A black dye composition, a preparation method thereof, a black coating, a preparation method thereof, and a usage method thereof

Abstract

The present invention discloses a black dye composition and its preparation method, a black coating and its preparation method and usage method. A black dye composition, the black dye composition comprises dye components of four structures: A preparation method of the black dye composition, the synthesis methods of the dyes A-D include the following two steps: Step (1): The starting material is stirred and reacted with phenylacetyl chloride in a dichloromethane solution containing triethylamine to generate an intermediate; Step (2): The intermediate is stirred and reacted with p-toluenesulfonyl azide in an acetonitrile solution containing 1,8-diazabicyclo[5.4.0]undec-7-ene to generate dyes A to D.

Description

Technical Field

[0001] The present invention belongs to the technical field of fine chemical engineering, and particularly relates to a black dye composition and a preparation method thereof, a black coating and a preparation method and a use method thereof. Background Art

[0002] The polyester (PET) aluminized film is a composite film of a PET film and metallic aluminum, and is a barrier film formed by stacking aluminum atoms on the PET film through vacuum aluminizing processes such as evaporation, sputtering, ion plating, etc. (Reference: Polymer Materials Science and Engineering, 2017, 33(03), 64 - 70). The PET aluminized film can be used to make polyester metallic yarn. Since the aluminum layer may be detached in the dyeing environment for the polyester metallic yarn, usually, the PET aluminized film is colored and then further processed into metallic yarn.

[0003] Due to the protective effect of the aluminized layer, it is difficult for dye molecules to penetrate into the PET layer. Therefore, usually, a coating method is adopted to coat a coating on the surface layer of the aluminized film to obtain a color (Reference: Liao Qixia, Guangzhou Chemical Industry, 2013, 41(24), 196 - 197 + 201). The prior art has at least the following problems: the color fastness of some colors of the PET aluminized film is not high enough, manifested as poor steam resistance and insufficient light resistance. This phenomenon is particularly prominent in black products. Summary of the Invention

[0004] In view of the above - mentioned disadvantages of the background art, the purpose of the present invention is to provide a black dye composition and a preparation method thereof, a black coating and a preparation method and a use method thereof, for producing a durable black coating for PET aluminized films.

[0005] To solve the above - mentioned technical problems, the purpose of the present invention is achieved as follows:

[0006] A black dye composition, which comprises dye components of the following four structures:

[0007]

[0008] (A)

[0009]

[0010] (B)

[0011]

[0012] (C)

[0013]

[0014] (D).

[0015] On the basis of the above solution and as the preferred solution of the above solution: The weight ratio of the four dye components is: Dye A 45%, Dye B 40%, Dye C 5%, Dye D 10%.

[0016] A method for preparing a black dye composition, the synthesis methods of the dye components A-D include the following two steps:

[0017] Step (1): The starting material and phenylacetyl chloride are stirred and reacted in a dichloromethane solution containing triethylamine to form an intermediate;

[0018] Step (2): The intermediate and p-toluenesulfonyl azide are stirred and reacted in an acetonitrile solution containing 1,8-diazabicyclo[5.4.0]undec-7-ene to form dyes A to D;

[0019] Among them, in step (1), the molar ratio of phenylacetyl chloride to the starting material is 2.2∶1, the molar ratio of triethylamine to the starting material is 4∶1, and the amount of dichloromethane used is such that the molar concentration of the starting material reaches 0.1~0.5 mol / L; the environmental temperature of the reaction in step (1) is 25 °C, and the reaction time is 1 h;

[0020] In step (2), the molar ratio of p-toluenesulfonyl azide to the starting material is 3∶1, the molar ratio of 1,8-diazabicyclo[5.4.0]undec-7-ene to the starting material is 4∶1, and the amount of acetonitrile used is such that the molar concentration of the starting material reaches 0.1~0.5 mol / L; the environmental temperature of the reaction in step (2) is 25 °C, and the reaction time is 24 h;

[0021] The starting material corresponding to Dye A is Compound 1a, and the corresponding intermediate is 2a;

[0022]

[0023] (1a)

[0024]

[0025] (2a)

[0026] The starting material corresponding to Dye B is Compound 1b, and the corresponding intermediate is 2b;

[0027]

[0028] (1b)

[0029]

[0030] (2b)

[0031] The starting material corresponding to Dye C is Compound 1c, and the corresponding intermediate is 2c;

[0032]

[0033] (1c)

[0034]

[0035] (2c)

[0036] The starting material corresponding to Dye D is Compound 1d, and the corresponding intermediate is 2d;

[0037]

[0038] (1d)

[0039]

[0040] (2d)。

[0041] A black coating, comprising the black dye composition described above; and comprising raw materials in the following weight ratios: 1% - 4% of the black dye composition, 0.5% - 2% of a dispersant, 0.1% of an antifoaming agent, 0.1% of a wetting agent, 71.3% - 77.8% of deionized water, 8% of an aqueous acrylic resin, 10% of an aqueous polyurethane resin, 1% of a crosslinking agent, 0.5% of an ultraviolet absorber, and 1% - 3% of a pH regulator.

[0042] A method for preparing a black coating, comprising the following steps;

[0043] Step (1): Grind the black dye composition together with the dispersant, antifoaming agent, wetting agent, ultraviolet absorber, and deionized water according to the given weight ratios to obtain a black dye dispersion; the weight ratio of the black dye composition to the dispersant is 2:1; the grinding time is 4 h;

[0044] Step (2): Add the aqueous acrylic resin, aqueous polyurethane resin, and crosslinking agent in the given weight ratios to the black dye dispersion obtained in Step (1), and stir evenly.

[0045] A method for using a black coating, wherein the black coating is used for coloring an aluminized film.

[0046] The prominent and beneficial technical effects of the present invention compared with the prior art are:

[0047] The present invention provides a black durable coating for coloring a PET polyester film, and the obtained black PET polyester film has a black effect with pure color tone, steam resistance, and sun exposure resistance.

[0048] The present invention first designed four dyes with an anthraquinone structure as the parent and a diazo structure as the reactive group. The advantages of this dye are as follows: 1. The anthraquinone chromophore itself has good lightfastness, laying the foundation for the good lightfastness of the final dye. 2. The diazo structure has good reactivity and can react with oxygen-hydrogen bonds, nitrogen-hydrogen bonds, and even carbon-hydrogen bonds in the environment only through high-temperature treatment, which lays the foundation for the dye in the final coating to react and graft into the polymer network. In addition, the dye molecules designed in the present invention contain two diazo groups, greatly increasing the ability of the dye to react with the coating polymerization network. 3. The four dyes provided by the present invention have structural similarity. When these four dyes are mixed to prepare a black dye composition, they have good compatibility. 4. The dye synthesis route is short, the synthesis operation is simple, and the raw materials are easily available.

[0049] The present invention also provides a black coating with durable properties. This coating uses the designed black dye composition as the colored substance, and the color of the obtained black PET polyester film is pure and durable. This coating uses an additional ultraviolet absorber to further improve the lightfastness of the obtained black PET polyester film. This coating also uses an additional aziridine crosslinking agent, which can further fix the coating polymer network, effectively seal the dye molecules, and increase the steaming resistance effect of the obtained black PET polyester film. Detailed implementation mode

[0050] The present invention will be introduced in detail and specifically through specific examples below to better understand the present invention. However, the following examples do not limit the scope of the present invention.

[0051] The starting material compound 1a can be obtained by purchasing commercially, or can be synthesized by oneself using the method in the literature (Journal of Applied Polymer Science, 2002, 83(6), 1252 - 1257). The starting materials 1b and 1c are obtained by purchasing commercially. The dispersant MF, defoamer NXZ, wetting agent PE100, ultraviolet absorber UV1130, waterborne acrylic resin, waterborne polyurethane resin, aziridine crosslinking agent C9, and ammonia water can all be obtained by purchasing commercially.

[0052] The PET aluminized film uses commercially available double-sided PET aluminized film materials, with the PET thickness being 0.012 - 0.015 mm and the aluminized layer thickness being 0.3 - 0.4 μm.

[0053] Synthesis example one of the dye: Dye A

[0054]

[0055] (1a) (2a)

[0056] Add the starting material 1a (10 mmol, 3.26 g) to a 250 mL three-necked flask placed in an oil bath at 25 °C. Subsequently, add dichloromethane (100 mL). After stirring to dissolve the solid, add phenylacetyl chloride (22 mmol, 3.4 g), and then add triethylamine (20 mmol, 2.02 g) dropwise. After stirring and reacting for 1 h, stop the reaction. Add deionized water (100 mL) to the three-necked flask, stir vigorously for 3 min, let it stand for 2 min, and use a dropper to suck out the aqueous layer, leaving the organic phase. Subsequently, wash the organic phase successively with 1 mol / L hydrochloric acid aqueous solution (100 mL) and saturated brine (100 mL). The obtained organic phase is dried with anhydrous magnesium sulfate, and finally the organic phase solvent is evaporated using a rotary evaporator. The residual solid is intermediate 2a, a blue solid, 5.29 g, with a yield of 94%. 1 H NMR (CDCl3, 400MHz) δ 7.69~7.65 (m, 2H), 7.57 (d, J = 6.8 Hz, 2H),7.44~7.35 (m, 4H), 7.28~7.19 (m, 6H), 7.02~6.95 (m, 2H), 4.48 (t, J = 7.2 Hz,4H), 3.57 (s, 4H), 3.55 (t, J = 7.2 Hz, 4H). 13 C NMR (CDCl3, 100MHz) δ 184.51,171.31, 146.70, 135.30, 134.35, 129.57, 129.16, 129.09, 127.12, 121.90,121.54, 118.85, 62.29, 42.06, 40.90. ESI-MS: m / z = 563 [M+H].

[0057]

[0058] (2a) (A)

[0059] To a 250 mL three-necked flask placed in an oil bath at 25 °C, add intermediate 2a (5 mmol, 2.81 g), p-toluenesulfonyl azide (15 mmol, 2.96 g), 1,8-diazabicyclo[5.4.0]undec-7-ene (20 mmol, 3.05 g), and acetonitrile (50 mL) in sequence. After stirring and reacting for 24 h, stop the reaction. Use a rotary evaporator to remove the acetonitrile in the reaction solution, and directly purify the residual solid by silica gel (200 - 300 mesh) column chromatography (eluent: V 石油醚 / V 乙酸乙酯 = 2 / 1) to obtain dye A, a blue solid, 2.55 g, with a yield of 83%. 1 1H NMR (CDCl3, 400MHz) δ 7.69~7.66 (m, 2H), 7.48~7.37(m, 8H), 7.21~7.14 (m, 6), 4.54 (t, J J = 7.2 Hz, 4H), 3.55 (t, J J = 7.2 Hz, 4H). 13 13C NMR (CDCl3, 100MHz) δ 184.51, 162.68, 146.70, 135.30, 129.52, 129.16, 129.06,128.80, 128.70, 121.90, 121.54, 118.85, 73.65, 63.62, 42.06. ESI-MS: m / z =615 [M+H].

[0060] Synthesis Example 2 of the Dye: Dye B

[0061]

[0062] (1b) (2b)

[0063] Except replacing the starting material 1a (10 mmol, 3.26 g) with the starting material 1b (10 mmol, 3.58 g), the synthesis of intermediate 2a is the same as others. Intermediate 2b, a blue-violet solid, 4.41 g, with a yield of 87%, 1 1H NMR (CDCl3, 400MHz) δ 8.04 (d, J J = 7.2 Hz, 2H), 7.30 (d, J= 7.2 Hz, 2H), 7.23~7.15 (m, 6H), 7.02~7.00(m, 2H), 3.81 (s, 4H). 13 C NMR (CDCl3, 100MHz) δ 186.16, 170.70, 159.53, 136.03,135.33, 129.65, 128.87, 127.12, 124.84, 117.55, 117.35, 116.76, 44.28. ESI-MS: m / z = 507 [M+H].

[0064]

[0065] (2b) (B)

[0066] Replace intermediate 2a (5 mmol, 2.81 g) with intermediate 2b (5 mmol, 2.53 g), and the others are the same as the synthesis of dye A. Dye B, blue-violet solid, 2.21 g, yield 79%. 1 H NMR (CDCl3, 400MHz) δ 8.05 (d, J = 7.2 Hz,2H), 7.61~7.55 (m, 4H), 7.41~7.34 (m, 4H), 7.23 (d, J = 7.2 Hz, 2H), 7.05~7.02(m, 2H). 13 C NMR (CDCl3, 100MHz) δ 186.16, 169.99, 159.30, 135.16, 129.52,128.67, 126.95, 125.90, 125.08, 117.55, 116.71, 63.21. ESI-MS: m / z = 559 [M+H].

[0067] Synthesis example of dye three: Dye C

[0068]

[0069] (1c) (2c)

[0070] Except for replacing the starting material 1a (10 mmol, 3.26 g) with the starting material 1c (10 mmol, 2.38 g), the others are the same as the synthesis of intermediate 2a. Compound 2c, purplish-red solid, 4.56 g, yield 96%. 11H NMR (CDCl3, 400 MHz) δ 8.66 (d, J J = 7.2 Hz, 2H), 8.07 (d, J J = 7.6 Hz, 2H), 7.62 (dd, J 1 J = 7.2 Hz, J 2 J = 7.6 Hz, 2H), 7.23 - 7.15 (m, 6H), 7.02 - 7.00 (m, 4H), 3.81 (s, 4H). 13 13C NMR (CDCl3, 100 MHz) δ 186.01, 170.70, 138.80, 136.03, 135.56, 134.69, 129.65, 128.87, 127.12, 125.87, 122.78, 119.47. ESI - MS: m / z = 475 [M + H].

[0071]

[0072] (2c) (C)

[0073] Replace intermediate 2a (5 mmol, 2.81 g) with intermediate 2c (5 mmol, 2.37 g), and the others are the same as the synthesis of dye A. Compound C, purple - red solid, 2.43 g, yield 92%, 1 1H NMR (CDCl3, 400 MHz) δ 8.57 (d, J J = 7.2 Hz, 2H), 8.06 (d, J J = 7.6 Hz, 2H), 7.64 (dd, J 1 J = 7.2 Hz, J 2 J = 7.6 Hz, 2H), 7.56 - 7.48 (m, 4H), 7.41 - 7.34 (m, 4H), 7.04 - 7.01 (m, 2H). 13 13C NMR (CDCl3, 100 MHz) δ186.91, 169.99, 138.25, 135.61, 134.42, 129.52, 128.67, 126.95, 125.90, 124.53, 122.78, 121.96, 63.21. ESI-MS: m / z = 527 [M+H].

[0074] Synthesis Example 4 of Dye: Dye D

[0075] The synthesis method of starting material 1d is as follows, in which compound 3 is synthesized by oneself according to the method of the literature (Dyes and Pigments 2019, 161, 16 - 23).

[0076]

[0077] (3) (1d)

[0078] In a 250 mL three-necked flask, successively add compound 3 (20 mmol, 7.42 g), sodium carbonate (20 mmol, 2.12 g), ethylene glycol (5 mL) and N , N N,N-dimethylformamide (100 mL). After heating to 50 °C and stirring for 2 h, add additional sodium carbonate (20 mmol, 2.12 g) and ethylene glycol (5 mL), and continue heating to 90 °C and stirring for 2 h. Stop the reaction. After cooling to room temperature, add the reaction solution to deionized water (500 mL) and stir to precipitate a solid. After standing for 10 min, filter. The obtained filter cake is further washed with deionized water (300 mL) and saturated brine (300 mL), and finally dried in an oven at 60 °C to obtain compound 1d, an orange solid, 6.93 g, with a yield of 82%. 1 H NMR (CDCl3, 400MHz) δ 8.50 (dd, J 1 J = 7.6Hz, J 2 J = 2.4 Hz, 1H), 8.34~8.28 (m, 3H), 7.95 (dd, J 1 J = 7.6 Hz, J 2 J = 2.4 Hz, 1H),7.86~7.84 (m, 1H), 7.54 (dd, J 1 J = 7.6 Hz, J 2= 7.2 Hz, 1H), 4.33 (t, J = 7.2 Hz,4H), 3.69 (t, J = 7.2 Hz, 4H). 13 C NMR (CDCl3, 100MHz) δ 186.94, 182.30, 170.02,162.14, 140.45, 134.55, 133.95, 133.82, 133.70, 133.46, 133.37, 126.66,126.62, 124.38, 122.30, 120.86, 67.11, 60.66. ESI-MS: m / z = 423 [M+H].

[0079]

[0080] (1d) (2d)

[0081] Except that the starting material 1a (10 mmol, 3.26 g) was replaced with the starting material 1d (10 mmol, 2.38 g), the synthesis of intermediate 2a was carried out as described above. Compound 2d, orange solid, 5.93 g, yield 90%. 1 H NMR (CDCl3, 400MHz) δ 8.50(dd, J 1 = 7.6 Hz, J 2 = 2.0 Hz, 1H), 8.34~8.27 (m, 3H), 7.95 (dd, J 1 = 7.2 Hz, J 2 = 2.0Hz, 1H), 7.86~7.84 (m, 1H), 7.54 (dd, J 1 = J 2 = 7.6 Hz, 1H), 7.41 (d, J = 7.6 Hz,2H), 7.35 (d, J = 7.6 Hz, 2H), 7.28~7.18 (m, 6H), 4.52 (t, J = 7.2 Hz, 4H), 4.45(t, J = 7.2 Hz, 4H), 3.57 (s, 4H). 1313C NMR (CDCl3, 100 MHz) δ 186.94, 182.30, 171.63, 170.02, 162.14, 140.45, 134.35, 133.95, 133.82, 133.70, 133.46, 133.37, 129.57, 129.09, 127.12, 126.66, 126.62, 124.38, 122.30, 120.86, 65.75, 62.86, 40.88. ESI-MS: m / z = 659 [M+H].

[0082]

[0083] (2d) (D)

[0084] Replace intermediate 2a (5 mmol, 2.81 g) with intermediate 2d (5 mmol, 2.37 g), and the others are the same as the synthesis of dye A. Dye D, orange solid, 3.10 g, yield 94%. 1 1H NMR (CDCl3, 400 MHz) δ 8.50 (dd, J 1 J = 7.6 Hz, J 2 J = 2.0 Hz, 1H), 8.34~8.28 (m, 3H), 7.95 (dd, J 1 J = 7.2 Hz, J 2 J = 2.0 Hz, 1H), 7.86~7.84 (m, 1H), 7.57~7.52 (m, 3H), 7.46 (dd, J 1 J = J 2 J = 7.2 Hz, 2H), 7.41~7.37 (m, 2H), 7.27 (dd, J 1 J = 7.6 Hz, J 2 J = 2.0 Hz, 1H), 7.18 (d, J J = 7.6 Hz, 2H), 4.54 (t, J J = 7.2 Hz, 4H), 4.52 (t, J J = 7.2 Hz, 4H). 1313C NMR (CDCl3, 100 MHz) δ 186.94, 182.30, 170.02, 162.68, 162.14, 140.45, 134.55, 133.95, 133.82, 133.70, 133.46, 133.37, 129.52, 129.06, 128.80, 128.70, 126.66, 126.62, 124.38, 122.30, 120.86, 73.65, 65.75, 62.74. ESI-MS: m / z = 711 [M+H].

[0085] Preparation Example of Black Dye Composition

[0086] The solid powders of Dye A (9 g), Dye B (8 g), Dye C (1 g) and Dye D (2 g) were added to a 250 mL three-necked flask and mixed thoroughly to obtain a black dye composition.

[0087] Black Coating Example 1

[0088] Take a black dye composition (1 g), dispersant MF (0.5 g), defoamer NXZ (0.1 g), wetting agent PE100 (0.1 g), ultraviolet absorber UV1130 (0.5 g) and deionized water (77.8 g) and place them in a grinder (equipped with zirconia beads with a diameter of 0.2 - 0.3 mm) for grinding for 4 h, then filter. The obtained filtrate is the dye pretreatment solution. Add aqueous acrylic resin (8 g), aqueous polyurethane resin (10 g), aziridine crosslinking agent C9 (1 g) to this pretreatment solution, and use ammonia water (1 g) to adjust the pH value of the mixed system to 8, then 100 g of black durable coating is prepared (if there is water loss during the production process, supplement a small amount of deionized water to make the total mass reach 100 g). Coat the coating evenly on the aluminized film, adjust the position of the scraper so that the coating thickness does not exceed 5 μm, then send the coated aluminized film into an oven at 180 °C and bake for 10 min, and then cool it down.

[0089] Black Coating Example 2

[0090] Take black dye composition (2 g), dispersant MF (1 g), defoamer NXZ (0.1 g), wetting agent PE100 (0.1 g), ultraviolet absorber UV1130 (0.5 g) and deionized water (76.3 g) and place them in a grinder (equipped with zirconia beads with a diameter of 0.2 - 0.3 mm) for grinding for 4 h, then filter. The obtained filtrate is the dye pretreatment solution. Add aqueous acrylic resin (8 g), aqueous polyurethane resin (10 g), aziridine crosslinking agent C9 (1 g) to this pretreatment solution, and use ammonia water (1 g) to adjust the pH value of the mixed system to 8, then 100 g of black durable coating is prepared (if there is water loss during the production process, supplement a small amount of deionized water until the total mass reaches 100 g). Apply the coating evenly on the aluminized film, adjust the position of the scraper so that the coating thickness does not exceed 5 μm, then send the coated aluminized film into an oven at 180 °C for baking for 10 min, and then cool it down.

[0091] Example 3 of black coating

[0092] Take black dye composition (4 g), dispersant MF (2 g), defoamer NXZ (0.1 g), wetting agent PE100 (0.1 g), ultraviolet absorber UV1130 (0.5 g) and deionized water (73.8 g) and place them in a grinder (equipped with zirconia beads with a diameter of 0.2 - 0.3 mm) for grinding for 4 h, then filter. The obtained filtrate is the dye pretreatment solution. Add aqueous acrylic resin (8 g), aqueous polyurethane resin (10 g), aziridine crosslinking agent C9 (1 g) to this pretreatment solution, and use ammonia water (1 g) to adjust the pH value of the mixed system to 8, then 100 g of black durable coating is prepared (if there is water loss during the production process, supplement a small amount of deionized water until the total mass reaches 100 g). Apply the coating evenly on the aluminized film, adjust the position of the scraper so that the coating thickness does not exceed 5 μm, then send the coated aluminized film into an oven at 180 °C for baking for 10 min, and then cool it down.

[0093] Comparative Example 1 of black coating (without using ultraviolet absorber)

[0094] Take 1 g of black dye composition, 0.5 g of dispersant MF, 0.1 g of defoamer NXZ, 0.1 g of wetting agent PE100, and 78.3 g of deionized water and place them in a grinder (equipped with zirconia beads with a diameter of 0.2 - 0.3 mm) for grinding for 4 h. After filtration, the obtained filtrate is the dye pretreatment solution. Add 8 g of aqueous acrylic resin, 10 g of aqueous polyurethane resin, and 1 g of aziridine crosslinking agent C9 to this pretreatment solution, and use 1 g of ammonia water to adjust the pH value of the mixed system to 8 to prepare 100 g of black coating (if there is water loss during the production process, supplement a small amount of deionized water until the total mass reaches 100 g). Spread the coating evenly on the aluminized film, adjust the position of the scraper so that the coating thickness does not exceed 5 μm, then send the coated aluminized film into an oven at 180 °C and bake for 10 min, and then cool it down.

[0095] Black coating comparative example 2 (without using a crosslinking agent)

[0096] Take 1 g of black dye composition, 0.5 g of dispersant MF, 0.1 g of defoamer NXZ, 0.1 g of wetting agent PE100, 0.5 g of ultraviolet absorber UV1130, and 78.8 g of deionized water and place them in a grinder (equipped with zirconia beads with a diameter of 0.2 - 0.3 mm) for grinding for 4 h. After filtration, the obtained filtrate is the dye pretreatment solution. Add 8 g of aqueous acrylic resin and 10 g of aqueous polyurethane resin to this pretreatment solution, and use 1 g of ammonia water to adjust the pH value of the mixed system to 8, then 100 g of black coating is prepared (if there is water loss during the production process, supplement a small amount of deionized water until the total mass reaches 100 g). Spread the coating evenly on the aluminized film, adjust the position of the scraper so that the coating thickness does not exceed 5 μm, then send the coated aluminized film into an oven at 180 °C and bake for 10 min, and then cool it down.

[0097] Black coating comparative example 3

[0098] Use intermediates 2a, 2b, 2c, and 2d to replace dyes A - D to prepare the black dye composition, and replace the black dye composition in black coating example 1, and the others are the same as black coating example 1.

[0099] Black coating comparative example 4

[0100] Use the one containing two bis - aziridine groups in the published patent (CN112409815B) Dyes 4, 5, and 6 are formulated into a black dye composition in a weight ratio of 10%, 5%, and 85%, and replace the black dye composition in Black Coating Example 1, with the rest being the same as in Black Coating Example 1. According to the patent (CN112409815B), the bisaziridine group is also reactive under high-temperature conditions.

[0101] (4)

[0103] (5)

[0105]

[0106] (6)。

[0107] Black Coating Comparative Example 5

[0108] Dyes 7, 8, and 9 containing two diazo groups in the patent (application number: 2023112310614) are formulated into a black dye composition in a weight ratio of 10%, 5%, and 85%, and replace the black dye composition in Black Coating Example 1, with the rest being the same as in Black Coating Example 1.

[0109] (7)

[0111] (8)

[0113] (9)

[0115] Black Coating Comparative Example 6

[0116] p-Toluenesulfonyl azide (15 mmol, 2.96 g) and 1,8-diazabicyclo[5.4.0]undec-7-ene (20 mmol, 3.05 g) were replaced with p-toluenesulfonyl azide (7.5 mmol, 1.48 g) and 1,8-diazabicyclo[5.4.0]undec-7-ene (10 mmol, 1.53 g), respectively, that is, the molar ratio of p-toluenesulfonyl azide to intermediate 2 was 1.5∶1, and the molar ratio of 1,8-diazabicyclo[5.4.0]undec-7-ene to intermediate 2a was 2∶1. Others were the same as the synthesis of dye A. Dye 10 was obtained from intermediate 2a, ESI-MS: m / z = 589 [M+H]; Dye 11 was obtained from intermediate 2b, ESI-MS: m / z = 533 [M+H]; Dye 12 was obtained from intermediate 2c, ESI-MS: m / z = 501 [M+H]; Dye 13 was obtained from intermediate 2d, ESI-MS: m / z = 685 [M+H]. Dyes 10 to 13 are all dyes containing one diazo group.

[0117] Dyes 10 to 13 were used to prepare a black dye composition instead of dyes A to D, and replaced the black dye composition in Example 1. Others were the same as in Example 1.

[0118] (10)

[0120] (11)

[0122] (12)

[0124]

[0125] (13)。

[0126] Black paint comparative example 7

[0127] In an existing technology, after a colorant, an adhesive, and a solvent are mixed and formulated into a coating, the coating is applied to an aluminized film to color the aluminized film. This technology uses a commercially available disperse dye filter cake (a hydrophobic dye) as the colorant, acrylic resin and polyurethane resin as the adhesives, and xylene and ethanol as the solvents. The specific formulation of the coating is as follows: 4% of commercially available disperse black ECT filter cake (compounded from disperse orange 288, disperse violet 93:1, disperse blue 291:3, and disperse orange 30:2), 15% of acrylic resin, 6% of polyurethane resin, 55% of xylene, and 20% of ethanol. The coating process is as follows: The coating is evenly blade-coated on the aluminized film, the position of the blade is adjusted so that the coating thickness does not exceed 5 μm, and then the colored aluminized film is sent into an oven at 180 °C and baked for 10 min, and then cooled.

[0128] Test 1. Color deviation test

[0129] Fifty black PET aluminized films obtained in Example 1 were tested using a colorimeter and compared with a standard color plate (JJG453-2002 standard color plate verification procedure) to obtain the color difference ΔE. If ΔE < 1, it is qualified.

[0130] Test 2. High-temperature steam test

[0131] Fifty 2 cm × 2 cm squares were cut from the obtained black PET aluminized films (only the finished products that were detected as qualified in Test 1 were tested, that is, if there were any unqualified products detected in Test 1, the unqualified products needed to be removed), placed in a 5 L steam pot containing 1 L of water, heated to 110 °C, and the aluminized films were subjected to high-temperature steam treatment for 30 min. Then, when the temperature dropped below 60 °C, the aluminized films were taken out. The color change (such as fading, discoloration, or blooming) of the aluminized films was checked by visual observation under a standard light source (D65, color temperature 6500K, power 18W). The aluminized films whose colors conform to the black color light on the standard color plate are qualified, and the aluminized films whose colors deviate from the black color light on the standard color plate are unqualified.

[0132] Test 3. Lightfastness test

[0133] Fifty black PET aluminized films (only the finished products that were detected as qualified in Test 1 were tested, that is, if there were any unqualified products detected in Test 1, the unqualified products needed to be removed) were exposed to sunlight under a standard xenon lamp for 24 h, and then compared with the black color light on the standard color plate under a standard light source (D65, color temperature 6500K, power 18W). The aluminized films whose colors conform to the black color light on the standard color plate are qualified, and the aluminized films whose colors deviate from the black color light on the standard color plate are unqualified.

[0134] Table 1

[0135]

[0136] The results of Examples 1 to 3 show that using the black dye composition provided by the present invention and the black coating prepared therefrom, the obtained black PET polyester film has a black color with stable quality, good reproducibility, good high-temperature steam resistance, and good lightfastness.

[0137] The result of Comparative Example 1 shows that in the coating formulation provided by the present invention, if the ultraviolet absorber is not used, the lightfastness qualification rate of the product will slightly decrease. In other words, the use of the ultraviolet absorber in the coating provided by the present invention further improves the durability of the obtained black PET polyester film.

[0138] The result of Comparative Example 2 shows that in the coating formulation provided by the present invention, if the crosslinking agent is not used, the steam resistance qualification rate of the product will slightly decrease. In other words, the use of the crosslinking agent in the coating provided by the present invention further improves the steam resistance of the obtained black PET polyester film.

[0139] The result of Comparative Example 3 shows that for the black dye composition and the corresponding black coating prepared using Intermediates 2a to 2d, the steam resistance of the obtained black PET polyester film significantly decreases. This is because these intermediates do not contain diazo groups in their structures and have no reactivity, and they are combined with adjacent substances by weak forces such as hydrogen bonds and van der Waals forces in the coating. Therefore, under high-temperature steam conditions, these dye molecules have the ability to penetrate the polymer network and migrate, resulting in a certain degree of change in the color shade. This comparative result shows that it is very necessary to introduce diazo groups into the dye molecules, which can significantly improve the color fastness of the coated film.

[0140] The result of Comparative Example 4 shows that using the reactive bisaziridine dye reported in the existing literature to prepare the black dye composition and the corresponding black coating for coating the PET polyester film, due to different dye components, the black color shade effect of the obtained black PET polyester film is very different from that of the black PET polyester film obtained by the present invention. In addition, the lightfastness of the obtained black PET polyester film is not good, and after being irradiated by strong light, the black color of most products has obvious color shade changes. This may be because the chromophores of these dyes are azo structures and their lightfastness grades are not high. Even if a small amount of ultraviolet absorber is doped in the present invention, the lightfastness cannot be significantly improved. In addition, the synthesis route of the dye used in Comparative Example 4 is long, the raw material price is expensive, and the synthesis operation is inconvenient, and the cost of using this dye is higher.

[0141] The results of Comparative Example 5 show that the black dye composition and the corresponding black coating are prepared by using a diazo dye with an azo color body, and are used to color a PET polyester film. Due to the different dye components, the black color effect of the obtained black PET polyester film is very different from that of the black PET polyester film obtained in the present invention. In addition, the light fastness of the obtained black PET polyester film is not good. After being irradiated with strong light, the black color of most products has undergone obvious color changes. This may be because these dye color bodies are azo structures, and the light fastness level itself is not high. Even if a small amount of ultraviolet absorber is doped in the present invention, its light fastness cannot be significantly improved.

[0142] The results of Comparative Example 6 show that when there is only one diazo group in the dye structure, the steam resistance test pass rate of the obtained black PET aluminum-plated film is 74%. This is because the reactivity of the dye is insufficient and it cannot completely react with the polymer network, resulting in a small amount of dye molecules permeating and migrating out of the polymer network under steaming conditions, and then the color light changes. In other words, the number of diazo groups must be more than one.

[0143] The results of Comparative Example 7 show that the PET polyester film is colored by the prior art (including non-reactive conventional dyes and conventional coatings). Firstly, due to the different dye components, the black color effect of the obtained black PET polyester film is very different from that of the black PET polyester film obtained by the present invention. Secondly, the steam resistance of the obtained black aluminized film is not good. Thirdly, the light resistance of the obtained black aluminized film is not good. In addition, the coating used in the prior art is an oily coating, which is not friendly to the environment and human health.

[0144] The test results of the above embodiments and comparative examples show that a qualified black PET aluminum-plated film can be obtained by adopting the dyeing method provided by the present invention, and the product quality is stable and durable, and the steam resistance and light resistance effects are good.

[0145] Finally, it should be noted that the above examples are only some specific embodiments of the present invention. Obviously, the present invention is not limited to the above embodiments, and there are many variations. All variations that can be directly derived or associated with the content disclosed by a person skilled in the art should be considered as the protection scope of the present invention.

Claims

1. A black dye composition, characterized in that: The black dye composition comprises dye components with the following four structures: （A） （B） （C） （D）。 2. The black dye composition according to claim 1, wherein: The weight ratios of the four dye components are as follows: Dye A 45%, Dye B 40%, Dye C 5%, and Dye D 10%.

3. A method for preparing the black dye composition according to claim 1, characterized in that: The synthesis methods of the dye components A - D include the following two steps: Step (1): The starting material reacts with phenylacetyl chloride by stirring in a dichloromethane solution containing triethylamine to form an intermediate. Step (2): The intermediate reacts with p - toluenesulfonyl azide by stirring in an acetonitrile solution containing 1,8 - diazabicyclo[5.4.0]undec - 7 - ene to form Dyes A - D. Among them, in Step (1), the molar ratio of phenylacetyl chloride to the starting material is 2.2∶1, the molar ratio of triethylamine to the starting material is 4∶1, and the amount of the dichloromethane solution is such that the molar concentration of the starting material reaches 0.1 - 0.5 mol / L; the ambient temperature for the reaction in Step (1) is 25 °C, and the reaction time is 1 h. In Step (2), the molar ratio of p - toluenesulfonyl azide to the starting material is 3∶1, the molar ratio of 1,8 - diazabicyclo[5.4.0]undec - 7 - ene to the starting material is 4∶1, and the amount of the acetonitrile solution is such that the molar concentration of the starting material reaches 0.1 - 0.5 mol / L; the ambient temperature for the reaction in Step (2) is 25 °C, and the reaction time is 24 h. The starting material corresponding to Dye A is Compound 1a, and the corresponding intermediate is 2a. （1a） （2a） The starting material corresponding to Dye B is Compound 1b, and the corresponding intermediate is 2b. （1b） （2b） The starting material corresponding to Dye C is Compound 1c, and the corresponding intermediate is 2c. （1c） （2c） The starting material corresponding to Dye D is Compound 1d, and the corresponding intermediate is 2d. （1d） （2d）。 4. A black coating, characterized in that: It contains the black dye composition as claimed in Claim 1; the raw materials with the following weight ratios: black dye composition 1% - 4%, dispersant 0.5% - 2%, defoamer 0.1%, wetting agent 0.1%, deionized water 71.3% - 77.8%, water - borne acrylic resin 8%, water - borne polyurethane resin 10%, cross - linker 1%, ultraviolet absorber 0.5%, pH regulator 1% - 3%.

5. A method for preparing the black paint according to claim 4, characterized in that: It includes the following steps; Step (1): Grind the black dye composition, dispersant, defoamer, wetting agent, ultraviolet absorber, and deionized water together according to the given weight ratios to obtain a black dye dispersion; the weight ratio of the black dye composition to the dispersant is 2:1; the grinding time is 4 h. Step (2): Add the water - borne acrylic resin, water - borne polyurethane resin, and cross - linker in the given weight ratios to the black dye dispersion obtained in Step (1), and stir evenly.

6. A method for using the black paint according to claim 4, characterized in that: The black coating is used for coloring aluminized films.

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