JP3900544B2 - Yellow pigment composition - Google Patents

Description

[0001]
BACKGROUND OF THE INVENTION
A relates pigment compositions useful yellow as a colorant of the present invention is chrome yellow alternative applications, more particularly, less change in hue due to aging, Ru excellent nighttime visibility yellow road marking material The present invention relates to a pigment composition and a road marking material containing the same .
[0002]
[Prior art]
The yellow pigment used for construction machinery painting and road marking materials used on the center line of paved roads, etc. has conventionally used yellow lead, but yellow lead is a compound composed of hexavalent chromium and lead. However, there are problems in terms of environmental pollution and occupational health, and an alternative to organic pigments is desired as a countermeasure.
[0003]
Various yellow organic pigments such as monoazo pigments, disazo pigments, and condensed polycyclic pigments are known. For example, monoazo pigments and condensed polycyclic pigments have excellent light resistance, and disazo pigments have excellent coloring power. Etc. However, since many of these yellow organic pigments are different from yellow lead in hue, in order to use them for road marking purposes, an orange to red pigment is added to these yellow pigments, so-called toning. There is a need. Examples of the orange to red pigment added to the yellow pigment include pyrazolone pigments, carmine 6B, 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 bengara Etc. are known.
[0004]
[Problems to be solved]
However, the light resistance and weather resistance of these orange to red pigments are remarkably different from those of yellow organic pigments, especially disazo yellow pigments. There was a problem that the hue change was large.
[0005]
The problem to be solved by the present invention is to provide a yellow organic pigment composition that is free from environmental pollution and occupational health problems, has the same hue as yellow lead, and has little hue change with time. There is.
[0006]
[Means for Solving the Problems]
As a result of extensive research on toning orange to red pigments that exhibit a time-dependent change behavior similar to that of yellow organic pigments, the present inventors have found that condensed azo red pigments have characteristics suitable for this purpose. The invention has been completed.
[0007]
That is, the present invention provides a yellow pigment composition for road marking materials, which contains an organic yellow pigment and a condensed azo red pigment in order to solve the above problems. The present invention also provides a road marking material containing the yellow pigment composition. Hereinafter, the yellow pigment composition for road marking materials may be simply abbreviated as a yellow pigment composition.
[0008]
DETAILED DESCRIPTION OF THE INVENTION
In the present invention, various known pigments can be used depending on 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. Disazo yellow pigments such as C.I. Pigment Yellow 12, 13, 13, 14, 17, 55, 81, 83, and 136; I. Monoazo yellow pigments such as C.I. Pigment Yellow 1, 3, 3, 65, 73, 74, 75, 116, 151, 154, 181; I. An azo lake yellow pigment such as C.I. Pigment Yellow 183; I. Condensed yellow pigments such as C.I. Pigment Yellow 93 and 95; I. Pigment Yellow 109 and 110, isoindolinone yellow pigments such as C.I. I. Pigment Yellow 139, an isoindoline yellow pigment such as C.I. I. And condensed polycyclic yellow pigments such as CI Pigment Yellow 24 and 108.
[0009]
Among these yellow pigments, C.I. is considered in consideration of economy, coloring power, ease of toning, weather resistance, heat resistance, and the like. I. CI Pigment Yellow 14, 17, 17, 55, 65, 73, 75, 83, 139, 181, 183, etc. are preferred. I. Pigment Yellow 83, 139, 181 and 183 are preferable.
[0010]
Examples of the condensed azo red pigment for toning include C.I. I. CI Pigment Red 144, 166, 215, 220, 221 and the like. C. is preferable in that it is easy to adjust colors and has little hue change with time after construction. I. Pigment Red 144, 166, and 220 are particularly preferable.
[0011]
The particle diameter of the condensed azo red pigment is preferably such that the average major axis is in the range of 0.05 to 1.5 μm, particularly preferably in the range of 0.1 to 1.0 μm. If the average major axis of the particle diameter is smaller than 0.05 μm, the weather resistance and light resistance tend to be lowered, and the temporal change behavior of the hue tends to be different. When the thickness is larger than 5 μm, it is difficult to adjust the color to chrome yellow, and the hue change with time tends to be different, which is not preferable.
[0012]
The amount of the condensed azo red pigment used in combination with the yellow pigment for toning varies depending on the coloring power of the yellow pigment used, the hue of the condensed azo red pigment, the coloring power, and the target hue. A value can be taken, but considering the toning effect on the hue, a range of 0.1 to 100,000 parts by weight with respect to 100 parts by weight of the yellow pigment is preferable. If the amount of the azo condensed azo red pigment used is small, the color is slightly reddish yellow, but the red increases as the amount of the combined azo condensed azo pigment is increased. . For example, C.I. I. Pigment red 220 and C.I. I. In the case of toning to a hue similar to yellow lead from CI Pigment Yellow 83, C.I. I. Pigment Yellow 83 per 100 parts by weight of C.I. I. It is preferable to use 0.5 to 5 parts by weight of CI Pigment Red 220.
[0013]
The mixing of the yellow pigment and the condensed azo red pigment may be a dry blend in which dry pigments are mixed together or a wet blend in which a wet cake of pigment is mixed. It is also possible to filter after dispersing the pigment in a suitable dispersion medium such as water.
[0014]
The yellow pigment toned with the condensed azo-based red pigment can be used as it is or in combination with other pigments for various coloring materials. However, when used as a road marking material, it may be used as it is or bengara (refractive (Ratio: 2.8), yellow iron oxide (refractive index: 2.0), and other inorganic pigments. In particular, when used together with white to pale yellow high refractive index inorganic pigments such as titanium white (refractive index: 2.7), titanium yellow (refractive index: 2.9), zirconium oxide (refractive index: 2.4), etc. The nighttime visibility can be remarkably improved without greatly changing the hue due to the retroreflective action. The amount of the inorganic pigment added for the purpose of improving visibility at night is preferably 10 to 500 parts by weight, particularly preferably 100 to 300 parts by weight, based on 100 parts by weight of the yellow pigment toned with the condensed azo red pigment.
[0015]
The mixture of the yellow pigment and the inorganic pigment toned with the condensed azo red pigment may be a dry blend or a wet blend. After the pigment is dispersed in an appropriate dispersion medium such as water, it may be 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 material having excellent nighttime visibility. This is presumably because the yellow pigment covers the surface of the high refractive index inorganic pigment and acts as a color filter against retroreflected light from the inorganic pigment particles. The coating of the inorganic pigment with the organic pigment can be performed mechanically by a dry process using an apparatus such as a hybridizer.
[0016]
The road marking material is prepared by mixing a filling material (aggregate), natural and / or synthetic resin in addition to the yellow pigment composition thus prepared.
[0017]
Examples of the filling material include chlorite, white sand, quartz powder, and glass beads. Examples of natural and synthetic resins include rosin resin, maleic acid-modified rosin ester, coumarone indene resin, petroleum resin, and xylene. Examples thereof include resins, ketone resins, terpene resins, castor oil, coconut oil, soybean oil, melamine resins, synthetic rubbers, phthalic acid resins, acrylic resins, and phenol resins.
[0018]
The road marking material is laid on a road or the like by a hot spray method or a heat melting method.
[0019]
【Example】
Hereinafter, the present invention will be described in more detail with reference to examples. In the following examples, parts means parts by weight.
[0020]
<Production Example> (Production of CI Pigment Red 166)
To a reactor equipped with a thermometer and a stirrer, 162 parts of 2,5-dichloroaniline, 615 parts of 35% hydrochloric acid and 2000 parts of water were added and heated to 90 ° C. to dissolve the contents. The mixture was allowed to cool to 30 ° C., 1000 parts of ice was added, and 350 parts of a 20% aqueous sodium nitrite solution was added to diazotize.
[0021]
In another reactor, 1600 parts of water, 415 parts of a 48% aqueous sodium hydroxide solution and 188 parts of 3-hydroxy-2-naphthoic acid were added and dissolved. The obtained solution was dropped into the diazotization reaction solution over about 30 minutes. After completion of dropping, the mixture was heated to 90 ° C. and held for 1 hour, then filtered, washed with hot water, and dried to obtain 340 parts of a red substance.
[0022]
Next, 2100 parts of xylene, 340 parts of red substance and 2 parts of dimethylformamide were added to a reactor equipped with a thermometer and a stirring device. The contents were heated to 80 ° C. with stirring, and 156 parts of thionyl chloride was added dropwise over about 30 minutes. After completion of the dropping, the temperature was gradually raised to 110 ° C. and kept at the same temperature 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.
[0023]
Furthermore, 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. A solution consisting of 57 parts of p-phenylenediamine and 1300 parts of o-dichlorobenzene heated to 90 ° C. was added thereto, and then the temperature was raised to 140 ° C. over about 2 hours, and kept at the same temperature for 3 hours. After cooling to 90 ° C., the product was filtered, and the residue was washed successively with dimethylformamide, methanol and hot water, dried and dried. I. 270 parts of Pigment Red 166 crude product were obtained.
[0024]
15 parts of the obtained crude product was charged into a sand grinder together with 500 parts of 0.5 μm zirconia beads, 100 parts of water and 50 parts of o-dichlorobenzene, and ground at 20 ° C. for 4 hours. After milling, the mixture was filtered, and the residue was washed with methanol, washed with hot water, and dried to obtain a C.I. I. Pigment Red 166 was obtained.
[0025]
Similarly obtained C.I. I. Pigment Red 166 was heat-treated in o-dichlorobenzene at various temperatures to prepare those having an average major axis of 0.15 μm, 0.3 μm, 0.7 μm, and 1.2 μm.
[0026]
<Example 1>
C. I. Pigment Yellow 83 (“Shimla First Yellow 4181NR” manufactured by Dainippon Ink & Chemicals, Inc.), C.I. I. 3 parts of Pigment Red 166 and 100 parts of Titanium White (“Taipek R-550” manufactured by Ishihara Sangyo Co., Ltd.) were sufficiently mixed using a mixer to obtain a yellow pigment composition.
[0027]
<Examples 2 to 5>
In Example 1, C.I. I. In place of Pigment Red 166, C.C. of average major diameters of 0.07 μm, 0.15 μm, 0.7 μm and 1.2 μm obtained in Production Examples were used. I. A yellow pigment composition was obtained in the same manner as in Example 1 except that CI Pigment Red 166 was used.
[0028]
<Example 6>
C. I. Pigment Yellow 83 (Shimla First Yellow 4181NR: manufactured by Dainippon Ink & Chemicals, Inc.) 215 parts of wet cake (pigment content 45%) and C.I. I. Six parts of Pigment Red 166 wet cake (pigment content 50%) were kneaded using a kneader, dried and pulverized, and then added with 100 parts of titanium white (Taipeke R-550: manufactured by Ishihara Sangyo Co., Ltd.) Mix well using a mixer to obtain a yellow pigment composition.
[0029]
<Example 7>
In a reactor equipped with a thermometer and a stirrer, 2000 parts of water, 57 parts of N- (2,5-dimethoxy-4-chlorophenyl) -3-oxobutanamide (manufactured by Samsung Chemical Co., Ltd.) and 25% hydroxylation 55 parts of an aqueous sodium solution was added and dissolved. To this solution, 100 parts of titanium white (“JR-602S” manufactured by Teikoku Kako Co., Ltd.) was added, and 21 parts of acetic acid was added dropwise with stirring to prepare a coupler solution. After the temperature of the coupler liquid was adjusted to 20 ° C., 33 parts of 3,3′-dichlorobenzidine hydrochloride tetrazotized aqueous solution was added dropwise over about 2 hours. I. A composite pigment of CI Pigment Yellow 83 and Titanium White was obtained. After completion of the dropwise addition, the mixture was further heated to 90 ° C. and stirred at the same temperature for 1 hour, and then C.I. I. Pigment Red [0030]
After adding 6 parts of 166 wet cake (pigment content: 50%) and stirring and dispersing sufficiently, it was filtered, washed with water and dried to obtain a yellow pigment composition.
[0031]
<Example 8>
In Example 1, C.I. I. Pigment Yellow 83, C.I. I. A yellow pigment composition was obtained in the same manner as in Example 1 except that CI Pigment Yellow 17 (“Shimler First Yellow 8GTF” manufactured by Dainippon Ink and Chemicals, Inc.) was used.
[0032]
<Example 9>
C. I. Pigment Yellow 183 (“Pariotole Yellow K2270” manufactured by BASF Corporation) 140 parts, C.I. I. 3 parts of Pigment Red 166 and 60 parts of Titanium White (“Typaque R-550”) were sufficiently mixed using a mixer to obtain a yellow pigment composition.
[0033]
<Example 10>
In Example 9, C.I. I. Pigment Yellow 183 instead of C.I. I. A yellow pigment composition was obtained in the same manner as in Example 9, except that 140 parts of Pigment Yellow 181 (“PV First Yellow H3R” manufactured by Ciba Geigy Co., Ltd.) was used.
[0034]
<Example 11>
In Example 9, C.I. I. Pigment Yellow 183 instead of C.I. I. A yellow pigment composition was obtained in the same manner as in Example 9 except that 140 parts of Pigment Yellow 139 (“Pariotol Yellow L1970” manufactured by BASF) was used.
[0035]
<Example 12>
In Example 1, C.I. I. Pigment Red 166 instead of C.I. I. A yellow pigment composition was obtained in the same manner as in Example 1 except that 3 parts of Pigment Red 144 (“chromophthal red BR”) was used.
[0036]
<Example 13>
In Example 1, C.I. I. Pigment Red 166 instead of C.I. I. A yellow pigment composition was obtained in the same manner as in Example 1 except that 3 parts of Pigment Red 220 (“chromophthal red G”) was used.
[0037]
<Example 14>
In Example 1, a yellow pigment composition was used in the same manner as in Example 1 except that 100 parts of titanium yellow (“Tipeke Yellow TY-70” manufactured by Ishihara Sangyo Co., Ltd.) was used instead of titanium white. Got.
[0038]
<Example 15>
C. I. Pigment Yellow 73 (“Shimra Fast Yellow 4117” manufactured by Dainippon Ink & Chemicals, Inc.), C.I. I. 3 parts of Pigment Red 166, 20 parts of yellow iron oxide (“Todacolor Yellow 48” manufactured by Toda Kogyo Co., Ltd.) and 20 parts of titanium yellow (“Typaque Yellow TY-70”) are thoroughly mixed using a mixer. Thus, a yellow pigment composition was obtained.
[0039]
<Comparative Examples 1-15>
In each of Examples 1 to 15, instead of the condensed azo red pigment used as the toning red pigment, an amount of C.I. I. Pigment Red 57: 1 (Shimla Brilliant Carmine 6B manufactured by Dainippon Ink and Chemicals, Inc.
306 ") was used to obtain a yellow pigment composition in the same manner as in each Example.
[0040]
<Comparative Examples 16-30>
In each of Examples 1 to 15, instead of the condensed azo red pigment used as the toning red pigment, an amount of C.I. I. A yellow pigment composition was obtained in the same manner as in each Example, except that CI Pigment Violet 19 (“First Gen Super Red YE” manufactured by Dainippon Ink and Chemicals, Inc.) was used.
[0041]
<Example 16> (Application to road marking material)
After melting and mixing 2 parts of the yellow pigment composition obtained in each of the above Examples and Comparative Examples and 98 parts of a petroleum resin-based molten road marking paint compound containing 16% by weight of glass beads GB153T at 190 ° C. The metal plate was coated with an applicator to a thickness of about 1 mm. This was subjected to an exposure test for 6 months at an exposure test facility in Kashima Factory, Dainippon Ink & Chemicals, Inc. (location: Kamisu-cho, Kashima-gun, Ibaraki Prefecture), and the hue change was evaluated visually.
[0042]
As a result, as compared with the test coating plate using the yellow pigment composition obtained in each example, the test coating plate using the pigment composition obtained in Comparative Examples 1 to 15 loses redness, while comparing The test coated plates using the pigment compositions obtained in Examples 16 to 30 were reddish, and the change in hue was extremely remarkable in all cases.
[0043]
【The invention's effect】
The yellow pigment composition of the present invention is a colorant that has no problems in terms of environmental pollution and occupational health and has little hue change with time, and can be suitably used especially for road marking materials.

Claims (13)

A yellow pigment composition for road marking materials containing an organic yellow pigment and a condensed azo red pigment. Condensed azo red pigment is C. I. The yellow pigment composition for road marking materials according to claim 1 , wherein the yellow pigment composition is one or more pigments selected from the group consisting of CI Pigment Red 144, 166 and 220. The average major axis road marking material for yellow pigment composition according to claim 1, wherein the range of 0.05~1.5μm of condensed azo-based red pigment primary particles. The yellow pigment composition for road marking materials according to claim 1, 2 or 3, comprising an organic pigment and an inorganic pigment. The yellow pigment composition for road marking materials according to claim 4 or 5, wherein the organic pigment is an inorganic pigment having a refractive index of 2.0 or more. The yellow pigment composition for road marking materials according to claim 4 or 5, wherein the inorganic pigment is one or more pigments selected from the group consisting of titanium, iron and nickel. The yellow pigment composition for road marking materials according to claim 4 or 5, wherein the inorganic pigment is one or more pigments selected from the group consisting of titanium, iron and nickel. The yellow pigment composition for road marking materials according to claim 4 or 5, wherein the inorganic pigment is at least one pigment selected from the group consisting of titanium white, titanium yellow and yellow iron oxide. The yellow pigment composition for road marking materials according to any one of claims 1 to 8, wherein the organic yellow pigment is an azo pigment. The yellow pigment composition for road marking materials according to any one of claims 1 to 8, wherein the organic yellow pigment is an organic isoindoline pigment. The yellow pigment composition for road marking materials according to any one of claims 1 to 8, wherein the organic yellow pigment is an isoindoline pigment. The organic yellow pigment is C.I. I. The yellow pigment composition for road marking materials according to claim 9, which is at least one pigment selected from the group consisting of CI Pigment Yellow 83, 181 and 183. A road marking material comprising the yellow pigment composition according to any one of claims 1 to 12.