Phthalocyanine quaternary ammonium salts, their preparation methods and applications

Abstract

This invention relates to a titanium cyanide quaternary ammonium salt compound, its preparation method, and its application. The titanium cyanide quaternary ammonium salt compound is the compound shown in the formula. The method for preparing the compound shown in the formula includes (1) preparing pyridine phthalocyanine from o-pyridine dinitrile as a starting material, and (2) quaternizing the pyridine phthalocyanine with the corresponding halogenated product to obtain the target compound. Adding the compound shown in the formula during the pigmentation process of zinc halide phthalocyanine crude pigment can not only improve the brightness and contrast of the zinc halide phthalocyanine pigment, but also enhance its dispersibility and storage stability. In the formula, R1~R4 are independently selected from C1~C4. 10 Alkyl groups, fluorine-containing C1~C 10 Alkyl groups, or C1-C groups substituted with 5-6 aryl groups. 10 One of the alkyl groups; X is an acid radical anion with balanced charge.

Description

Technical Field

[0001] This invention relates to a titanium cyanine quaternary ammonium salt compound, its preparation method, and its application. Background Technology

[0002] Phthalocyanine, metallic phthalocyanine, and their derivatives are mainly used as pigments or dyes. Blue and green pigments or dyes made from phthalocyanine have very bright colors, high tinting strength, and excellent heat and weather resistance, which are unmatched by other varieties. They are widely used in printing inks, coatings, plastics, rubber, leather, textiles, and food.

[0003] Zinc halide phthalocyanine pigments possess excellent lightfastness, weather resistance, heat stability, and solvent resistance. They are popular for their vibrant yellow-green hue, superior tinting strength, and excellent durability, and are widely used in color filters for liquid crystal displays. However, zinc halide phthalocyanine pigments face several challenges (such as their brightness, contrast, dispersibility, and storage stability).

[0004] CN106716190A provides a method to improve the brightness and contrast of zinc halide phthalocyanine pigments by adding zinc halide phthalocyanine derivatives (zinc halide phthalocyanine containing alkylene-bonded phthalimide skeletal functional groups) during the pigmentation process of zinc halide phthalocyanine crude pigments, which has achieved certain results. However, there is still room for improvement in the overall performance (brightness, contrast, dispersibility, and storage stability) of zinc halide phthalocyanine pigments. Summary of the Invention

[0005] Through extensive and in-depth research, the inventors of this invention have discovered that adding phthalocyanine quaternary ammonium salt compounds during the pigmentation process of zinc halophthalocyanine crude pigments can not only improve the brightness and contrast of zinc halophthalocyanine pigments, but also enhance their dispersibility and storage stability.

[0006] One object of the present invention is to disclose a novel phthalocyanine quaternary ammonium salt compound.

[0007] The phthalocyanine quaternary ammonium salt compound of the present invention is of the formula: The compound shown:

[0008]

[0009] Mode In the above, R1~R4 are independently selected from: C1~C 10 Alkyl groups, fluorine (F) C1~C 10 Alkyl groups, or C1-C groups substituted with 5-6 aryl groups. 10 One of the alkyl groups; X is an acid radical anion with balanced charge.

[0010] Another object of the present invention is to provide a method for preparing the phthalocyanine quaternary ammonium salt compound (formula) described in this invention. The method for (the compound shown).

[0011] The method includes the following steps:

[0012] (1) o-pyridinium nitrile (formula) Using the compound shown as the starting material, from formula The compound shown is used to prepare pyridine phthalocyanine (formula). The steps for the compound shown; and,

[0013] (2) From the formula The compound shown undergoes a quaternization reaction with the corresponding halide to give the target compound (formula). The steps for (the compound shown).

[0014]

[0015] In the formula, R1~R4 and X have the same meaning as described above.

[0016] Another object of the present invention is to disclose a phthalocyanine quaternary ammonium salt compound (formula) provided by the present invention. The uses of the compound shown. That is, the compound of formula... The compound shown can be used to prepare zinc halide phthalocyanine pigments. Detailed Implementation

[0017] To more clearly illustrate the present invention, the following description, in conjunction with preferred embodiments, further clarifies the invention. Those skilled in the art should understand that the specific descriptions below are illustrative rather than restrictive, and should not be construed as limiting the scope of protection of the present invention.

[0018] In a preferred embodiment of the present invention, R1~R4 are each independently selected from: C1~C 10 Alkyl groups, fluorine (F) C1~C 10 Alkyl groups, or C1-C substituted with phenyl groups. 10 One of the alkyl groups;

[0019] In a further preferred embodiment, R1 to R4 are each independently selected from one of the following: ethyl, octyl, fluorohexyl, fluorohexadecanyl or benzyl;

[0020] In a further preferred embodiment, R1 to R4 are each independently selected from one of the following: ethyl, octyl, fluorohexyl, fluorohexadecanyl or benzyl; and R1 to R4 are all identical.

[0021] In another preferred embodiment of the present invention, X is a halide anion;

[0022] In a further preferred embodiment, X is a bromide anion.

[0023] A method for preparing the phthalocyanine quaternary ammonium salt compound (formula) of the present invention A method for (the compound shown) includes the following steps:

[0024] (1) o-pyridinedionitrile (formula) The compound shown) and a protic polar solvent were placed in a reactor equipped with a stirrer, stirred and heated, with ammonia gas introduced during the process, and reacted at 250°C for at least 4 hours. After cooling and filtration, the filter cake was washed to obtain pyridine phthalocyanine (formula omitted). (The compound shown).

[0025] (2) Pyridine phthalocyanine (formula) The compound shown, its corresponding halide, and an aprotic polar solvent were placed in a reactor equipped with a stirrer. Under the presence of an inert gas, the mixture was stirred and heated to 90°C, and maintained at this temperature for at least 24 hours. The reaction solvent was then evaporated, and the residue was recrystallized to obtain the target compound (formula omitted). The compound shown.

[0026] The aprotic polar solvent is preferably N,N-dimethylformamide (DMF) or acetonitrile, and the halogenated product is preferably one or more of bromooctane, bromoethane, benzyl bromide, and bromofluoroalkanes.

[0027] The phthalocyanine quaternary ammonium salt compound (formula) provided by this invention The compound shown can be used to prepare zinc halide phthalocyanine pigments. It not only improves the brightness and contrast of zinc halide phthalocyanine pigments, but also enhances their dispersibility and storage stability.

[0028] To more clearly illustrate the present invention, the following description, in conjunction with preferred embodiments, further clarifies the invention. Those skilled in the art should understand that the specific descriptions below are illustrative rather than restrictive, and should not be construed as limiting the scope of protection of the present invention.

[0029] Example 1

[0030] (1) Pyridine phthalocyanine (formula) Preparation of the compound shown:

[0031]

[0032] 2 g of pyridine dinitrile (Shanghai Titan Technology Co., Ltd.) and 10 mL of N,N-dimethylaniline (DMF) were placed in a reactor equipped with a stirrer, stirred and heated, with ammonia gas introduced during the reaction, and reacted at 250°C for at least 4 hours. After filtration, the filter cake was washed with ethanol or acetone to obtain pyridine phthalocyanine (formula omitted). (The compound shown).

[0033] (2) Preparation of the target compound (the compound shown in formula Ia):

[0034] Pyridine phthalocyanine (formula) The compound shown, 0.4 mmol), 6 mmol of bromoethane (Shanghai Titan Technology Co., Ltd., purity 99%) and DMF were placed in a reactor equipped with a stirrer. Under the presence of argon, the mixture was stirred and heated to 90 °C and maintained at this state for at least 24 hours. The reaction solvent (DMF) was removed by evaporation, and the residue was recrystallized from diethyl ether to give a purple-red solid (the compound shown in formula Ia) with a yield of 86%.

[0035]

[0036] Example 2

[0037] Mode Preparation of the compound shown in b:

[0038]

[0039] Except for replacing bromoethane in Example 1 with 1-bromooctane (Shanghai Maclean Biochemical Technology Co., Ltd.), everything else was the same as in Example 1, yielding a reddish-brown powder (formula...). Compound b), yield 86%.

[0040]

[0041] Example 3

[0042] Mode Preparation of the compound shown in c:

[0043]

[0044] Except for replacing bromoethane in Example 1 with benzyl bromide (Shanghai Titan Technology Co., Ltd.), everything else was the same as in Example 1, yielding a reddish-brown powder (formula...). (Compound shown in c), yield 85%.

[0045]

[0046] Example 4

[0047] Mode Preparation of the compound shown in d:

[0048]

[0049] Divided by polyfluorohexane ( (Shanghai Titan Technology Co., Ltd.) Except for replacing bromoethane in Example 1, everything else was the same as in Example 1, yielding a reddish-brown powder (Formula... (Compound shown in d), yield 86%.

[0050]

[0051] Example 5

[0052] Mode Preparation of the compound shown in e:

[0053]

[0054] Divided by polyfluorodecane bromide ( (Shanghai Titan Technology Co., Ltd.) Except for replacing bromoethane in Example 1, everything else was the same as in Example 1, yielding a reddish-brown powder (Formula... (Compound shown in e), yield 86%.

[0055]

[0056] Applications and Comparative Examples

[0057] Application Example 1

[0058] 19.5g of crude zinc halide phthalocyanine pigment A, 0.5g of formula The compound shown in Figure a, 150g of sodium chloride powder (250 mesh) and 18g of polyethylene glycol (Shanghai Maclean Biochemical Technology Co., Ltd.) were placed in a kneader and kneaded at 30°C for 4 hours. The kneaded mixture was then added to 2000g of hot water and stirred for 1 hour. The mixture was filtered, and the filter cake was rinsed with deionized water until the conductivity of the filtrate was ≤20us / cm. The mixture was dried at 110°C to constant weight and then pulverized to obtain the pigment composition Ga.

[0059] The preparation method of crude zinc halide phthalocyanine pigment A is as follows: 91g of sulfonyl chloride (Shanghai Maclean Biochemical Technology Co., Ltd.), 109g of anhydrous aluminum chloride (Tianjin Yongda Chemical Reagent Co., Ltd.), 15g of sodium chloride (Tianjin Yongda Chemical Reagent Co., Ltd.), 30g of zinc phthalocyanine (Lily Group Co., Ltd.), and 108g of bromine (Tianjin Yongda Chemical Reagent Co., Ltd.) are added to a reactor, and the temperature is raised to 130℃ and maintained for 25 hours. The reaction product is poured into an ice-water mixture, a solid precipitates, and the mixture is filtered. The filter cake is washed with water to obtain crude zinc halide phthalocyanine pigment A (average bromine number of 13.1 and average chlorine number of 2.4).

[0060] Application Example 2

[0061] Divide by Example 1 shows the application of compound replacement shown in b. Except for the compound shown in Example a, the other components are the same as in Application Example 1, resulting in pigment composition Gb.

[0062] Application Example 3

[0063] Divide by Example 1 shows the application of the compound substitution shown in c. Except for the compound shown in Example a, the other components are the same as in Application Example 1, resulting in pigment composition Gc.

[0064] Application Example 4

[0065] Divide by The compound shown in d is used in Example 1 for substitution application. Except for the compound shown in Example a, the other components are the same as in Application Example 1, resulting in the pigment composition Gd.

[0066] Application Example 5

[0067] Divide by Example 1 of the compound substitution application shown in e is as follows: Except for the compound shown in example a, the other components are the same as in application example 1, resulting in the pigment composition Ge.

[0068] Comparative Example 1 (see CN106716190A)

[0069] 90g of sulfonyl chloride (Shanghai Maclean Biochemical Technology Co., Ltd.), 105g of anhydrous aluminum chloride (Tianjin Yongda Chemical Reagent Co., Ltd.), 14g of sodium chloride (Tianjin Yongda Chemical Reagent Co., Ltd.), 27g of zinc phthalocyanine (Lily Group Co., Ltd.), and 45g of bromine (Tianjin Yongda Chemical Reagent Co., Ltd.) were added to a reactor, and the temperature was raised to 130℃ and maintained for 1 hour. After the temperature maintenance, the reaction product was poured into an ice-water mixture, and a solid precipitated out. The solid was filtered, and the filter cake was washed with water to obtain zinc halide phthalocyanine B (average bromine number of 8.6 and average chlorine number of 2.5).

[0070] 3g of zinc halide phthalocyanine B, 27g of concentrated sulfuric acid (Chengdu Kelong Chemical Co., Ltd.), 5g of phthalimide (Shanghai Maclean Biochemical Technology Co., Ltd.), and 2g of paraformaldehyde (Shanghai Maclean Biochemical Technology Co., Ltd.) were heated at 80℃ for 1 hour, poured into water, and the solid precipitated out. After filtration, the filter cake was washed with water and dried to obtain phthalimide-methylated zinc halide phthalocyanine derivative (the average number of methyl substitutions of phthalimide was 0.6).

[0071] 19g of crude zinc halide phthalocyanine pigment A, 1g of phthalimide-methylated zinc halide phthalocyanine derivative, 140g of sodium chloride (250 mesh) and 32g of diethylene glycol (Shanghai Maclean Biochemical Technology Co., Ltd.) were kneaded using the kneading process described in Application Example 1 to obtain pigment composition Da.

[0072] Comparative Example 2 (see CN115667416A)

[0073] 30g of crude zinc halide phthalocyanine pigment A and 600g of water were slurried into a uniform slurry. The pH of the system was adjusted to 5.5 with dilute hydrochloric acid. The mixture was then transferred to a high-pressure sealed autoclave and slowly heated to 200℃ and pressured at 1.55MPa over 2 hours. The mixture was kept at 200℃ for 5 hours and then cooled to room temperature. After filtration, the filter cake was washed with water, dried, and pulverized to obtain pigment composition Db.

[0074] Application Example 6

[0075] 75g of zirconium beads (0.3~0.4mm), 23.66g of propylene glycol methyl ether acetate, 2.48g of BYK-LPN6919 (manufactured by BYK Chemical Company, a methacrylic acid AB block copolymer (LPN6919), amine value 121mg-KOH / g, solid content 60%), and 11.81g of acrylic resin (solid content 40%) were placed in different containers with 4.96g of the pigment composition (Ga~Ge and Da~Db) described above, and dispersed by shaking for 2 hours to obtain pigment composition slurries (CGa~CGe and CDa~CDb).

[0076] The pigment composition slurries (CGa~CGe and CDa~CDb) were uniformly coated onto soda-lime glass substrates using a spin coater. For each sample, three glass substrates with different coating thicknesses were obtained by adjusting the spin coater speed to 500 rpm, 1000 rpm, and 1500 rpm. After spin coating, the glass substrates were dried at 150°C for 1 minute on a heating plate, followed by baking at 230°C for 1 hour. The chromaticity coordinates (x, y, Y) of the coatings (samples) on the glass substrates before and after baking were measured using a colorimeter. Simultaneously, the contrast ratio of the samples after baking at 230°C for 1 hour was measured using a contrast analyzer. The results are shown in Table 1. The pigment particle size was tested using a Malvern particle size analyzer, and the viscosity was measured using a Brinell rotational viscometer. The results are shown in Table 2.

[0077] A higher contrast ratio indicates better sample quality. Changes in the chromaticity coordinates (x) before and after baking, especially changes in luminance (y), are also important; smaller changes in y indicate better sample quality. Furthermore, the viscosity and viscosity stability of the pigment are also crucial indicators for product evaluation. Particle size data serves as a supplementary reference; smaller particle sizes generally result in higher contrast, and more uniform particle size distribution typically correlates with better viscosity and viscosity stability.

[0078] Table 1

[0079]

[0080] Table 2

[0081]

[0082] As shown in Tables 1 and 2, the phthalocyanine quaternary ammonium salt compound (formula) provided by this invention is used in the pigmentation process of crude zinc phthalocyanine. a~ The compound shown in e) yields a zinc halide phthalocyanine pigment with superior overall performance (brightness, contrast, dispersibility, and storage stability) compared to existing technologies. In particular, the use of formula e... The compound shown in c and the formula The compound shown in e is a pigmented zinc halide phthalocyanine.

[0083] The above description is merely a preferred embodiment of the present invention and is not intended to limit the present invention in any way. Although the present invention has been disclosed above with reference to preferred embodiments, it is not intended to limit the present invention. Any person skilled in the art can make some modifications or alterations to the above-described technical content to create equivalent embodiments without departing from the scope of the present invention. Any simple modifications, equivalent changes, and alterations made to the above embodiments based on the technical essence of the present invention without departing from the scope of the present invention shall still fall within the scope of the present invention.

Claims

1. A phthalocyanine quaternary ammonium salt compound, having the formula... The compound shown: ； Mode In the above, R1~R4 are independently selected from: C1~C 10 Alkyl groups, fluorine-containing C1~C 10 Alkyl groups, or C1-C groups substituted with 5-6 aryl groups. 10 One of the alkyl groups; X is an acid radical anion with balanced charge.

2. The phthalocyanine quaternary ammonium salt compound as described in claim 1, characterized in that, R1 to R4 are each independently selected from: C1 to C 10 Alkyl groups, fluorine-containing C1~C 10 Alkyl groups, or C1-C substituted with phenyl groups. 10 One of the alkyl groups.

3. The phthalocyanine quaternary ammonium salt compound as described in claim 2, characterized in that, R1 to R4 are each independently selected from one of the following: ethyl, octyl, fluorohexyl, fluorohexadecanyl or benzyl.

4. The phthalocyanine quaternary ammonium salt compound as described in claim 3, characterized in that, R1 to R4 are each independently selected from one of the following: ethyl, octyl, fluorohexyl, fluorohexadecanyl or benzyl; and R1 to R4 are all the same.

5. The phthalocyanine quaternary ammonium salt compound as described in claim 1, characterized in that, Where X is a bromide anion.

6. A method for preparing the phthalocyanine quaternary ammonium salt compound as described in any one of claims 1 to 5, comprising the following steps: (1) The step of preparing pyridine phthalocyanine from o-pyridine dinitrile as a starting material; and, (2) The step of quaternizing pyridine phthalocyanine with the corresponding halide to obtain the target product.

7. The method as described in claim 6, characterized in that, Step (1) includes the following steps: o-pyridine dinitrile and aprotic polar solvent are placed in a reactor equipped with a stirrer, stirred and heated, with ammonia gas introduced during the process, and reacted at 250°C for at least 4 hours. After cooling and filtration, the filter cake is washed to obtain pyridine phthalocyanine.

8. The method as described in claim 6, characterized in that, Step (2) includes the following steps: Pyridine phthalocyanine, the corresponding halogenated product, and an aprotic polar solvent are placed in a reactor equipped with a stirrer. Under the presence of an inert gas, the mixture is stirred and heated to 90°C, and maintained at this temperature for at least 24 hours. The reaction solvent is then evaporated, and the residue is recrystallized to obtain the target product.

9. The use of the phthalocyanine quaternary ammonium salt compound as described in any one of claims 1 to 5 in the preparation of zinc halide phthalocyanine pigments.

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