JPH09100420A - Yellow pigment composition - Google Patents

Abstract

PROBLEM TO BE SOLVED: To obtain a yellow pigment composition which contains an organic yellow pigment and a condensed azo red pigment and is suitably useful as a material for road indication without hue change with the passage of time and without causing problem on environmental pollution and labor hygiene. SOLUTION: This pigment composition contains (A) an organic yellow pigment (suitably azo pigment, isoindoline pigment, C.I. pigment yellow 83, 181, 183, particularly C.I. pigment 139) and (B) a condensed azo red pigment (suitably C.I. pigment 144, 166, or 220 with an average major axis of primary particles of 0.05-1.5μm). In an preferred embodiment, this composition contains the component A and (C) an inorganic pigment, at least one of metal oxides selected from oxides of the metal group of titanium, iron and nickel having an refractive index of >=2.0, particularly a composite pigment of the component A and any one from titan white, titan yellow and yellow iron oxide.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a yellow pigment composition which is useful as a colorant for use as a substitute for yellow lead, and more specifically, it exhibits little change in hue over time and is excellent in nighttime visibility. Therefore, the present invention relates to a yellow pigment composition which can be particularly suitably used for road marking materials.

[0002]

2. Description of the Related Art Yellow lead has been conventionally used as a yellow pigment used for coating construction machinery and as a road marking material used for the center line of paved roads, but yellow lead is hexavalent chromium and lead. It is a compound consisting of, and has problems in terms of environmental pollution and occupational health, and as a countermeasure against it, substitution with organic pigments is desired.

Various yellow organic pigments are known, such as monoazo pigments, disazo pigments and condensed polycyclic pigments. For example, monoazo pigments and condensed polycyclic pigments have excellent light resistance, and disazo pigments are colored. It has features such as excellent power. However, since many of these yellow organic pigments are different in hue from yellow lead, in order to use them for road marking purposes, orange to red pigments are added to these yellow pigments, so-called toning is performed. There is a need. The orange to red pigments used in addition to the yellow pigments include pyrazolone pigments, carmine 6
B, azo lake pigments such as Watching Red, insoluble azo pigments such as Naphthol AS, condensed polycyclic pigments such as quinacridone, and inorganic pigments such as red iron oxide are known.

[0004]

[Problems to be solved] However, these orange-
Since the light resistance and weather resistance of red pigments are significantly different from those of yellow organic pigments, especially disazo yellow pigments, when used for road marking, there is a large change in hue with aging after installation. Had a point.

The problem to be solved by the present invention is that there is no problem in terms of environmental pollution or occupational health, the hue is equivalent to that of yellow lead, and the yellow organic pigment composition has little change in hue with aging. To provide.

[0006]

The inventors of the present invention have conducted extensive research on toning orange-red pigments exhibiting similar time-varying behavior as yellow organic pigments, and as a result, condensed azo red pigments are suitable for this purpose. The present invention has been completed by discovering that it has the above characteristics.

In other words, the present invention provides a yellow pigment composition containing an organic yellow pigment and a condensed azo red pigment in order to solve the above problems.

[0008]

BEST MODE FOR CARRYING OUT THE INVENTION In the present invention, various known yellow pigments can be used according to the purpose, as the yellow pigment toned by the combined use with the condensed azo red pigment. Examples of yellow pigments that can be used include C.I. I. Pigment Yellow 12, 13, 13, 14, 17, 55, 81, 83, 136, and other disazo yellow pigments such as C.I. I. Pigment Yellow 1, Same 3, Same
65, ibid 73, ibid 74, ibid 75, ibid 116, ibid
151, 154, 181 and monoazo yellow pigments such as C.I. I. Pigment Yellow 183, an azo lake type yellow pigment such as C.I. I. Pigment yellow
93 and 95, condensed azo yellow pigments such as C.I. I. Pigment Yellow 109 and Isoindolinone yellow pigments such as C.I. I. Pigment Yellow 139, an isoindoline yellow pigment such as C.I. I. Pigment Yellow 24 and Condensed Polycyclic Yellow Pigments such as 108.

Among these yellow pigments, in consideration of economical efficiency, coloring power, ease of color matching, weather resistance, heat resistance, etc.,
C. I. Pigment Yellow 14, the same 17, the same
55, ibid 65, ibid 73, ibid 75, ibid 83, ibid
139, 181, 183 and the like are preferable, and especially C.I. I. Pigment Yellow 83, 13
9, 181 and 183 are preferable.

Examples of condensed azo red pigments for toning include C.I. I. Pigment Red 144, 166,
No. 215, No. 215, No. 221 and the like are listed, but C.I. is preferable in that the toning is easy and the hue change with the aging change after construction is small. I. Pigment Red
144, 166, and 220 are particularly preferable.

The condensed azo red pigment preferably has an average major axis in the range of 0.05 to 1.5 μm.
Those in the range of 0.1 to 1.0 μm are particularly preferable.
When the average major axis of the particle size is smaller than 0.05 μm, the weather resistance and the light resistance tend to be deteriorated, and the behavior of hue over time tends to be different, which is not preferable, and the average major axis of the particle size is 1. When it is larger than 5 μm, it is difficult to adjust the color to yellow lead, and the behavior of hue over time tends to be different, which is not preferable.

The amount of the condensed azo red pigment used together with the yellow pigment for toning varies depending on the coloring power of the yellow pigment used, the hue and the coloring power of the condensed azo red pigment, and the target hue. Although any value can be taken, in consideration of the toning effect on the hue, the range of 0.1 to 100,000 parts by weight is preferable with respect to 100 parts by weight of the yellow pigment. If the combined amount of the azo-condensed azo red pigment is small, the color is slightly reddish yellow, but as the combined amount increases, the redness increases, and most of the azo-condensed azo red pigment becomes yellowish red. . For example, C.I. I. Pigment Red 220 and C.I. I. Pigment Yellow 83 and tones similar to that of yellow lead are used, C.I. I. Pigment Yellow 83 100 parts by weight, and C.I. I. Pigment Red 220 0.5 to 5 parts by weight is preferably used in combination.

The mixture of the yellow pigment and the condensed azo red pigment is
It may be a dry blend in which dry pigments are mixed,
A wet blend in which a wet cake of pigment is mixed may be used. The pigment may be dispersed in a suitable dispersion medium such as water and then filtered.

The yellow pigment toned with the condensed azo red pigment can be used as it is or together with other pigments for various colorant applications, but when it is used for road marking materials, it may be used as it is, Red iron oxide (refractive index: 2.8),
It can also be used together with an inorganic pigment such as yellow iron oxide (refractive index: 2.0). Especially titanium white (refractive index:
2.7), titanium yellow (refractive index: 2.9), zirconium oxide (refractive index: 2.4), and other high-refractive-index inorganic pigments of white to pale yellow, the hue of which is due to its retroreflective effect. The night visibility can be significantly improved without making a large change. The amount of the inorganic pigment added for the purpose of improving nighttime visibility is preferably 10 to 500 parts by weight, and particularly preferably 100 to 300 parts by weight, relative to 100 parts by weight of the yellow pigment toned with the condensed azo red pigment.

The yellow pigment toned with the condensed azo red pigment and the inorganic pigment may be mixed by dry blending or wet blending. The pigment may be dispersed in a suitable dispersion medium such as water and then filtered. Furthermore, a yellow pigment may be synthesized in a system in which an inorganic pigment is dispersed. When a pigment having a high refractive index such as titanium white or titanium yellow is used as the inorganic pigment, this method is particularly effective as a method for producing a yellow pigment for road marking materials having excellent night visibility. It is considered that this is because the surface of the high-refractive-index inorganic pigment is covered with a yellow pigment and acts as a color filter against the retroreflected light from the inorganic pigment particles. The inorganic pigment can be coated with the organic pigment mechanically by a dry process using a device such as a hybridizer.

The road marking material includes, in addition to the yellow pigment composition thus prepared, a filling material (aggregate), natural and / or
Alternatively, it is prepared by mixing a synthetic resin or the like.

Examples of the filling material include cold water stone, white sand, quartz powder, glass beads and the like. Examples of natural and synthetic resins include rosin resin, maleic acid modified rosin ester, coumarone indene resin and petroleum. Resin, xylene resin, ketone resin, terpene resin, castor oil, coconut oil, soybean oil, melamine resin, synthetic rubber, phthalic acid resin,
Acrylic resins, phenol resins and the like can be mentioned.

The road marking material is laid on a road or the like by a hot spray type or a heat melting type.

[0019]

The present invention will be described in more detail with reference to the following examples. In the following examples, parts means parts by weight.

<Production Example> (Production of CI Pigment Red 166) In a reactor equipped with a thermometer and a stirrer, 162 parts of 2,5-dichloroaniline, 615 parts of 35% hydrochloric acid and 20 parts of water.
00 parts was added and heated to 90 ° C. to dissolve the contents. After allowing to cool to 30 ° C. and adding 1000 parts of ice, 350 parts of 20% aqueous sodium nitrite solution is added,
Diazotized.

In another reactor, 1600 parts of water, 415 parts of 48% sodium hydroxide aqueous solution, and 3-hydroxy-2-
188 parts of naphthoic acid was added and dissolved. The resulting solution was added dropwise to the above diazotization reaction solution over about 30 minutes. After completion of the dropping, heat to 90 ° C and hold for 1 hour, then filter,
It was washed with warm water and dried to obtain 340 parts of a red substance.

Next, 2100 parts of xylene, 340 parts of a red substance and 2 parts of dimethylformamide were added to a reactor equipped with a thermometer and a stirrer. The contents were heated to 80 ° C. with stirring, and 156 parts of thionyl chloride was added dropwise over about 30 minutes. After the dropping was completed, the temperature was gradually raised to 110 ° C. and the temperature was maintained for 1 hour. After cooling to 5 ° C, the mixture was filtered and the cake obtained as a residue was washed with 300 parts of o-dichlorobenzene.

Further, 2000 parts of o-dichlorobenzene and the wet cake obtained above were added to a reactor equipped with a thermometer and a stirrer and heated to 80 ° C. To this, 90
After adding a solution of 57 parts of p-phenylenediamine and 1300 parts of o-dichlorobenzene heated to 0 ° C, the temperature was raised to 140 ° C over about 2 hours, and the temperature was maintained for 3 hours. After allowing to cool to 90 ° C., the product was filtered, and the residue was washed with dimethylformamide, methanol, and hot water successively, and dried to give C.I. I. 270 parts of a crude product of Pigment Red 166 was obtained.

15 parts of the obtained crude product was charged in a sand grinder together with 500 parts of 0.5 μm zirconia beads, 100 parts of water and 50 parts of o-dichlorobenzene, and 20
Triturated at ℃ for 4 hours. After milling, the mixture was filtered, the residue was washed with methanol, washed with warm water and dried to give C.I. having an average major axis of about 0.07 µm. I. Pigment Red 166 was obtained.

C. obtained in the same manner. I. Pigment Red 166 was heat-treated in o-dichlorobenzene at various temperatures to give an average major axis of 0.15 μm, 0.3 μm, 0.
7 μm and 1.2 μm were prepared.

<Example 1> C. I. Pigment Yellow 83 (“Shimla” manufactured by Dainippon Ink and Chemicals, Inc.
First Yellow 4181NR ") 97 parts, and C.I. I. Pigment Red 166 (3 parts) and titanium white (“Taipec R-550” manufactured by Ishihara Sangyo Co., Ltd.) (100 parts) were sufficiently mixed using a mixer to obtain a yellow pigment composition.

<Examples 2 to 5> In Example 1, the C.I. I. Pigment Red 166
In place of the average major axis of 0.07 μm, 0.
C. of 15 .mu.m, 0.7 .mu.m and 1.2 .mu.m. I. Pigment Red 166 was used, and a yellow pigment composition was obtained in the same manner as in Example 1.

<Example 6> C.I. I. Pigment Yellow 83 (Shimla First Yellow 4181N
R: 215 parts of wet cake (pigment content 45%) manufactured by Dainippon Ink and Chemicals, Inc. and the average major axis 0.3 μm obtained in the production example.
m. I. Pigment Red 166 wet cake (pigment content 50%) 6 parts was kneaded using a kneader, dried and crushed, and then 100 parts of titanium white (Taipec R-550: manufactured by Ishihara Sangyo Co., Ltd.) was added, The mixture was thoroughly mixed with a mixer to obtain a yellow pigment composition.

Example 7 A reactor equipped with a thermometer and a stirrer was charged with 2000 parts of water and N- (2,5-dimethoxy-4-chlorophenyl) -3-oxobutanamide (manufactured by Samsung Chemicals Co., Ltd.). ) 57 parts and 55 parts of 25% sodium hydroxide aqueous solution were added and dissolved. To this solution was added 100 parts of titanium white (“JR-602S” manufactured by Teikoku Kako Co., Ltd.), and 21 parts of acetic acid was added dropwise with stirring to prepare a coupler solution. After setting the liquid temperature of the coupler liquid to 20 ° C.,
An aqueous tetrazotized solution of 33 parts of 3,3′-dichlorobenzidine hydrochloride was added dropwise over about 2 hours, and C.I. I. Pigment Yellow 83 and titanium white were obtained as a composite pigment. After completion of the dropping, the mixture was further heated to 90 ° C. and stirred at the same temperature for 1 hour, and then the C.I.
I. Pigment Red

166 wet cake (pigment content 50%)
After adding 6 parts, thoroughly stirring and dispersing, filter, wash with water,
A yellow pigment composition was obtained by drying.

<Embodiment 8> In the first embodiment, C.I. I.
Pigment Yellow 83, instead of C.I. I. Pigment Yellow 17 (“Shimla Fast Yellow 8GTF” manufactured by Dainippon Ink and Chemicals, Inc.) was used to obtain a yellow pigment composition in the same manner as in Example 1.

<Example 9> C. I. Pigment Yellow 183 ("Pariotor Yellow K2270" manufactured by BASF Corp.) 140 parts, and the average major axis of 0.
3 μm C.I. I. Pigment Red 166 3 parts and Titanium White (“Taipaque R-550”) 60
Parts were thoroughly mixed using a mixer to obtain a yellow pigment composition.

<Example 10> In Example 9, C.I.
I. Pigment Yellow 183, C.I. I.
Pigment Yellow 181 (“PV First Yellow H3R” manufactured by Ciba-Geigy Co., Ltd.) was used in the same manner as in Example 9 to obtain a yellow pigment composition.

<Embodiment 11> In the ninth embodiment, C.I.
I. Pigment Yellow 183, C.I. I.
Pigment Yellow 139 (“Pariotor Yellow L1970” manufactured by BASF) was used in the same manner as in Example 9 to obtain a yellow pigment composition.

<Embodiment 12> In Embodiment 1, the C.I. I. Pigment Red 166, instead of C.I. I. Pigment Red 144 (“Chromophtal red BR”) was used in the same manner as in Example 1 except that 3 parts were used.

<Example 13> In Example 1, the C.I. I. Pigment Red 166, instead of C.I. I. Pigment Red 220 (“Chlomophthale Red G”) 3 parts, except that 3 parts were used.
A yellow pigment composition was obtained in the same manner as in.

<Example 14> Example 1 was repeated except that 100 parts of titanium yellow ("Taipaque yellow TY-70" manufactured by Ishihara Sangyo Co., Ltd.) was used in place of titanium white. A yellow pigment composition was obtained in the same manner as in.

<Example 15> C.I. I. Pigment Yellow 73 ("Shimla Fast Yellow 4117" manufactured by Dainippon Ink and Chemicals, Inc.), 90 parts of C.I. I. Pigment Red 166
3 parts, yellow iron oxide ("Toda Color" manufactured by Toda Kogyo Co., Ltd.)
Yellow 48 ") 20 parts and titanium yellow (" Taipaque yellow TY-70 ") 20 parts were sufficiently mixed using a mixer to obtain a yellow pigment composition.

<Comparative Examples 1 to 15> In each of Examples 1 to 15, instead of the condensed azo red pigment used as the red pigment for toning, an amount of C.I. I. Pigment Red 57: 1 (Dainippon Ink and Chemicals, Inc.)
"Shimla Brilliant Carmine 6B30
6 ”) was used, and a yellow pigment composition was obtained in the same manner as in each of the examples.

<Comparative Examples 16 to 30> In each of Examples 1 to 15, instead of the condensed azo red pigment used as the red pigment for toning, an amount of C.I. I. Pigment Violet 19 (Dainippon Ink and Chemicals
"First Gen Super Red Y" manufactured by
E ”) was used, and a yellow pigment composition was obtained in the same manner as in each example.

<Example 16> (Application to road marking material) A petroleum resin-based melt type road surface containing 2 parts of the yellow pigment composition obtained in each of the above Examples and Comparative Examples and 16% by weight of glass beads GB153T. Melt and mix 98 parts of marking paint compound at 190 ° C, then use applicator for about 1m
It was applied to a metal plate to a thickness of m. This was subjected to an exposure test for 6 months at an exposure test facility in Kashima Plant of Dainippon Ink and Chemicals, Inc. (Location: Kamisu Town, Kashima County, Ibaraki Prefecture), and the hue change was visually evaluated.

As a result, in comparison with the test coated plates using the yellow pigment compositions obtained in the respective examples, the test coated plates using the pigment compositions obtained in Comparative Examples 1 to 15 lost redness, On the other hand, the test coated plate using the pigment composition obtained in Comparative Examples 16 to 30,
The reddishness became strong, and the hue change was extremely remarkable in all cases.

[0043]

INDUSTRIAL APPLICABILITY The yellow pigment composition of the present invention is a colorant which does not cause any problems in terms of environmental pollution or occupational hygiene and has little change in hue with aging, and is particularly suitable for use as road marking materials. be able to.

Claims (13)

[Claims] 1. A yellow pigment composition comprising an organic yellow pigment and a condensed azo red pigment. 2. A condensed azo yellow pigment is C.I. I. The pigment composition according to claim 1, which is one or more pigments selected from the group consisting of Pigment Red 144, Pigment Red 166, and Pigment Red 220. 3. The pigment composition according to claim 1, wherein the primary particle diameter of the condensed azo red pigment primary particles is in the range of 0.05 to 1.5 μm. 4. The pigment composition according to claim 1, which contains an organic pigment and an inorganic pigment. 5. The pigment composition according to claim 1, which contains a composite pigment of an organic yellow pigment and an inorganic pigment. 6. The pigment composition according to claim 4, wherein the inorganic pigment is an inorganic pigment having a refractive index of 2.0 or more. 7. The pigment composition according to claim 4, wherein the inorganic pigment is an inorganic pigment containing an oxide of at least one metal selected from the group consisting of titanium, iron and nickel. 8. The pigment composition according to claim 4, wherein the inorganic pigment is one or more pigments selected from the group consisting of titanium white, titanium yellow and yellow iron oxide. 9. The organic yellow pigment is an azo pigment.
9. The pigment composition according to any one of items 8 to 8. 10. The pigment composition according to claim 1, wherein the organic yellow pigment is an isoindoline pigment. 11. An organic yellow pigment is C.I. I. Pigment
The pigment composition according to claim 9, which is one or more pigments selected from the group consisting of Yellow 83, Yellow 181, and Yellow 183. 12. The organic yellow pigment is C.I. I. Pigment
The pigment composition according to claim 10, which is Yellow 139. 13. A road marking material comprising the pigment composition according to any one of claims 1 to 12.