Anthraquinone blue solid solution pigment and preparation method and application thereof

Abstract

The present invention discloses an anthraquinone blue solid solution pigment and a preparation method and application thereof, and relates to the technical field of anthraquinone blue (pigment blue 60) improvement. The anthraquinone blue solid solution pigment of the present invention comprises a main pigment and a guest pigment; the main pigment is anthraquinone blue; the weight of the guest pigment is 0.1-50% based on the weight of the main pigment being 100%. The present invention forms a "solid solution" by adding a second or more pigments or dyes during the preparation and treatment of the pigment, thereby obtaining Pigment Blue 60 with better dispersibility. The anthraquinone blue solid solution pigment provided by the present invention is novel, and when used as a pigment, it has good application properties, such as dispersibility, rheological properties, thermal stability, migration fastness, light resistance and weather resistance, as well as color strength and color saturation. The uses of these solid solutions include but are not limited to color pastes, color filters, electronic photography, automotive paint systems and various polymer fibers.

Description

Technical Field

[0001] The invention relates to the technical field of anthraquinone blue (pigment blue 60) improvement, and in particular to an anthraquinone blue solid solution pigment and a preparation method and application thereof. Background Art

[0002] HAO Z and HONTI SB mentioned in Chinese patent CN1509320 that "if the X-ray diffraction pattern of a multi-component pigment is different from the X-ray diffraction pattern 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' type solid solutions and 'binary solid compound' type solid solutions. For clarity, 'mixed crystal' type solid solutions are derived from equimolar compositions, while binary solid compounds have the crystal structure of mixed crystals, but have a significantly smaller range of pigment components. The X-ray diffraction pattern of the 'host-guest' type solid solution is essentially the same as the X-ray diffraction pattern of one of its components, called the 'host'. The host component can accept other components, namely the 'guest', in its crystal lattice. The 'binary solid compound' is a combination of two components that form an X-ray diffraction pattern that is different from the X-ray diffraction pattern of any one of the components or the physical mixture of each component."

[0003] The article proposes a supplementary improvement to the classification of solid solutions, and proposes the concepts of "single-phase solid solution", "multi-phase solid solution" and "mixed crystal". Among them, "single-phase solid solution" refers to a solid solution whose lattice is the same as the lattice of one of its components. A component is embedded in the lattice of the "host" as a "guest". Within a certain range, the different proportions of the components have no effect on the lattice results. "Multi-phase solid solution" refers to a physical mixture without a precise uniform lattice, and the difference between it and the individual components is that the lattice of at least one component is partially or completely changed, and the signal in the X-ray diffraction pattern is shifted at the 2θ angle, and the result of the change will vary with the different ratios of the components. "Mixed crystals" have a precise uniform lattice and are different from the lattices of all individual components. Different proportions of the components lead to the same lattice results within a certain range. Furthermore, the article mentions the preparation of a "host-guest" solid solution of "p-dimethyl DPP" and "p-dichloro DPP".

[0004] U.S. Patent No. 4,783,540 also has similar reports on solid solutions of 1,4-diketopyrrolo[3,4-c]pyrrole (DPP) series pigments. U.S. Patent No. 5,708,188 describes 1,4-diketopyrrolo[3,4-c]pyrrole as a mixed crystal and solid solution, in which it is mentioned that the crystal structure of the binary solid solution actually has the same crystal structure as the corresponding asymmetric diketopyrrolopyrrole pigment. U.S. Patent No. 5,529,623 not only describes a binary solid solution of a DPP pigment, but also mentions a ternary solid solution of pyrrolo[3,4-c]pyrrole pigment and quinacridone. U.S. Patent Nos. 4,810,304, 5,472,496, and 5,821,373 also have similar reports.

[0005] EHRICH reported in US Pat. No. 3,160,510 a method for preparing binary and higher binary solid solutions of quinacridone, which can broaden the color gamut of pigments and potentially improve light resistance.

[0006] Pigment Blue 60 (also known as Indanthrene Blue, Anthraquinone Blue) is a reddish blue, an anthraquinone pigment, with the same chemical structure as the vat dye Vat Blue 4, obtained by pigmenting the original powder of Vat Blue 4. It has excellent light resistance, heat resistance, weather resistance, high transparency and solvent resistance. It is mainly used for automotive original topcoat, repair paint, industrial coil coating, powder coating, especially metal car paint. Because its weather resistance is better than that of phthalocyanine pigments, it can be used in places where phthalocyanine pigments are not competent. One of its major characteristics is that it does not contain heavy metals in the molecule, which is very popular in some non-toxic equipment coloring fields. Pigment Blue 60 is suitable for the coloring of synthetic fiber (commonly known as "pre-spinning coloring" or "spinning-grade masterbatch"), especially when used for the coloring of polypropylene fiber, its application fastness is higher than that of phthalocyanine pigments. Pigment Blue 60 is also suitable for plastic coloring. Due to price factors, it is limited to special occasions that require extremely high application fastness. Pigment Blue 60 is also suitable for the coloring of offset ink, solvent ink (including plastic composite ink), pen ink and printer ink. It is particularly suitable for high-grade coinage ink due to its excellent acid resistance, alkali resistance, organic solvent resistance and weather resistance. Pigment Blue 60 can also be used for the coloring of industrial leather.

[0007] However, there are few reports on the solid solution of Pigment Blue 60. Summary of the invention

[0008] The technical problem to be solved by the present invention is to provide an anthraquinone blue solid solution pigment and a preparation method and application thereof.

[0009] In order to solve the above technical problems, the technical solution of the present invention is:

[0010] One of the objects of the present invention is to provide an anthraquinone blue solid solution pigment.

[0011] The anthraquinone blue solid solution pigment of the present invention comprises a main pigment and a guest pigment;

[0012] The main pigment is anthraquinone blue or vat blue 4; since the chemical structure of pigment blue 60 is consistent with that of vat dye vat blue 4, and is obtained by pigmenting vat blue 4 raw powder, the main pigment in the present application can also directly use vat blue 4 known to those skilled in the art;

[0013] The object pigment is phthalocyanine, quinacridone, quinacridonequinone, quinophthalone, dioxazine, indanthrone, anthraquinone, indigo, isoindolinone, isoindolinone, perylene, pyrrolidine, 1,4-diketo-2,5-diarylpyrrolo[3,4-c]pyrrole, azo condensation pigment and a structural formula At least one of the pigments of, wherein X is at least one of fluorine, chlorine, bromine, iodine, nitro, carboxyl, ester, ketone, amide, sulfonamide, sulfonic acid and its salt, a linear or branched alkyl group having 1 to 30 carbon atoms, an aromatic group with a linear or branched alkyl group having 1 to 30 carbon atoms, and a sulfanyl group with a linear or branched alkyl group having 1 to 30 carbon atoms, and n is 0.1 to 4;

[0014] Based on the weight of the main pigment being 100%, the weight of the guest pigment is 0.1-50%.

[0015] In a preferred embodiment of the present invention:

[0016] Taking the weight of the main pigment as 100%, the weight of the guest pigment is 0.5-20%, preferably 1-10%, and more preferably 3-5%. Different amounts of guest pigments can be used according to different target uses, especially for applications in coatings. Under different usage ratios, mixed crystals rather than solid solutions can be formed, but in terms of the use effect, there will not be significant differences that do not conform to the gradual change due to the difference between the two crystals, so they are collectively referred to as solid solutions in the present invention without distinction.

[0017] In a preferred embodiment of the present invention:

[0018] The object pigment is 1,4-diketo-2,5-diarylpyrrolo[3,4-c]pyrrole, anthraquinone belonging to the same class of pigments as 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, etc.), indanthrone and a structural formula At least one of the pigments of the present invention, wherein X is at least one of chlorine, bromine, iodine, carboxyl, sulfonamide, sulfonic acid and its salts and sulfanyl with a straight or branched alkyl group having 1 to 30 carbon atoms, n is 0.1 to 4, preferably anthraquinone and the structural formula is At least one of the pigments of the present invention, wherein X is at least one of chlorine, bromine, sulfonic acid group and its salt and sulfanyl group with a straight or branched alkyl group with 1 to 30 carbon atoms, and n is 0.1 to 2.

[0019] In a preferred embodiment of the present invention:

[0020] The components of the solid solution pigment of the present invention include two or more components, and those skilled in the art can make adaptive adjustments according to needs; the types of the guest pigments are 1 to 100, preferably 1 to 7, and more preferably 1 to 2.

[0021] A second object of the present invention is to provide a method for preparing the anthraquinone blue solid solution pigment as described in one of the objects of the present invention.

[0022] The preparation method of the anthraquinone blue solid solution pigment of the present invention comprises one of the following three methods:

[0023] Method 1: adding the main pigment and the guest pigment into an organic solvent and stirring evenly, optionally heating for reaction, filtering, washing and drying to obtain the solid solution pigment;

[0024] Method 2: adding the main pigment and the guest pigment into concentrated sulfuric acid to dissolve them, adding them into water to precipitate them, filtering and washing the free acid, and then drying them, optionally adding them into an organic solvent to form a suspension, and then heating them for reaction to obtain the solid solution pigment;

[0025] Method 3: Grind the main pigment, guest pigment, grinding medium and optional organic solvent thoroughly (in a grinding device, adding or not adding organic solvent according to the type of grinding device, and the grinding process must contain enough grinding medium to have the effect of sufficiently changing the pigment particle size), pour into the solution after grinding, stir to react, filter, wash and dry to obtain the solid solution pigment.

[0026] Among them, in method 2: the water used for precipitation added to water is excess water, and technical personnel in this field can add an appropriate amount according to needs; in method 3: the grinding equipment is selected from at least one of a kneader, a ball mill, a grinding drum, a sand mill, a pin mill, a jet mill, and a flash dryer with a knife head; the solution poured in after the grinding is an excess solution, which can be a dilute sulfuric acid aqueous solution or water.

[0027] Different grinding equipment and methods are different. For example, when using a kneader, after adding pigment, grinding medium (inorganic salt) and organic solvent, the stirring paddle is rotated for grinding. At the end of kneading, the material is added into water to dissolve the inorganic salt, and then filtered, washed, dried and crushed to obtain the finished pigment. Another example is when using a sand mill, the main pigment, the guest pigment and the organic solvent are pulped and dispersed, and then ground by a sand mill. After the grinding, the materials are filtered, washed and dried and crushed to obtain the finished product. And so on. All kinds of grinding operations are carried out according to the methods well known to technicians in this field.

[0028] In a preferred embodiment of the present invention:

[0029] The organic solvent is at least one of an alcohol solvent, an organic acid solvent, an ether solvent, a ketone solvent, an aromatic hydrocarbon solvent, an ester solvent, an amide solvent, and other solvents; preferably,

[0030] The alcohol solvent is at least one of methanol, ethanol, ethylene glycol, polyethylene glycol, propylene glycol, diethylene glycol, diacetone alcohol, and glycerol; and / or,

[0031] The organic acid solvent is a low molecular weight organic acid solvent, preferably formic acid and / or acetic acid; and / or,

[0032] 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,

[0033] The ketone solvent is at least one of acetone, benzophenone, 1,3-dioxolane-2-one and methyl ethyl ketone; and / or,

[0034] The aromatic hydrocarbon solvent is at least one of toluene, xylene, trimethylbenzene, chlorobenzene, dichlorobenzene, nitrobenzene, chloronaphthalene, biphenyl, p-terphenyl, m-terphenyl, o-terphenyl, dibenzyltoluene, α-methylnaphthalene, β-methylnaphthalene and acetophenone; and / or,

[0035] The ester solvent is at least one of methyl benzoate, dimethyl phthalate, methyl salicylate, triacetin, and γ-butyrolactone; and / or,

[0036] The amide solvent is at least one of formamide, dimethylformamide and N-methylpyrrolidone; and / or,

[0037] The other solvent is at least one of nitromethane, dimethyl sulfoxide and sulfolane;

[0038] More preferably, the organic solvent is at least one of ethylene glycol, polyethylene glycol, diacetone alcohol, toluene, xylene, trimethylbenzene, chlorobenzene and dichlorobenzene.

[0039] In a preferred embodiment of the present invention:

[0040] The grinding medium is at least one of sodium chloride and its hydrate, potassium chloride and its hydrate, calcium chloride and its hydrate, zinc chloride and its hydrate, aluminum chloride and its hydrate, sodium sulfate and its hydrate, aluminum sulfate and its hydrate, calcium carbonate and its hydrate, sodium acetate and its hydrate, calcium acetate and its hydrate, sodium citrate and its hydrate, potassium tartrate and its hydrate, steel balls, zirconium balls, and steel nails, preferably at least one of sodium sulfate, potassium chloride, aluminum sulfate, sodium chloride, steel balls, zirconium balls, and steel nails.

[0041] In a preferred embodiment of the present invention:

[0042] In method 1:

[0043] The mass ratio of the organic solvent to the main pigment and the guest pigment is (10-35):1; and / or,

[0044] When the heating reaction is carried out, the reaction temperature of the heating reaction is 150-200° C., and / or the reaction time is 1-3 hours; and / or,

[0045] Method 2:

[0046] The mass ratio of the concentrated sulfuric acid to the main pigment and the guest pigment is (1-10): 1; and / or,

[0047] When an organic solvent is added, the mass ratio of the organic solvent to the main pigment and the guest pigment is (10-30):1; and / or,

[0048] When the heating reaction is carried out, the reaction temperature of the heating reaction is 150-200° C., and / or the reaction time is 1-3 hours.

[0049] In a preferred embodiment of the present invention:

[0050] Method 3:

[0051] The mass ratio of the grinding media to the main pigment and the guest pigment is (5-130):1; and / or,

[0052] When an organic solvent is added, the mass ratio of the organic solvent to the grinding medium is (5-10):1; and / or,

[0053] The grinding time is 10-24 hours; and / or,

[0054] The reaction temperature of the stirring reaction is 50-100° C., and / or the reaction time is 1-5 hours.

[0055] The third object of the present invention is to provide an anthraquinone blue solid solution pigment as described in one of the objects of the present invention or an anthraquinone blue solid solution pigment prepared by the method described in the second object of the present invention as a pigment for coating on an object to be colored. Preferably, the object to be colored is a natural organic matter and its modified product and / or a synthetic organic matter.

[0056] The object to be colored may be derived from natural organic matter and its modified substances and / or synthetic organic matter; the natural organic matter may include, for example, natural resin, rubber or casein; the modified substances of natural organic matter may include, for example, chlorinated rubber, oil-modified alkyd resin, viscose, cellulose ether or ester (such as cellulose acetate, cellulose propionate, cellulose acetobutyrate or nitrocellulose); the synthetic organic matter (thermosetting or thermoplastic) may be obtained by polycondensation or polyaddition reaction, such as polyolefins (polyethylene, polypropylene, polyisobutylene, etc.), substituted polyolefins (polymers or copolymers of vinyl chloride, vinyl acetate, styrene, acrylonitrile, acrylate, methacrylate, butadiene, such as ABS or EVA, etc.).

[0057] In the series of addition polymerization resins and condensation polymerization resins, the condensation products of formaldehyde with phenols are called phenolic resins, the condensation products of formaldehyde with urea, thiourea and melamine are called amino resins, polyesters used as paint resins, as well as saturated resins such as alkyd resins and unsaturated resins such as maleic resins, as well as linear polyesters and polyamides or siloxanes.

[0058] The substances to be colored may be present alone or in a mixture, in the form of a plastic mass or melt, and if desired, may be spun into fibers. They may also be present in monomeric form or in a polymerized state in dissolved form as film formers or binders for coatings or printing inks, such as linseed oil, nitrocellulose, alkyd resins, melamine resins, urea-formaldehyde resins or acrylic resins.

[0059] The method that solid solution pigment of the present invention is coated on the object to be colored can adopt roller mill, mixer or grinding equipment to adopt the form of concentrated color body or dispersion of solid solution pigment as required, calendaring, compression molding, extrusion, spreading, casting or injection molding. In order to manufacture non-rigid molded products or in order to reduce brittleness, plasticizer can be introduced into solid solution pigment of the present invention. The plasticizer is at least one of phosphate, phthalate, sebacate. The plasticizer can also be introduced into the object to be colored. Further possible is that, in order to obtain different tones, in addition to the pigment composition, filler and / or other coloring components such as white, color or black pigment etc. can also be added to the object to be colored, and the specific addition amount can be added according to actual needs by those skilled in the art.

[0060] When using the solid solution pigment of the present invention for coloring coatings and printing inks, the object to be colored and the solid solution pigment of the present invention are usually finely dispersed or dissolved in an organic and / or aqueous solvent alone or together with additives (such as fillers, other pigments, driers or plasticizers, etc.).

[0061] The present invention forms a "solid solution" by adding a second or multiple pigments or dyes during the preparation and treatment of the pigment, thereby obtaining Pigment Blue 60 with better dispersibility.

[0062] The anthraquinone blue solid solution pigment provided by the present invention is novel and has good application properties when used as a pigment, such as dispersion performance, rheological properties, thermal stability, migration fastness, light fastness and weather resistance, as well as color strength and color saturation. The uses of these solid solutions include but are not limited to color pastes, color filters, electronic photography, automotive paint systems and various polymer fibers. DETAILED DESCRIPTION

[0063] The specific embodiments of the present invention are further described below. It should be noted that the description of these embodiments is used to help understand the present invention, but does not constitute a limitation of the present invention. In addition, the technical features involved in each embodiment of the present invention described below can be combined with each other as long as they do not conflict with each other.

[0064] Example 1

[0065] 10.0 g of Vat Blue 4, 0.3 g of a compound having the following structure (1) and 40.0 g of 16-hydrated Al2(SO4)3 were added to a 1.0 L ball mill equipped with 1200 g of steel balls and 100 g of steel nails as grinding media. After the ball mill was rotated at 100 rpm for 18 hours, the material was discharged and separated from the grinding media. The obtained ground powder was stirred with a 2% aqueous sulfuric acid solution at 90° C. for 2 hours. The obtained slurry was filtered, washed with hot water until neutral and salt-free, and the filter cake was dried at 80° C. and crushed to obtain the product.

[0066]

[0067] Comparative Example 1A

[0068] The difference from Example 1 is that the compound having structure (1) is not added, and the other steps are the same.

[0069] Comparative Example 1B

[0070] 10.0 g of the product of Comparative Example 1A was physically mixed with 0.3 g of the compound of structure (1) to be uniformly mixed.

[0071] Example 2

[0072] 10.0 g of vat blue 4 powder, 0.5 g of a compound having the following structure (2) and 55.0 g of 16-hydrated Al2(SO4)3 were added to a 1.0 L ball mill equipped with 1200 g of steel balls and 100 g of grinding media. After the ball mill was rotated at 100 rpm for 24 hours, the material was discharged and separated from the grinding media. The obtained ground powder was stirred with a 2% aqueous sulfuric acid solution at 80° C. for 1 hour. The obtained slurry was filtered, washed with hot water until neutral and salt-free, and the filter cake was dried at 100° C. and crushed to obtain the product.

[0073]

[0074] Comparative Example 2A

[0075] The difference from Example 2 is that the compound having structure (2) is not added, and the other steps are the same.

[0076] Comparative Example 2B

[0077] 10.0 g of the product of Comparative Example 2A was physically mixed with 0.5 g of the compound of Structure 2 to be uniform.

[0078] Example 3

[0079] 500 g of crushed sodium chloride and 70 g of Vat Blue 4, 2 g of Pigment Red 177 were added to a 1-liter kneader with Sigma blades. The mixture was mixed for 10 minutes, and then 90 g of ethylene glycol was added. The uniform pigment paste was ground for 10 hours at a temperature of 40-45°C, and ethylene glycol was added as needed to maintain the uniformity of the paste. The pigment paste was poured into 1200 ml of water and stirred evenly, and the resulting slurry was stirred at 90°C for 1 hour. The solid components were collected by filtration, washed with water, dried, and ground to obtain the product.

[0080]

[0081] Comparative Example 3A

[0082] The difference from Example 3 is that Pigment Red 177 is not added, and the other steps are the same.

[0083] Comparative Example 3B

[0084] 70.0 g of the product of Comparative Example 3A was physically mixed with 2 g of the compound of Pigment Red 177 to be uniformly mixed.

[0085] Example 4

[0086] Into a 1-liter kneading machine with Sigma blades, 600 g of crushed sodium chloride and 100 g of Vat Blue 4, 2.5 g of the compound of structure (3) were added, the mixture was mixed for 10 minutes, and then 110 g of xylene was added. The resulting uniform pigment paste was ground at a temperature of 40-45°C for 20 hours, and xylene was added as needed to maintain the uniformity of the paste. The pigment paste was poured into 1500 ml of water and acidified with dilute hydrochloric acid to a pH of less than 2. The resulting slurry was stirred at 90°C for 2 hours.

[0087] The solid component was collected by filtration, washed with methanol and water, dried and ground to obtain the product.

[0088]

[0089] Comparative Example 4A

[0090] The difference from Example 4 is that the compound having structure (3) is not added, and the other steps are the same.

[0091] Comparative Example 4B

[0092] 100.0 g of the product of Comparative Example 4A was physically mixed with 2.5 g of the compound of Structure 3 to obtain a uniform mixture.

[0093] Example 5

[0094] Use a 1-liter flask equipped with a thermometer, agitator and a condenser, then add 20 g of Pigment Blue 60, 1 g of Pigment Red 254 and 500 ml of o-dichlorobenzene. Stir the suspension, heat and pressurize to 180°C, and keep stirring for 2 hours. Cool the suspension to room temperature and filter. Then wash the filter cake with methanol, then with water, and dry at 80-130°C.

[0095]

[0096] Comparative Example 5A

[0097] The difference from Example 5 is that Pigment Red 254 is not added, and the other steps are the same.

[0098] Comparative Example 5B

[0099] 20.0 g of the product of Comparative Example 5A was physically mixed with 1 g of the compound of Pigment Red 254 to be uniformly mixed.

[0100] Example 6

[0101] Dissolve 10 g of vat blue 4 and 0.5 g of the compound of structure (4) in 100 g of concentrated sulfuric acid. Keep the temperature below 30°C and stir evenly until the reaction is fully reacted. After 1 hour, add the material to 1000 ml of ice-water mixture. Keep the temperature at 0°C throughout the process. Stir evenly for 0.5 hour, filter, and wash the free acid with water.

[0102] Use a 1-liter flask equipped with a thermometer, agitator and a condenser, then add the filter cake and 500 ml of trimethylol. Stir the suspension, heat it to boiling point after the water evaporates, then continue to pressurize it to 180°C and keep stirring for 1 hour. Cool the suspension to room temperature and filter it. Then wash the filter cake with methanol, then with water, and dry it at 80-130°C.

[0103]

[0104] Comparative Example 6A

[0105] The difference from Example 6 is that structure (4) is not added, and the other steps are the same.

[0106] Comparative Example 6B

[0107] 10.0 g of the product of Comparative Example 6A was physically mixed with 0.5 g of the compound of structure (4) to be uniformly mixed.

[0108] Example 7

[0109] 20 g of Vat Blue 4, 0.8 g of the compound of structure (5) and 250 ml of xylene were added to a 500 ml flask, stirred evenly, and then pumped into a sand mill equipped with zirconium beads and circulated back and forth. After 3 hours, the suspended material was pumped out and filtered.

[0110] The filter cake was then washed with methanol, then with water, and dried at 80-100°C.

[0111]

[0112] Comparative Example 7A

[0113] The difference from Example 7 is that structure (5) is not added, and the other steps are the same.

[0114] Comparative Example 7B

[0115] 20.0 g of the product of Comparative Example 7A was physically mixed with 0.8 g of the compound of structure (5) to be uniformly mixed.

[0116] Example 8

[0117] 80 g of Vat Blue 4, 0.9 g of the compound of structure (6) and 1000 ml of ethanol were added to a 2000 ml reactor, stirred evenly, and then pumped into a sand mill equipped with zirconium beads and circulated back and forth. After 3 hours, the suspended material was pumped out and filtered.

[0118] The filter cake was then washed with methanol, then with water, and dried at 80-110°C.

[0119]

[0120] Comparative Example 8A

[0121] The difference from Example 8 is that structure (6) is not added, and the other steps are the same.

[0122] Comparative Example 8B

[0123] 80.0 g of the product of Comparative Example 8A was physically mixed with 0.9 g of the compound of structure (6) to be uniformly mixed.

[0124] Solvent-based paint ingredients:

[0125] Pigment dispersion:

[0126] In a 250 ml wide-mouthed glass bottle, 48 g of acrylic resin, 10.5 g of 45% acrylic resin dissolved in xylene, 4.3 g of BYK161 (produced by BYK) dispersant, and 38 g of solvent (xylene 20%, n-butanol 40%, toluene 40%) were placed. 19.2 g of the pigment prepared according to the above examples and comparative examples and 220 g of glass beads with a diameter of 1.0 to 1.2 mm were added, and the mixture in the wide-mouthed bottle was vibrated on a Skandex vibrator for 2 hours.

[0127] Paint preparation:

[0128] 82.9 grams of the above pigment dispersion, 63.4 grams of a transparent unpigmented resin solvent solution containing an amino resin catalyst, a water-free dispersion resin and a UV absorber with a solid content of 47.8%, and 28.5 grams of a transparent unpigmented polyester urethane resin solvent solution with a solid content of 58% are mixed together to obtain a full-color paint. Then the obtained color paste is diluted with a paint made by the same method using titanium dioxide at a ratio of 1:10 to obtain a diluted paint.

[0129] Color card production:

[0130] The full color / diluted paint is coated on a black and white color card using an automatic coating machine, and then air-dried for 10 minutes, and then "baked" in an oven at a temperature of 120° C. for 30 minutes to obtain a color card.

[0131] Water-based paint ingredients:

[0132] Pigment dispersion:

[0133] In a 250 ml wide-mouth glass bottle, 20.8 g of Tego Dispers 760W (35%, dispersant purchased from Tego), 48.4 g of deionized water, and 0.3 g of Tego Foamex 830 (defoamer purchased from Tego) were pre-mixed and then adjusted to pH 8.5-9.0 by adding AMP 90. 10.4 g of the pigment prepared according to the above examples and comparative examples and 100 g of glass beads with a diameter of 1.5-2.0 mm were added, and the mixture in the wide-mouth bottle was vibrated on a Skandex vibrator for 1 hour. After the dispersion operation was completed, the paint was filtered into a 150 ml plastic beaker using a filter. The pH was then checked again and adjusted to a value of 8.2-8.7 by adding AMP90 to obtain a pigment dispersion.

[0134] Paint preparation:

[0135] 5.6 g of the above pigment dispersion was diluted with 24.4 g of Alberdingk U710 polyurethane dispersion (30%), and then stirred for 10 minutes with a stirrer to obtain a full-color paint. The obtained full-color paint was then diluted with a paint made by the same method using titanium dioxide at a ratio of 1:10 to obtain a diluted paint.

[0136] Color card production:

[0137] The full color / diluted paint is coated on a black and white color card using an automatic coating machine, and then air-dried for 10 minutes, and then "baked" in an oven at a temperature of 120° C. for 30 minutes to obtain a color card.

[0138] The color cards were tested using a DeltaColor colorimeter, with Comparative Examples 1A-8A as test standard samples, and the results of Examples 1-8 and Comparative Examples 1B-8B were shown in Table 1 below.

[0139] Table 1

[0140]

[0141]

[0142] It can be seen from the data in Table 1 above that the solid solution pigments prepared in Examples 1-8 of the present invention have significantly improved transparency and tinting strength compared to the pigments in Comparative Examples 1A-8A and Comparative Examples 1B-8B.

[0143] The embodiments of the present invention are described in detail above, but the present invention is not limited to the described embodiments. For those skilled in the art, various changes, modifications, substitutions and variations of these embodiments are made without departing from the principles and spirit of the present invention, and still fall within the protection scope of the present invention.

Claims

1. An anthraquinone blue solid solution pigment, comprising a main pigment and a guest pigment; The main pigment is anthraquinone blue; The guest pigment has a structural formula of At least one of the pigments, wherein X is at least one of fluorine, chlorine, bromine, iodine, nitro, carboxyl, ester, ketone, amide, sulfonamide, a linear or branched alkyl group having 1 to 30 carbon atoms, an aromatic group having a linear or branched alkyl group having 1 to 30 carbon atoms, and a sulfanyl group having a linear or branched alkyl group having 1 to 30 carbon atoms, and n is 0.1 to 4; Based on the weight of the main pigment being 100%, the weight of the guest pigment is 0.1-50%.

2. The solid solution pigment according to claim 1, characterized in that: Based on the weight of the main pigment being 100%, the weight of the guest pigment is 0.5-20%.

3. The solid solution pigment according to claim 1, characterized in that: Based on the weight of the main pigment being 100%, the weight of the guest pigment is 1-10%.

4. The solid solution pigment according to claim 1, characterized in that: Based on the weight of the main pigment being 100%, the weight of the guest pigment is 3-5%.

5. The solid solution pigment according to claim 1, characterized in that: The guest pigment has a structural formula of At least one of the pigments of the invention, wherein X is at least one of chlorine, bromine, iodine, carboxyl, sulfonamide and sulfanyl with a linear or branched alkyl group having 1 to 30 carbon atoms, and n is 0.1 to 4.

6. The solid solution pigment according to claim 1, characterized in that: The guest pigment has a structural formula of At least one of the pigments of the present invention, wherein X is at least one of chlorine, bromine and a sulfanyl group having a linear or branched alkyl group with 1 to 30 carbon atoms, and n is 0.1 to 2.

7. The solid solution pigment according to claim 1, characterized in that: The number of the guest pigments is 1 to 100.

8. The solid solution pigment according to claim 1, characterized in that: The types of the guest pigments are 1-7.

9. The solid solution pigment according to claim 1, characterized in that: The types of the guest pigment are 1-2.

10. A method for preparing the anthraquinone blue solid solution pigment according to any one of claims 1 to 9, comprising one of the following three methods: Method 1: adding the main pigment and the guest pigment into an organic solvent and stirring evenly, optionally heating for reaction, filtering, washing and drying to obtain the solid solution pigment; Method 2: adding the main pigment and the guest pigment into concentrated sulfuric acid to dissolve them, adding them into water to precipitate them, filtering and washing the free acid, and then drying them, optionally adding them into an organic solvent to form a suspension, and then heating them for reaction to obtain the solid solution pigment; Method three: fully grind the main pigment, the guest pigment, the grinding medium and the optional organic solvent, pour them into the solution after grinding, stir and react, filter, wash and dry to obtain the solid solution pigment.

11. The method according to claim 10, characterized in that: The organic solvent is at least one of alcohol solvents, organic acid solvents, ether solvents, ketone solvents, aromatic hydrocarbon solvents, ester solvents, amide solvents, and other solvents.

12. The method according to claim 11, characterized in that: 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 organic acid solvent is a low molecular weight organic acid solvent; and / or, 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 ketone solvent is at least one of acetone, benzophenone, 1,3-dioxolane-2-one and methyl ethyl ketone; and / or, The aromatic hydrocarbon solvent is at least one of toluene, xylene, trimethylbenzene, chlorobenzene, dichlorobenzene, nitrobenzene, chloronaphthalene, biphenyl, p-terphenyl, m-terphenyl, o-terphenyl, dibenzyltoluene, α-methylnaphthalene, β-methylnaphthalene and acetophenone; and / or, The ester solvent is at least one of methyl benzoate, dimethyl phthalate, methyl salicylate, triacetin, and γ-butyrolactone; and / or, The amide solvent is at least one of formamide, dimethylformamide and N-methylpyrrolidone; and / or, The other solvent is at least one of nitromethane, dimethyl sulfoxide and sulfolane.

13. The method according to claim 12, characterized in that: The organic acid solvent is formic acid and / or acetic acid.

14. The method according to claim 11, characterized in that: The organic solvent is at least one of ethylene glycol, polyethylene glycol, diacetone alcohol, toluene, xylene, trimethylbenzene, chlorobenzene and dichlorobenzene.

15. The method according to claim 10, characterized in that: The grinding medium is at least one of sodium chloride and its hydrate, potassium chloride and its hydrate, calcium chloride and its hydrate, zinc chloride and its hydrate, aluminum chloride and its hydrate, sodium sulfate and its hydrate, aluminum sulfate and its hydrate, calcium carbonate and its hydrate, sodium acetate and its hydrate, calcium acetate and its hydrate, sodium citrate and its hydrate, potassium tartrate and its hydrate, steel balls, zirconium balls, and steel nails.

16. The method according to claim 15, characterized in that: The grinding medium is at least one of sodium sulfate, potassium chloride, aluminum sulfate, sodium chloride, steel balls, zirconium balls, and steel nails.

17. The method according to claim 10, characterized in that: In method 1: The mass ratio of the organic solvent to the main pigment and the guest pigment is (10-35):1; and / or, When the heating reaction is carried out, the reaction temperature of the heating reaction is 150-200° C., and / or the reaction time is 1-3 hours; and / or, Method 2: The mass ratio of the concentrated sulfuric acid to the main pigment and the guest pigment is (1-10): 1; and / or, When an organic solvent is added, the mass ratio of the organic solvent to the main pigment and the guest pigment is (10-30):1; and / or, When the heating reaction is carried out, the reaction temperature of the heating reaction is 150-200° C., and / or the reaction time is 1-3 hours.

18. The method according to claim 10, characterized in that: Method 3: The mass ratio of the grinding media to the main pigment and the guest pigment is (5-130):1; and / or, When an organic solvent is added, the mass ratio of the organic solvent to the grinding medium is (5-10):1; and / or, The grinding time is 10-24 hours; and / or, The reaction temperature of the stirring reaction is 50-100° C., and / or the reaction time is 1-5 hours.

19. Use of the anthraquinone blue solid solution pigment according to any one of claims 1 to 9 or the anthraquinone blue solid solution pigment prepared by the method according to any one of claims 10 to 18 as a pigment for coating on an object to be colored.

20. The use according to claim 19, characterized in that: The object to be colored is a natural organic matter and a modified product thereof and / or a synthetic organic matter.

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