JPS6317102B2 - - Google Patents

Description

[Detailed description of the invention]

The present invention relates to a pigment composition that is suitable for use, particularly excellent in non-aggregation and non-crystallinity. In general, practically useful pigments that exhibit vivid color tones and high tinting power in various coating compositions are composed of fine particles. However, when dispersed in non-aqueous vehicles such as offset inks, gravure inks and paints, the fine particles of pigments make it difficult to obtain stable dispersions, which has a significant impact on manufacturing operations and the value of the resulting products. This often results in a variety of problems that can cause problems. For example, dispersions containing pigments made of fine particles often have a high viscosity, making it difficult to remove the product from the dispersion machine and transport it, and even worse, gelation occurs during storage, making it difficult to use. It may become. Also, when using a mixture of different pigments,
Phenomena such as color separation due to aggregation or sedimentation may result in color unevenness or a significant decrease in coloring power in the developed product. Furthermore, the surface of the paint film of the developed product may suffer from poor conditions such as reduced gloss and poor leveling. Further, although not directly related to pigment dispersion, some organic pigments experience a phenomenon that involves a change in the crystalline state of the pigment. In other words, in non-aqueous vehicles such as offset inks, gravure inks, and paints, pigment crystal particles, which are energetically unstable, change their size and shape and shift to a stable state, resulting in a noticeable hue in the developed product. Product value may be impaired due to changes in color, decrease in coloring power, generation of coarse particles, etc. Many proposals have been made so far, mainly copper phthalocyanine and quinacridone pigments, for the purpose of improving the non-aggregation properties and crystal stability of pigments. For example, as typified by Japanese Patent Publication No. 41-2466 and USP 2761865, compounds obtained by using an organic pigment as a base core and introducing substituents such as a sulfon group, sulfonamide group, aminomethyl group, or phthalimidomethyl group into the side chain. This is a method of mixing. These methods have a remarkable effect on pigment disaggregation, crystal stability, etc. in a non-aqueous vehicle, and are very advantageous judging from the ease of assembling the pigment composition. . However, there has not been much research into the method of mixing azo pigments, and Japanese Patent Publications No. 45-11026 and No. 53-35090 proposed a method of mixing azo pigments with alkaline earth metal sulfonates and organic amine salts. It's just that it's being done. The present inventors have developed an offset ink as described above,
In order to solve various problems that occur in non-aqueous vehicles such as gravure inks and paints, we have developed a pigment composition that is excellent in practical use. That is, the present invention is a pigment composition containing 100 parts by weight of a pigment and 0.3 to 30 parts by weight of an azo compound represented by the following general formula (). General formula ()

[Formula] In the formula, Q: Residue A of azo dye; represents -SO ₂ NR'- or -CONR'-,
R' represents a hydrogen atom or an alkyl group having 1 to 20 carbon atoms. R ₁ , R ₂ ; Alkyl group having 1 to 20 carbon atoms, or R ₁ ,
R ₂ represents a heterocycle containing a nitrogen or oxygen atom. n: an integer of 1 to 4 m; an integer of 1 to 4 When the azo compound represented by the general formula () according to the present invention is mixed with a pigment, an alkaline earth metal sulfonate or an organic amine salt of the azo compound is mixed. It has become clear that the effect on pigment non-aggregation, crystal stability, etc. in a non-aqueous vehicle is significantly greater than in the non-aqueous vehicle. In addition, the azo compound represented by the general formula () is much easier to filter and wash than sulfonic acid alkaline earth metal salts and organic amine salts, and there is no loss during washing, making it extremely advantageous in terms of production. One thing became clear. The azo compound represented by the general formula () can be produced by the following three methods. The first method involves aromatic amines having the following general formula: (However, n, R ₁ , R ₂ and A in formula [] are
The same numbers and groups as n, R ₁ , R ₂ and A in the formula [] are shown. R ₃ and R ₄ represent the same or different hydrogen atoms, alkyl groups, methoxy groups, halogen atoms, sulfone groups, and nitro groups. ) according to a conventional method and coupled with industrially useful couplers such as phenols, naphthols, acetoacetanilides, pyrazolones, oxyquinolines, etc. The second method is, for example, the following general formula []
〔〕〔〕〔〕〔〕 (However, n in the formula [] [] [] [] []
R ₁ , R ₂ , R ₃ , R ₄ and A represent the same numbers and groups as n, R ₁ , R ₂ , R ₃ , R ₄ and A in formula []. ) is diazotized and coupled with an industrially useful base. The third method uses an azo compound as a raw material and converts it into, for example, a chlorosulfonated compound or a carboxylic acid chloride, and then converts it into the general formula [] in the presence of a solvent. (However, in the formula [], n, R ₁ and R ₂ are []
Indicates the same numbers and groups as n, R ₁ and R ₂ in the formula. ) can be obtained by dehydrochlorination reaction with amines represented by: In this method, 1 to 4 substituents are introduced as described in the production example. Two or more substituents can also be introduced by the first and second methods. For example, it can be obtained by coupling an aromatic amine of the formula [] with the following coupler component. (However, in the formula [], [], [XI], n, R ₁ , R ₂ ,
R ₃ , R ₄ and A are n, R ₁ ,
The same numbers and groups as R ₂ , R ₃ , R ₄ and A are shown. ) As the pigment in the present invention, azo pigments such as soluble and insoluble azo pigments and condensed azo pigments have particularly favorable effects, but phthalocyanine pigments, quinacridone pigments, isoindolinone pigments, and perylene/berinone pigments are used. Pigments, organic pigments such as dioxazine pigments, vat dye pigments, basic dye pigments, and carbon black, titanium oxide, yellow lead, cadmium yellow, cadmium red, Bengara, iron black, zinc white, navy blue, ultramarine blue. It is also possible to use inorganic pigments such as. The compound represented by the general formula () according to the present invention is blended into the pigment based on 100 parts by weight of the pigment.
0.5 to 30 parts by weight is preferred. If the amount is less than 0.5 parts by weight, the effect of the compound represented by the general formula () cannot be obtained, and even if it is used in an amount greater than 30 parts by weight, the effect corresponding to the amount used cannot be obtained. As for the preparation method of the pigment composition according to the present invention, the desired effect can be obtained by simply mixing the pigment powder and the powder of the compound represented by the general formula [] according to the present invention, but it is possible to obtain the desired effect by simply mixing the pigment powder and powder of the compound represented by the general formula Mix mechanically using a lighter, super mill, various types of pulverizers, etc., or add a solution containing the compound represented by the general formula [] according to the present invention to a suspension system of the pigment in water or an organic solvent to coat the surface of the pigment. The compound represented by the general formula [] is deposited, or the organic pigment and the compound represented by the general formula [] are co-dissolved in a solvent with strong dissolving power such as sulfuric acid, and the compound represented by the general formula [] is co-dissolved and co-precipitated with a phagocytic solvent such as water. Even better results can be obtained by using an intimate mixing method. The pigment composition thus obtained can be used in offset ink vehicles such as various rosin-modified resins, gravure inks such as lime rosin varnish, polyamide resin varnish, or vinyl chloride resin varnish, or when used in gravure inks such as nitrocellulose lacquer, amino alkyd varnish, etc. Resin air-drying or baking paint, acrylic lacquer, amino acrylic resin baking paint,
When used in urethane resin paints, etc., it shows good fluidity, such as lower dispersion viscosity and lower structural viscosity, compared to when pigments are used alone, and at the same time, prints without problems such as color separation or crystal changes. Alternatively, a beautiful product with a high gloss coating can be obtained. An outline of the synthesis method for a typical compound represented by the general formula [] will be described below as a production example. In the examples, parts and % indicate parts by weight and % by weight. Production Example 1 Acid chloride was synthesized by heating and stirring β-oxynaphthoic acid with an equimolar amount of thionyl chloride in benzene or acetone under reflux for 1 hour, and after the reaction was completed, various amines were added and further under reflux. The mixture was heated and stirred for 1 hour to obtain the following coupler component. The following azo dyes were obtained by diazotizing and coupling various bases to these coupling components. Production example 2 P-acetylaminosulfonyl chloride and N,
N-diethylaminoethylamine or N,N
- A sulfonamide obtained by heating and stirring diethylaminopropylamine in benzene or acetone under reflux for 2 hours was hydrolyzed by boiling and refluxing in dilute hydrochloric acid for 1 hour to obtain the following diazo component. These bases were diazotized according to conventional methods and coupled with various couplers to obtain the following azo dyes. The coupler (C) was synthesized in the same manner as in Production Example 1. Production Example 3 The base of Production Example 2 was diazotized and coupled with various couplers according to conventional methods to obtain the following disazo dyes. Production Example 4 P-Nitrobenzoyl chloride was stirred with various amines in benzene under reflux for 1 hour to synthesize a carboxylic acid amide, and then the nitro group was reduced according to a conventional method to obtain the following diazo component. These bases were diazotized according to conventional methods,
The following azo dyes were obtained by coupling with various couplers. Production Example 5 The base of Production Example 4 was diazotized and coupled with various couplers according to conventional methods to obtain the following disazo dyes. Production Example 6 The base of Production Example 2 and equimolar amounts of diketene were heated and stirred in xylene under reflux for 1 hour to obtain a coupler component having the following structure. By diazotizing and coupling various bases to this coupler component, the following azo dyes were obtained. Production Example 7 The coupler component of Production Example 6 was tetrazotized with diamines according to a conventional method, and coupling was carried out to obtain the following disazo dye. Production Example 8 The base of Production Example 4 and equimolar amounts of diketene were heated and stirred in xylene under reflux for 1 hour to obtain a coupler component having the following structure. By diazotizing and coupling various bases to these couplers, the following azo dyes were obtained. Production Example 9 The coupler component of Production Example 8 was tetrazotized with diamines according to a conventional method, and coupling was performed to obtain the following disazo dye. Production example 10 Azo dye with the following structure and equimolar amount of thionyl chloride were heated and stirred in xylene under reflux for 2 hours to form an acid chloride, then various amines were added, and further heated and stirred under reflux for 1 hour to obtain an azo dye having the following structure. Production example 11 Azo dye with the following structure and equimolar amount of thionyl chloride were heated and stirred in xylene under reflux for 2 hours to form an acid chloride, then various amines were added, and further heated and stirred under reflux for 1 hour to obtain an azo dye having the following structure. Production Example 12 10 parts of an azo dye having the following structure were stirred with 50 parts of chlorosulfonic acid at about 50°C for 1 hour, poured into ice water, filtered, and washed with water. Various amines were added dropwise to this slurry and stirred at 10 to 20°C for 5 hours to obtain an azo dye (y) having the following structure. Analysis by reductive decomposition of the azo group revealed that two chlorsulfone groups were introduced into the naphthalene nucleus and one into the benzene nucleus. Production example 13 Azo dye with the following structure was heated and stirred for 2 hours under reflux in 2 times the mole of thionyl chloride and xylene to obtain acid chlorite, and then various amines were added and heated and stirred for 2 hours under reflux to obtain an azo dye with the following structure. . Examples and comparative examples will be described below. In addition, the chemical structure of each compound indicated by alphanumeric characters corresponds to that shown in the production example. Comparative Examples and Examples 1 to 15 Gravure Ink Test Various pigments alone (comparative examples) or mixtures of various pigments and various compounds shown in Production Examples 1 to 13 were added to vinyl chloride varnish for gravure, each with a pigment content of 10%.
Alternatively, a gravure ink was prepared by blending it at a concentration of 25% (when using an inorganic pigment), and its viscosity was examined. The results are shown in Table 1, and the material according to the present invention has excellent fluidity. Furthermore, excellent results were obtained in terms of color clarity, coloring power, and gloss of printed matter printed with the gravure ink.

【table】

[Table] Examples 16 to 36 Various pigments alone (comparative example) or mixtures of various pigments and each compound shown in Production Examples 1 to 13 were added to aminoalkyd resin varnish for baking paints, with a pigment content of 6% or 25%, respectively. (In the case of inorganic pigments) A paint was prepared by blending the pigments, and its viscosity was measured. The results are shown in Table 2. The aminoalkyd paints according to Examples had excellent fluidity and crystal stability, and also had excellent color beauty, coloring power, and gloss in the coating film. Furthermore, the storage stability was also excellent with little change in viscosity.

【table】

[Table] In addition, regarding dispersion stability, we will compare examples with regard to color separation stability, which is a particular problem in applications. The paint shown in the second example is cut with a titanium oxide base paint prepared in advance using aminoalkyd varnish so that the ratio of pigment to titanium oxide is 1/10 to obtain a light-colored paint. The light-colored paint was further diluted with xylene, the viscosity was adjusted to 20 seconds (25°C) using a food cup No. 4, and the results were injected into a test tube and observed for changes in the glass wall surface. Table 3 shows the results.
Shown below.

[Table] In all cases, the products according to the present invention show excellent results. Examples 37-51 CIPigment on nitrocellulose lacquer
Blue15 alone (comparative example) or CIPigment
Table 4 shows the viscosity of a paint prepared by blending a 95:5 mixed pigment composition of Blue 15 and a compound so that the pigment content was 5.5%. Similarly, Table 4 shows test results regarding the viscosity on nitrocellulose lacquer of combinations of other pigments and various compounds related to the present invention. In all cases, the composition according to the present invention had excellent fluidity and exhibited excellent results in terms of gloss, sharpness of color tone, and tinting power in the developed coating film.

[Table] Table 5 shows the results of storing the paints shown in the examples in Table 4 at 50°C for 3 months and measuring the viscosity thereafter.

[Table] As is clear from the results in Table 5, all the products according to the present invention exhibit excellent storage stability. Example 52 Aminoacrylic baking paint CI on aminoacrylic baking paint varnish
Pigment Orange36 alone (comparative example) or CI
When the fluidity of paints prepared using a 90:10 mixed pigment composition of Pigment Orange 36 and Compound d with a pigment content of 6% was compared, the paint according to the present invention showed significantly superior results. Furthermore, even in the case of a paint prepared by cutting the above-prepared paint using an aluminum paint base prepared in advance with aminoacrylic paint varnish so that the ratio of pigment to aluminum is 1/5, the paint according to the present invention has a markedly clear color tone and is excellent. It showed a glossy shine. Example 53 Urethane paint varnish CIPigment Yellow95 on urethane paint varnish
Single (comparative example) or CIPigment
A comparison of the fluidity and state of the developed paint film of paints prepared using a 90:10 mixed pigment composition of Yellow 95 and Compound It was excellent in color tone and gloss of the developed color coating. Example 54 Rosin-modified phenolic resin offset ink A rosin-modified phenolic resin offset ink varnish was coated with CIPigment Red 57 alone (comparative example) or a mixed pigment composition containing CIPigment Red 57 and compound c at a ratio of 85:15. is 30
%, prepare offset ink,
When their fluidity was compared using a parallel plate viscometer, the one according to the present invention showed significantly superior results. In addition, printed matter according to the present invention is
It showed excellent results in terms of color clarity, tinting strength, and transparency.

Claims (1)

[Scope of Claims] 1. A pigment composition containing 100 parts by weight of a pigment and 0.3 to 30 parts by weight of an azo compound represented by the following general formula (). General formula () [Formula] In the formula, Q: Residue A of an azo dye; represents -SO ₂ NR'- or -CONR'-,
R' represents a hydrogen atom or an alkyl group having 1 to 20 carbon atoms. R ₁ , R ₂ ; Alkyl group having 1 to 20 carbon atoms, or R ₁ ,
R ₂ represents a heterocycle containing a nitrogen or oxygen atom. n: an integer of 1 to 4 m; an integer of 1 to 4