阅读说明：本技术 一种纳米颜料晶型控制方法 (Nano pigment crystal form control method ) 是由 何贵平 李明峰 王荣文 于 2019-05-20 设计创作，主要内容包括：本发明公开的一种纳米颜料晶型控制方法,包括以下步骤：(1)将有机颜料烧结粉碎,添加无机盐及极性溶剂利用辊磨机预分散；(2)添加分子量为1000～1000000的水性感光树脂至步骤(1)的混合物中,利用砂磨机分散,所述水性感光树脂含酸性或碱性取代基,所述水性感光树脂为含有羰基、磺基或氨基的环氧丙烯酸树脂；(3)将步骤(2)所得的混合物添加至水中,并加热搅拌；(4)水洗,并干燥,通过将盐磨和添加水性的感光树脂结合,利用盐磨法是颜料粒径界面均一化,而添加水性的感光树脂将与均一化的颜料粒径作用,使之稳定的分散均匀,达到粘度稳定性良好、具有非聚集性、非结晶性、涂膜的光泽度高的特性。(The invention discloses a nano pigment crystal form control method, which comprises the following steps: (1) sintering and crushing the organic pigment, adding inorganic salt and a polar solvent, and pre-dispersing by using a roller mill; (2) adding aqueous photosensitive resin with the molecular weight of 1000-1000000 into the mixture obtained in the step (1), and dispersing by using a sand mill, wherein the aqueous photosensitive resin contains an acidic or basic substituent, and the aqueous photosensitive resin is epoxy acrylic resin containing carbonyl, sulfo or amino; (3) adding the mixture obtained in the step (2) into water, heating and stirring; (4) the pigment is washed with water and dried, and the salt milling and the water-based photosensitive resin are combined, so that the pigment particle size interface is homogenized by the salt milling method, and the water-based photosensitive resin acts with the homogenized pigment particle size to stably and uniformly disperse the pigment, thereby achieving the characteristics of good viscosity stability, non-aggregative property, non-crystallinity and high glossiness of a coating.)

1. A method for controlling the crystal form of a nano pigment is characterized by comprising the following steps: (1) sintering and crushing the organic pigment, adding inorganic salt and a polar solvent, and pre-dispersing by using a roller mill; (2) adding aqueous photosensitive resin with the molecular weight of 1000-1000000 into the mixture obtained in the step (1), and dispersing by using a sand mill, wherein the aqueous photosensitive resin contains an acidic or basic substituent, and the aqueous photosensitive resin is epoxy acrylic resin containing carbonyl, sulfo or amino; (3) adding the mixture obtained in the step (2) into water, and heating and stirring, wherein the heating temperature in the step (3) is 30-80 ℃; (4) washed with water and dried.

2. The method for controlling the crystal form of the nano pigment according to claim 1, wherein the polar solvent is one or more of diethylene glycol and polyethylene glycol.

3. The method for controlling the crystal form of the nano pigment according to claim 1, wherein the stirring time in the step (3) is 2-30 h.

4. The method for controlling the crystal form of the nano pigment according to claim 1, wherein the inorganic salt is one or more of sodium chloride, sodium sulfate and calcium chloride.

5. The method for controlling the crystal form of the nano pigment according to claim 1, wherein the organic pigment is one or more of quinacridone and azo pigments.

6. The method for controlling the crystal form of the nano pigment according to claim 1, wherein in the step (1), the roller mill is replaced by a kneader.

7. The method for controlling the crystal form of the nano pigment according to claim 1 or 6, wherein in the step (1), the pre-dispersion temperature is 40 ℃, and the pre-dispersion time is 1 h.

8. The method for controlling the crystal form of the nano pigment according to claim 1, wherein in the step (2), the temperature for dispersing is 40 ℃ and the time for dispersing is 1 h.

9. The method for controlling the crystal form of the nano pigment according to claim 1, wherein in the step (4), the drying temperature is 90 ℃ and the drying time is 12 h.

Technical Field

The invention relates to the field of pigments, in particular to a method for controlling a crystal form of a nano pigment.

Background

In recent years, attention has been paid to techniques for refining pigment and some functional material particles, and these refined particles can be applied to various fields and improve the added value of products. By making the pigment fine, the color can be made more vivid and the coloring power can be improved.

However, in practical use, the situation where the intended effect cannot be achieved due to problems such as difficulty in controlling the finely divided pigment is a large proportion, and the difficulty in controlling is mainly due to the increased difficulty in dispersing the pigment particles after they are finely divided, and it is difficult to eventually present the pigment particles in the final product, and the reason why the finely divided pigment cannot be suitably used is mainly due to the surface activity of the pigment (pigment) particles and the non-uniformity of the particles themselves.

For example, the micronized pigment dispersion has a high viscosity, and it is not easy to take out the product from a dispersion machine, and it is not easy to transfer the color paste to a storage tank, and it is not possible to use the pigment in a gel form during storage in the storage tank, and there are also problems in quality such as pigment sedimentation due to aggregation of the pigment in the color paste, uneven coating, reduction in tinting strength, reduction in functionality, reduction in surface gloss of a coating film, poor flatness, poor conductivity, and poor insulation.

Disclosure of Invention

In order to solve the problems, the invention provides a method for controlling the crystal form of the nano pigment, and the prepared nano pigment has the characteristics of good viscosity stability with time, non-aggregative property, non-crystallinity and high glossiness of a coating film.

The technical scheme of the invention is that a method for controlling the crystal form of the nano pigment comprises the following steps: (1) sintering and crushing the organic pigment, adding inorganic salt and a polar solvent, and pre-dispersing by using a roller mill; (2) adding aqueous photosensitive resin with the molecular weight of 1000-1000000 into the mixture obtained in the step (1), and dispersing by using a sand mill, wherein the aqueous photosensitive resin contains an acidic or basic substituent, and the aqueous photosensitive resin is epoxy acrylic resin containing carbonyl, sulfo or amino; (3) adding the mixture obtained in the step (2) into water, and heating and stirring, wherein the heating temperature in the step (3) is 30-80 ℃; (4) washed with water and dried.

Preferably, the polar solvent is one or more of diethylene glycol and polyethylene glycol.

Preferably, the stirring time in the step (3) is 2-30 h.

Preferably, the inorganic salt is one or more of sodium chloride, sodium sulfate and calcium chloride.

Preferably, the organic pigment is one or more of quinacridone and azo pigments.

Preferably, in step (1), the roll mill is replaced by a kneader.

Preferably, in the step (1), the pre-dispersion temperature is 40 ℃, and the pre-dispersion time is 1 h.

Preferably, in the step (2), the temperature of the dispersion is 40 ℃, and the time of the dispersion is 1 h.

Preferably, in the step (4), the drying temperature is 90 ℃, and the drying time is 12 h.

The step (1) and the step (2) in this embodiment relate to a pigment salt milling method, and are a production method in which a mixture of a pigment sinter-ground salt, an organic solvent, and the like is subjected to high-viscosity kneading by a stirrer, a kneader, or the like to make the particle diameter (interface) of the pigment uniform and fine. The pigment is subjected to particle size (interface) homogenization by a salt milling method, a water-soluble additive (with the molecular weight of 1000-1000000) containing an acidic or basic substituent is added after one or two processes of micronization for surface treatment, the surface formed by the pigment in the particle size (interface) homogenization process is treated, the reason that the molecular weight of the additive is selected from 1000-1000000 is that the required surface treatment effect is difficult to achieve by the additive with the molecular weight of less than 1000 in consideration of the surface treatment effect and the viscosity requirement during salt milling and mulling, and the particle size of the pigment is difficult to control due to the fact that the salt milling viscosity is remarkably improved by the fact that the molecular weight of the additive exceeds 1000000.

The photosensitive resin is a high molecular material which is rapidly changed chemically under the action of illumination so as to cause certain physical properties to be obviously changed, in the scheme, carbonyl, sulfo or amino groups of the photosensitive resin are combined with pigment groups to improve the dispersibility and the color paste stability, the photosensitive resin per se is epoxy acrylic resin which is crosslinked or polymerized due to the original characteristics of the photosensitive resin, meanwhile, the epoxy acrylic resin containing carbonyl, sulfo or amino groups used in the scheme can be adsorbed on pigment particles and also has a steric hindrance function, a common dispersing agent cannot be well adsorbed on the surfaces of micronized pigment particles, and the pigment is hydrophobic, so that a large amount of dispersing agent is required for long-time dispersing treatment, the subsequent coating performance of ink is influenced, an over-dispersion phenomenon is easy to occur, the storage stability is poor, and the like, on the other hand, the carbonyl, sulfo or amino group-containing epoxy acrylic resin used in the present invention has a steric hindrance function due to the presence of the carbonyl, sulfo or amino group which is adsorbable to the pigment particles, and therefore, the epoxy acrylic resin itself has good dispersibility, good viscosity stability with time, non-aggregative properties, non-crystalline properties and high gloss of the coating film.

The invention has the advantages that the salt milling and the water-based photosensitive resin are combined, the interface of the pigment particle size is homogenized by the salt milling method, and the water-based photosensitive resin acts with the homogenized pigment particle size to ensure that the pigment particle size is stably and uniformly dispersed, thereby achieving the characteristics of good viscosity stability, non-aggregative property, non-crystallinity and high glossiness of a coating.

Detailed Description

In order to make the present invention more comprehensible, the technical solutions of the present invention are further described below with reference to specific embodiments, but the present invention is not limited thereto.

Example 1

100g of quinacridone pigment (BASF corporation, 4500J) is sintered and crushed, 200g of sodium chloride and 110g of diethylene glycol are added into a stainless kneading machine (manufactured by UK corporation), the mixture is kneaded at 40 ℃ for 1 hour to be homogenized, 10g of carbonyl epoxy acrylic resin (Bikk 9152) is added, the mixture is dispersed in a sand mill, the kneading is carried out at 40 ℃ for 1 hour, the kneaded mixture is added into warm water, the mixture is heated to 50 ℃ and stirred for 1 hour, the filtration and water washing processes are repeated, the sodium chloride and the diethylene glycol are removed, and the mixture is dried at 90 ℃ for 12 hours to obtain the surface-treated red pigment 1.

Example 2

100g of quinacridone pigment (BASF corporation "" 4500J "") is sintered and pulverized, 200g of sodium chloride and 110g of diethylene glycol are added into a stainless steel kneader (manufactured by UK corporation), the mixture is kneaded at 40 ℃ for 1 hour to be homogenized, 10g of amino epoxy acrylic resin (BASF corporation "" Efka4701 "") is added and dispersed in a sand mill, the kneading is further carried out at 40 ℃ for 1 hour, the kneaded product is added into warm water, the mixture is heated to 50 ℃ and stirred for 1 hour, the filtration and water washing processes are repeated, the sodium chloride and the diethylene glycol are removed, and the mixture is dried at 90 ℃ for 12 hours to obtain the surface-treated red pigment 2.

Example 3

100g of quinacridone pigment (BASF corporation, 4500J) is sintered and crushed, 200g of sodium chloride and 110g of diethylene glycol are added into a stainless steel kneader (manufactured by Umbelliferae), the mixture is kneaded at 40 ℃ for 1 hour to be homogenized, 10g of carboxyl epoxy acrylic resin (SORBITOL) is added, the mixture is dispersed in a sand mill, the mixture is kneaded at 40 ℃ for 1 hour, the kneaded mixture is added into warm water, the mixture is heated to 50 ℃ and stirred for 1 hour, the filtration and washing processes are repeated, the sodium chloride and the diethylene glycol are removed, and the mixture is dried at 90 ℃ for 12 hours to obtain the surface-treated red pigment 3.

Example 4

100g of azo pigment (Ink Jet Yellow 5GX-W, Clariant Co.) was fired and pulverized, 200g of sodium chloride and 110g of diethylene glycol were added to a stainless steel kneader (manufactured by Otto Co., Ltd.), and kneaded at 40 ℃ for 1 hour for homogenization, 10g of carboxyl epoxy acrylic resin (SORBITOL, Kao) was added thereto, and the mixture was dispersed in a sand mill, kneaded at 30 ℃ for 1 hour, and then the kneaded product was added to warm water, heated to 50 ℃ and stirred for 1 hour, and the filtration and washing processes were repeated, and after removing sodium chloride and diethylene glycol, the mixture was dried at 90 ℃ for 12 hours, to obtain surface-treated Yellow pigment 1.

Example 5

100g of azo pigment (Ink Jet Yellow 5GX-W, Clariant Co.) was fired and pulverized, 200g of sodium chloride and 110g of diethylene glycol were added to a stainless steel kneader (manufactured by Kokai Co., Ltd.) and kneaded at 40 ℃ for 1 hour for homogenization, 10g of amino epoxy acrylic resin (Efka 4701, BASF Co.) was added thereto and dispersed in a sand mill, further kneaded at 80 ℃ for 1 hour, then the kneaded mixture was added to warm water and stirred at 50 ℃ for 1 hour, and the filtration, washing with water were repeated to remove sodium chloride and diethylene glycol, and then dried at 90 ℃ for 12 hours to obtain surface-treated Yellow pigment 2.

Example 6

100g of azo pigment (Ink Jet Yellow 5GX-W, Clariant) was sintered and pulverized, 200g of sodium chloride and 110g of diethylene glycol were added to a stainless-steel kneader (manufactured by Otto Co., Ltd.), and kneaded at 40 ℃ for 1 hour for homogenization, 10g of carbonyl epoxy acrylic resin (Pick BYK 9152) was added thereto, and the mixture was dispersed in a sand mill, kneaded at 30 ℃ for 1 hour, and then the kneaded product was added to warm water, heated to 50 ℃ and stirred for 1 hour, and the filtration and washing processes were repeated, and after removing sodium chloride and polyethylene glycol, the mixture was dried at 90 ℃ for 12 hours, to obtain a surface-treated Yellow pigment 3.

Example 7

100g of azo pigment (BASF corporation, D7088) was sintered and pulverized, 200g of sodium chloride and 110g of diethylene glycol were added to a stainless kneader (manufactured by Umbelliferae), kneaded at 40 ℃ for 1 hour to homogenize the mixture, 10g of carboxyl epoxy acrylic resin (SORBITOL) was added thereto, the mixture was dispersed in a sand mill, kneaded at 30 ℃ for 1 hour, kneaded in warm water, heated to 50 ℃ and stirred for 1 hour, and the filtration, washing with water, sodium chloride and diethylene glycol were removed, and then dried at 90 ℃ for 12 hours to obtain surface-treated blue pigment 1.

Example 8

100g of azo pigment (BASF corporation, D7088) was sintered and pulverized, 200g of sodium chloride and 110g of diethylene glycol were added to a stainless kneader (manufactured by UK corporation), and kneaded at 40 ℃ for 1 hour to homogenize the mixture, and then 10g of amino epoxy acrylic resin (BASF corporation, Efka 4701) was added thereto, and the mixture was dispersed in a sand mill, and kneaded at 80 ℃ for 1 hour, and then the kneaded mixture was added to warm water, heated to 50 ℃ and stirred for 1 hour, and filtration, washing with water, and after removing sodium chloride and diethylene glycol, drying at 90 ℃ for 12 hours to obtain surface-treated blue pigment 2.

Example 9

100g of azo pigment (BASF corporation, D7088) was sintered and pulverized, 200g of sodium chloride and 110g of diethylene glycol were added to a stainless kneader (manufactured by UK corporation), and kneaded at 40 ℃ for 1 hour to homogenize the mixture, then 10g of carbonyl epoxy acrylic resin (Bike, BYK 9152) was added to the mixture and dispersed in a sand mill, and kneaded at 30 ℃ for 1 hour, and then the kneaded mixture was added to warm water, heated to 50 ℃ and stirred for 1 hour, and filtered repeatedly, washed with water, and after sodium chloride and polyethylene glycol were removed, dried at 90 ℃ for 12 hours to obtain a surface-treated blue pigment 3.

Example 10

The viscosity of the pigments prepared in examples 1 to 9 was changed, and it was found that the viscosity stability with time was good, wherein the viscosity was measured by the following method: the pigment was prepared as a pigment dispersion, and the viscosity was measured at 25 ℃ with a cone and plate viscometer, where the viscosity after high temperature storage was one month at 50 ℃.

The above description is only a preferred embodiment of the present invention, and all equivalent changes and modifications made in accordance with the claims of the present invention should be covered by the present invention.