CN118599336A

CN118599336A - Anthraquinone blue solid solution pigment and preparation method and application thereof

Info

Publication number: CN118599336A
Application number: CN202410637828.1A
Authority: CN
Inventors: 刘丽民; 申井会; 聂万红; 王敏敏
Original assignee: Ningxia Caiyan Technology Co ltd
Current assignee: Ningxia Caiyan Technology Co ltd
Priority date: 2024-05-22
Filing date: 2024-05-22
Publication date: 2024-09-06

Abstract

The invention discloses an anthraquinone blue solid solution pigment, a preparation method and application thereof, and relates to the technical field of improvement of anthraquinone blue (pigment blue 60); the main pigment is anthraquinone blue; the guest pigment is present in an amount of 0.1 to 50% by weight based on 100% by weight of the host pigment. The invention obtains pigment blue 60 with better dispersibility by adding a second pigment or pigments or dyes to form a "solid solution" during the preparation and processing of the pigment. The anthraquinone blue solid solution pigment provided by the invention is novel, and has good application properties such as dispersibility, rheological property, thermal stability, migration fastness, light resistance and weather resistance, and also has strong color and color saturation when being used as pigment. Uses for these solid solutions include, but are not limited to, color pastes, color filters, electrophotography, automotive paint systems, and various polymer fibers.

Description

Anthraquinone blue solid solution pigment and preparation method and application thereof

Technical Field

The invention relates to the technical field of improvement of anthraquinone blue (pigment blue 60), in particular to an anthraquinone blue solid solution pigment, a preparation method and application thereof.

Background

HAO Z and HONTI S B mention in chinese patent CN1509320 that "if the X-ray diffraction pattern of a multi-component pigment is different from that of a physical mixture of its components, the pigment is called a solid solution. They are mainly two types of well-defined solid solutions, namely 'host-guest' solid solutions and 'binary solid compound' solid solutions. For clarity, the 'mixed crystal' solid solutions are derived from equimolar compositions, whereas the binary solid compounds have a mixed crystal structure, but with a significantly smaller range of pigment components. The X-ray diffraction pattern of a 'host-guest' solid solution is substantially the same as the X-ray diffraction pattern of one of its components, referred to as 'host'. The host component is able to accept other components, i.e. "guests", in its crystal lattice. The 'binary solid compound' is a compound in which two components are associated with each other, resulting in an X-ray diffraction pattern that is different from the X-ray diffraction pattern of either or a physical mixture of the components.

Additional improvements to solid solution classification are presented herein, and the "single phase solid solution", "multiphase solid solution" and "mixed crystal" concepts are presented. Wherein "single phase solid solution" refers to a solid solution having a lattice identical to that of one of its components. A component is embedded as a "guest" in a crystal lattice of a "host", and within a certain range, different proportions of the components have no influence on the crystal lattice result. "multiphase solid solution" refers to a solid solution that is not precisely homogeneous in lattice, and differs from a physical mixture of individual components therein in that the lattice of at least one component is partially or completely altered, the signal in the X-ray diffraction pattern being displaced at the angle 2 theta, the result of the alteration being different with different ratios of the components. The "mixed crystals" have a precisely uniform lattice and are different from the lattices of all the individual components. The different proportions of the components lead to the same lattice result within a certain range. Furthermore, it is mentioned that a "host-guest" solid solution of "para-dimethyl DPP" and "para-dichloro DPP" is prepared.

U.S. patent No. 4783540 also reports in which solid solutions of pigments of the 1, 4-diketo-pyrrolo [3,4-c ] pyrrole (DPP) series are used. U.S. Pat. No.5,08188 describes 1, 4-diketopyrrolo [3,4-c ] pyrrole describing mixed crystals and solid solutions, wherein reference is made to the crystal structure of binary solid solutions having practically the same structure as the corresponding pigment of the unsymmetrical diketopyrrolopyrrole. US patent No. 5529623 describes not only a binary solid solution of DPP pigments, but also a ternary solid solution of pyrrolo [3,4-c ] pyrrole pigments and quinacridones. Similar reports are also available in US 48110304, US5472496, and US 5821373.

EHRICH in US3160510, a process for the preparation of quinacridone binary and binary or higher solid solutions is reported, by means of which the pigment gamut can be widened and the potential for improved lightfastness can be achieved.

Pigment blue 60 (also called indanthrene blue and anthraquinone blue) is red light blue, is an anthraquinone pigment, has a chemical structure consistent with vat dye vat blue 4, and is obtained by pigment formation on the basis of vat blue 4 raw powder. Has excellent light fastness, heat resistance, weather fastness, high transparency and solvent fastness. The paint is mainly used for automobile original finish, repair paint, industrial coil steel paint and powder paint, especially metal car paint, and can be used in the occasions where phthalocyanine pigment is insufficient due to better weather fastness than phthalocyanine pigment. One of the main characteristics is that the dye contains no heavy metal in the molecule, and the dye is very popular in the field of coloring of some nontoxic appliances. Pigment blue 60 is suitable for the dope coloration of synthetic fibers (commonly known as "pre-spin coloration" or "spinning grade masterbatch"), and particularly when used for dope coloration of polypropylene fibers, each application fastness is above that of phthalocyanine pigment; pigment blue 60 is also suitable for coloring plastics, and for reasons of price, is limited to special occasions requiring extremely high application fastness, pigment blue 60 is also suitable for coloring offset ink, solvent ink (including plastic composite ink) pen ink and printer ink, and is particularly suitable for high-grade coinage printing ink due to excellent acid resistance, alkali resistance, organic solvent resistance and weather resistance. Pigment blue 60 may also be used for the coloration of industrial leather.

However, few solid solutions of pigment blue 60 have been reported.

Disclosure of Invention

The invention aims to provide an anthraquinone blue solid solution pigment, a preparation method and application thereof,

In order to solve the technical problems, the technical scheme of the invention is as follows:

It is an object of the present invention to provide an anthraquinone blue solid solution pigment.

The anthraquinone blue solid solution pigment comprises a host pigment and a guest pigment;

The main pigment is anthraquinone blue or vat blue 4; since the chemical structure of pigment blue 60 is consistent with vat blue 4, and is obtained by pigment formation based on vat blue 4 raw powder, the main pigment of the application can also directly adopt vat blue 4 known by the person skilled in the art;

The guest pigment is phthalocyanine, quinacridone quinone, quinophthalone, dioxazine, indanthrone, anthraquinone, indigo, isoindolinone, isoindoline, perylene, piclone, 1, 4-diketo-2, 5-diaryl pyrrolo [3,4-c ] pyrrole, azo condensation pigment and the structural formula is Wherein X is at least one of fluorine, chlorine, bromine, iodine, nitro, carboxyl, ester, ketone, amide, sulfonamide, sulfonic acid and salts thereof, straight-chain or branched alkyl group having 1 to 30 carbon atoms, aromatic group having straight-chain or branched alkyl group having 1 to 30 carbon atoms, sulfanyl group having straight-chain or branched alkyl group having 1 to 30 carbon atoms, and n is 0.1 to 4;

the guest pigment is present in an amount of 0.1 to 50% by weight based on 100% by weight of the host pigment.

In a preferred embodiment of the invention:

The guest pigment is present in an amount of 0.5 to 20%, preferably 1 to 10%, more preferably 3 to 5% by weight based on 100% by weight of the host pigment. Depending on the intended use, different amounts of guest pigments may be used, especially for applications in paints. At different dosage ratios, mixed crystals can be formed instead of solid solutions, but the use effect is not significantly different from gradual change due to the difference of two crystals, so that the solid solutions are not distinguished in the invention.

In a preferred embodiment of the invention:

The guest pigment is 1, 4-diketo-2, 5-diaryl pyrrolo [3,4-c ] pyrrole, anthraquinone which belongs to the same pigment class with pigment blue 60 (such as pigment yellow 108, pigment red 177, pigment yellow 147, pigment yellow 193, pigment yellow 199, pigment yellow 202, pigment red 83, pigment violet 5, pigment violet 5:1 and the like), indanthrone and the structural formula Wherein X is at least one of chlorine, bromine, iodine, carboxyl, sulfonamide, sulfonic acid group and salts thereof and sulfanyl group having a linear or branched alkyl group having 1 to 30 carbon atoms, n is 0.1 to 4, preferably anthraquinone and has the structural formulaWherein X is at least one of chlorine, bromine, a sulfonic acid group and salts thereof, and a sulfanyl group having a linear or branched alkyl group having 1 to 30 carbon atoms, and n is 0.1 to 2.

In a preferred embodiment of the invention:

The solid solution pigment comprises two or more components, and can be adaptively adjusted according to requirements by a person skilled in the art; the kind of the guest pigment is 1 to 100, preferably 1 to 7, more preferably 1 to 2.

It is another object of the present invention to provide a method for producing an anthraquinone blue solid solution pigment according to one of the objects of the present invention.

The preparation method of the anthraquinone blue solid solution pigment provided by the invention comprises one of the following three methods:

the method comprises the following steps: adding a host pigment and a guest pigment into an organic solvent, uniformly stirring, optionally performing heating reaction, filtering, washing and drying to obtain the solid solution pigment;

the second method is as follows: adding a host pigment and a guest pigment into concentrated sulfuric acid for dissolution, adding water for precipitation, filtering, washing free acid, drying, optionally adding into an organic solvent to form a suspension, and then heating for reaction to obtain the solid solution pigment;

And a third method: the solid solution pigment is prepared by sufficiently grinding a host pigment, a guest pigment, a grinding medium and optionally an organic solvent (the grinding is carried out in grinding equipment, the organic solvent is not added or added according to the type of the grinding equipment, and the grinding process needs to contain enough grinding medium to have the effect of sufficiently changing the particle size of the pigment), pouring the mixture into a solution for stirring reaction after the grinding is finished, and filtering, washing and drying the mixture.

Wherein, in the second method: the water adopted by the precipitation in the water is excessive water, and a person skilled in the art can add the water in proper amount according to the requirement; in the third method: the grinding device is at least one selected from a kneader, a ball mill, a grinding roller, a sand mill, a needle mill, an air flow mill and a flash dryer with a cutter head; the solution poured after finishing grinding is an excess solution, and can be dilute sulfuric acid aqueous solution or water.

Different grinding devices are adopted, for example, a kneader is used, namely, after pigment, grinding medium (inorganic salt) and organic solvent are added, a stirring paddle is rotated to grind, and after the material is added into water to dissolve the inorganic salt after the kneading is finished, the material is filtered, washed, dried and crushed to obtain a finished pigment; in addition, for example, the use of a sand mill is that after the main pigment, the guest pigment and the organic solvent are pulped and dispersed, the main pigment, the guest pigment and the organic solvent are ground by the sand mill, filtered and washed after the grinding is finished, and then dried and crushed to obtain a finished product; and the like, according to the procedures of such grinding, are all well known to those skilled in the art.

In a preferred embodiment of the invention:

The organic solvent is at least one of alcohol solvent, organic acid solvent, ether solvent, ketone solvent, aromatic hydrocarbon solvent, ester solvent, amide solvent and other solvents; preferably, the method comprises the steps of,

The alcohol solvent is at least one of methanol, ethanol, ethylene glycol, polyethylene glycol, propylene glycol, diethylene glycol, diacetone alcohol and glycerol; and/or the number of the groups of groups,

The organic acid solvent is a low molecular weight organic acid solvent, preferably formic acid and/or acetic acid; and/or the number of the groups of groups,

The ether solvent is at least one of dioxane, tetrahydrofuran, ethylene glycol monoethyl ether, ethylene glycol ether, oligomeric polyethylene glycol ether, diaryl ether and triaryl ether; and/or the number of the groups of groups,

The ketone solvent is at least one of acetone, benzophenone, 1, 3-dioxolan-2-one and methyl ethyl ketone; and/or the number of the groups of groups,

The aromatic solvent is at least one of toluene, dimethylbenzene, trimethylbenzene, chlorobenzene, dichlorobenzene, nitrobenzene, chloronaphthalene, biphenyl, para-terphenyl, meta-terphenyl, ortho-terphenyl, dibenzyltoluene, alpha-methylnaphthalene, beta-methylnaphthalene and acetophenone; and/or the number of the groups of groups,

The ester solvent is at least one of methyl benzoate, dimethyl phthalate, methyl salicylate, triacetin and gamma-butyrolactone; and/or the number of the groups of groups,

The amide solvent is at least one of formamide, dimethylformamide and N-methylpyrrolidone; and/or the number of the groups of groups,

The other solvent is at least one of nitromethane, dimethyl sulfoxide and sulfolane;

more preferably, the organic solvent is at least one of ethylene glycol, polyethylene glycol, diacetone alcohol, toluene, xylene, trimethylbenzene, chlorobenzene, dichlorobenzene.

In a preferred embodiment of the invention:

The grinding medium is at least one of sodium chloride and hydrate thereof, potassium chloride and hydrate thereof, calcium chloride and hydrate thereof, zinc chloride and hydrate thereof, aluminum chloride and hydrate thereof, sodium sulfate and hydrate thereof, aluminum sulfate and hydrate thereof, calcium carbonate and hydrate thereof, sodium acetate and hydrate thereof, calcium acetate and hydrate thereof, sodium citrate and hydrate thereof, potassium tartrate and hydrate thereof, steel balls, zirconium beads and steel nails, preferably at least one of sodium sulfate, potassium chloride, aluminum sulfate, sodium chloride, steel balls, zirconium beads and steel nails.

In a preferred embodiment of the invention:

In the first method:

the mass ratio of the organic solvent to the total mass of the host pigment and the guest pigment is (10-35): 1, a step of; and/or the number of the groups of groups,

When the heating reaction is carried out, the reaction temperature of the heating reaction is 150-200 ℃ and/or the reaction time is 1-3 hours; and/or the number of the groups of groups,

In the second method:

the total mass ratio of the concentrated sulfuric acid to the host pigment and the guest pigment is (1-10): 1, a step of; and/or the number of the groups of groups,

When an organic solvent is added, the mass ratio of the organic solvent to the total of the host pigment and the guest pigment is (10-30): 1, a step of; and/or the number of the groups of groups,

When the heating reaction is performed, the reaction temperature of the heating reaction is 150 to 200 ℃, and/or the reaction time is 1 to 3 hours.

In a preferred embodiment of the invention:

In the third method:

the grinding medium and the main pigment and the guest pigment have the total mass ratio of (5-130): 1, a step of; and/or the number of the groups of groups,

When an organic solvent is added, the mass ratio of the organic solvent to the grinding medium is (5-10): 1, a step of; and/or the number of the groups of groups,

The grinding time is 10-24 hours; and/or the number of the groups of groups,

The reaction temperature of the stirring reaction is 50-100 ℃, and/or the reaction time is 1-5 hours.

It is a further object of the present invention to provide an anthraquinone blue solid solution pigment according to one of the objects of the present invention or an anthraquinone blue solid solution pigment produced by a method according to the second object of the present invention as a pigment for application to an object to be colored, preferably a natural organic substance and its modified and/or synthetic organic substance.

The substance to be colored can be from natural organic substances and modified substances and/or synthetic organic substances thereof; such as natural resins, rubber or casein; modifications of the natural organics such as chlorinated rubber, oil modified alkyd resin, viscose, cellulose ether or ester (e.g. cellulose acetate, cellulose propionate, cellulose acetobutyrate or nitrocellulose); the synthetic organic substances (thermoset or thermoplastic) are produced by polycondensation or polyaddition reactions, such as polyolefins (polyethylene, polypropylene, polyisobutylene, etc.), substituted polyolefins (polymers or copolymers of vinyl chloride, vinyl acetate, styrene, acrylonitrile, acrylic esters, methacrylic esters, butadiene, such as ABS or EVA, etc.).

Among the series of polyaddition resins and polycondensation resins, condensates of formaldehyde with phenols are known as phenolic resins, condensates of formaldehyde with urea, thiourea and melamine are known as amino resins, polyesters used as paint resins and saturated resins such as alkyd resins and unsaturated resins such as maleic resins, and also linear polyesters and polyamides or silicones.

The substances to be coloured may be present individually or in the form of mixtures, in the form of plastic masses or melts, if desired textile fibres. They may also be present in monomeric or in polymerized form in dissolved form as film formers or binders for coatings or printing inks, such as linseed paint, nitrocellulose, alkyd resins, melamine resins, urea-formaldehyde resins or acrylic resins.

The method of applying the solid solution pigment of the present invention to an object to be colored may employ roll milling, a mixer or a grinding apparatus to roll, press, extrude, spread, cast or injection mold the solid solution pigment in the form of a concentrated color body or dispersion as required. Plasticizers may be incorporated into the solid solution pigments of the invention in order to produce non-rigid mouldings or in order to reduce brittleness. The plasticizer is at least one of phosphate, phthalate and sebacate. The plasticizer may also be incorporated into the object to be colored. It is further possible that, in addition to the pigment composition, fillers and/or other coloring components such as white, colored or black pigments and the like may be added to the object to be colored in order to obtain different hues, and specific addition amounts may be added as required by those skilled in the art.

For the use of the solid solution pigment of the present invention for coloring paints and printing inks, it is usual to employ the object to be colored and the solid solution pigment of the present invention alone or together with additives such as fillers, other pigments, siccatives or plasticizers, etc., by finely dispersing or dissolving in an organic and/or aqueous solvent.

The invention obtains pigment blue 60 with better dispersibility by adding a second pigment or pigments or dyes to form a "solid solution" during the preparation and processing of the pigment.

The anthraquinone blue solid solution pigment provided by the invention is novel, and has good application properties such as dispersibility, rheological property, thermal stability, migration fastness, light resistance and weather resistance, and also has strong color and color saturation when being used as pigment. Uses for these solid solutions include, but are not limited to, color pastes, color filters, electrophotography, automotive paint systems, and various polymer fibers.

Detailed Description

The following describes the invention in more detail. The description of these embodiments is provided to assist understanding of the present invention, but is not intended to limit the present invention. In addition, the technical features of the embodiments of the present invention described below may be combined with each other as long as they do not collide with each other.

Example 1

10.0G of vat blue 4, 0.3g of a compound having the following structure (1) and 40.0g of 16-hydrate Al ₂(SO₄)₃ were charged into a 1.0L ball mill equipped with 1200g of steel balls and 100g of steel nails as grinding media. After grinding for 18 hours at 100rpm of the ball mill, the material was discharged and separated from the grinding media. The resulting ground powder was stirred with 2% aqueous sulfuric acid at 90℃for 2 hours. Filtering the obtained slurry, washing with hot water until neutral and salt-free, drying the filter cake at 80 ℃, and pulverizing to obtain the product.

Comparative example 1A

The difference from example 1 is that the compound having structure (1) is not added, the other steps being identical.

Comparative example 1B

A10.0 g product of comparative example 1A was thoroughly and physically mixed with 0.3g of the compound of structure (1).

Example 2

10.0G of vat blue 4 powder, 0.5g of a compound having the following structure (2), and 55.0g of 16-hydrate Al ₂(SO₄)₃ were charged into a 1.0L ball mill equipped with 1200g of steel balls and 100g as a grinding medium. After 24 hours of rotation at 100rpm of the ball mill, the material was discharged and separated from the grinding media. The resulting ground powder was stirred with 2% aqueous sulfuric acid at 80℃for 1 hour. Filtering the obtained slurry, washing with hot water until neutral and salt-free, drying the filter cake at 100 ℃, and pulverizing to obtain the product.

Comparative example 2A

The difference from example 2 is that the compound having structure (2) is not added, the other steps being identical.

Comparative example 2B

A10.0 g product of comparative example 2A was thoroughly physically mixed with 0.5g compound of Structure 2.

Example 3

500G of crushed sodium chloride and 70g of vat blue 4,2g of pigment red 177 were added to a Sigma blade kneader having a capacity of one liter, and the mixture was mixed for 10 minutes, followed by addition of 90g of ethylene glycol. The resulting uniform pigment paste was ground for 10 hours at a temperature of 40-45 c, with ethylene glycol added as needed to maintain paste uniformity. The pigment paste was poured into 1200ml of water and stirred well, and the resulting slurry was stirred at 90 ℃ for 1 hour. The solid component was collected by filtration, washed with water, dried and crushed and ground to give the product.

Comparative example 3A

Unlike example 3, pigment red 177 was not added, other steps were consistent.

Comparative example 3B

70.0G of the product of comparative example 3A are used with 2g of the compound of pigment Red 177 in a sufficiently physical mixture.

Example 4

600G of crushed sodium chloride and 100g of vat blue 4,2.5g of compound having structure (3) were added to a Sigma blade kneader having a capacity of one liter, and the mixture was mixed for 10 minutes, followed by addition of 110g of xylene. The resulting uniform pigment paste was ground at a temperature of 40-45 ℃ for 20 hours, and xylene was added as needed to maintain paste uniformity. The pigment paste was poured into 1500ml of water and acidified with dilute hydrochloric acid to a pH of less than 2. The resulting slurry was stirred at 90℃for 2 hours.

The solid components are collected by filtration, washed by methanol and water, dried, crushed and ground to obtain the product.

Comparative example 4A

Unlike example 4, the other steps were identical without adding the compound having structure (3).

Comparative example 4B

100.0G of the product of comparative example 4A was thoroughly physically mixed with 2.5g of the compound of structure 3.

Example 5

A1 liter flask equipped with a thermometer, stirrer and condenser was used, followed by 20g of pigment blue 60, 1g of pigment red 254 and 500ml of o-dichlorobenzene. The suspension was stirred, heated and pressurized to 180 ℃ and kept stirring for 2 hours. The suspension was cooled to room temperature and filtered. The filter cake is then washed with methanol and then with water and dried at 80-130 ℃.

Comparative example 5A

Unlike example 5, pigment red 254 was not added, other steps were consistent.

Comparative example 5B

A mixture of 20.0g of the product of comparative example 5A with 1g of the compound of pigment Red 254 was thoroughly and physically mixed.

Example 6

10G of vat blue 4 and 0.5g of compound of structure (4) are dissolved in 100g of concentrated sulfuric acid, the temperature is kept below 30 ℃ during dissolution, the mixture is stirred uniformly to fully react, after 1 hour, the materials are added into 1000ml of ice-water mixture, the whole process is kept at 0 ℃ for 0.5 hour, the mixture is stirred uniformly, filtered, and the free acid is washed by water.

A1 liter flask equipped with a thermometer, a stirrer and a condenser was used, and then the above-mentioned cake and 500ml of pseudocumene were added. The suspension was stirred, heated to boiling point after water had evaporated, then pressurized to 180 ℃ and kept stirring for 1 hour. The suspension was cooled to room temperature and filtered. The filter cake is then washed with methanol and then with water and dried at 80-130 ℃.

Comparative example 6A

Unlike example 6, structure (4) was not added and the other steps were identical.

Comparative example 6B

A mixture of 10.0g of the product of comparative example 6A with 0.5g of the compound of structure (4) was thoroughly and physically mixed.

Example 7

20G of vat blue 4, 0.8g of the compound of structure (5) and 250ml of xylene are added to a 500ml flask, after stirring well, the mass is pumped into a sand mill with zirconium beads and recycled back and forth. After 3 hours the suspension was pumped out and filtered.

The filter cake is then washed with methanol and then with water and dried at 80-100 ℃.

Comparative example 7A

Unlike example 7, structure (5) was not added and the other steps were identical.

Comparative example 7B

A mixture of 20.0g of the product of comparative example 7A with 0.8g of the compound of structure (5) was thoroughly and physically mixed.

Example 8

80G of vat blue 4, 0.9g of the compound of structure (6) and 1000ml of ethanol are added to a 2000ml reaction vessel, after stirring uniformly, the mass is pumped into a sand mill with zirconium beads and recycled. After 3 hours the suspension was pumped out and filtered.

The filter cake is then washed with methanol and then with water and dried at 80-110 ℃.

Comparative example 8A

Unlike example 8, structure (6) was not added and the other steps were identical.

Comparative example 8B

80.0G of the product of comparative example 8A are used, which is thoroughly and physically mixed with 0.9g of the compound of structure (6).

Solvent-based paint formulation:

Pigment dispersion:

A250 ml large glass bottle was charged with 48 g of acrylic resin, 10.5 g of 45% acrylic resin dissolved in xylene, 4.3 g of BYK161 (manufactured by Pick Co.) dispersant, 38 g of solvent (xylene 20%, n-butanol 40%, toluene 40%). 19.2 g of the pigment prepared according to the above examples and comparative examples and 220 g of glass beads having a diameter of 1.0 to 1.2mm were added, and the mixture in the large-mouth flask was vibrated on a Skandex vibrator for 2 hours.

Preparing a color paint:

82.9 g of the above pigment dispersion, 63.4 g of a clear unpigmented resin solvent solution containing an amino resin catalyst, a non-aqueous dispersion resin and a UV absorber, having a solids content of 47.8%, and 28.5 g of a clear unpigmented polyester urethane resin solvent solution having a solids content of 58% were mixed together to give a full color paint. Then mixing the obtained color paste with a color paint prepared by adopting the same method and using titanium dioxide according to the following weight ratio of 1:10, the diluted paint is obtained.

And (3) color card manufacturing:

The full color/light color paint described above was applied to a black and white color card using an automatic coater, then dried in air for 10 minutes, and then "baked" in an oven at 120 ℃ for 30 minutes to give a color card.

Water-based paint ingredients:

Pigment dispersion:

A250 ml large glass bottle was charged with 20.8 g of Tego Dispers 760W (35% dispersant from Tego), 48.4g deionized water, 0.3g of Tego Foamex 830 (defoamer from Tego) and pre-mixed uniformly and the pH was adjusted to 8.5-9.0 by addition of AMP 90. 10.4 g of the pigment prepared according to the above examples and comparative examples and 100g of glass beads having a diameter of 1.5 to 2.0mm were added, and the mixture in the large-mouth flask was vibrated on a Skandex vibrator for 1 hour. After the end of the dispersing operation, the paint was filtered using a sieve into a 150ml plastic beaker. The pH was then again checked and adjusted to a value of 8.2-8.7 by the addition of AMP 90 to give a pigment dispersion.

And (3) color paint modulation:

5.6 g of the above pigment dispersion, 24.4g of the polyurethane dispersion (30%) of Alberdingk U710 used was diluted and stirred with a stirrer for 10 minutes to give a full color paint. Then, the obtained full-color paint and the paint prepared by adopting the same method and using titanium pigment are mixed according to the following ratio of 1:10, the diluted paint is obtained.

And (3) color card manufacturing:

The above color chart was tested using DeltaColor's color difference meter, and the results of measuring examples 1 to 8 and comparative examples 1B to 8B using comparative examples 1A to 8A as a test standard are shown in the following table 1.

TABLE 1

As is clear from the data of Table 1 above, the solid solution pigments prepared in examples 1 to 8 of the present invention are significantly improved in transparency and tinting strength as compared with the pigments of comparative examples 1A to 8A and comparative examples 1B to 8B.

The embodiments of the present invention have been described in detail above, but the present invention is not limited to the described embodiments. It will be apparent to those skilled in the art that various changes, modifications, substitutions and alterations can be made to these embodiments without departing from the principles and spirit of the invention, and yet fall within the scope of the invention.

Claims

1. An anthraquinone blue solid solution pigment comprising a host pigment and a guest pigment;

The main pigment is anthraquinone blue;

2. The solid solution pigment according to claim 1, characterized in that:

the guest pigment is present in an amount of 0.5 to 20%, preferably 1to 10%, more preferably 3to 5% by weight based on 100% by weight of the host pigment.

3. The solid solution pigment according to claim 1, characterized in that:

The guest pigment is 1, 4-diketo-2, 5-diaryl pyrrolo [3,4-c ] pyrrole, anthraquinone, indanthrone and the structural formula is Wherein X is at least one of chlorine, bromine, iodine, carboxyl, sulfonamide, sulfonic acid group and salts thereof and sulfanyl group having a linear or branched alkyl group having 1 to 30 carbon atoms, n is 0.1 to 4 (if the components are a mixture, there may be no substitution, or may be mono-or di-substitution, etc., where n is an average value), preferably anthraquinone and the structural formula areWherein X is at least one of chlorine, bromine, a sulfonic acid group and salts thereof, and a sulfanyl group having a linear or branched alkyl group having 1 to 30 carbon atoms, and n is 0.1 to 2.

4. The solid solution pigment according to claim 1, characterized in that:

the kind of the guest pigment is 1 to 100, preferably 1 to 7, more preferably 1 to 2.

5. A method of preparing the anthraquinone blue solid solution pigment of any one of claims 1-4, comprising one of three methods:

And a third method: and fully grinding the host pigment, the guest pigment, the grinding medium and optionally the organic solvent, pouring the ground materials into a solution for stirring reaction, filtering, washing and drying to obtain the solid solution pigment.

6. The method according to claim 5, wherein:

7. The method according to claim 5, wherein:

8. The method according to claim 5, wherein:

In the first method:

In the second method:

9. The method according to claim 5, wherein:

In the third method:

The grinding time is 10-24 hours; and/or the number of the groups of groups,

10. Use of an anthraquinone blue solid solution pigment according to any one of claims 1 to 4 or an anthraquinone blue solid solution pigment produced according to any one of claims 5 to 7 as a pigment coating on an object to be colored, preferably a natural organic substance and its modifications and/or a synthetic organic substance.