Sun-resistant blue lotus lake pigment and preparation method thereof

Abstract

The application relates to the technical field of lake, and discloses a lightfast blue lake and a preparation method thereof. The lightfast blue lake is prepared from trihydroxyethyl melamine, epichlorohydrin, dodecyl N,N-dimethyl tertiary amine and the like as raw materials through substitution reaction and quaternary ammonium reaction to obtain a quaternary ammonium salt melamine pigment additive. Then, basic violet 5BN, the quaternary ammonium salt melamine pigment additive, basic dye, disodium hydrogen phosphate and the like are added into deionized water for stirring and dispersing, filtering, washing, drying, crushing and grinding to obtain the lightfast blue lake. The lightfast blue lake prepared by the application has stable color light, stable coloring intensity, stable quality and good lightfastness.

Description

TECHNICAL FIELD

[0001] The present application relates to the technical field of color lake, in particular to a light-fast cyan color lake and a preparation method thereof. BACKGROUND

[0002] The light-fast cyan color lake is a special organic pigment, which has the characteristics of strong coloring power and bright color, and is mainly applied in the fields of printing ink and coating coloring in various printing processes. However, the quality of the main raw material basic violet seriously affects the color light and coloring strength of the light-fast cyan color lake. This is because the domestic basic violet itself has low purity, which leads to the color light of the basic violet from blue to red, thereby causing the color light and coloring strength of the prepared light-fast cyan color lake to be unstable.

[0003] For example, the patent with the application publication number CN108017932 A discloses a preparation method of a light-fast cyan color lake for ink, which uses rosin soap to solve the problem of unstable pigment red. The patent with the application publication number CN102863818 A discloses a preparation method of pigment violet 3, which prepares a heteropolyacid to solve the problem of complete dye lake.

[0004] However, the above methods can only adjust the particle size of the pigment to make the color lake reaction more complete, and cannot solve the product quality problem caused by unstable quality of the raw material. SUMMARY

[0005] (I) Technical problems solved

[0006] The present application is to make up for the deficiencies in the prior art and solve the problem of unstable color light of the light-fast cyan color lake caused by unstable color light of the raw material basic violet. By adding other basic dyes to adjust the color light of the basic violet, and by preparing a cationic surfactant to disperse the pigment, a light-fast cyan color lake with stable color light, stable coloring strength, stable quality and good light-fastness is prepared.

[0007] (II) Technical solutions

[0008] A light-fast cyan color lake, which comprises the following components in percentage by weight: 10-25% of basic violet 5BN, 1-5% of glacial acetic acid, 1-5% of tris quaternary ammonium salt melamine pigment additive, 1-5% of basic dye, 1-5% of disodium hydrogen phosphate, 20-35% of sodium tungstate, 5-20% of sodium molybdate, and 25-30% of hydrochloric acid.

[0009] The preparation method of the light-fast cyan color lake is prepared by the following method:

[0010] Basic violet 5BN, glacial acetic acid, triquaternary ammonium salt of s-triazine pigment auxiliary, basic dye are added into deionized water, stirred and dispersed, heated to 80-90 DEG C, stirred for 20-40 min, filtered, then sodium phosphate dibasic, sodium tungstate, sodium molybdate are added into the aqueous solution, stirred and dispersed, then hydrochloric acid is added, stirred for 30-60 min, filtered, continue to stir for 40-80 min, filtered, washed with deionized water, dried, crushed, to obtain light-fast cyan lotus lake pigment.

[0011] Preferably, the basic dye is one or two of basic fuchsin, basic rose, basic roseine, basic blue, basic blue BO.

[0012] Preferably, the preparation method of the triquaternary ammonium salt of s-triazine pigment auxiliary is as follows:

[0013] (1) trihydroxyethyl s-triazine, epichlorohydrin, sodium hydroxide aqueous solution are added into toluene solvent, stirred and dispersed, then tetrabutyl tin bromide is added, heated to 45-60 DEG C, reacted for 3-7 h, after the reaction, cooled to room temperature, suction filtered, washed with toluene, distilled, to obtain intermediate 1.

[0014] (2) intermediate 1 is added into deionized water, stirred and dispersed, then hydrochloric acid aqueous solution, dodecyl N,N-dimethyl tertiary amine are added, heated to 40-55 DEG C, reacted for 4-8 h, after the reaction, distilled under reduced pressure, to obtain the triquaternary ammonium salt of s-triazine pigment auxiliary.

[0015] Preferably, in the step (1), the molar ratio of trihydroxyethyl s-triazine, epichlorohydrin, tetrabutyl tin bromide is 1:3-5:0.05-0.08.

[0016] Preferably, in the step (1), the concentration of sodium hydroxide aqueous solution is 40-50%.

[0017] Preferably, in the step (1), the molar ratio of intermediate 1, dodecyl N,N-dimethyl tertiary amine is 1:3-4.

[0018] Preferably, in the step (1), the concentration of hydrochloric acid aqueous solution is 30-40%.

[0019] (III) Beneficial technical effects

[0020] The present application takes trihydroxyethyl s-triazine, epichlorohydrin, dodecyl N,N-dimethyl tertiary amine as raw materials, through substitution reaction, quaternary amination reaction, to obtain the triquaternary ammonium salt of s-triazine pigment auxiliary. Then basic violet 5BN, the triquaternary ammonium salt of s-triazine pigment auxiliary, basic dye, sodium phosphate dibasic, etc. are added into deionized water, stirred and dispersed, filtered, washed, dried, crushed, to obtain light-fast cyan lotus lake pigment.

[0021] The triquaternary ammonium salt s-triazine pigment auxiliary prepared by the application can firmly adsorb on the surface of the pigment, so that the surface of the pigment has positive charge, the electrostatic repulsion between the pigment particles is increased, and the pigment particles are better dispersed in deionized water to form a stable dispersion system; and the color light of the basic violet is adjusted by adding other basic dyes to achieve the effects of stable color light and coloring intensity. The application prepares a solar fast cyan lotus color lake with stable color light, stable coloring intensity, stable quality and good solar fastness. BRIEF DESCRIPTION OF DRAWINGS

[0022] Figure 1 is a preparation route of the triquaternary ammonium salt s-triazine pigment auxiliary. DETAILED DESCRIPTION

[0023] The following will be described in more details. The following is a solar fast cyan lotus color lake and a preparation method thereof.

[0024] Example 1

[0025] (1) 80 mmol of trihydroxyethyl s-triazine, 240 mmol of epichlorohydrin and 50% sodium hydroxide aqueous solution were added to toluene solvent, stirred and dispersed, 5 mmol of tetrabutylammonium bromide was added, the temperature was increased to 50°C, and the reaction was carried out for 6 h. After the reaction was completed, the temperature was cooled to room temperature, filtration was performed, toluene was used for washing, and distillation was performed to obtain intermediate 1.

[0026] (2) 50 mmol of intermediate 1 was added to deionized water, stirred and dispersed, 35% hydrochloric acid aqueous solution and 200 mmol of dodecyl N,N-dimethyl tertiary amine were added, the temperature was increased to 40°C, and the reaction was carried out for 5 h. After the reaction was completed, distillation was performed under reduced pressure to obtain the triquaternary ammonium salt s-triazine pigment auxiliary.

[0027] (3) 20% basic violet 5BN (color light blue phase), 1% glacial acetic acid, 5% triquaternary ammonium salt s-triazine pigment auxiliary, and 4% basic magenta were added to deionized water, stirred and dispersed, the temperature was increased to 85°C, and stirring was performed for 40 min. Filtration was performed, 3% disodium hydrogen phosphate, 32% sodium tungstate, and 5% sodium molybdate were added to the aqueous solution, stirred and dispersed, 30% hydrochloric acid was added, stirring was performed for 60 min, filtration was performed, stirring was continuously performed for 60 min, filtration was performed, deionized water was used for washing, drying was performed, and crushing was performed to obtain the solar fast cyan lotus color lake.

[0028] Example 2

[0029] (1) 80 mmol of trihydroxyethyl s-triazine, 300 mmol of epichlorohydrin, 48% sodium hydroxide aqueous solution were added to toluene solvent, stirred and dispersed, 6.4 mmol of tetrabutylammonium bromide was added thereto, warmed to 45°C, reacted for 7 h, after the reaction was completed, cooled to room temperature, suction filtered, washed with toluene, distilled to obtain intermediate 1.

[0030] (2) 50 mmol of intermediate 1 was added to deionized water, stirred and dispersed, 40% hydrochloric acid aqueous solution, 160 mmol of dodecyl N,N-dimethyl tertiary amine were added thereto, warmed to 55°C, reacted for 8 h, after the reaction was completed, distilled under reduced pressure to obtain a triquaternary ammonium salt s-triazine pigment assistant.

[0031] (3) 20% by weight of basic violet 5BN (color light blue phase), 1% by weight of glacial acetic acid, 5% by weight of triquaternary ammonium salt s-triazine pigment assistant, 4% by weight of basic pink were added to deionized water, stirred and dispersed, warmed to 90°C, stirred for 40 min, filtered, 3% by weight of disodium hydrogen phosphate, 32% of sodium tungstate, 5% by weight of sodium molybdate were added to the aqueous solution, stirred and dispersed, 30% by weight of hydrochloric acid was added thereto, stirred for 40 min, filtered, continued to stir for 60 min, filtered, washed with deionized water, dried, crushed to obtain a light-fast blue lotus lake.

[0032] Example 3

[0033] (1) 80 mmol of trihydroxyethyl s-triazine, 400 mmol of epichlorohydrin, 40% sodium hydroxide aqueous solution were added to toluene solvent, stirred and dispersed, 4 mmol of tetrabutylammonium bromide was added thereto, warmed to 60°C, reacted for 3 h, after the reaction was completed, cooled to room temperature, suction filtered, washed with toluene, distilled to obtain intermediate 1.

[0034] (2) 50 mmol of intermediate 1 was added to deionized water, stirred and dispersed, 30% hydrochloric acid aqueous solution, 150 mmol of dodecyl N,N-dimethyl tertiary amine were added thereto, warmed to 50°C, reacted for 4 h, after the reaction was completed, distilled under reduced pressure to obtain a triquaternary ammonium salt s-triazine pigment assistant.

[0035] (3) 24wt% of Basic Violet 5BN (color light blue phase), 1wt% of glacial acetic acid, 5wt% of the quaternary ammonium salt melamine pigment additive were added into deionized water, stirred and dispersed, heated to 85°C, stirred for 40 min, filtered, 3wt% of disodium hydrogen phosphate, 32wt% of sodium tungstate, 5wt% of sodium molybdate were added into the aqueous solution, stirred and dispersed, 30wt% of hydrochloric acid was added, stirred for 60 min, filtered, stirred for another 60 min, filtered, washed with deionized water, dried, crushed, to obtain the light-fast blue lotus lake pigment.

[0036] Comparative Example 1

[0037] (1) 80 mmol of trihydroxyethyl melamine, 240 mmol of epichlorohydrin, 50% aqueous sodium hydroxide solution were added into toluene solvent, stirred and dispersed, 5 mmol of tetrabutyltin bromide was added, heated to 50°C, reacted for 6 h, after the reaction was completed, cooled to room temperature, suction filtered, washed with toluene, distilled, to obtain intermediate 1.

[0038] (2) 50 mmol of intermediate 1 was added into deionized water, stirred and dispersed, 35% hydrochloric acid aqueous solution, 200 mmol of dodecyl N,N-dimethyl tertiary amine were added, heated to 40°C, reacted for 5 h, after the reaction was completed, distilled under reduced pressure, to obtain the quaternary ammonium salt melamine pigment additive.

[0039] (3) 24wt% of Basic Violet 5BN (color light blue phase), 1wt% of glacial acetic acid, 5wt% of the quaternary ammonium salt melamine pigment additive were added into deionized water, stirred and dispersed, heated to 85°C, stirred for 40 min, filtered, 3wt% of disodium hydrogen phosphate, 32wt% of sodium tungstate, 5wt% of sodium molybdate were added into the aqueous solution, stirred and dispersed, 30wt% of hydrochloric acid was added, stirred for 60 min, filtered, stirred for another 60 min, filtered, washed with deionized water, dried, crushed, to obtain the light-fast blue lotus lake pigment.

[0040] Comparative Example 2

[0041] (1) 80 mmol of trihydroxyethyl melamine, 240 mmol of epichlorohydrin, 50% aqueous sodium hydroxide solution were added into toluene solvent, stirred and dispersed, 5 mmol of tetrabutyltin bromide was added, heated to 50°C, reacted for 6 h, after the reaction was completed, cooled to room temperature, suction filtered, washed with toluene, distilled, to obtain intermediate 1.

[0042] (2) 50mmol of intermediate 1 is added to deionized water, stirred and dispersed, 35% hydrochloric acid aqueous solution, 200mmol of dodecyl N,N-dimethyl tertiary amine are added thereto, the temperature is raised to 40℃, and the reaction is carried out for 5h. After the reaction is completed, vacuum distillation is carried out to obtain a tris quaternary ammonium salt s-triazine pigment auxiliary agent.

[0043] (3) 24% by weight of basic violet 5BN (color light red phase), 1% by weight of glacial acetic acid, and 5% by weight of tris quaternary ammonium salt s-triazine pigment auxiliary agent are added to deionized water, stirred and dispersed, the temperature is raised to 85℃, and stirred for 40min. Filtration is carried out, 3% by weight of disodium hydrogen phosphate, 32% of sodium tungstate, and 5% by weight of sodium molybdate are added to the aqueous solution, stirred and dispersed, 30% by weight of hydrochloric acid is added thereto, stirred for 60min, filtration is carried out, stirring is continued for 60min, filtration is carried out, deionized water washing is carried out, drying is carried out, and crushing is carried out to obtain a fast blue lotus lake pigment.

[0044] Referring to HG / T 2083-2006, the properties of the fast blue lotus lake pigment are tested.

[0045] Table 1: Properties of the fast blue lotus lake pigment

[0046] Gloss Color strength Tint Example 1 4.4 105 Red Example 2 4.3 106 Red Example 3 4.6 107 Red Comparative Example 1 4.0 95 Blue Comparative Example 2 4.9 120 Red

[0047] As shown in the table, the fast blue lotus lake pigment prepared by the present application has excellent characteristics such as color light stability and color strength stability.

[0048] The applicant declares that the polyurethane coating, the preparation method and the application thereof of the present application are illustrated by the above examples, but the present application is not limited to the above examples, that is, it does not mean that the present application must rely on the above examples to be implemented. It should be understood by those skilled in the art that any improvement of the present application, equivalent replacement of each raw material of the product of the present application, addition of auxiliary ingredients, selection of specific modes, etc. fall within the protection scope and disclosure scope of the present application.

Claims

1. A sun-resistant lotus lake, characterized in that, The lightfast cyan lake comprises the following components by weight percentage: 10-25% basic violet 5BN, 1-5% glacial acetic acid, 1-5% triquaternary ammonium salt triazine pigment additive, 1-5% basic dye, 1-5% disodium hydrogen phosphate, 20-35% sodium tungstate, 5-20% sodium molybdate, and 25-30% hydrochloric acid; The sun-resistant lotus lake was prepared by the following method: Add basic violet 5BN, glacial acetic acid, triquaternary ammonium salt triazine pigment additive, and basic dye to deionized water, stir and disperse, heat to 80-90℃, stir for 20-40 min, filter, then add disodium hydrogen phosphate, sodium tungstate, and sodium molybdate to the aqueous solution, stir and disperse, then add hydrochloric acid, stir for 30-60 min, filter, continue stirring for 40-80 min, filter, wash with deionized water, dry, and pulverize to obtain lightfast cyan lake; The basic dye is one or two of the following: basic fuchsin, basic pink, basic rose syrup, basic fuchsin blue, and basic fuchsin blue BO. The preparation method of the triquaternary ammonium salt triazine pigment additive is as follows: (1) Trihydroxyethyltriazine, epichlorohydrin and sodium hydroxide aqueous solution were added to toluene solvent, stirred and dispersed, and then tetrabutyltin ammonium bromide was added. The temperature was raised to 45-60℃ and the reaction was carried out for 3-7 hours. After the reaction was completed, the mixture was cooled to room temperature, filtered, washed with toluene, and distilled to obtain intermediate 1. (2) Add intermediate 1 to deionized water, stir and disperse, then add hydrochloric acid aqueous solution and dodecyl N,N-dimethyl tertiary amine, heat to 40-55℃, react for 4-8h, and after the reaction is completed, distill under reduced pressure to obtain triquaternary ammonium salt triazine pigment additive.

2. The sun-resistant lotus lake according to claim 1, characterized in that, In step (1), the molar ratio of trihydroxyethyltriazine, epichlorohydrin, and tetrabutyltin ammonium bromide is 1:3-5:0.05-0.

08.

3. The sun-resistant lotus lake according to claim 1, characterized in that, In step (1), the concentration of the sodium hydroxide aqueous solution is 40-50%.

4. The sun-resistant lotus lake according to claim 1, characterized in that, In step (2), the molar ratio of intermediate 1 and dodecyl N,N-dimethyl tertiary amine is 1:3-4.

5. The sun-resistant lotus lake according to claim 1, characterized in that, In step (2), the concentration of the hydrochloric acid aqueous solution is 30-40%.

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