JP2503749B2 - Traffic marking pigment composition - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION [Industrial field of application] The present invention relates to a heat melting type road marking paint, a water-based or oil-based paint type so-called paint type road marking paint, and a pasting type road marking material. The present invention relates to a pigment composition for traffic marking, which is suitable for use as a paint for road marking materials and other various traffic markings and has excellent night visibility.

[Conventional technology]

Road marking paints are used for the center line of the paved road surface, lane division,
It is a coating material for stop lines, pedestrian crossings, and airfield runways. In addition, various road signs are indispensable for observing traffic rules and traffic safety, and in order for these materials to exhibit the functions suited to their purposes, a paint with a clear and distinct color is desired.

Yellow pigment, which is an important hue for road traffic management,
Currently, yellow lead pigments are used.

[Problems to be Solved by the Invention]

However, since yellow lead is an inorganic pigment containing chromium and lead, it always has problems in terms of pollution control, and it has been a long time since a substitute for a non-polluting organic pigment was desired.

Organic pigments are sharper than inorganic pigments, have coloring power, are of various types, are compatible with various hues, and are excellent in heat resistance and weather resistance. However, replacement with organic pigments has not progressed so far.

One of the things that the substitution of organic pigments has not progressed is the yellow road marking paint used for the center line of paved roads. For the yellow center line, visibility at night is particularly important for traffic safety.

The night visibility of the road marking paint means that the color of the center line and the like can be sufficiently identified by the lights of street lights and vehicle headlights at night. Road marking paints colored with organic pigments lack night visibility, and the amount of light is low even when yellow paints with sufficient sharpness and color density that can be identified in daylight are applied on the road. At night, a headlight of a vehicle or the like has a drawback that the amount of retro-reflected light becomes extremely small, and a driver of a vehicle may not recognize yellow.

The present inventors have conducted intensive studies in view of such circumstances, and as a result, a pigment composition in which an organic pigment is attached to the surface of an inorganic pigment has excellent night visibility and is suitable as a pigment for traffic marking. After finding out that, the present invention has been completed.

That is, the present invention provides a traffic marking pigment composition comprising a pigment composition (hereinafter, referred to as a composite pigment) in which an organic pigment is attached to the surface of inorganic pigment particles. .

 The details of the present invention will be described below.

The inorganic pigment used in the present invention is not particularly limited as long as it has a hue corresponding to the desired hue and is not particularly limited, but among them, an inorganic pigment having a refractive index of 1.7 or more, preferably 2.0 or more is preferable. For example, when the desired hue is yellow, rutin-type titanium dioxide, anatase-type titanium dioxide, and those coated with aluminum oxide or silica, yellow iron oxide, chromatic inorganic pigments such as yellow mica titanium. Among them, titanium dioxide is preferable.

The hue of the organic pigment attached to the surface of the core inorganic pigment is essentially any hue required for traffic marking, and is not particularly limited. Therefore, the type of organic pigment is not particularly limited. By way of example, monoazo pigments, disazo pigments, phthalone pigments, metal complex pigments, quinacridone pigments, peridene pigments, phthalocyanine pigments and the like can be mentioned. However, if it is used for traffic signs, weather resistance is required, and if it is a road marking paint, heat-melting type is heat resistant, paint type is solvent resistant,
In addition, it becomes necessary and it is important to select a pigment that satisfies these conditions.

The present inventors have found a simple and economical method for producing a composite pigment using these existing inorganic and organic pigments. This production method is basically a method of depositing an organic pigment in the presence of an inorganic pigment to deposit the organic pigment on the surface of the inorganic pigment. The outline will be described below, but the method for producing the composite pigment used in the present invention is not limited thereto.

The first method is a production method in which an organic pigment is synthesized in a solvent in which an inorganic pigment to be used as a core material is dispersed and deposited to adhere the organic pigment to the surface of the inorganic pigment. Typical organic pigments that can be produced by this method are monoazo pigments and disazo pigments.

The second method is to disperse the inorganic pigment to be used as the core material in a solution in which the organic pigment is dissolved, add the mixture to a diluting liquid to precipitate the organic pigment, and It is a manufacturing method in which an organic pigment is adhered to. Typical examples of the organic pigment component which can be produced by this method include phthalocyanine pigments and quinacridone pigments.

In the composite pigment thus synthesized, the particles of the organic pigment adhered to the surface of the inorganic pigment can be confirmed by a high magnification electron micrograph. It can also be confirmed by measuring the ζ potential that a third ζ potential value different from the ζ potential of the organic pigment or the inorganic pigment used is observed.

As the composite pigment according to the present invention, it is not always necessary that all the organic pigments are attached to the surface of the inorganic pigment.

The traffic marking pigment composition of the present invention can be obtained by further mixing the composite pigment with other composite pigments, inorganic pigments, organic pigments, etc., if necessary.

〔Example〕

Hereinafter, the present invention will be specifically described with reference to Examples, Comparative Examples and Test Examples.

Example 1 300 ml of 0.066 mol of acetoaceto-2,5-dimethoxy-4-chloroanilide corresponding to 0.066 mol were dissolved with an equimolar amount of sodium hydroxide to make the total amount 500 ml. To this, 24.5 g of titanium dioxide (R-500 manufactured by Ishihara Sangyo, the same applies below) was added, and 100 ml of acetic acid corresponding to 0.15 mol was added dropwise with stirring to prepare a coupler solution. Next, to this solution, 250 ml of a tetrazotized aqueous solution of 3,3'-dichlorobenzidine corresponding to 0.03 mol was added dropwise over about 2 hours.
Raise the temperature to 0 ° C and continue stirring for 60 minutes, then filter, wash with water, and
A composite pigment was obtained by drying at ° C. The organic dye synthesized here was the disazo pigment CI Pigment YeIIow 83, and the composition of the obtained composite pigment was inorganic pigment: organic pigment = 1: 1 (weight ratio, the same applies hereinafter).

Example 2 As a coupler, acetoaceto-2,5-dimethoxy-
A composite pigment was obtained in the same manner as in Example 1 except that 0.064 mol of 4-chloroanilide and 0.002 mol of 1-phenyl-3-methyl-5-pyrazolone were used for co-coupling. The hue of this composite pigment is the yellow lead (Toho Pigment's Eternal Nile Yellow 3500R, which is used in the current road marking paints,
The same applies hereinafter).

Example 3 A composite pigment was obtained in the same manner as in Example 1 except that the same coupler component as in Example 2 was used and the amount of titanium dioxide serving as the core material was changed to 12.3 g. The composition of this composite pigment was inorganic pigment: organic pigment = 1: 2. The hue was the same as in Example 2, but the coloring density was superior to that of yellow lead.

Example 4 A composite pigment was obtained in the same manner as in Example 1 except that the same coupler component as in Example 2 was used and the amount of titanium dioxide serving as the core material was changed to 49 g. The composition of this composite pigment was inorganic pigment: organic pigment = 2: 1. The hue was the same as in Example 2.

Example 5 A composite pigment was obtained in the same manner as in Example 1 except that the same coupler component as in Example 1 was used and the amount of titanium dioxide serving as the core material was changed to 52 g. However, immediately after the end of the reaction, 1.6 g of a quinacridone pigment (CIPigment VioIet19, the same applies hereinafter) was added in the form of a slurry to match the hue with that of yellow lead. The composition of this composite pigment was inorganic pigment: organic pigment = 2: 1.

Example 6 A composite pigment was obtained in the same manner as in Example 1 except that the same coupler component as in Example 1 was used and the amount of titanium dioxide serving as the core material was changed to 78 g. However, immediately after the reaction was completed, 6 g of quinacridone pigment was added in the form of a slurry to match the hue with that of yellow lead. The composition of this composite pigment is: inorganic pigment: organic pigment = 3:
Was one.

Example 7 A composite pigment was obtained in the same manner as in Example 1 except that the same coupler component as in Example 1 was used and the amount of titanium dioxide serving as the core material was changed to 104 g. The composition of this composite pigment was inorganic pigment: organic pigment = 4: 1.

Comparative Examples 1 to 7 Organic pigments corresponding to Examples 1 to 7 were synthesized, and this and an inorganic pigment were dispersed and mixed at a ratio corresponding to Examples 1 to 7 by a micro pulverizer to obtain a mixed pigment for comparison. Prepared.

Test Example 1 (Tinting Power Test) The composite pigments of Examples 1 to 7 and the mixed pigments of Comparative Examples 1 to 7 were compared with each other in correspondence with each other. The test method is a method in which a pigment and a rosin-modified phenol resin varnish are ground with a Hoover Mahler under the conditions of 1501b and 300 times load, and a sufficiently dispersed ink paste is spread on a test paper to measure the color difference. Adopted. Example 1
Each of the composite pigments of Nos. 7 to 7 had a tinting strength of 20 to 30% better than that of the corresponding mixed pigment of Comparative Example.

Test Example 2 (night visibility test) A night visibility test was performed using the composite pigments of Examples 5 to 6 and the mixed pigments of Comparative Examples 5 to 6 by the following method. Resin compound 98 for petroleum resin heat melting type road marking paint containing 2 parts by weight of pigment and 16% by weight of glass beads GB153T
Part by weight was melt-mixed at 190 ° C., applied to a plate with an applicator to a thickness of about 1 mm, and a glass plate No. 1 for road marking paint was quickly spread over the plate to prepare a coated plate. These were lined up on the road at night, and the headlights of passenger cars were illuminated to observe retroreflectivity. As a result, with the composite pigments of Examples 5 and 6, both night visibility was comparable to that of the colored coated plate similarly prepared with yellow lead. However, when the mixed pigments of Comparative Examples 5 and 6 were used, the coating color was also pale yellow, and nighttime visibility was not recognized.

Example 8 A solution prepared by dissolving 1 g of copper phthalocyanine in 15 g of concentrated sulfuric acid and 1 g of titanium dioxide dispersed therein was poured into 150 ml of water with stirring. This was filtered, the wet cake was washed with water and dried at 90 ° C. to obtain a bright blue composite pigment of inorganic pigment: organic pigment = 1: 1. The paint prepared by using this composite pigment was superior in coloring power by about 30% as compared with the paint prepared by using the mixed pigment obtained in the same manner as in Comparative Example 1 with the same composition.

Example 9 100 g of titanium dioxide was dispersed in 600 g of polyphosphoric acid, 111 g of dianilinoterephthalic acid was added, and the mixture was reacted at 120 ° C. for 3 hours. The reaction completed liquid was taken out in water, filtered, washed with water and dried to obtain a quinacridone composite pigment of inorganic pigment: organic pigment = 1: 1. An ink prepared using this composite pigment in the same manner as in Test Example 1 has a coloring power of about 30% as compared with an ink prepared using the mixed pigment obtained in the same composition as in Comparative Example 1 in the same manner. Was excellent.

〔The invention's effect〕

Since the traffic marking pigment composition of the present invention has no pollution and is excellent in night visibility, it can be suitably used as a paint for road marking materials and other various traffic markings.

Claims (5)

(57) [Claims] 1. A traffic marking pigment composition comprising a pigment composition in which an organic pigment is adhered to the surface of inorganic pigment particles. 2. The pigment composition according to claim 1, wherein the inorganic pigment is an inorganic pigment having a refractive index of 2.0 or more. 3. The pigment composition according to claim 1, wherein the inorganic pigment is at least one inorganic pigment selected from the group consisting of titanium dioxide, yellow iron oxide and red iron oxide. 4. The inorganic pigment is titanium dioxide.
The pigment composition described. 5. The organic pigment is at least one organic pigment selected from the group consisting of monoazo pigments, disazo pigments, phthalone pigments, quinacridone pigments, perylene pigments, phthalocyanine pigments and metal complex pigments. The pigment composition according to claim 2, 3 or 4.