JPS63235376A - Pigment composition and production thereof - Google Patents

Abstract

PURPOSE:To obtain a pigment compsn. useful as a colorant for paints, synthetic resins, etc. and excellent in light resistance, by mixing an azo pigment obtd. by coupling a specific coupler with a diazo component with an azo pigment obtd. by coupling another conventional coupler with a diazo component. CONSTITUTION:A 5-aminobenzotriazole compd. (a) of formula I (wherein R1 and R2 are each H, an alkyl or an aryl and at least one of R1 and R2 is always a group other than H) and a diketene or an acetoacetic ester, etc. (b) are dissolved or dispersed in an inert org. solvent such as xylene. The mixture is reacted at room temp. to 150 deg.C for several min to several hr to carry out an acetoacetylation reaction, thus obtaining a coupler (A) of formula II. 0.5-100pts. wt. azo pigment obtd. by coupling the component A with a diazo component is mixed with 100pts.wt. azo pigment obtd. by coupling a conventional coupler (B) other than the component (A) (e.g., an acetoanilide coupler) with a diazo component.

Description

DETAILED DESCRIPTION OF THE INVENTION (Industrial Application Field) The present invention relates to an azo pigment composition, and more specifically, it concerns not only the light fastness of the resulting pigment itself but also the light fastness of the material to be colored that is colored by the pigment. The present invention also relates to pigment compositions that can be improved.

(Prior Art) Conventionally, various azo pigments have been known. Among these azo pigments, for example, an azo pigment called an anilide azo pigment uses an acetoacedoanilite compound as a coupler. However, it is obtained by coupling a diazonium salt or tetrazonium salt of an aromatic primary monoamine or diamine to this.

(Problem to be Solved by the Invention) The coupling component of the above anilite azo pigment is obtained by acetoacetylating the amino group of aniline or an aniline derivative, and the azo pigment obtained using these couplers Properties such as hue, clarity, light resistance, weather resistance, solvent resistance, etc. are primarily determined by the structure of the coupler and the structure of the aromatic primary amine coupled to the coupler. There are many cases.

Therefore, in order to improve various physical properties of the resulting azo pigment, couplers and/or aromatic primary amines with various structures have been proposed, and these couplers, aromatic primary amines, or a combination thereof Many azo pigments are known. Although these azo pigments generally have a W-rich hue and are characterized by clear tones,
In particular, there are no satisfactory results regarding light resistance.

Therefore, for example, these azo pigments can be used in plastics,
When used as a coloring agent for printing inks or paints, great consideration must be given to the light resistance of the azo pigment used.

For example, if an azo pigment with insufficient light resistance is used, it will not only cause discoloration or fading of the colored product, but also affect the light resistance of the colored material itself, such as the coating of plastic, ink, or paint. There is a problem of lowering the

The above problems of discoloration and deterioration of the colored material can be solved by using other pigments with excellent light resistance, such as polycyclic pigments, but these pigments with good light resistance are expensive. can be,
It cannot be used economically for general purposes, and it cannot be used for one minute because its hue, sharpness, etc. are limited.

Therefore, when coloring paints, printing inks, plastics, etc. with azo pigments, light stabilizers such as ultraviolet absorbers and deterioration inhibitors are also used, but these light stabilizers Because it is a relatively unstable organic compound with a paper content of 7-1, it is known to cause various problems in resins and binders, and its uses are extremely limited and it lacks versatility. Ta.

Therefore, there is a demand for the development of a technology that can provide azo pigments with excellent light resistance in eight colors and at low cost.

(1st Step to Solve the Problems) In response to the demands of the prior art as described above, the present inventor has conducted extensive research to provide an inexpensive azo pigment with excellent light resistance, and has found that it can be used to form an azo pigment. It has been found that the object of the present invention can be achieved by employing a coupler having a specific structure.

That is, the present invention consists of two inventions, the first of which is an azo pigment obtained by coupling a diazo component to a general coupler other than the following general formula (I) and the above general formula (I). A pigment composition comprising an azo pigment obtained by coupling a diazo component to a coupler represented by When producing pigments, the following general formula (
This is a method for producing a pigment composition characterized by using a coupler represented by I).

(However, R1 and R2 in the above formula are a hydrogen atom f, an alkyl group, or an aryl group, but are not hydrogen atoms at the same time.

) (Preferred Embodiment) Next, to explain the present invention in more detail, the coupler of the above general formula (I), which mainly characterizes the present invention, is represented by the following formula (
A conventionally known 5-aminobenzotriazole compound represented by I (in the formula, R1 and R2 are the same as defined above) is mixed with diketene or acetoacetic acid in the same manner as in the conventional method for producing an anilide coupler. It is obtained by acylation with ester or the like.

The compound represented by the above general formula (II) is a conventionally known compound. For example, preferred compounds include (a) 2-(3'-methyl-2'-hydroxyphenyl)-5-aminobenzotriazole, (ro) )2-(
3',5''-dimethyl-2'-hydroxyphenyl)-
5-aminobenzotriacyl, (c) 2-(3'-t-butyl-5'-methyl-2'-
hydroxyphenyl)-5-aminobenzotriazole, (d) 2-(3',5'-di-t-butyl-2'-hydroxyphenyl)-5-aminobenzotriazole, (e) 2-(3", 5'-di-t-amyl-2'-hydroxyphenyl)-5-aminobenzotriazole, (to)2-(3',5''-di-t-octyl-2'-hydroxyphenyl)-5-amino Benzotriazole; , α-dimethylbenzyl)-5
'-Methyl-2'-hydroxyphenyl]-5-aminohencitriazole, (su)2-[3'-(α1.α-
dimethylbenzyl)-s'-t-butyl-2'-hydroxyphenyl]-5-aminobenzotriazole, (nu)2-[3'-(α,α-dimethylbenzyl)-5”-
t-octyl-2'-hydroxyphenyl]-5-aminobenzotriazole, (l)2-[3''-t-butyl-5'-(α,α-dimethylbenzyl)~2'-hydroxyphenyl]-5 -aminobenzotriazole, (o)2-[3'--5'-(α).

α-dimethylbenzyl)-2′-hydroxyphenyl]
-5-aminohencitriazole, (wa')2-[3'
-(α-methylbenzyl)-5”-t-cutyl-2′
-Hydroxyphenyl 1-s-aminobenzotriazole, (power) 2- (3'-benzy-5'-t-butyl-2'-hydroxyphenyl)-5-aminobenzotriazole (yo)2- (3''-N- Phenylcarboxamide-5'
Examples include -t-butyl-2'-hydroxyphenyl)-5-aminobenzotriazole(ri)2-(3'-t-butyl-5'-methoxy2'-hydroxyphenyl)-5-aminobenzotriazole.

Acetoacetylation of the 5-aminobenzotriazole compound of the general formula (n) as shown below with diketene or acetoacetate can be carried out, for example, by adding the compound of the general formula (II) in an inert organic solvent such as benzene, xylene, toluene, etc.
It is easily carried out by dissolving or dispersing the compound and reacting it with diketene or acetoacetate for several minutes to several hours at an appropriate temperature, for example, room temperature to about 150°C. The coupler of the present invention can be obtained, and the manufacturing method itself may be in accordance with any conventionally known method.

Examples of preferred couplers of general formula (I) in the present invention are as follows.

(1) 2-(3″-Methyl-2′-hydroxyphenyl)-5-acetoacetylaminobenzotriazole.

(2) 2-(3',5''-dimethyl-2'-hydroxyphenyl)-5-acetoacetylaminobenzotriazole, (3) 2-(3'-t-butyl-5-nimethyl-2'
-hydroxyphenyl)-5-acetoacetylaminobenzotriazole, [4) 2-(3', 5'-t-butyl-2
'-Hydroxyphenyl)-5-acetoacetylaminobenzotriazole, (・5)2- (:3'',5''-di-t-amyl-2'
-hydroxyphenyl)-5-acetoacetylaminobenzotriazole, (6) 2- (3'', 5'-di-t-octyl-2'-hydroxyphenyl)-5-acetoacetylaminobenzotriazole, (7) 2- [ 3′,5″-di(α,α-dimethylbenzyl)-2′-hydroxyphenylgo 5-acetoacetylaminobenzotriazole, (8) 2-[3
”-(α,α-dimethylbenzyl)-5”-methyl-2
'-Hydroxyphenylgo 5-acetoacetylaminobenzotriazole, (9) 2-[3'-(α,α-dimethylbenzyl)-
5'-t-butyl-2'-hydroxyphenyl go 5-
Acetoacetylaminobenzotriazole, (10) 2-[3'-(α,α-dimethylhensyl)-5'-t-octyl-2'-hydroxyphenyl]
-5-acetoacetylaminohencytriazole, (11) 2-[3''-t-butyl-5'-(α.

α-dimethylbenzyl)-2'- and troxyphenyl]
-5-acetoacetylaminobenzotriazole, (12) 2-[3'-t-octyl-5'-(α, α
-dimethylhensyl)-2'-hydroxyphenylgo-5-acetoacetylaminobenzotriazole, (13) 2-[3'-(α-methylbenzyl)-5'
-t-octyl-2'-hydroxyphenylgo-5-acetoacetylaminobenzotriazole, (14) 2-[3'-benzyl-5'-7-butyl-2
'-Hydroxyphenylgo-5-acetoacetylaminobenzotriazole, (17)2-(3'-N-phenylcarboxamide-5
"-t-butyl-2'-hydroxyphenyl)-5-(
2″-hydroxy-3″-naphthoyl)aminobenzotriazole (18) 2-(3′-t-butyl-5′-methoxy-
2'-hydroxyphenyl)-5-(2''-hydroxy-3''-naphthoyl)aminobenzotriazole and the like.

The couplers used in the present invention as described above are useful as couplers for azo pigments, and diazotized primary amines of the Hoya family, such as those used in the production of conventionally known azo pigments, are useful as couplers for azo pigments. Alternatively, by tetrazotizing and coupling, an azo pigment with excellent light resistance can be easily provided.

For example, by using an aromatic monoamine as the aromatic primary amine, a monoazo pigment is obtained, and by using an aromatic diamine as the aromatic primary amine, a disazo pigment is easily provided.

The pigment obtained using the above coupler is itself useful as a pigment having excellent light resistance.

The pigment composition of the present invention is a pigment composition comprising an azo pigment obtained from the above-mentioned specific coupler and a conventionally known azo pigment, and the pigment composition can be obtained, for example, by the method of the present invention described above.

(1) Using the above-mentioned specific coupler, the azo pigment containing the above-mentioned specific coupler is made up to 2% in the same manner as in the conventionally known azo pigment manufacturing method, and this azo pigment is mixed with the conventionally known azo pigment. .

According to this method, a conventionally known azo pigment of 100Il! By adding and mixing at a ratio of about 0.5 to 1001 u parts per part by weight, the light resistance of the resulting pigment composition and the light resistance of the colored material containing the azo pigment are significantly improved.

(2) When manufacturing a conventionally known azo pigment, a specific coupler is added and mixed into a conventionally known coupler to be used in a proportion that accounts for 0.5 to about 50 mol% of the entire coupler to obtain a mixed coupler. A method of preparing a pigment composition of an azo pigment containing the above-mentioned specific coupler and an azo pigment not containing the coupler by carrying out a coupling reaction according to a conventional method.

According to this method, an azo pigment containing a specific coupler is
Since the azo pigment is more uniformly distributed in the resulting pigment composition, the light resistance improving effect of the azo pigment is more preferably exhibited.

The azo pigment consisting of a coupler other than the specific coupler used in the pigment composition of the present invention may be any conventionally known azo pigment and is not particularly limited, but particularly preferred azo pigments are homologues of the above-mentioned specific coupler. This is a known acetoacetanilide azo pigment obtained from a conventionally known acetoacetanilide coupler.

Although any conventionally known couplers can be used as the coupler used in the second aspect of the present invention, a particularly preferred coupler is an acetoacetanilide coupler as described below.

4'-Be-0-acetoacetotoluidide, 4'-α-
Benzoylacetamide-2',5''-dimethoxybencyanilide, α, α'-prephthaloyl bis[5-chloro-2,4-dimethoxyacedoanilide], α, α
'-Terephthaloyl bis[4-chloro-5-methyl-〇-acedoanidite], 2-α-acetoacetamido-6-nitoxybenzothiazole, acetoacedoanilite, 0-chloroacetoacetanilide , p-chloroacetoacetanilide, 4-chloro-2゜5-dimethoxyacetoacetanilide, 2゜5-dimethoxyacetoacetanilide, 0-acetoacetoanidide, O-acetoacetotoluidide, 2 .4-acetoacetoxylidide, p-acetoacedoanididite, p-
Acetoacetotoluidide, 4-chloro-2-methylacetoacetoanilite, P-ethoxyacetoacetoanilite, 4-nitro-2-methylacetoacetoanilide, and the like.

Of course, couplers other than those mentioned above can be used or used in combination.

Further, the diazo component to be coupled to the E coupler may be any conventionally known diazo component, ie, aromatic primary mono- and diamines, and is not particularly limited, but particularly preferred diazo components include the following examples.

Aniline, o-, m- and p-chloroaniline.

0-Chlor-p-nitroaniline, 0-nitro-p-chloroaniline, 2-nitro-5-chlora, niline, 2.4-dichloroaniline, 2.5-dichloroaniline, 3.4-dichloraniline Aniline, 2,5-dimethoxyaniline, m-nitroaniline, 0-nitroaniline, p
-nitroaniline, 2.4.6-)limethylaniline,
P-benzyloxyaniline, 2-benzyloxy-5
-Chloraniline, 5-chloro-2-(p-chlorophenoxy)-aniline, o-(p-chlorophenoxy)aniline, 5-chloro-2-phenoxyaniline, p-cyclohexylaniline, 3.5-dichlor -2-7 enoxyaniline, p, p”-methylene dianiline, 0-phenoxyaniline, P-phenylazoaniline, 0-(
Aniline and its derivatives such as phenylsulfonyl)-aniline: o-, m- and p-1 luidine, 6-chloro-α, α,
α-Trifluoro m-toluidine, 6-(ethylsulfonyl)-α,α,α-trifluoro m-toluidine, 4.
4'-methylenedi-m-toluidine, 4-m-tolylazo-m-toluidine, 3-chloro-0-toluidine,
4-Chlor-0-toluidine, 5-chloro-0-toluidine, chlor-α,α,α-trifluoro-m-toluidine, 6-chloro-0-toluidine, 4-cyclohexyl-〇-toluidine, 4-nitro -o-toluidine, 5-
Nitro-〇-toluidine, 4-o=tolylazo-0-
Toluidines such as toluidine, 3-chloro-p-toluidine, 2-nitro-p-toluidine, α, α, α-trifluoro-2-nitro-p-toluidine, 4-amino-5-chloro-0-toluylnitrile; Its derivatives: 2
, 4-, 2.5-, 2.6- and 3.5-xylidine,
6-(2,4-xylylazo)-2,4-xylidine, 4,4'-methylenedi-2,5-xylidine, α, α
, α, α′, α′, α′-hexafluoro-3,5-xylidine and derivatives thereof; o-, m-
and p-anisidine, 4-chloro-0-anisidine, 5
-Chlor-0-anisidine, 5-chloro-4-nitroanisidine, 4-nitro-0-anisidine, 5-nitro-
0-anisidine, 2-nitro-p-anisidine, 3-chloro-p-anisidine, 5-(ethylsulfonyl)-0
-anisidine, 5-(p-phenylsulfonyl)-0-
Anisidine, 3-amino-p-anisanilite, 3-amino-ρ-anisic acid, 5-(benzylsulfonyl)-0
-anisidine, 5-methyl-〇-anisidine, 5-methyl-4-nitro-〇-anisidine, 0-anisidine-4
- Anisidines and their derivatives such as sulfonediethylamide and 0-anisidine-4-sulfonebutyramide; phenitidines and their derivatives such as 〇- and p-phenitidine and 5-methyl-〇-phenytidine; m-aminobenzo Benzonitriles such as nitrile, p-amino-2,4-dimethoxyhendinitrile; phenylenediamine, 2,6-dichloro-ρ-phenylenediamine, N,N-dimethyl-p-phenylenediamine, 2-methoxy-N -Phenyl-p-phenylenediamine and other phenylenediamines; m-amino-N-butylbenzamide, 4'-amino-
2'', 5'-diethoxybenzanilide, 4'-amino-2=,5=-dimethoxybenzanilide, 4'
-Amino-N-ethylbenzanilide, 4'-amino-4-nitrobenzanilide, 3,3'-diaminocarpoanilide, 4,4'-diaminocarpoanilide, 4'-amino-6 '-Methyl-m-henzuanilite, 4'-amino-5'-chloro-〇-henzuanisidide, 4''-(4-amino-m-1-ruyl)-0-
Benzamide derivatives such as penztoluidide, 5'-amino J2.4-penzoxylidite, etc.: benzidine, 3.3'-dichlorobenzidine, 3.3'
Henresins such as -dimethyl-benzidine, 3,3'-dichlorobenzidine, 3,3'-dimethoxy-2,2'-dichlorobenzidine, 3-ethoxyhenzidine, 2-nitrobenzidine; 2-biphenylamine, 4-biphenylamine 56.6
Biphenyls such as '-diamino-m, m'-biphenol, 4,4'-diamino-3,3'-biphenyldicarboxylic acid: 3,3'-diaminocarpoanilide, 4,4'-diaminocarpoanilide Carbonianilides such as: 4.4'-diaminodiphenylamine, 4.4'-diamino-di-m-tolylamine, P-aminodiphenylamine, 3-methoxy-4-aminodiphenylamine,
Diphenylamines such as 4'-methoxy-4-aminodiphenylamine; naphthylamines such as α-naphthylamine and β-naphthylamine: Of course, various diazo components other than those mentioned above can also be used or used in combination.

The method for producing a monoazo or disazo pigment composition using the coupler and diazo component described above may be carried out in accordance with conventionally known production conditions, as shown in Examples below, and no special conditions are required.

(Action/Effect) The pigment composition of the present invention obtained as described above has a structure in which it can absorb ultraviolet rays well and reduce the energy level of the rays. It has excellent light resistance compared to azo pigments with a similar structure, and is suitable for paints,
It is useful as a coloring agent for printing inks or materials to be colored such as synthetic resins.

In particular, the pigment composition of the present invention acts as an ultraviolet absorber or a light stabilizer for colored materials colored with the composition, so it can be used as a UV absorber or light stabilizer for colored materials, such as paint films, ink films, etc.
It also has the effect of improving the light resistance of the coloring material itself, such as synthetic resin.

Next, the present invention will be further explained in detail by giving reference examples, working examples, comparative examples, etc. In the text, parts or percentages are based on weight unless otherwise specified.

Reference example 1 2-[3”,5”-di(α,α-dimethylbenzyl)-
46.2 parts of 2'-hydroxyphenyl]-5-aminobenzotriazole (the above exemplified compound) was dispersed in 670 parts of xylene, and the temperature of the dispersion was adjusted to 50 to 55°C.
The diketene IO portion was added dropwise into the mixture over 30 minutes, and after further stirring for 60 minutes, the temperature was raised to 80°C, and it took an additional 3 hours to complete the reaction, resulting in a slightly yellowish brown color. A white product was obtained. This product is ethanol-
The product was recrystallized and purified from a mixed solvent of ethyl acetate (weight ratio 1:1) to obtain 36.5 parts of the coupler of the present invention (Coupler 7) as white crystals with a melting point of 285 to 287°C.

Reference Example 2 The above-mentioned exemplary coupler was obtained in the same manner as in Reference Example 1, except that the 5-aminobenztriazole compound (I) in Reference Example 1 was replaced with the above-mentioned exemplary compounds (I) by chilling force. The properties and melting point were as follows.

Coupler (1) White crystal, melting point 147-149℃
Coupler (2) White crystal, melting point 159-161t
:Coupler (3) White crystal Melting point 80-182
°C coupler (4) White crystal Melting point 195-197
°C coupler (5) White crystal Melting point 206-209
°C coupler (6) White crystal, melting point 2 - 213 °C
Coupler (8) White crystal Melting point 256-258℃
Coupler (9) White crystal Melting point 265-267℃
Coupler (lO) White crystal Melting point 269-271
°C coupler (!I) White crystal Melting point 262-26
4℃ coupler 02) White crystal, melting point 274-27
6℃ Kasibura (13) White crystal Melting point 250-2
52℃ coupler (14) White crystal Melting point 246~
248°C Example 1 5.5 parts of the coupler (7) of the present invention obtained in Reference Example 1 and 45.5 parts of acetoaceto-2,5-dimethoxy-4-chloroanilide were mixed together with 18.4 parts of caustic soda. water 1,
000 parts. After adding 9.5 parts of sodium acetate, the temperature was adjusted to 20°C and 70 tons of 40% acetic acid aqueous solution was added.
4 was added dropwise over 30 minutes to precipitate both coupler components at the same time to obtain a subsoaking liquid.

Separately, a tetrazonium salt consisting of 25.7 parts of 3,3'-dichlorobenzine hydrochloride was prepared by a conventional method, and added dropwise over 60 minutes to the previously prepared submerging solution adjusted to 20°C. Stirring was continued at 20°C for 60 minutes and at 40°C for 60 minutes to complete the reaction, and then an emulsion consisting of xylene-polyoxyethylene alkyl ether was added.
Pigmentation was carried out at 0° C. for 60 minutes to obtain a yellow azo pigment composition.

Example 2 12.9 parts of 3.3'-dichlorbenzine hydrochloride was added to 60 parts of
of concentrated hydrochloric acid with vigorous stirring.
．． Add 1 part and continue stirring for an additional 60 minutes. After cooling to 0°C, 40% nitrous acid aqueous solution 17.8. add part,
3. A tetrazonium salt of 3'-dichlorohenthidine was obtained.

Separately, 54.6 parts of the coupler (7) of Reference Example 1 was dissolved in 800 parts of methanol containing 9.2 parts of caustic soda,
After adding 7.3 parts of sodium acetate.

15.3 parts of 90% acetic acid is added dropwise to prepare a subsoaking solution.

After this Fi11 liquid was cooled to below 0°C, the tetrazonium salt of 3,3'-dichlorobendine prepared previously was added dropwise at 0 to 5°C for 30 minutes. Dripping 110~5℃
After further reaction for 1 hour to complete the coupling, the mixture is heated to the boiling point. After aging at boiling point for 1 hour, filter and wash.

Drying and pulverization were performed to obtain a disazo pigment powder into which a substituted benzotriazole group was introduced. 7 parts of this disazo pigment into which a substituted benzotriazole group has been introduced and 6.1. Pigment Yellow (PY)-8393 parts were uniformly mixed to obtain an azo pigment composition.

Comparative Example I 10 parts each of the azo pigment compositions of C, 1, PY-83 and Examples 1 and 2 were added to an alkyd resin varnish (N, V).

60%) 26.4 parts, melamine resin r) Varnish (N, V,
50%) 13.6 parts and xylene/n-butanol = 8
The mixture was placed in a mayonnaise bottle together with 20 parts of thinner consisting of /2 (weight Tht ratio), glass peas were added, and the mixture was dispersed in a paint shaker for 60 minutes. After dispersion, a mixed varnish of alkyd and melamine as described above [alkyd/melamine=0
1 was diluted with 48.3 parts (solid content 7/3) to prepare a dark enamel.

In addition, the obtained four-color enamel is piH/TiO, = 1
A light-colored enamel was prepared by mixing it with autoenamel to give a ratio of /20.

The dark and light colored enamels prepared in this manner were diluted with thinner (xylene/n-butanol-8/2) to a spraying viscosity, and applied onto a tin plate using an air spray gun at 120°C. Bake for 30 minutes. The prepared coated plates were subjected to a Sunshine Weather-Ometer to examine their weather resistance. The results are shown in Table 1 below.

(Left below) Weather resistance test using γJ 1-111 Sunshine Weatherometer (melamine/alkyd baking paint) Example i ooo △ Example 2 0 0 0 Δ G, [, PY-83Q ○ △ × Example 100 △ X Example 200 Δ × (:, 1.PY-83Q Δ X X
In addition, the evaluation criteria in the above table are: O means no discoloration, △
indicates that there is discoloration or fading, and X indicates that there is significant discoloration or fading.

In addition, coated plates prepared in the same manner were placed outdoors at @S#i (Iwaguchi 1 City, Shizuoka Prefecture, facing south, at a 60° angle), and the ΔE value and condition of the coating film were measured. The results shown in Table 2 below were obtained.

γ 2-F Weather resistance test by outdoor exposure (melamine/alkyd baking paint) Example 1 0.5 0.8 +, 2 2
．． 0 Example 2 0.4 0.6 +, 3
1.8C,1,PY-830,71,32,93,8
Example 1 0.7 1.3 CI 1
1.4 Example 2 0.8 +, 5 3.7
13.0C, 1, PY-830, 82, 41Q, 3
+8.17, 3 -F= Deterioration test of paint film due to outdoor exposure (melamine/alkyd baking paint) Example 1 to 00 0 Example 2
00 0 △C, r, PY-8:l
○ Δ Δ × Judgment was made by visual inspection of the state of deterioration such as gloss, darkening, chalking, cracking, etc., and was determined in 3 stages: O: Almost no deterioration, Δ: Deterioration observed, ×: Deteriorated parts.

Example 3 Coupler (2) was used instead of coupler (7) in Reference Example 1.
) 1.7 parts and acetoacetic acid-0 to chloranilide 12
．． 1 part is dissolved in 400% water containing 6.5 parts of caustic soda. Next, 17.6 parts of sodium acetate was added and dissolved, the temperature was adjusted to 20"C, and 25 parts of a 40% acetic acid aqueous solution was added.
The mixture was added dropwise over 30 minutes to form a submerged liquid.

Separately, a diazonium salt containing 17.3 parts of 2-nitro-4-chloroaniline was prepared by the usual p method and added dropwise to the above-mentioned submerging solution over 30 minutes. 60 minutes at 20°C, 40
Stirring was continued for 60 minutes at ℃ to complete the reaction, then an emulsion consisting of xylene-polyoxyethylene alkyl ether was added, and pigmentation was performed at 85 ℃ for 30 minutes to obtain a greenish yellow azo pigment composition. .

Comparative Example 2 C, 1 PY-3 and each of the azo pigment compositions of Example 3
0 parts of air-dry alkyd resin varnish (N, V, 50%) 40
and 20 parts of turpentine were added to a mayonnaise bottle, and dispersed with glass beads and a paint shaker for 60 minutes. After dispersion, the mixture was further diluted with 160 parts of air-dry alkyd varnish to prepare a dark enamel. After diluting the obtained dark enamel with a turpentine to a spraying viscosity and adding a dryer,
It was applied onto a tin plate using an air spray gun and the coating film was cured.

The obtained coated plate was exposed outdoors (60 Minamimukai, Iwata City, Shizuoka Prefecture)
The condition of the paint film was visually judged and the results shown in Table 4 below were obtained. 0 judgment measures the state of deterioration such as gloss, darkening, chalking, and color change of the paint film. O: Hardly any deterioration, Δ: Deterioration is noticeable, ×: Deterioration part is 3
I went in stages.

γ1;4 Deterioration test of paint film due to outdoor exposure (air-dry alkyd paint) l, n,
4 Example 3 0 0 0 0 0 ΔC
, 1, PY-3000Δ Δ × Example 4 In place of coupler (7) of Reference Example 1, coupler (1
2) Dissolve 10.8 parts and 27.4 parts of 1,4-di-acetoacetylamino-2,5-di-methylbenzene in 800 parts of methanol containing 24 parts of caustic soda, and further add 44 parts of sodium acetate. After that, 100 parts of methanol containing 38 parts of glacial acetic acid was added dropwise at 20°C to obtain a subsoaking solution.

Separately, a solution of diazonium salt containing 60 parts of 3-amino-4-chloro-2'-methyl-5'-chlorobenzanilide prepared by the usual sulfuric acid method was added to the submerging solution at 0°C or below for 60 parts.
The solution was added dropwise over a period of minutes, and stirring was continued at 0° C. or lower until no diazonium salt was observed.

Then, after filtering and washing the resulting pigment, the aqueous paste of the cake was peptized in 2,000 parts of water containing 30 parts of caustic soda, and an emulsion of nitrobenzene-polyoxyethylene sorbitan acid ester was added to give 85-90% Crystallization was performed at ℃ for 4 hours to obtain a reddish yellow azo pigment composition.

Comparative Example 3 C, 1, PY-95 and the azo pigment composition of Example 4 are each mixed with zinc stearate to create a dark dry color. In addition, each pigment was mixed with rutile titanium oxide and pig:
Mix so that Ti02=1:5, and further add zinc stearate to create a light dry color. Each dark color and light color dry color is dark color 0. IPHR%
The mixture was mixed with polyethylene resin so as to have a light color of 0.5 PHR, formed into a pellet shape using an extruder, and then a plate was created using an injection molding machine.

The resulting plate was run through a fade meter and each Δ
The ε value was measured and the results shown in Table 5 below were obtained.

γJ 5 - Deterioration test using a phase meter (polyethylene) Example 4, 0.7 2.6 3.8 5
．． 4C, 1, PY-950, 93, 26, 28, 5 Example 4 0.8 1.9 3.3 4.6C,
1, PY-950, 72, + 3.8 5.8
Example 5 A submerging solution of 5-acetoacetylaminobenzimidacylon containing 10% of the coupler (7) of Example 1 was cupped with the diazonium salt of 2-nitro-4-chloroaniline diazotized in a conventional manner. The mixture was ringed and subjected to pigmentation treatment to obtain an orange azo pigment composition.

Comparative Example 4 C81, Pigment Orange (PG)-36, and the azo pigment composition synthesized in Example 5 were made into a paint according to the method of Comparative Example 1, and the coated plates obtained in the same manner were exposed outdoors to examine the condition of each coating film. was measured. Judgment is made by visually observing the state of deterioration such as gloss, darkening, discoloration, etc. of the paint film. O: Almost no deterioration, △: Deterioration is strong, ×:
The deterioration was performed in three stages. The results shown in Table 6 below were obtained.

γJ 6-=7- Weather resistance test by outdoor exposure (melamine alkyd baking paint) Example 5 0 0 00 C,1,PO-3600Δ Δ Example 6 1-phenyl-3- containing 5% of coupler (2) Using the liquid solution of carboxyethyl-5-pyrazolone and the tetrazonium salt of 3,3'-dichlorobendine prepared by a conventional method, the two were coupled and pigmented with a xylene emulsion to produce yellow. 11 red azo pigment compositions? Ta.

In Comparative Example 5, 1. Pigment Red (PR)-38 and Example 6
Each air-drying alkyd paint was prepared using the azo pigment composition obtained in Comparative Example 2, and the coated plate obtained in the same manner as above was exposed outdoors and the state of the paint film was visually determined. .

Deterioration such as gloss, darkening, chalking, and hue change and fading of the paint film is visually observed. O: Almost no deterioration 1. Judgment was made on a three-level scale: △: Deterioration was observed; X: Deterioration was observed. The results shown in Table 7 below were obtained.

γJ 7 Weather resistance test by outdoor exposure (air-dry alkyd paint)
00 0 Δ △(:, 1. To PR-38000 × ×Example 7 C, T, Pigment Violet (PV)-1950
1 part was mixed with 50 parts of the azo pigment composition synthesized in Example 5 to prepare a mixed pigment.

Example 8 50 parts of C,1PR-5 was added to Example 5 in the same manner as in Example 7.
A mixed pigment was prepared by mixing with 50 parts of the azo pigment composition synthesized in .

Example 9 A mixed pigment was prepared by mixing 50 parts of C,1,PY-11, 45 parts of the azo pigment composition synthesized in Example 1, and 5 parts of the azo pigment synthesized in Example 2 into which a substituted benzotriazole group was introduced. Created.

Example 10 C,1,PY-8330 parts, (:,1.PY-1104
0 parts and 30 parts of the azo pigment into which a substituted benzotriazole group synthesized in Example 2 was mixed to prepare a mixed pigment.

Comparative Example 6 To compare the effects of the mixed pigments of Examples 7 to 10,
An existing azo pigment containing the coupler component of the present invention and a corresponding existing pigment were mixed to prepare mixed pigments shown in Table 8 below.

γJ 8 J 屹 Mixed pigment composition comparison example 6-A C, 1, PV-1950C, 1, P
O-3650 Comparative Example 6-B (:, 1.PR-550C, 1,
PO-: +6 50 Comparative Example 6-CG, 1
．． PY-11050 (:, 1-PY-8350 Comparative Example 6- D C, 1, PY-8360C, 1,
PY-11040 A melamine-alkyd baking paint was prepared according to the method of Comparative Example 1 using the mixed pigments of Examples 7 to 10 and Comparative Example 6, and the coated plate obtained in the same manner as above was exposed outdoors. The effects were compared by measuring the deterioration of the coating film, such as gloss, darkening, jigging, and color change.

Judgment was made visually and was given in three stages: 0: almost no deterioration, △: deterioration observed, ×: slight deterioration. The results shown in Table 9 below were obtained.

:J 9 ; ~ Weather resistance test by outdoor exposure (melamine/alkyd baking paint) Example 7 0000 Comparative example 6-A OO△ △ Example 8 0 0 0 △ Comparative example 6-Bo
o △ X Example 9 000 Δ Comparative Example 6-Coo △
Example 1 except that a coupler from Table 0 was used.
Various couplers were prepared in the same manner as in Comparative Example 1, and the results shown in Table 1θ below were obtained.

γJ10 Knee 4 Weather resistance test using sunshine weather meter (melamine/alkyd baking paint) Coupler (1) OOO△ coupler (
2) OO○ Δh coupler 3) OOO△ coupler (4)
OOO△Coupler (5) 'O
OO△ coupler (6) OOO△b-I
Poor (8) OOO△b9 Blur (9
) OO○ △ coupler (10) OOOOΔ coupler (II)
OOO△Coupler (12) OO
OΔ coupler (+3) OOOΔ coupler (14) ○ OO△C,
1, PY-8:II ○ OΔ
Coupler (+) OO△
X coupler (2) OO△
X coupler (3) OO△
X coupler (4) OO△
X coupler (5) ○
O△X coupler (6)
OOΔ X coupler (8),
OO△ X coupler (9)
OO△ X coupler (10)
○ ○ Δ
X coupler (+'l) OO△
X coupler (12) ○ O
△ X coupler (13) ○
O△X coupler (14
) OO△ ×C,1,PY
−830Δ××Note that the =f value standard is the same as in Comparative Example 1.

Claims (4)

[Claims] (1) An azo pigment obtained by coupling a diazo component to a general coupler other than the following general formula (I) and an azo pigment obtained by coupling a diazo component to a coupler represented by the following general formula (I). A pigment composition consisting of. ▲There are mathematical formulas, chemical formulas, tables, etc.▼ (I) (However, R_1 and R_2 in the above formula are hydrogen atoms, alkyl groups, or aryl groups, but are not hydrogen atoms at the same time.) (2) The pigment composition according to claim (1), wherein the general coupler is an acetoacetanilide coupler other than general formula (I). (3) 0.5 to 5 of the total coupler components in the pigment composition
The pigment composition according to claim (1), wherein 0 mol % is a coupler represented by general formula (I). (4) When producing a pigment by coupling a diazo component to a general coupler other than the following general formula (I),
A method for producing a pigment composition, characterized in that a coupler represented by the following general formula (I) is used as a part of the coupler. ▲There are mathematical formulas, chemical formulas, tables, etc.▼ (I) (However, R_1 and R_2 in the above formula are hydrogen atoms, alkyl groups, or aryl groups, but are not hydrogen atoms at the same time.)