Pigment synergist as well as preparation method and application thereof

Abstract

The invention relates to the technical field of organic pigments, in particular to a pigment synergist as well as a preparation method and application thereof. The structure of the pigment synergist is shown as a formula 1. The invention also provides a preparation method of the pigment synergist. The preparation method comprises the following steps: firstly, enabling amino phthalonitrile to react with cyanuric chloride and N, N-dimethyl propane diamine to prepare a phthalocyanine fragment of a phthalonitrile unit containing triazine, and then enabling the phthalocyanine fragment to react with metal salt under the action of a catalyst. The pigment synergist prepared by the invention can effectively inhibit aggregation of pigment particles and endow an optical filter with excellent heat resistance. # imgabs0 #

Description

Technical Field

[0001] The present invention relates to the technical field of organic pigments, and in particular to a pigment synergist and a preparation method and application thereof. Background Art

[0002] Organic pigments for color filters require brighter brightness and contrast, and generally require the use of micronized pigments with an average primary particle size of less than 100nm.

[0003] However, fine organic pigments are more likely to aggregate, and when the filter undergoes a thermal process, there are problems such as reduced brightness, resulting in poor heat resistance of the filter. The existing technical solution is to add pigment derivatives to the pigment or coat the surface of the pigment with resin to inhibit the aggregation of the pigment.

[0004] Chinese invention patent CN107430224A defines a combination of a polysubstituted phthalimide-based phthalocyanine pigment derivative and a phthalocyanine pigment for use in a color filter, so that the composition can withstand the high temperature heat history in the color filter manufacturing process, and the brightness reduction is small, forming a color filter with high heat resistance. However, in the phthalimide-based phthalocyanine pigment derivative, the bonding unit between the phthalimide and the phthalocyanine ring is a flexible unit such as an alkyl group, and its heat resistance may not be good, and the ability to control the pigment particle size is also limited. Moreover, the phthalimide-based phthalocyanine pigment derivative is a blue phase, and the use of the phthalimide-based phthalocyanine pigment in a green phase pigment will cause color deviation.

[0005] Chinese invention patent CN102272237B coats the surface of green G58 pigment with modified polyamine and acrylic polymer resin to obtain a pigment dispersion composition with excellent contrast. However, the coating technology is in-situ free radical polymerization, which has a fast reaction speed and high requirements for monomer concentration. When a small amount of polymer resin needs to be coated on the surface of the pigment, the monomer concentration in the system is low, the free radical concentration is low, the polymerization reaction is difficult to occur, and the resin coating efficiency is very low; in addition, once the free radical reaction occurs, it will end quickly, which will cause the resin to coat multiple primary particles at the same time, making it very difficult to disperse the resin composition again.

[0006] Chinese invention patent CN102015910A discloses that polyurethane resin is coated on a pigment film by a method of pressurizing and heating to improve heat resistance. In this coating process, the diffusion ability of polyurethane macromolecules is poor and cannot be effectively diffused on all pigment surfaces. Therefore, there is a problem of coating multiple pigment particles at the same time, and the coated multiple pigment particles may still aggregate. Summary of the invention

[0007] In view of the above deficiencies in the prior art, the object of the present invention is to provide a pigment synergist and a preparation method and application thereof.

[0008] To achieve the above objectives, the technical solutions adopted are:

[0009] A pigment synergist having a structure shown in Formula 1:

[0010]

[0011] Wherein, M is a metal atom, and n represents an integer of 1-4.

[0012] Preferably, the metal atom is Cu or Zn.

[0013] The second object of the present invention is to provide a method for preparing the pigment synergist, comprising the following steps: firstly, aminophthalonitrile is reacted with cyanuric chloride and N,N-dimethylpropylenediamine to prepare a phthalocyanine fragment of a phthalonitrile unit containing triazine, and then the phthalocyanine fragment is reacted with a metal salt under the action of a catalyst to prepare the pigment synergist.

[0014] Preferably, the preparation method of the pigment synergist specifically comprises the following steps: adding cyanuric chloride and an acidifying agent to solvent one, adding aminophthalonitrile while stirring in an ice-water bath for 2 to 4 hours, then slowly adding N, N-dimethylpropylenediamine, maintaining the reaction temperature at 0-100°C, and continuing the reaction for 0.5-48 hours. After the reaction is completed, the reaction system is poured into ice water, filtered, washed, and dried to obtain a phthalocyanine fragment containing a phthalonitrile unit of triazine. The phthalocyanine fragment and the metal salt are mixed in solvent two and a catalyst, reacted at a temperature of 130-220°C, and the reaction time is 2-24 hours, and the pigment synergist with n=4 in formula 1 can be obtained.

[0015] Preferably, the molar ratio of the phthalocyanine fragment of the triazine-containing phthalonitrile unit to the metal salt is 1:(0.2-3).

[0016] Preferably, the preparation method of the pigment synergist specifically comprises the following steps: adding cyanuric chloride and an acidifying agent to solvent one, adding aminophthalonitrile while stirring in an ice-water bath for 2 to 4 hours, then slowly adding N, N-dimethylpropylenediamine, maintaining the reaction temperature at 0-100°C, and continuing the reaction for 0.5-48 hours. After the reaction is completed, the reaction system is poured into ice water, and after filtering, washing, and drying, a phthalocyanine fragment containing a phthalonitrile unit of triazine is obtained. The phthalocyanine fragment, phthalonitrile, and metal salt are mixed in solvent two and a catalyst, and reacted at a temperature of 130-220°C for a reaction time of 2-24 hours to obtain the pigment synergist wherein n in formula 1 is 1 to 4.

[0017] Preferably, the solvent 1 is at least one of water, acetone, tetrahydrofuran and chloroform.

[0018] Preferably, the acidifying agent is preferably but not limited to potassium carbonate, triethylamine, and pyridine.

[0019] Preferably, the metal salt is zinc chloride or cuprous chloride.

[0020] Preferably, the molar ratio of the phthalocyanine fragment of the triazine-containing phthalonitrile unit, phthalonitrile, and metal salt is 1:(0-10):(0.2-3).

[0021] Preferably, the second solvent is at least one of n-pentanol, n-heptanol, nitrobenzene, o-dichlorobenzene, and trichlorobenzene. When the second solvent is n-pentanol or n-heptanol, the catalyst is preferably DBU (1,8-diazabicyclo[5.4.0]undec-7-ene); when the second solvent is nitrobenzene, o-dichlorobenzene or trichlorobenzene, the catalyst is preferably molybdic acid.

[0022] The third object of the present invention is to provide a pigment composition comprising a phthalocyanine pigment and the pigment synergist.

[0023] Preferably, the mass ratio of the pigment synergist to the phthalocyanine pigment is 0.1-50:100, more preferably 0.1-10:100.

[0024] Preferably, the phthalocyanine pigment is at least one of CI Pigment Blue 15, CI Pigment Blue 15:1, CI Pigment Blue 15:3, CI Pigment Blue 15:6, CI Pigment Green 7, CI Pigment Green 36, and CI Pigment Green 58.

[0025] Optionally, the pigment composition may be prepared by mechanical mixing or kneading or a combination of the two.

[0026] The mechanical mixing refers to a method of mixing the pigment synergist and the phthalocyanine pigment in a mixing device at a certain temperature for a certain time. The mixing device can be a mixer, a roller burnisher, an ultrafine grinder, etc. The mixing time is 1-100 hours and the mixing temperature is 0-200°C.

[0027] The kneading refers to a method of putting the pigment synergist, phthalocyanine pigment, inorganic salt and organic solvent into a kneading device for mixing and kneading. The kneading device used can be a kneader, a ball mill, a bead mill, a sand mill, an ultrafine crusher, etc.

[0028] Preferably, the inorganic salt may be a water-soluble inorganic salt, such as sodium chloride, potassium chloride, sodium sulfate, etc. The particle size of the inorganic salt may be 0.5-50 μm. The amount of the inorganic salt used, by mass, may be 1-100 parts, preferably 5-20 parts, relative to 1 part of the phthalocyanine pigment.

[0029] The organic solvent can be a water-soluble organic solvent, for example, ethylene glycol, diethylene glycol, propylene glycol, glycerol, liquid polyethylene glycol, liquid polypropylene glycol, ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, ethylene glycol monobutyl ether, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, diethylene glycol monobutyl ether, triethylene glycol, triethylene glycol monomethyl ether, triethylene glycol monoethyl ether, 1-methoxy-2-propanol, 1-ethoxy-2-propanol, dipropylene glycol, dipropylene glycol monomethyl ether, dipropylene glycol monoethyl ether, etc. The amount of the organic solvent can be 0.01-20 parts, preferably 1-10 parts, relative to 1 part of the phthalocyanine pigment, in parts by mass.

[0030] Preferably, the kneading temperature is 20-150° C., and the kneading time is 1-100 h.

[0031] After kneading, the material is put into a large amount of water, filtered, washed and dried to obtain the pigment composition of the present invention.

[0032] A fourth object of the present invention is to provide a color paste dispersion, the pigment synergist or the pigment composition.

[0033] Preferably, the color paste dispersion is directly prepared from the pigment synergist and the phthalocyanine pigment, or the pigment synergist and the phthalocyanine pigment are first mixed to prepare a pigment composition, and then the color paste dispersion is prepared.

[0034] A fifth object of the present invention is to provide application of the pigment synergist in the field of color filters.

[0035] Compared with the prior art, the present invention has the following advantages:

[0036] The pigment synergist of the present invention comprises a phthalocyanine unit and a bulky, electron-rich isomeric unit. The phthalocyanine unit has a similar molecular structure to that of the phthalocyanine pigment particles, has a strong interaction force, and can be tightly adsorbed on the surface of the pigment particles. After the pigment synergist is adsorbed on the surface of the pigment particles, its isomeric unit will be exposed on the surface of the pigment particles. Its large steric hindrance effect and electron-rich mutual repulsion can inhibit the mutual aggregation of similar pigment particles, enhance the repulsion between similar pigment particles, and weaken the accumulation of pigment particles, thereby achieving the purpose of inhibiting the aggregation of pigment particles; the pigment dispersion, photoresist and filter using the pigment synergist of the present invention have the advantages of high brightness and strong heat resistance. BRIEF DESCRIPTION OF THE DRAWINGS

[0037] Figure 1 This is an infrared spectrum of the phthalocyanine fragment of the phthalonitrile unit containing triazine in the intermediate 1 in the embodiment of the present invention.

[0038] Figure 2 It is the infrared spectrum of the synergist 1 in the embodiment of the present invention.

[0039] Figure 3 It is the ultraviolet absorption spectrum of synergist 1, synergist 2 and zinc phthalocyanine in the embodiment of the present invention. DETAILED DESCRIPTION

[0040] The following specific embodiments illustrate the implementation of the present invention, and those skilled in the art can easily understand other advantages and effects of the present invention from the contents disclosed in this specification. Although the description of the present invention will be introduced in conjunction with the preferred embodiment, this does not mean that the features of this invention are limited to this implementation. On the contrary, the purpose of introducing the invention in conjunction with the implementation is to cover other options or modifications that may extend based on the claims of the present invention. In order to provide a deep understanding of the present invention, the following description will include many specific details. The present invention can also be implemented without using these details. In addition, in order to avoid confusion or blurring the focus of the present invention, some specific details will be omitted in the description. It should be noted that the embodiments of the present invention and the features in the embodiments can be combined with each other without conflict.

[0041] 1. Synthesis of synergist

[0042] (1) Preparation of phthalocyanine fragments containing triazine phthalonitrile units (intermediate 1)

[0043]

[0044] 12.9g of cyanuric chloride was added to 100g of acetone, stirred and dissolved, the reaction system was placed in an ice-water bath, and then 20g of anhydrous potassium carbonate was added, and then 5g of 4-aminophthalonitrile was slowly added, stirred for 4h, and then 21.4g of N,N-dimethylpropylenediamine and 200g of water were added, the ice-water bath was removed, the system temperature was slowly raised to room temperature, and then heated to 50°C for reaction for 12h, and then continued to rise to 95°C for reaction for 24h. After the reaction was completed, the reaction system was poured into 500mL of ice water, filtered, washed, and dried to obtain intermediate 1. The intermediate 1 obtained was soluble in solvents such as methanol, acetone, and DMF (N,N-dimethylformamide), but not in chloroform, and had different solubility properties from the raw material 4-aminophthalonitrile. The above reaction products were dissolved in acetone, and no spots of the raw material 4-aminophthalonitrile were detected by TLC, indicating that the raw material 4-aminophthalonitrile had reacted completely. In infrared spectroscopy ( Figure 1 ) detected the stretching vibration absorption peak of cyano group (2231cm -1 ), proving that a phthalocyanine fragment containing a triazine-containing phthalonitrile unit was obtained.

[0045] (2) Synthesis of synergist 1

[0046]

[0047] In a 250mL three-necked flask, 100g of n-pentanol, 20g (47mmol) of intermediate 1, 10.8g (71mmol) of DBU, and 2.1g (15mmol) of zinc chloride were added in sequence, and the temperature was raised to 160°C for reaction for 24h, and then the temperature was lowered. After the temperature dropped to room temperature, the material was poured into 300g of ethanol, filtered, washed, and dried to obtain an emerald green product, which is synergist 1. In formula 1, n=4, and the intermediate metal atom is a zinc atom. Synergist 1 is soluble in concentrated sulfuric acid, concentrated hydrochloric acid, acetic acid, and slightly soluble in DMF, DMSO and other solvents. Infrared spectrum ( Figure 2 ) in 2231cm -1 No stretching vibration absorption peak of cyano group was detected at 1400 cm -1 Up to 1600cm -1 range, overlapping with the absorption peaks of the C=N bond and CN bond in the triazine unit. UV absorption spectrum ( Figure 3 ), an absorption peak was detected at 702 nm, which is the characteristic absorption peak of the Q band of the phthalocyanine unit, indicating that the phthalocyanine unit has been successfully prepared. Figure 3 The ultraviolet absorption spectrum of zinc phthalocyanine is also given. Compared with the ultraviolet absorption spectrum of zinc phthalocyanine (the maximum absorption wavelength is 669nm), the Q band absorption peak of enhancer 1 is obviously red-shifted, indicating that after the triazine unit is bonded, the conjugation degree of the phthalocyanine unit increases.

[0048] (3) Synthesis of synergist 2

[0049]

[0050] In a 250mL three-necked flask, 100g of n-pentanol, 10.0g (24mmol) of intermediate 1, 3.0g (24mmol) of phthalonitrile, 10.8g (71mmol) of DBU, and 2.1g (15mmol) of zinc chloride were added in sequence, and the temperature was raised to 160°C for reaction for 24h, and then the temperature was lowered. After the temperature dropped to room temperature, the material was poured into 300g of ethanol, filtered, washed, and dried to obtain a cyan product, which is synergist 2, corresponding to a mixture of n=1, 2, 3, and 4 in formula 1, and the intermediate metal atom is a zinc atom. Synergist 2 is soluble in concentrated sulfuric acid, concentrated hydrochloric acid, and acetic acid, and is slightly soluble in solvents such as DMF and DMSO. In the infrared spectrum, at 2231cm -1 No stretching vibration absorption peak of cyano group was detected at 1400 cm -1 Up to 1600cm -1 range, overlapping with the absorption peaks of the C=N bond and CN bond in the triazine unit. UV absorption spectrum ( Figure 3), an absorption peak was detected at 673nm, which is the characteristic absorption peak of the Q band of the phthalocyanine unit, indicating that the phthalocyanine unit has been successfully prepared. Compared with the ultraviolet absorption spectrum of zinc phthalocyanine (maximum absorption wavelength at 669nm), the Q band absorption peak of synergist 2 is slightly red-shifted.

[0051] 2. Preparation of pigment composition

[0052] Add 80g Pigment Green 58, 1.6g Synergist 1, 800g sodium chloride, and 120g diethylene glycol into a kneader, maintain the temperature at 80°C, and knead for 24h. Pour the kneaded material into water, wash with water until the conductivity is the same as that of water, and dry the material to obtain a pigment composition 1.

[0053] Add 80g Pigment Green 58, 2.4g Synergist 2, 800g sodium chloride, and 120g diethylene glycol into a kneader, maintain the temperature at 80°C, and knead for 24h. Pour the kneaded material into water, wash with water until the conductivity is the same as that of water, and dry the material to obtain pigment composition 2.

[0054] 3. Color paste preparation

[0055] Prepare pigment paste according to the proportions in Table 1 below;

[0056] Table 1. Color paste formula of examples and comparative examples

[0057]

[0058] The above-mentioned materials were added into a glass bottle in order, and 150 g of 0.3 mm zirconium balls were added. The glass sheet was put into a shaker and shaken for 24 hours, and the zirconium balls were filtered out to obtain the color pastes of the embodiment and the comparative example.

[0059] 4. Color paste evaluation

[0060] The particle size of nano pigment in the color paste was tested by a particle size analyzer, and the results are shown in Table 2;

[0061] Take 1 mL of the color paste and spin-coat it on a glass slide at a speed of 600 rpm. Place the coated glass slide on a hot plate at 120°C for 3 minutes. Use a colorimeter and a contrast meter to test the color coordinates and contrast. Place the glass slide in a 230°C oven and continue to bake for 60 minutes. Use a colorimeter and a contrast meter to test the color coordinates and contrast again. The results are shown in Table 2.

[0062] Table 2. Color paste properties of examples and comparative examples

[0063]

[0064] As can be seen from Table 2, the particle sizes of color paste examples 1-3 and color paste comparative example 1 are not much different. The brightness and contrast of the films prepared by color paste examples 1-3 are improved compared with comparative example 1. After baking at 230°C, the brightness change is lower than that of comparative example 1, indicating that the brightness, contrast and heat resistance are improved after the addition of the synergist.

Claims

1. A pigment synergist, characterized in that: It has the structure shown in Formula 1: Wherein, M is a metal atom, and n represents an integer of 1-4.

2. The pigment synergist according to claim 1, characterized in that: The metal atom is Cu or Zn.

3. A method for preparing the pigment synergist according to any one of claims 1 to 2, characterized in that: The method comprises the following steps: firstly, aminophthalonitrile is reacted with cyanuric chloride and N,N-dimethylpropylenediamine to prepare a phthalocyanine fragment of a phthalonitrile unit containing triazine, and then the phthalocyanine fragment is reacted with a metal salt under the action of a catalyst to prepare the phthalocyanine fragment.

4. The method for preparing the pigment synergist according to claim 3, characterized in that: The specific steps include: Cyanuric chloride and an acidifying agent are added to solvent one, and then aminophthalonitrile is added to react, and then N, N-dimethylpropylenediamine is slowly added. After continuing the reaction, the reaction system is poured into ice water, and after filtering, washing and drying, a phthalocyanine fragment of a phthalonitrile unit containing triazine is obtained. The phthalocyanine fragment and a metal salt are mixed in solvent two and a catalyst, and reacted to obtain the pigment synergist.

5. The method for preparing the pigment synergist according to claim 3, characterized in that: The specific steps include: Cyanuric chloride and an acidifying agent are added to solvent one, and then aminophthalonitrile is added to react, and then N, N-dimethylpropylenediamine is slowly added. After continuing the reaction, the reaction system is poured into ice water, and after filtering, washing and drying, a phthalocyanine fragment containing a phthalonitrile unit of triazine is obtained. The phthalocyanine fragment, phthalonitrile and a metal salt are mixed in solvent two and a catalyst, and reacted to obtain the pigment synergist.

6. The method for preparing the pigment synergist according to any one of claims 4 to 5, characterized in that: The acidifying agent is at least one of potassium carbonate, triethylamine and pyridine.

7. A pigment composition, characterized in that The invention comprises a phthalocyanine pigment and the pigment synergist according to any one of claims 1 to 2.

8. The pigment composition according to claim 7, characterized in that: The mass ratio of the pigment synergist to the phthalocyanine pigment is 0.1-50:100; The phthalocyanine pigment is at least one of CI Pigment Blue 15, CI Pigment Blue 15:1, CI Pigment Blue 15:3, CI Pigment Blue 15:6, CI Pigment Green 7, CI Pigment Green 36, and CI Pigment Green 58.

9. A color paste dispersion, characterized in that: The method comprises the pigment synergist according to any one of claims 1 to 2 or the pigment composition according to any one of claims 7 to 8.

10. Use of the pigment synergist according to any one of claims 1 to 2 in the field of color filters.

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