阅读说明：本技术 一种溶剂墨用酞菁绿颜料的制备工艺 (Preparation process of phthalocyanine green pigment for solvent ink ) 是由 李庆豹 常江涛 郑进峰 于 2021-07-12 设计创作，主要内容包括：本发明涉及酞菁绿颜料生产技术领域,提出了一种溶剂墨用酞菁绿颜料的制备工艺,包括以下步骤：S1、将氯代铜酞菁和硫酸混合搅拌经过升温保温降温得S1混合物；S2、S1混合物稀释过滤水洗；S3、加水、氢氧化钠调节pH,经过升温保温降温得S3混合物备用；S4、在水中加入醋酸升温后加入脂肪胺,溶解至半透明,降温后与S3混合物搅拌；S5、过滤水洗得酞菁衍生物滤饼备用；S6、将酞菁衍生物滤饼中加入酞菁绿颜料进行搅拌；S7、过滤干燥后得到酞菁绿颜料。通过上述技术方案,解决了现有技术中酞菁绿颜料易发生结晶膨胀、絮凝的问题。(The invention relates to the technical field of phthalocyanine green pigment production, and provides a preparation process of a phthalocyanine green pigment for solvent ink, which comprises the following steps: s1, mixing and stirring the chlorinated copper phthalocyanine and the sulfuric acid, and heating, preserving heat and cooling to obtain an S1 mixture; diluting, filtering and washing the mixture of S2 and S1; s3, adding water and sodium hydroxide to adjust the pH value, and heating, preserving heat and cooling to obtain an S3 mixture for later use; s4, adding acetic acid into water, heating, adding fatty amine, dissolving until the mixture is semitransparent, cooling, and stirring with the mixture S3; s5, filtering and washing to obtain a phthalocyanine derivative filter cake for later use; s6, adding phthalocyanine green pigment into the phthalocyanine derivative filter cake and stirring; and S7, filtering and drying to obtain the phthalocyanine green pigment. Through the technical scheme, the problems that phthalocyanine green pigment is easy to crystallize, expand and flocculate in the prior art are solved.)

1. A process for preparing a phthalocyanine green pigment for solvent ink, which is characterized by comprising the following steps:

s1, mixing and stirring the chlorinated copper phthalocyanine and the sulfuric acid, and heating, preserving heat and cooling to obtain an S1 mixture;

diluting, filtering and washing the mixture of S2 and S1;

s3, adding water and sodium hydroxide to adjust the pH value, and heating, preserving heat and cooling to obtain an S3 mixture for later use;

s4, adding acetic acid into water, heating, adding fatty amine, dissolving until the mixture is semitransparent, cooling, and stirring with the mixture S3;

s5, filtering and washing to obtain a phthalocyanine derivative filter cake for later use;

s6, adding phthalocyanine green pigment into the phthalocyanine derivative filter cake and stirring;

and S7, filtering and drying to obtain the phthalocyanine green pigment.

2. The process for preparing a phthalocyanine green pigment for solvent ink according to claim 1, wherein in step S1, the mass ratio of the chlorinated copper phthalocyanine to the sulfuric acid is 1 (6-20), the mass content of chlorine in the chlorinated copper phthalocyanine is 1-5%, and the sulfuric acid is 98% concentrated sulfuric acid; the heating, heat preservation and cooling specifically comprises the following steps: heating to 70-98 ℃, stirring and preserving heat for 0.5-5 h, and cooling to 40-80 ℃.

3. The process for preparing a phthalocyanine green pigment for solvent ink according to claim 1, wherein in step S2, 10 to 100 parts of water for dilution are added, 20 to 120 parts of ice are added during dilution, the temperature is controlled to 10 to 50 ℃, and the mixture is washed with water to have a pH of 4 to 6.

4. The process for preparing phthalocyanine green pigment for solvent ink according to claim 1, wherein in step S3, 30-80 parts of water is added, and sodium hydroxide is added to adjust the pH value to 7-8, wherein the temperature raising and temperature keeping is carried out by raising the temperature to 70-98 ℃, keeping the temperature for 1-1.5 h, and lowering the temperature to 65-80 ℃.

5. The process for preparing a phthalocyanine green pigment for solvent ink according to claim 1, wherein the step S4 is to add acetic acid to adjust the pH value to 1-5 under the condition of stirring in 10-30 parts of water, heat up to 70-98 ℃, add 1.2-2.2 parts of fatty amine, dissolve until translucent, then cool down to 30-70 ℃, and stir with the mixture S3 for 0.5-4 h.

6. The process for preparing a phthalocyanine green pigment for solvent ink according to claim 5, wherein the fatty amine comprises one or more of dimethyltallow amine, dimethyloctadecyl amine, dodecyl amine, lauryl amine, tallow propylene diamine, di-hydrogenated tallow dimethyl ammonium chloride, and di-dodecyl dimethyl ammonium chloride.

7. The process for producing a phthalocyanine green pigment for solvent ink according to claim 1, wherein in step S5, the phthalocyanine green pigment is washed with water to pH 7 to 8.

8. The process for producing a phthalocyanine green pigment for solvent ink according to claim 1, wherein the amount of the phthalocyanine derivative cake charged in step S6 is 3 to 15% by mass of the phthalocyanine green pigment, and the stirring time is 0.5 to 2 hours.

9. The process for producing a phthalocyanine green pigment for solvent ink according to claim 1, wherein the drying temperature in step S7 is 80 to 120 ℃.

Technical Field

The invention relates to the technical field of phthalocyanine pigment production, in particular to a preparation process of a phthalocyanine green pigment for solvent ink.

Background

Phthalocyanine green is a halogenated compound of copper phthalocyanine and is used as an important organic pigment in the fields of paints, coatings, inks, rubbers, plastics, leathers, synthetic fibers, and the like. Phthalocyanine green as an organic coloring pigment has the advantages of convenient manufacture and excellent performance, and the application field of the phthalocyanine green is gradually expanded.

Since organic pigments are generally used in a highly dispersed state, many disadvantages occur during production, use and storage, such as phthalocyanine green in chlorinated polypropylene, polyamide, polyurethane in solvent ink system and toluene, xylene, acetone, chlorine vinegar, which are solvents, easy crystal expansion, viscosity thickening in the system, difficulty in printing or spraying, and uneven color.

Disclosure of Invention

The invention provides a preparation process of a phthalocyanine green pigment for solvent ink, which solves the problems that the phthalocyanine green pigment is easy to crystallize, expand and flocculate in the prior art.

The technical scheme of the invention is as follows:

a process for preparing phthalocyanine green pigment for solvent ink comprises the following steps:

s1, mixing and stirring the chlorinated copper phthalocyanine and the sulfuric acid, and heating, preserving heat and cooling to obtain an S1 mixture;

diluting, filtering and washing the mixture of S2 and S1;

s3, adding water and sodium hydroxide to adjust the pH value, and heating, preserving heat and cooling to obtain an S3 mixture for later use;

s4, adding acetic acid into water, heating, adding fatty amine, dissolving until the mixture is semitransparent, cooling, and stirring with the mixture S3;

s5, filtering and washing to obtain a phthalocyanine derivative filter cake for later use;

s6, adding phthalocyanine green pigment into the phthalocyanine derivative filter cake and stirring;

and S7, filtering and drying to obtain the phthalocyanine green pigment.

According to a further technical scheme, in the step S1, 1-2.5 parts by mass of chlorinated copper phthalocyanine and 1 (6-20) mass ratio of sulfuric acid are adopted, wherein the mass content of chlorine in the chlorinated copper phthalocyanine is 1% -5%, and the sulfuric acid is 98% concentrated sulfuric acid; the heating, heat preservation and cooling specifically comprises the following steps: heating to 70-98 ℃, stirring and preserving heat for 0.5-5 h, and cooling to 40-80 ℃.

As a further technical scheme, in the step S2, 10-100 parts of water for dilution are added, 20-120 parts of ice is added in the dilution process, the temperature is controlled to be 10-50 ℃, and the mixture is washed with water until the pH value is 4-6.

As a further technical scheme, in the step S3, 30-80 parts of water is added, sodium hydroxide is added to adjust the pH value to 7-8, and the heating, heat preservation and cooling are specifically carried out by heating to 70-98 ℃, preserving heat for 1-1.5 hours, and cooling to 65-80 ℃.

According to a further technical scheme, in the step S4, acetic acid is added to 10-30 parts of water under the condition of stirring to adjust the pH value to 1-5, the temperature is raised to 70-98 ℃, preferably to 80-90 ℃, 1.2-2.2 parts of fatty amine are added to dissolve the mixture until the mixture is semitransparent, then the temperature is lowered to 30-70 ℃, preferably to 50-70 ℃, and the mixture is stirred with the S3 for 0.5-4 hours.

As a further technical scheme, the fatty amine comprises one or more of dimethyl tallow amine, dimethyl octadecyl amine, dodecyl amine, lauryl amine, tallow propylene diamine, di-hydrogenated tallow dimethyl ammonium chloride and di-dodecyl dimethyl ammonium chloride.

In a further technical scheme, in the step S5, the water is washed until the pH value is 7-8.

In a further embodiment, in step S6, the amount of the phthalocyanine derivative cake added is 3% to 15% by mass of the phthalocyanine green pigment, and the stirring time is 0.5 to 2 hours, preferably, the amount of the phthalocyanine derivative cake added is 6% to 10% by mass of the phthalocyanine green pigment, and the stirring time is 0.5 to 2 hours.

In a further technical scheme, in the step S7, the drying temperature is 80 to 120 ℃, preferably 90 to 100 ℃.

The invention has the beneficial effects that:

1. the preparation process of phthalocyanine green pigment for anti-crystallization and anti-flocculation solvent ink includes preparation of phthalocyanine derivative, addition of the derivative and addition mode of the derivative. The invention overcomes the defects of the prior art and provides a preparation process of crystallization-resistant flocculation-resistant phthalocyanine green for solvent ink, the preparation process utilizes crystallization-resistant flocculation-resistant phthalocyanine derivative to produce the crystallization-resistant flocculation-resistant phthalocyanine green pigment, and low-chlorine copper phthalocyanine is used for replacing copper phthalocyanine when preparing the phthalocyanine derivative, so that the prepared phthalocyanine derivative contains partial chlorine, the affinity and crystallization-resistant performance of the prepared phthalocyanine derivative and the phthalocyanine green pigment are improved, the production difficulty is reduced, and the production process is simplified. The phthalocyanine green pigment is not easy to generate crystal expansion in solvent ink system chlorinated polypropylene, polyamide, polyurethane, solvent toluene, xylene, acetone and chlorine vinegar, and the viscosity is not thickened in the system. The downstream printing efficiency is greatly improved.

2. The production raw materials comprise a crude product of the chlorinated copper phthalocyanine, a phthalocyanine derivative and a phthalocyanine green pigment for the solvent ink, wherein the purity of the crude product of the chlorinated copper phthalocyanine is more than 97%, and the particle size of the crude product of the chlorinated copper phthalocyanine is 10-200 mu m.

Detailed Description

The technical solutions in the embodiments of the present invention will be clearly and completely described below with reference to the embodiments of the present invention, and it is obvious that the described embodiments are only a part of the embodiments of the present invention, and not all of the embodiments. All other embodiments, which can be derived by a person skilled in the art from the embodiments given herein without making any inventive step, are intended to be within the scope of the present invention.

Example 1

S1, mixing and stirring 200kg of chlorinated copper phthalocyanine (with chlorine content of 3%) and 1.6t of 98% sulfuric acid, stirring at the rotating speed of 60 r/m, heating to 90 ℃, stirring and preserving heat for 2 hours, and cooling to 60 ℃ to obtain an S1 mixture;

adding 6t of water into the mixture of S2 and S1, controlling the temperature of ice blocks to be 8t and 30 ℃, diluting, filtering and washing with water until the pH value is 5;

s3, adding 4t of water and sodium hydroxide to adjust the pH value to 7, heating to 80 ℃, preserving heat for 1h, and cooling to 70 ℃ to obtain an S3 mixture for later use;

s4, adding 99% acetic acid into 2t of water to adjust the pH value to be 4, heating to 85 ℃, adding 195kg of dimethyl tallow amine, dissolving until the mixture is semitransparent, cooling to 60 ℃, and stirring with the mixture of S3 for 1 h;

s5, filtering and washing with water until the pH value is 8 to obtain a phthalocyanine derivative filter cake for later use;

s6, adding phthalocyanine green pigment into the phthalocyanine derivative filter cake, stirring, wherein the input amount of the phthalocyanine derivative filter cake is 8% of the mass of the phthalocyanine green pigment, stirring for 1h to obtain solvent-resistant crystallization-resistant flocculation-resistant phthalocyanine green pigment slurry, and completely coating the slurry by the phthalocyanine derivative in the stirring process;

s7, filtering and drying at 90 ℃ to obtain the phthalocyanine green pigment.

Example 2

S1, mixing and stirring 250kg of chlorinated copper phthalocyanine (with chlorine content of 3%) and 2.5t of 98% sulfuric acid, stirring at the rotation speed of 50 r/min, heating to 85 ℃, stirring and preserving heat for 3 hours, and cooling to 50 ℃ to obtain an S1 mixture;

adding 6t of water into the mixture of S2 and S1, controlling the temperature of ice blocks at 9t and 28 ℃, diluting, filtering and washing the mixture until the pH value is 5;

s3, adding 3t of water and sodium hydroxide to adjust the pH value to 7, heating to 90 ℃, preserving heat for 1h, and cooling to 60 ℃ to obtain an S3 mixture for later use;

s4, adding 99% acetic acid into 2t of water to adjust the pH value to 3, heating to 85 ℃, adding 205kg of dihydrogenated tallow dimethyl ammonium chloride, dissolving until the mixture is semitransparent, cooling to 50 ℃, and stirring with the mixture of S3 for 2 hours;

s5, filtering and washing with water until the pH value is 8 to obtain a phthalocyanine derivative filter cake for later use;

s6, adding phthalocyanine green pigment into the phthalocyanine derivative filter cake, stirring, wherein the input amount of the phthalocyanine derivative filter cake is 6% of the mass of the phthalocyanine green pigment, stirring for 1.5h to obtain solvent-resistant crystallization-resistant flocculation-resistant phthalocyanine green pigment slurry, and completely coating the slurry by the phthalocyanine derivative in the stirring process;

s7, filtering and drying at 100 ℃ to obtain the phthalocyanine green pigment.

Example 3

S1, mixing and stirring 200kg of chlorinated copper phthalocyanine (with chlorine content of 4%) and 2t of 98% sulfuric acid, stirring at the rotation speed of 50 r/min, heating to 85 ℃, stirring and preserving heat for 3 hours, and cooling to 50 ℃ to obtain an S1 mixture;

adding water into the mixture of S2 and S1 for 5t, controlling the temperature of ice blocks for 8t, diluting at 32 ℃, filtering, washing with water until the pH value is 5;

s3, adding 4t of water and sodium hydroxide to adjust the pH value to 7, heating to 88 ℃, preserving heat for 1h, and cooling to 70 ℃ to obtain an S3 mixture for later use;

s4, adding 99% acetic acid into 1.5t of water to adjust the pH value to 2, heating to 80 ℃, adding 195kg of tallow propylene diamine, dissolving until the mixture is translucent, cooling to 65 ℃, and stirring with the mixture of S3 for 2 hours;

s5, filtering and washing with water until the pH value is 7 to obtain a phthalocyanine derivative filter cake for later use;

s6, adding phthalocyanine green pigment into the phthalocyanine derivative filter cake, stirring, wherein the input amount of the phthalocyanine derivative filter cake is 10% of the mass of the phthalocyanine green pigment, stirring for 2h to obtain solvent-resistant crystallization-resistant flocculation-resistant phthalocyanine green pigment slurry, and completely coating the slurry by the phthalocyanine derivative in the stirring process;

s7, filtering and drying at 100 ℃ to obtain the phthalocyanine green pigment.

Example 4

S1, mixing and stirring 200kg of chlorinated copper phthalocyanine (with chlorine content of 3%) and 3t of 98% sulfuric acid, stirring at the rotation speed of 45 revolutions per minute, heating to 85 ℃, stirring and preserving heat for 3 hours, and cooling to 55 ℃ to obtain an S1 mixture;

adding water into the mixture of S2 and S1 for 5t, controlling the temperature of ice blocks to be 8.3t and 30 ℃, diluting, filtering and washing with water until the pH value is 5;

s3, adding 7t of water and sodium hydroxide to adjust the pH value to 7, heating to 75 ℃, preserving heat for 1h, and cooling to 65 ℃ to obtain an S3 mixture for later use;

s4, adding 99% acetic acid into 2t of water to adjust the pH value to be 4, heating to 75 ℃, adding 195kg of laurylamine, dissolving to be semitransparent, cooling to 40 ℃, and stirring with the mixture of S3 for 3 hours;

s5, filtering and washing with water until the pH value is 7.5 to obtain a phthalocyanine derivative filter cake for later use;

s6, adding phthalocyanine green pigment into the phthalocyanine derivative filter cake, stirring, wherein the input amount of the phthalocyanine derivative filter cake is 7% of the mass of the phthalocyanine green pigment, stirring for 1h to obtain solvent-resistant crystallization-resistant flocculation-resistant phthalocyanine green pigment slurry, and completely coating the slurry by the phthalocyanine derivative in the stirring process;

s7, filtering and drying at 100 ℃ to obtain the phthalocyanine green pigment.

Example 5

S1, mixing and stirring 100kg of chlorinated copper phthalocyanine (with chlorine content of 5%) and 1.2t of 98% sulfuric acid, stirring at the rotating speed of 60 r/m, heating to 98 ℃, stirring and preserving heat for 0.5h, and cooling to 80 ℃ to obtain an S1 mixture;

adding water into the mixture of S2 and S1 for 1t, controlling the temperature of ice blocks for 2t to be 50 ℃, diluting, filtering and washing the mixture until the pH value is 4;

s3, adding 3t of water and sodium hydroxide to adjust the pH value to 8, heating to 98 ℃, preserving heat for 1h, and cooling to 80 ℃ to obtain an S3 mixture for later use;

s4, adding 99% acetic acid into 1t of water to adjust the pH value to 2, heating to 80 ℃, adding 120kg of dimethyl octadecylamine, dissolving to be semitransparent, cooling to 70 ℃, and stirring with the mixture of S3 for 0.5 h;

s5, filtering and washing with water until the pH value is 8 to obtain a phthalocyanine derivative filter cake for later use;

s6, adding phthalocyanine green pigment into the phthalocyanine derivative filter cake, stirring, wherein the input amount of the phthalocyanine derivative filter cake is 3% of the mass of the phthalocyanine green pigment, stirring for 0.5h to obtain solvent-resistant crystallization-resistant flocculation-resistant phthalocyanine green pigment slurry, and completely coating the slurry by the phthalocyanine derivative in the stirring process;

s7, filtering and drying at 80 ℃ to obtain the phthalocyanine green pigment.

Example 6

S1, mixing and stirring 150kg of chlorinated copper phthalocyanine (with chlorine content of 1%) and 3t of 98% sulfuric acid, stirring at the rotating speed of 80 r/m, heating to 75 ℃, stirring and preserving heat for 2 hours, and cooling to 45 ℃ to obtain an S1 mixture;

adding water into the mixture of S2 and S1 for 8t, controlling the temperature of ice blocks for 11t to be 25 ℃, diluting, filtering and washing with water until the pH value is 5;

s3, adding 7t of water and sodium hydroxide to adjust the pH value to 7, heating to 70 ℃, preserving heat for 1.5h, and cooling to 65 ℃ to obtain an S3 mixture for later use;

s4, adding 99% acetic acid into 2.5t of water to adjust the pH value to 3, heating to 75 ℃, adding 120kg of didodecyldimethylammonium chloride, dissolving to be semitransparent, cooling to 70 ℃, and stirring with the mixture of S3 for 0.5 h;

s5, filtering and washing with water until the pH value is 8 to obtain a phthalocyanine derivative filter cake for later use;

s6, adding phthalocyanine green pigment into the phthalocyanine derivative filter cake, stirring, wherein the input amount of the phthalocyanine derivative filter cake is 5% of the mass of the phthalocyanine green pigment, stirring for 1.5h to obtain solvent-resistant crystallization-resistant flocculation-resistant phthalocyanine green pigment slurry, and completely coating the slurry by the phthalocyanine derivative in the stirring process;

s7, filtering and drying at 80 ℃ to obtain the phthalocyanine green pigment.

Example 7

S1, mixing and stirring 250kg of chlorinated copper phthalocyanine (with chlorine content of 5%) and 1.5t of 98% sulfuric acid, stirring at the rotating speed of 80 r/m, heating to 98 ℃, stirring and preserving heat for 2 hours, and cooling to 80 ℃ to obtain an S1 mixture;

adding water into the mixture of S2 and S1 for 10t, controlling the temperature of ice blocks for 12t to be 28 ℃, diluting, filtering and washing with water until the pH value is 6;

s3, adding 8t of water and sodium hydroxide to adjust the pH value to 8, heating to 98 ℃, preserving heat for 1.5h, and cooling to 80 ℃ to obtain an S3 mixture for later use;

s4, adding 99% acetic acid into 3t of water to adjust the pH value to 5, heating to 98 ℃, adding 220kg of dimethyl octadecylamine, dissolving to be semitransparent, cooling to 70 ℃, and stirring with the mixture of S3 for 4 hours;

s5, filtering and washing with water until the pH value is 7 to obtain a phthalocyanine derivative filter cake for later use;

s6, adding phthalocyanine green pigment into the phthalocyanine derivative filter cake, stirring, wherein the input amount of the phthalocyanine derivative filter cake is 15% of the mass of the phthalocyanine green pigment, stirring for 8 hours to obtain solvent-resistant crystallization-resistant flocculation-resistant phthalocyanine green pigment slurry, and completely coating the slurry by the phthalocyanine derivative in the stirring process;

s7, filtering and drying at 120 ℃ to obtain the phthalocyanine green pigment.

The pigments obtained in the examples were subjected to the following tests.

Weighing 200 parts of alkyd resin and 30 parts of MS mixed solvent (xylene: n-butanol: 70: 30 (mass ratio)) to obtain resin solution, adding 5 parts of TiO into 1 part of sample₂Adding 200 parts of polyurethane and 30 parts of mixed solvent (dimethylbenzene: n-butyl alcohol is 70: 30 (mass ratio)) to uniformly disperse and vibrate uniformly to obtain pigment color paste, scraping out paint chips by using an automatic film coating machine, airing, and testing the strength difference of each example by using a color measuring instrument (the same color paste prepared by using standard white enamel is used as a standard sample). The fluidity of the pigment paste is measured by an ink sample fluidity tester for 30min, and the viscosity values of the pigment paste after being placed for different times are measured by a rotational viscometer at the rotating speed of 10 r/min.

TABLE 1 pigment test results obtained in the examples

Examples 1 to 3 of the present invention are the best overall performance examples, and the phthalocyanine green pigments obtained in examples 4 to 7 are slightly lower than those in examples 1 to 3. The phthalocyanine green pigment prepared by the embodiment of the invention is not easy to generate crystallization expansion in solvent ink system chloropolyurethane and solvent xylene, the viscosity does not become thick after being placed in the system for a long time, the smaller the delta value is, the better anti-flocculation performance is shown, the downstream printing efficiency of the pigment is greatly improved, and the coloring strength is high.

The present invention is not limited to the above preferred embodiments, and any modifications, equivalent substitutions, improvements, etc. within the spirit and principle of the present invention should be included in the protection scope of the present invention.