JPH07331113A - Pigment composition for traffic paint and preparation thereof - Google Patents

Abstract

PURPOSE:To prepare a pigment compsn. for a pollution-free traffic paint, comprising an inorg. particle and an org. pigment deposited on the surface thereof, which has excellent covering power, weather resistance, heat resistance, and retroreflection by mechanically mixing an inorg. particle with an org. pigment and grinding the mixture. CONSTITUTION:At least one inorg. particle selected from an iron oxide yellow pigment, contg. not less than 5wt.%, pref. 10 to 40wt.% inorg. pigment having a refractive index of not less than 2.2, such as a titanium dioxide or titan yellow pigment, calcium carbonate, barium sulfate, and mica and an org. pigment, such as a monoazo, condensed azo, or isoindoline pigment, are mechanically mixed and ground in a solid state to prepare a pigment compsn., for a traffic paint, wherein an org. pigment is deposited on the surface of an inorg. particle.

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a novel pigment composition for traffic paints and a method for producing the same, and more specifically, to a hiding property, a weather resistance, a heat resistance and a heat resistance which are obtained by adhering an organic pigment on the surface of inorganic particles. The present invention relates to a pigment composition for traffic paint having excellent retroreflectivity, and a method for producing the pigment composition by mechanically mixing and grinding inorganic particles and an organic pigment.

[0002]

2. Description of the Related Art Paint used for marking lines and markings on roads,
So-called traffic paints are generally paint type for normal temperature (1 type), heating type (2 types) and melting type (3 types).
Seeds) are used. For normal temperature, the temperature is normal temperature, and for heating, the coating is heated to 50 to 80 ° C. at the time of construction. In addition, the melting type is a powdery paint that uses a thermoplastic resin as a color-developing agent,
It is melted at a high temperature of 180 to 220 ° C. and is constructed using a dedicated coating machine.

Conventionally, as the yellow coloring components of these traffic paints, yellow lead, iron oxide yellow, titanium yellow, organic pigments, etc. have been used in the paint type.
Yellow lead is mainly used, and heat-resistant improved lead is used in the melting type.

However, in recent years, pollution control of heavy metals has been strengthened from the viewpoint of countermeasures against global environmental pollution, and lead and lead pollution due to abrasion of road surface display materials in snowfall areas. The use of yellow lead containing chromium as a main component is quite difficult, and there is a demand for early development of a pollution-free yellow pigment or colorant that replaces yellow lead.

As a non-polluting yellow pigment that replaces the heat-resistant yellow lead in the melt type paint, Japanese Patent Publication No. 49-118725.
4,4'-bis [acetoacet (2 ", 5" -dimethoxy-4 "-chloro) anilide-2-azo] -3,3 'described in Japanese Patent Publication No. 50-74634 and Japanese Patent Publication No. 50-74634.
-Methods using dichlorodiphenyl (disazo pigment) or heat treated products thereof are known. As another method, Japanese Patent Publication No. 4-132770 describes a method of depositing an organic pigment in the presence of an inorganic pigment and depositing the organic pigment on the surface of the inorganic pigment.

[0006]

Among the above methods, the method using a disazo pigment is such that when the heating temperature at the time of application is 200 ° C. or higher and the residence time is relatively long, it is partially pyrolyzed. It has been shown to generate trace amounts of aromatic amines, including 3,3'-dichlorobenzidine. 3,3 '
-Dichlorobenzidine is a substance designated as a first-class substance under the Industrial Safety and Health Act's Regulations for the Prevention of Specified Chemical Substances, and is currently used at temperatures of 180-220 ° C used in the heating and melting formula. It has been found that the disazo pigment cannot be used as a pigment for a heat-melting type traffic paint because of a large change in hue as compared with heat-resistant modified yellow lead.

The method of depositing an organic pigment on the surface of an inorganic pigment is as follows: a method of synthesizing an organic pigment in the presence of the inorganic pigment, depositing the organic pigment, and depositing the organic pigment on the surface of the inorganic pigment; After dissolving the organic pigment and dispersing the inorganic pigment to be the core material in this, the poor solvent of the organic pigment is added to this dispersion solution to precipitate the organic pigment, and the organic pigment is attached to the surface of the inorganic pigment. There is a method.

Both methods require a step of dispersing an inorganic pigment in an organic solvent, but it is not easy to obtain a uniform and stable slurry slurry, and further, the adhesion of the organic pigment to the inorganic pigment is not easy. It has a certain degree of selectivity, and there are many free organic pigments that do not adhere to the inorganic pigments, and there are many disadvantages in terms of process control and economically.

Therefore, an object of the present invention is to solve the above-mentioned problems of the prior art, to be easily manufactured, and to be concealable in place of yellow lead.
It is intended to provide a pollution-free pigment composition for traffic paint having excellent weather resistance, heat resistance and retroreflective property, and a method for producing the same. The present inventors have conducted extensive studies to achieve this object, and as a result of mechanically mixing and grinding the inorganic particles in the presence of the organic pigment, a pigment having the organic pigment adhered to the surface of the inorganic particle is obtained. It has been found that the purpose can be achieved by using the composition.

[0010]

According to the present invention, an organic pigment and inorganic particles containing 5% by weight or more of an inorganic pigment having a refractive index of 2.2 or more, the organic pigment being present on the surface of the inorganic particle. Provided is a pigment composition for traffic paint, which is characterized by being adhered. Further, according to the present invention,
Provided is a method for producing a pigment composition for traffic paint, which comprises mechanically mixing and milling an organic pigment and the inorganic particles in a solid state.

[0011]

The inorganic pigment particles are mechanically mixed and ground in the presence of the organic pigment to adhere the organic pigment to the surface of the inorganic particles, thereby facilitating the production and concealing property, weather resistance, and alternative to yellow lead. Provided is a pollution-free pigment composition for traffic paint, which is excellent in heat resistance and retroreflectivity.

[0012]

BEST MODE FOR CARRYING OUT THE INVENTION Next, the present invention will be described in more detail with reference to preferred embodiments. The inorganic particles used in the present invention need to contain 5% by weight or more of an inorganic pigment having a refractive index of 2.2 or more, and the other inorganic particles are not particularly limited. Examples of the pigment having a refractive index of 2.2 or more include anatase type titanium dioxide pigment, rutile type titanium dioxide pigment, and titanium yellow pigment, and at least one of them is used.

When the content of the inorganic pigment is less than 5% by weight, the concealing property and retroreflective property comparable to those of yellow lead are not sufficiently exhibited.
It is preferably 10 to 40% by weight. If it exceeds 40% by weight, the coating film tends to be whitened, and the amount of the organic pigment tends to increase, which is not economically preferable. Examples of the inorganic particles other than the above inorganic pigments include iron oxide yellow pigment, calcium carbonate, barium sulfate, and mica, and these are used alone or in combination of two or more.

The organic pigment used in the present invention can be appropriately selected depending on whether the pigment composition of the present invention is used for a paint type traffic paint or a melt type traffic paint. For paint-type normal temperature and heating purposes that do not require heat resistance, monoazo pigments, disazo pigments, condensed azo pigments and the like are usually used. In the case of the melting type that requires heat resistance, a pigment having good heat resistance such as isoindolinone pigment, perinone pigment, perylene pigment, quinacridone pigment, diketopyrrolopyrrole pigment or condensed azo pigment. Etc. are usually used.

The pigment composition of the present invention is produced by mechanically mixing and grinding the above-mentioned inorganic particles and organic pigment in a solid state. The use ratio of the inorganic particles and the organic pigment is not particularly limited, but the organic pigment is generally about 50 to 250 parts by weight per 100 parts by weight of the inorganic particles.

Upon mixing, it is necessary to use a mixer in which the mixing chamber (container) is fixed and mixing is performed by compression and shearing action of rollers or mixing blades rotating at high speed. As such a mixer, a Muller type mixer, a Pugmill type mixer, a particle stapling type mixer, a flow type mixer or the like is used. Specifically, high speed mixer (Mitsui Mining Co., Ltd.), super mixer (Kawata Co., Ltd.), turbosphere mixer (Moritz Co., Ltd.)
Etc. Even if a mixer such as a ball mill in which the mixing chamber is rotated does not generate a compressive shearing action, the object of the present invention is not achieved even if such a mixer is used.

To mix the inorganic particles and the organic pigment, both of them are placed in a mixing chamber of a mixer and mixed at a temperature of 25 to 80 ° C. for 20 to 60 minutes. The rotation speed of the mixing blade is usually 300 to 1000 rpm. Mixing usually ends when the desired hue is obtained. After the mixing is completed, a particulate pigment composition in which the organic pigment is attached to the surface of the inorganic particles is obtained. When the obtained pigment composition is used for traffic paint, it is desirable that the particle diameter is about 0.1 to 500 μm from the viewpoint of easy mixing with other components. For that purpose, it is preferable to use inorganic particles having a particle diameter of about 0.1 to 2 μm when producing the pigment composition.

If necessary, a known coupling agent such as a silane coupling agent, a titanium coupling agent or a zircoaluminate coupling agent is coexistent in order to promote the adhesion of the organic pigment to the surface of the inorganic particles during mixing. Can be made. The amount of the coupling agent used is 5% by weight or less based on the total amount of the organic pigment and the inorganic particles.

[0019]

EXAMPLES The present invention will be described more specifically with reference to Examples and Comparative Examples below. In Examples and the like, “part” or “%” is based on weight unless otherwise specified. Example 1 A pigment composition was manufactured by mixing the raw materials according to the following formulation and using a 10-liter high speed mixer (manufactured by Mitsui Mining Co., Ltd.). Rotation speed 1000 rpm, room temperature 3
The pigment composition obtained by stirring and mixing for 0 minutes was taken out.
The hue of the pigment composition was a vivid orange, which was not any of the hues of the pigments used.

Condensed azo pigment (C.I.Pigment Yellow 95) 800 parts Monoazo pigment (C.I.Pigment Orange 36) 50 parts Iron oxide yellow 50 parts Titanium dioxide 600 parts Calcium carbonate 200 parts Barium sulfate 280 parts Silane coupling agent 20 parts

Example 2 According to the following formulation, raw materials were mixed using a 10-liter high speed mixer (manufactured by Mitsui Mining Co., Ltd.) to prepare a pigment composition. Rotation speed 1000 rpm, room temperature 4
The pigment composition obtained by stirring and mixing for 5 minutes was taken out.
The hue of the pigment composition was a vivid orange, which was not any of the hues of the pigments used.

Isoindolinone pigment (C.I.Pigment Yellow 110) 820 parts Isoindolinone pigment (C.I.Pigment Orange 61) 30 parts Titanium dioxide 650 parts Calcium carbonate 200 parts Barium sulfate 280 parts Silane coupling agent 20 parts

Comparative Example 1 A pigment composition was produced by mixing the raw materials using a ball mill according to the following formulation. The pigment composition obtained by rotating and mixing at room temperature for 10 minutes at a rotation speed of 60 rpm was taken out. Condensed azo pigment (CIPigment Yellow 95) 800 parts Monoazo pigment (CIPigment Orange 36) 50 parts Iron oxide yellow 50 parts Titanium dioxide 600 parts Calcium carbonate 200 parts Barium sulfate 280 parts Silane coupling agent 20 parts

Comparative Example 2 A pigment composition was produced by mixing the raw materials in a ball mill according to the following formulation. The pigment composition obtained by rotating and mixing at room temperature for 10 minutes at a rotation speed of 60 rpm was taken out. Isoindolinone pigment (CIPigment Yellow 110) 820 parts Isoindolinone pigment (CIPigment Orange 61) 30 parts Titanium dioxide 650 parts Calcium carbonate 200 parts Barium sulfate 280 parts Silane coupling agent 20 parts

Evaluation Example 1 Using each of the pigment compositions obtained in Example 1 and Comparative Example 1 and the commonly used reddish G-colored yellow lead pigment, a coating composition was prepared according to the following formulation and was flow coated. A coated plate was prepared by the method. The coated part was naturally dried and the hue was evaluated. Permanently dry alkyd resin 100 parts Mineral terpene 10 parts Facial agent 5 parts

When the pigment composition obtained in Example 1 was used, a clear hue of orange was exhibited as in the case of using the yellow lead pigment. However, when the pigment obtained in Comparative Example 1 was used, the hue was slightly whitish and dull yellow. As a result of observation with a scanning microscope at a magnification of 30,000, it was confirmed that in the pigment composition obtained in Example 1, the organic pigment was attached to the surface of the inorganic particles, but Comparative Example 1
No adhesion of organic pigment was observed in the pigment composition of 1.

Evaluation Example 2 Each of the pigment compositions obtained in Example 1 and Comparative Example 1 and the commonly used reddish G-colored yellow lead pigment were adjusted to a particle size of 1 with a paint conditioner using a nitrification cotton clear lacquer.
It was dispersed until it became 0 to 20 μm. Furthermore, an additional nitrified cotton clear lacquer was added, and the paint was applied again to the paint conditioner to prepare the paint. The resulting paint was spread on a hiding power test paper with a 6 mil applicator. The applied part was naturally dried, and the black band part was evaluated with the naked eye. Example 1
The pigment composition obtained in 1. had a hiding power equivalent to that of the yellow lead pigment, but the hiding power of the pigment composition obtained in Comparative Example 1 was insufficient.

Evaluation Example 3 Each of the paints prepared in Evaluation Example 2 was spread on an aluminum test panel with a 6 mil applicator and naturally dried. Next, the coated plate was irradiated with a weatherometer for 200 hours, and the change in hue with that of the unirradiated coated plate was compared with a color difference meter. The results are shown in Table 1. The results in Table 1 show that the pigment composition obtained in Example 1 has better weather resistance than the yellow lead pigment. The pigment composition obtained in Comparative Example 1 was
It shows that the weather resistance is inferior to any of them.

[0029]

[Table 1]

Evaluation Example 4 Pigment composition obtained in Example 2 and Comparative Example 2 and redness G
Each of the color-improved heat-resistant yellow lead has the following formulation and 220
A welding type traffic paint melted at a temperature of ° C was dispersed with a dissolver to prepare a paint. A part of this molten paint was taken out, and a coated plate was prepared using a three-kind applicator. At this time, the coated plate prepared by sampling 5 minutes after the pigment composition or the pigment was added was used as a blank, and the hue change between the coated plate prepared by sampling 1 hour and 2 hours later and the blank was measured by a color difference meter. Compared with. The results are shown in Table 2. The results in Table 2 show that the pigment composition obtained in Example 2 has excellent heat resistance.

Cold water stone 250 parts Calcium carbonate 250 parts Petroleum resin 150 parts Plasticizer 10 parts Glass beads 150 parts

[0032]

[Table 2]

3 of the pigment compositions of Example 2 and Comparative Example 2 were used.
As a result of observing with a scanning microscope at a magnification of 10,000 times, in the pigment composition of Example 2, it was confirmed that the organic pigment adhered to the surface of the inorganic particles, but the pigment composition of Comparative Example 2 No adhesion of organic pigment was observed.

Evaluation Example 5 A part of each of the welding paints using the pigment composition of Example 2 and the heat-resistant improved yellow lead prepared in Evaluation Example 4 was taken out, a coated plate was prepared with a 3 type applicator, and the coating film was formed. Glass beads No. 1 were sprinkled on the coating film while not curing. When each of the obtained coated plates was irradiated with a light in a dark place and its retroreflectivity was confirmed, the same visibility was obtained.

[0035]

INDUSTRIAL APPLICABILITY The pigment composition obtained by the method of the present invention is a pollution-free alternative to yellow lead and is useful as a pigment composition for traffic paint which is excellent in hiding property, weather resistance, heat resistance and retroreflective property. .

Claims (6)

[Claims] 1. A traffic comprising an organic pigment and inorganic particles containing 5% by weight or more of an inorganic pigment having a refractive index of 2.2 or more, wherein the organic pigment adheres to the surface of the inorganic particle. Pigment composition for paint. 2. The pigment composition according to claim 1, wherein the inorganic pigment is a titanium dioxide pigment or a titanium yellow pigment. 3. The pigment composition according to claim 1, wherein the inorganic particles are at least one selected from iron oxide yellow pigment, calcium carbonate, barium sulfate and mica. 4. The organic pigment is an isoindolinone pigment,
The pigment composition according to claim 1, which is at least one selected from perinone pigments, perylene pigments, quinacridone pigments, diketopyrrolopyrrole pigments, condensed azo pigments, monoazo pigments and disazo pigments. 5. A pigment composition for traffic paint, which comprises mechanically mixing and grinding an organic pigment and inorganic particles containing 5% by weight or more of an inorganic pigment having a refractive index of 2.2 or more in a solid state. Manufacturing method. 6. The method for producing a pigment composition according to claim 5, wherein the mixture is ground by mixing under the action of compression and shearing.