhesion, a heat treatment was performed at 105 ° C. for 60 minutes using a dryer to obtain a green composite iron oxide hydroxide fine particle powder. The stirring speed at this time was 22 rpm.

The obtained fine green pigment has an average major axis diameter of 0.0722 μm, an average minor axis diameter of 0.0082 μm,
It was an acicular particle powder having an axial ratio of 8.8. The geometric standard deviation value is 1.33, the BET specific surface area value is 153.6 m ² / g,
The L ^* value is 31.6, the a ^* value is -8.7, and the b ^* value is 0.
3, h value is 178.0 °, coloring power is 123%, hiding power is 159 cm ² / g, and acid resistance among chemical resistance is Δ
The E ^* value was 1.14, and the alkali resistance was ΔE ^* value of 1.06.
The heat resistance is 257 ° C., the desorption rate of the organic blue pigment is 7.1%, and the coating amount of the organosilane compound generated from methyltriethoxysilane is 0.30 in terms of Si.
% By weight.

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 was adhered to the organosilane compound coating formed from methyltriethoxysilane. Was.

<Production of Solvent-Based Paint Containing Fine Green Pigment> The fine green pigment 5 was placed in a 250 ml glass bottle.
g and a coating composition base material were mixed in the following ratio, and mixed and dispersed together with 160 g of 3 mmφ glass beads using a paint shaker for 120 minutes to prepare a mill base. 9.9 parts by weight of fine green pigment, melamine resin (Super Peckamine J-820-60: trade name: manufactured by Dainippon Ink and Chemicals, Inc.) 19.8 parts by weight, alkyd resin (Beccosol 1307-60EL: product) 39.6 parts by weight, xylene 29.7 parts by weight, butanol 1.0 part by weight.

The viscosity of the solvent-based paint obtained was 1,67.
6 cP, storage stability of paint is ΔE ^*The value is 0.87
Was.

The above-mentioned solvent-based paint is used as a clear base film.
150 µm (6 mil) applied and dried
The coated film has a gloss of 86.1% and a hue of L^*Value is 32.
3, a ^*Value is -16.3, b^*Value 2.0, h value 17
3.0 °, linear absorption coefficient 0.0184 μm^-1So
Was.

Next, the solvent-based paint was applied to a transparent glass plate (0.8 mm (thickness) × 70 mm (width) × 150 mm (length)) with a thickness of 150 μm (6 mil) to obtain an acid-resistant coating film. The property was 8.2% in ΔG value, and the alkali resistance was 7.7% in ΔG value.

Next, in order to determine the heat-resistant temperature of the coating film, five coating plates were prepared in the same manner using the above-mentioned solvent-based coating material, and the coating plates were prepared at 210 ° C., 230 ° C., 250 ° C., 270 ° C. and 2 ° C., respectively.
Put into a gear oven heated to 90 ° C., heat-treat for 15 minutes, take out, measure the hue value of the coated plate, determine ΔE ^* value based on the hue value before heat treatment, and determine the difference between heat treatment temperature and ΔE ^* value. The temperature at which the ΔE ^* value was 1.5 was determined from the relationship, and was 269 ° C.

<Production of water-based paint containing fine green pigment> 5 g of the fine green pigment was placed in a 250 ml glass bottle.
And a paint composition base material were blended at the following ratio, and mixed and dispersed together with 160 g of 3 mmφ glass beads for 120 minutes using a paint shaker to prepare a mill base. Fine green pigment 10.1 parts by weight, water-soluble melamine resin 9.3 parts by weight, (trade name: S-695: manufactured by Dainippon Ink and Chemicals, Inc.) water-soluble alkyd resin 40.7 parts by weight, (product Name: S-118: manufactured by Dainippon Ink and Chemicals, Inc.) 0.2 parts by weight of an antifoaming agent (trade name: Nopco 8034: manufactured by San Nopco Co., Ltd.) 28.2 parts by weight of water, 11.5 parts by weight of butyl cellosolve.

The water-based paint obtained had a paint viscosity of 2,184.
The cP and storage stability were 0.92 in ΔE ^* value.

[0165] The above-mentioned water-based paint was applied to a clear base film.
The glossiness of the coating film obtained by coating and drying at a thickness of 50 μm (6 mil) was 82.3%, the hue was L ^* value of 32.9,
a ^* value is -16.2, b ^* value is 2.1, and h value is 172.
At 6 °, the linear absorption coefficient was 0.0199 μm ⁻¹ .

Then, the above water-based paint was applied to a transparent glass plate (0.8 mm (thickness) × 70 mm (width) × 150 mm (length)) with a thickness of 150 μm (6 mil) to obtain an acid-resistant coating film. Was 8.7% in ΔG value and alkali resistance was 8.0% in ΔG value.

Next, in order to determine the heat resistance temperature of the coating film, five coating plates were prepared in the same manner using the above-mentioned water-based coating material, and the coating plates were respectively 210 ° C., 230 ° C., 250 ° C., 270 ° C. and 29 ° C.
Put in a gear oven heated to 0 ° C., heat-treat for 15 minutes, take out, measure the hue value of the coated plate, determine ΔE ^* value based on the hue value before heat treatment, and determine the difference between heat treatment temperature and ΔE ^* value. When the temperature at which the ΔE ^* value was 1.5 was determined from the relationship, it was 264 ° C.

<Production of Resin Composition> 0.5 g of the above fine green pigment and polyvinyl chloride resin powder 103EP8D
49.5 g (manufactured by Nippon Zeon Co., Ltd.) was weighed, placed in a 100 ml polybeaker, and mixed well with a spatula to obtain a mixed powder.

To the obtained mixed powder, 1.0 g of calcium stearate was added and mixed. The clearance of a hot roll heated to 160 ° C. was set to 0.2 mm, and 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 form a plate having a thickness of 1 mm. Was obtained. The hue of the obtained colored resin plate has an L ^* value of 32.4 and a ^*
Value of -12.6, b ^* value of 2.4, h value of 169.2
°, dispersion state: 5, linear absorption coefficient: 0.0192 μm ^-1
Met.

Next, the heat resistant temperature of the resin composition was determined.
5 pieces of 5cm square test pieces of colored resin plate
185 ° C, 200 ° C, 215 ° C, 2
Insert into hot press heated to 30 ° C and 245 ° C
98MPa (1 ton / cm²)
After 10 minutes heat treatment, take out
The hue value is measured, and ΔE is determined based on the hue value before the heat treatment.^*
The heat treatment temperature and ΔE ^*ΔE^*value
Was found to be 1.5,
Was.

[0172]

The most important point in the present invention is that the particle surface of the iron oxide hydroxide fine powder is coated with an organosilane compound or polysiloxane formed from alkoxysilane, and an organic blue pigment is attached to the coating. The fact is that fine green pigments are harmless green pigments having excellent chemical resistance and coloring power and improved heat resistance.

In the present invention, the reason why a pigment exhibiting a green color can be obtained is that, when a blue transparent film is superimposed on a yellow film, a green color is obtained. We believe that by coating the fine particle powder, it looks green.

The reason why the fine green pigment according to the present invention is excellent in chemical resistance is that iron oxide hydroxide fine particles, which are core particles, are excellent in chemical resistance and adhere to the particle powder. It is considered that by selecting organic blue pigments having excellent chemical resistance, the chemical resistance of the whole particles is further improved.

The reason why the fine green pigment according to the present invention is excellent in coloring power is that among inorganic pigments, the surface of the iron oxide hydroxide fine powder having excellent coloring power is coated with an organosilane compound or a polysiloxane coating. It is believed that the organic blue pigment was firmly fixed to form a composite and thus a pigment having excellent coloring power could be obtained.

The reason that the heat resistance of the fine green pigment according to the present invention is excellent is that iron oxide hydrous fine particles which are originally poor in heat resistance are coated with an organosilane compound or polysiloxane excellent in heat resistance. It is considered that by fixing an organic blue pigment having excellent heat resistance on the coating, the heat resistance of the fine green pigment is improved.

The fine green pigment according to the present invention includes:
Because it does not contain harmful elements and compounds, it is a pigment that is excellent in hygiene and safety, and that also takes into consideration the prevention of environmental pollution.

[0178]

Next, examples and comparative examples will be described.

Core Particles 1-4: Iron oxide hydroxide fine particles having the properties shown in Table 1 were prepared as core particles.

[0180]

[Table 1]

Core particle 5: A slurry containing needle-like goethite fine particle powder was obtained using 20 kg of the needle-like goethite fine particle powder of core particle 1 and 150 l of water. After adjusting the pH value of the redispersed slurry containing the obtained acicular goethite fine 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 5444 ml of a 5.0 mol / l sodium aluminate solution (equivalent to 5% by weight in terms of Al with respect to the acicular goethite fine particle powder) was added to the slurry, and the mixture was added for 30 minutes. After holding, the pH was adjusted to 7.5 using acetic acid. After being kept in this state for 30 minutes, it was filtered, washed with water, dried and pulverized to obtain acicular goethite fine particle powder whose particle surface was coated with aluminum hydroxide.

The production conditions at this time are shown in Table 2, and various properties of the obtained surface-treated acicular goethite fine particle powder are shown in Table 3.

Core particles 6 to 8: The surface of the particles was adjusted in the same manner as in the case of the core particles 5 except that the powders of the respective iron-containing hydroxides of the core particles 2 to 4 were used and the type and amount of the surface coating were variously changed. An iron oxide hydroxide fine particle powder coated with the coating material was obtained.

Table 2 shows the production conditions and Table 3 shows the properties of the obtained surface-treated hydrous iron oxide fine particles.

[0185]

[Table 2]

[0186]

[Table 3]

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

Organic blue pigments A to C: Copper phthalocyanines having various properties shown in Table 4 were prepared as organic blue pigments.

[0189]

[Table 4]

Examples 1 to 8 and Comparative Examples 1 to 5: Types of core particles, types and amounts of additives in the coating step with alkoxysilane, polysiloxane and silicon compound, line load and time of edge runner treatment, organic Except for changing the type and amount of the organic blue pigment in the step of attaching the blue pigment, the line load and the time of the edge runner treatment in various ways, the same procedure as in the embodiment of the present invention was carried out to obtain a green composite iron oxide hydroxide fine powder. Was.

Table 5 shows the production conditions and Table 6 shows the properties of the obtained green composite iron oxide hydroxide fine particle powder.

[0192]

[Table 5]

[0193]

[Table 6]

Examples 9 to 16 and Comparative Examples 6 to 10: Solvent-based coatings were obtained in the same manner as in the embodiment of the present invention, except that the kind of fine green pigment was variously changed.

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

[0196]

[Table 7]

Examples 17 to 24 and Comparative Examples 11 to 15: Water-based paints were obtained in the same manner as in the embodiment of the invention except that the kind of fine green pigment was changed in various ways.

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

[0199]

[Table 8]

Examples 25 to 32 and Comparative Examples 16 to 20: Resin compositions were obtained in the same manner as in the embodiment of the invention except that the kind of fine green pigment was changed variously.

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

[0202]

[Table 9]

[0203]

The fine green pigment according to the present invention is harmless, has improved chemical resistance and heat resistance, and has excellent transparency by using the fine green pigment. Since a paint and a resin composition can be obtained, it is suitable as a coloring pigment for a resin, a paint, a printing ink and the like.

The paint and the resin composition according to the present invention are excellent in heat resistance and chemical resistance and use harmless fine green pigments, so that environmental pollution is considered and transparency is excellent. It is suitable as a greenish paint and a resin composition.

──────────────────────────────────────────────────続 き Continued on the front page (51) Int.Cl. ⁷ Identification code FI Theme coat ゛ (Reference) C09D 201/00 C09D 201/00 F term (Reference) 4J002 AA011 AA021 AC001 AC011 BB021 BB111 BB171 BC021 BD031 CL001 DE116 FB096 FD096 4J037 AA15 CA08 CA12 CA23 CA24 CB23 CB28 CC28 DD01 DD10 EE02 EE03 EE04 FF02 FF07 FF13 FF25 4J038 DL032 EA011 HA216 HA436 HA446 JC32 JC38 KA06 KA08 KA14 KA15 KA20 NA01 NA04 NA14

Claims (4)

[Claims] 1. An average major axis diameter of 0.005 μm or more in which the particle surface of an iron oxide hydroxide fine particle powder is coated with an organosilane compound or polysiloxane formed from alkoxysilane and an organic blue pigment is attached to the coating. A fine green composite iron oxide hydroxide fine particle powder having a particle diameter of less than 0.1 μm, wherein the amount of the organic blue pigment is 5 to 30 parts by weight based on 100 parts by weight of the iron oxide hydroxide fine particle powder. Fine green pigment. 2. The intermediate of claim 1, wherein the surface of the fine particles of the iron oxide hydroxide contains at least one selected from the group consisting of aluminum hydroxide, aluminum oxide, silicon hydroxide and silicon oxide. A fine green pigment characterized by being coated with a coating. 3. A paint characterized in that the fine green pigment according to claim 1 is blended in a paint constituting base material. 4. A resin composition which is colored by using the fine green pigment according to claim 1 or 2.