Preparation method of high-flowability heat-resistant ink

Abstract

The invention relates to the technical field of ink, and discloses a preparation method of high-flowability heat-resistant ink. The ink is prepared from the following raw materials: acrylamide, methacrylic acid, methacryloyloxyethyl succinate, 3-methacryloxypropyl methyl dimethoxy silane, alkenyl-terminated polybutadiene, modified mica powder, sodium dodecyl benzene sulfonate, an initiator, dimethyl silicone oil, pigment and deionized water. Wherein the alkenyl-terminated polybutadiene is prepared by carrying out a reaction on gallic acid modified polybutadiene and diallyl carbamoyl chloride; the gallic acid modified polybutadiene is prepared from epoxy-terminated polybutadiene and gallic acid through a reaction; the modified mica powder is prepared by modifying the surface of mica powder with 1-adamantanecarboxylic acid. The ink prepared by the invention has excellent wear resistance, heat resistance, oxidation resistance and adhesive force, the application field of the ink is greatly expanded, and the ink has longer service life.

Description

Technical Field

[0001] The invention relates to the technical field of inks, and in particular to a method for preparing a high-fluidity heat-resistant ink. Background Art

[0002] In today's world where printing technology is changing with each passing day, ink, as a medium connecting creativity and reality in the printing process, has its performance optimization directly related to the quality and application areas of printed products. With the rapid development of modern industry and technology, the market demand for high-quality printed products is growing, and the performance of traditional inks can no longer meet the requirements of current development. The fluidity of traditional inks is average, which can easily lead to poor ink transmission during the printing process, causing blockage of printing equipment, affecting printing speed and quality. At the same time, traditional inks have weak adhesion and are prone to fall off and cracking during use, affecting the aesthetics of printed products and greatly shortening the service life of printed products. Secondly, traditional inks have poor wear resistance, which makes it difficult to clean printed products. In addition, traditional inks have poor heat resistance and are difficult to maintain stable performance in high temperature environments, limiting their use in electronic products, automotive parts and other fields.

[0003] In order to solve the above problems, the patent with publication number CN114672192B discloses a high-fluidity and high-adhesion gravure printing ink and a preparation method thereof. The ink includes an aqueous polylactic acid emulsion, an inorganic pigment, a thickener, a defoaming agent, a leveling agent, a polyacrylamide-modified zeolite powder, a coupling agent and deionized water. The high-fluidity and high-adhesion gravure printing ink is obtained by mixing and stirring. The ink has excellent fluidity and adhesion, can effectively ensure the printing quality, is not easy to fall off and has good durability. However, the wear resistance and heat resistance of the ink need to be further improved, which limits the field of use. Summary of the invention

[0004] The purpose of the present invention is to provide a method for preparing a high-flow heat-resistant ink, which solves the following technical problems: (1) the problem that traditional inks have poor fluidity and adhesion and are easy to fall off during use; (2) the problem that the heat resistance and wear resistance of traditional inks need to be improved.

[0005] The purpose of the present invention can be achieved through the following technical solutions: A method for preparing a high-flow heat-resistant ink, the ink comprising the following raw materials in parts by weight: 15-20 parts of acrylamide, 20-25 parts of methacrylic acid, 12-15 parts of methacryloyloxyethyl succinate, 5-6 parts of 3-methacryloxypropylmethyldimethoxysilane, 10-12 parts of terminal olefin polybutadiene, 8-10 parts of modified mica powder, 2-6 parts of sodium dodecylbenzene sulfonate, 3-5 parts of initiator, 1-3 parts of dimethyl silicone oil, 3-5 parts of pigment, and 20-30 parts of deionized water; the terminal olefin polybutadiene is prepared by reacting gallic acid-modified polybutadiene with diallylcarbamoyl chloride under the action of a catalyst; the gallic acid-modified polybutadiene is prepared by reacting terminal epoxy polybutadiene with gallic acid under the action of tetrabutylammonium bromide; the modified mica powder is prepared by modifying the surface of mica powder with 1-adamantanecarboxylic acid.

[0006] Furthermore, the initiator is any one of benzoyl peroxide and diisopropylbenzene peroxide; the pigment is any one of carbon black, phthalocyanine blue, red iron oxide, iron black, and titanium dioxide.

[0007] Furthermore, the preparation method of the terminal olefin polybutadiene comprises the following steps: S1: placing epoxy-terminated polybutadiene in toluene, adding gallic acid and tetrabutylammonium bromide, heating to react, removing the solvent by distillation under reduced pressure, and collecting the product to obtain gallic acid-modified polybutadiene; S2: Place gallic acid modified polybutadiene in N,N-dimethylformamide, mix and stir thoroughly, add diallylcarbamoyl chloride and a catalyst, raise the temperature to 60-65°C and react for 2-3h, collect the product after reduced pressure distillation, and obtain terminal olefin polybutadiene.

[0008] Through the above technical scheme, under the action of tetrabutylammonium bromide, the epoxy group in the terminal epoxy polybutadiene structure and the carboxyl group in the gallic acid structure undergo a ring-opening reaction to obtain gallic acid-modified polybutadiene, and then under the action of a catalyst, the active hydroxyl group in the gallic acid-modified polybutadiene structure reacts with the acyl chloride group in the diallylcarbamoyl chloride structure to obtain terminal olefinic polybutadiene. The terminal olefinic polybutadiene structure has multiple olefinic groups at both ends, which can participate in the preparation process of the ink, and produce a cross-linking reaction between the ink matrix material to form a network structure, effectively enhancing the density of the ink matrix material, thereby improving the high temperature resistance of the ink, and at the same time, the gallic acid structure in the terminal olefinic polybutadiene structure has a pyrogallol structure, which can effectively enhance the adhesion of the ink, so that the ink is not easy to fall off and break during use, effectively expanding the use field of the ink, and significantly extending the service life of the ink.

[0009] Furthermore, in step S1, the temperature of the temperature-raising reaction is 85-95° C. and the time is 3-5 hours.

[0010] Furthermore, in step S2, the catalyst is triethylamine.

[0011] Furthermore, the preparation method of the modified mica powder comprises the following steps: The mica powder is placed in anhydrous ethanol, ultrasonically dispersed for 10-15 minutes, 1-adamantanecarboxylic acid is added, the temperature is raised and stirred, and the product is collected after filtering, washing, and drying to obtain modified mica powder.

[0012] Through the above technical scheme, the hydroxyl groups on the surface of the mica powder interact with the carboxyl groups in the 1-adamantanecarboxylic acid structure, and the adamantane structure is modified on the surface of the mica powder to obtain a modified mica powder whose surface is coated with the adamantane structure. The surface of the modified mica powder is coated with organic matter, which can effectively enhance the compatibility with the ink matrix material and the wear resistance of the ink. The unique lamellar structure of the mica powder can effectively block high temperature and improve the high temperature resistance of the ink. At the same time, the adamantane structure coated on its surface can further enhance the wear resistance and high temperature resistance of the ink, and jointly enhance the wear resistance and heat resistance of the ink, so that the prepared ink can meet the use requirements in a variety of environments, greatly expanding the use field of the ink.

[0013] Furthermore, the temperature of the heating and stirring is 55-60°C, the stirring speed is 300-350r / min, and the time is 5-6h.

[0014] A method for preparing a high-flow heat-resistant ink comprises the following steps: Step 1: Mix acrylamide, methacrylic acid, methacryloyloxyethyl succinate, 3-methacryloxypropylmethyldimethoxysilane, terminal olefin polybutadiene, modified mica powder, sodium dodecylbenzene sulfonate, initiator, and dimethyl silicone oil, heat to 45-55° C., and stir for 2-3 hours to obtain an ink base material; Step 2: Add pigment and deionized water to the ink base, mix and stir thoroughly for 1-2 hours, then disperse in a sand mill, and collect the product to obtain ink.

[0015] Through the above technical scheme, acrylamide, methacryloyloxyethyl succinate, and 3-methacryloxypropylmethyldimethoxysilane all have active alkenyl groups that can undergo free radical polymerization reaction with the four active alkenyl groups at both ends of terminal alkenyl polybutadiene to form a cross-linked network structure, which effectively enhances the adhesion and heat resistance of the ink. At the same time, the modified mica powder is added, which has good compatibility with the matrix, further enhances the heat resistance of the ink, and improves the wear resistance. In addition, the added sodium dodecylbenzene sulfonate can effectively enhance the compatibility between the components. At the same time, dimethyl silicone oil is used as a leveling agent to enhance the fluidity of the ink, so that it can adapt to different printing methods and substrates, and obtain a more excellent printing effect. This scheme greatly improves the printing performance and quality of the ink through the coordination between the components.

[0016] Beneficial effects of the present invention: The present invention prepares terminal olefin polybutadiene and modified mica powder and participates in the preparation process of ink, so that the prepared ink has excellent wear resistance, heat resistance, oxidation resistance and adhesion, greatly expands the application field of ink, and makes it have a longer service life.

[0017] Of course, any product implementing the present invention does not necessarily need to achieve all of the advantages described above at the same time. BRIEF DESCRIPTION OF THE DRAWINGS

[0018] In order to more clearly illustrate the technical solutions of the embodiments of the present invention, the accompanying drawings required for describing the embodiments will be briefly introduced below. Obviously, the accompanying drawings described below are only some embodiments of the present invention. For ordinary technicians in this field, other accompanying drawings can be obtained based on these accompanying drawings without paying creative work.

[0019] Figure 1 The figure is a flow chart of the preparation of the ink of the present invention. DETAILED DESCRIPTION

[0020] The following will be combined with the drawings in the embodiments of the present invention to clearly and completely describe the technical solutions in the embodiments of the present invention. Obviously, the described embodiments are only part of the embodiments of the present invention, not all of the embodiments. Based on the embodiments of the present invention, all other embodiments obtained by ordinary technicians in this field without creative work are within the scope of protection of the present invention.

[0021] The preparation methods of terminal olefin polybutadiene and modified mica powder in the following examples and comparative examples of the present invention are as follows: 1. Preparation of terminal olefin polybutadiene S1: 3 g of epoxy-terminated polybutadiene was placed in 60 ml of toluene, 2.8 g of gallic acid and 0.2 g of tetrabutylammonium bromide were added, the temperature was raised to 85°C for reaction for 3 h, the solvent was removed by vacuum distillation, and the product was collected to obtain gallic acid-modified polybutadiene; S2: 3.5 g of gallic acid-modified polybutadiene was placed in 80 ml of N,N-dimethylformamide, and the mixture was thoroughly mixed and stirred. 3 g of diallylcarbamoyl chloride and 0.5 g of triethylamine were added, and the mixture was heated to 60°C for reaction for 2 h. The product was collected after reduced pressure distillation to obtain terminal olefin polybutadiene.

[0022] 2. Preparation of modified mica powder 3 g of mica powder was placed in 100 ml of anhydrous ethanol, and ultrasonically dispersed for 10 min. 3.2 g of 1-adamantanecarboxylic acid was added, and the temperature was raised to 55° C., and the mixture was stirred at a speed of 300 r / min for 5 h. The product was collected after filtration, washing, and drying to obtain modified mica powder. Example

[0023] Ink preparation Step 1: 15 parts of acrylamide, 20 parts of methacrylic acid, 12 parts of methacryloyloxyethyl succinate, 5 parts of 3-methacryloxypropylmethyldimethoxysilane, 10 parts of terminal olefin polybutadiene, 8 parts of modified mica powder, 2 parts of sodium dodecylbenzene sulfonate, 3 parts of benzoyl peroxide, and 1 part of dimethyl silicone oil were mixed, heated to 45° C. and stirred for 2 hours to obtain an ink base; Step 2: Add 3 parts of carbon black and 20 parts of deionized water to the ink base material, mix and stir thoroughly for 1 hour, then disperse in a sand mill, and collect the product to obtain ink. Example

[0024] Ink preparation Step 1: 18 parts of acrylamide, 23 parts of methacrylic acid, 13 parts of methacryloyloxyethyl succinate, 5.5 parts of 3-methacryloxypropylmethyldimethoxysilane, 11 parts of terminal olefin polybutadiene, 9 parts of modified mica powder, 4 parts of sodium dodecylbenzene sulfonate, 4 parts of diisopropyl peroxide, and 2 parts of dimethyl silicone oil were mixed, heated to 50° C. and stirred for 2.5 hours to obtain an ink base material; Step 2: Add 4 parts of phthalocyanine blue and 25 parts of deionized water to the ink base material, mix and stir thoroughly for 1.5 hours, then disperse in a sand mill, and collect the product to obtain ink. Example

[0025] Ink preparation Step 1: Mix 20 parts of acrylamide, 25 parts of methacrylic acid, 15 parts of methacryloyloxyethyl succinate, 6 parts of 3-methacryloxypropylmethyldimethoxysilane, 12 parts of terminal olefin polybutadiene, 10 parts of modified mica powder, 6 parts of sodium dodecylbenzene sulfonate, 5 parts of benzoyl peroxide, and 3 parts of dimethyl silicone oil, heat to 55° C. and stir for 3 hours to obtain an ink base; Step 2: Add 5 parts of red iron oxide and 30 parts of deionized water to the ink base material, mix and stir thoroughly for 2 hours, then disperse in a sand mill, and collect the product to obtain ink.

[0026] Comparative Example 1 Ink preparation Step 1: 18 parts of acrylamide, 23 parts of methacrylic acid, 13 parts of methacryloyloxyethyl succinate, 5.5 parts of 3-methacryloxypropylmethyldimethoxysilane, 9 parts of modified mica powder, 4 parts of sodium dodecylbenzene sulfonate, 4 parts of diisopropyl peroxide, and 2 parts of dimethyl silicone oil were mixed, heated to 50° C. and stirred for 2.5 hours to obtain an ink base material; Step 2: Add 4 parts of phthalocyanine blue and 25 parts of deionized water to the ink base material, mix and stir thoroughly for 1.5 hours, then disperse in a sand mill, and collect the product to obtain ink.

[0027] Comparative Example 2 Ink preparation Step 1: 18 parts of acrylamide, 23 parts of methacrylic acid, 13 parts of methacryloyloxyethyl succinate, 5.5 parts of 3-methacryloxypropylmethyldimethoxysilane, 11 parts of terminal olefin polybutadiene, 4 parts of sodium dodecylbenzene sulfonate, 4 parts of diisopropyl peroxide, and 2 parts of dimethyl silicone oil were mixed, heated to 50° C. and stirred for 2.5 hours to obtain an ink base material; Step 2: Add 4 parts of phthalocyanine blue and 25 parts of deionized water to the ink base material, mix and stir thoroughly for 1.5 hours, then disperse in a sand mill, and collect the product to obtain ink.

[0028] Comparative Example 3 Ink preparation Step 1: 18 parts of acrylamide, 23 parts of methacrylic acid, 13 parts of methacryloyloxyethyl succinate, 5.5 parts of 3-methacryloxypropylmethyldimethoxysilane, 11 parts of gallic acid modified polybutadiene, 9 parts of modified mica powder, 4 parts of sodium dodecylbenzene sulfonate, 4 parts of diisopropyl peroxide, and 2 parts of dimethyl silicone oil were mixed, heated to 50° C. and stirred for 2.5 hours to obtain an ink base material; Step 2: Add 4 parts of phthalocyanine blue and 25 parts of deionized water to the ink base material, mix and stir thoroughly for 1.5 hours, then disperse in a sand mill, and collect the product to obtain ink.

[0029] Performance Testing The inks prepared in Examples 1 to 3 and Comparative Examples 1 to 3 were used as samples, and the adhesion fastness of the samples was tested with reference to the standard GB / T13217.7-2023; the disc flowability of the samples was tested with reference to the standard GB / T14624.3-2008; the samples were scraped onto the PET surface and dried, and then baked at 150°C for 12 hours to observe whether there were cracks, bubbling, shedding and other phenomena on the surface of the samples, and to judge the heat resistance of the samples; the samples were tested for wear resistance using a friction tester, and the samples were cut into a size of 20cm×5cm and fixed on the anti-wear instrument, and blank A4 paper was cut into a size of 20cm×5cm and fixed on the friction slider, the pressure was set to 5 pounds, and the number of frictions was 150 times. After the test was completed, the floating color on the surface of the blank A4 paper was observed to judge the discoloration of the sample surface; the specific test results are shown in the table below:

[0030] It can be seen from the above table that the samples prepared in Examples 1 to 3 all have excellent adhesion, fluidity, heat resistance and wear resistance. In the sample prepared in Comparative Example 1, no terminal olefin polybutadiene is added, and no network structure is formed. Although modified mica powder is added therein, the adhesion of the sample is poor, and the heat resistance and wear resistance are not as good as those in the embodiment. In the sample prepared in Comparative Example 2, no modified mica powder is added. The adhesion of the sample is good, but the heat resistance and wear resistance are not as good as those in the embodiment. In the sample prepared in Comparative Example 3, gallic acid-modified polybutadiene and modified mica powder are directly added. Although the pyrogallol structure enhances the adhesion of the sample, since no cross-linked network structure is formed, the adhesion, heat resistance and wear resistance are not as good as those of the samples in the embodiment.

[0031] In the description of this specification, the description with reference to the terms "one embodiment", "some embodiments", "example", "specific example", or "some examples" etc. means that the specific features, structures, materials or characteristics described in conjunction with the embodiment or example are included in at least one embodiment or example of the present invention. In this specification, the schematic representations of the above terms do not necessarily refer to the same embodiment or example. Moreover, the specific features, structures, materials or characteristics described may be combined in any one or more embodiments or examples in a suitable manner. In addition, those skilled in the art may combine and combine the different embodiments or examples described in this specification and the features of the different embodiments or examples, without contradiction.

[0032] The above contents are merely examples and explanations of the concept of the present invention. The technicians in this technical field may make various modifications or additions to the specific embodiments described or replace them in a similar manner. As long as they do not deviate from the scope defined by the concept of the invention, they should all fall within the protection scope of the present invention.

Claims

1. A method for preparing a high-flow heat-resistant ink, characterized in that: The ink comprises the following raw materials in parts by weight: 15-20 parts of acrylamide, 20-25 parts of methacrylic acid, 12-15 parts of methacryloyloxyethyl succinate, 5-6 parts of 3-methacryloxypropylmethyldimethoxysilane, 10-12 parts of terminal olefin polybutadiene, 8-10 parts of modified mica powder, 2-6 parts of sodium dodecylbenzene sulfonate, 3-5 parts of initiator, 1-3 parts of dimethyl silicone oil, 3-5 parts of pigment, and 20-30 parts of deionized water; the terminal olefin polybutadiene is prepared by reacting gallic acid modified polybutadiene with diallylcarbamoyl chloride under the action of a catalyst; the gallic acid modified polybutadiene is prepared by reacting terminal epoxy polybutadiene with gallic acid under the action of tetrabutylammonium bromide; and the modified mica powder is prepared by modifying the surface of mica powder with 1-adamantanecarboxylic acid.

2. The method for preparing a high-flow heat-resistant ink according to claim 1, characterized in that: The initiator is any one of benzoyl peroxide and dicumyl peroxide; the pigment is any one of carbon black, phthalocyanine blue, red iron oxide, iron black and titanium dioxide.

3. The method for preparing a high-flow heat-resistant ink according to claim 1, characterized in that: The preparation method of the terminal olefin-based polybutadiene comprises the following steps: S1: placing epoxy-terminated polybutadiene in toluene, adding gallic acid and tetrabutylammonium bromide, heating to react, removing the solvent by distillation under reduced pressure, and collecting the product to obtain gallic acid-modified polybutadiene; S2: Place gallic acid modified polybutadiene in N,N-dimethylformamide, mix and stir thoroughly, add diallylcarbamoyl chloride and a catalyst, raise the temperature to 60-65°C and react for 2-3h, collect the product after reduced pressure distillation, and obtain terminal olefin polybutadiene.

4. The method for preparing a high-flow heat-resistant ink according to claim 3, characterized in that: In step S1, the temperature of the temperature-raising reaction is 85-95° C. and the time is 3-5 hours.

5. The method for preparing a high-flow heat-resistant ink according to claim 3, characterized in that: In step S2, the catalyst is triethylamine.

6. The method for preparing a high-flow heat-resistant ink according to claim 1, characterized in that: The preparation method of the modified mica powder comprises the following steps: The mica powder is placed in anhydrous ethanol, ultrasonically dispersed for 10-15 minutes, 1-adamantanecarboxylic acid is added, the temperature is raised and stirred, and the product is collected after filtering, washing, and drying to obtain modified mica powder.

7. The method for preparing a high-flow heat-resistant ink according to claim 6, characterized in that: The temperature of the heating and stirring is 55-60°C, the stirring speed is 300-350r / min, and the time is 5-6h.

8. The method for preparing a high-flow heat-resistant ink according to claim 1, characterized in that: The following steps are involved: Step 1: Mix acrylamide, methacrylic acid, methacryloyloxyethyl succinate, 3-methacryloxypropylmethyldimethoxysilane, terminal olefin polybutadiene, modified mica powder, sodium dodecylbenzene sulfonate, initiator, and dimethyl silicone oil, heat to 45-55° C., and stir for 2-3 hours to obtain an ink base material; Step 2: Add pigment and deionized water to the ink base, mix and stir thoroughly for 1-2 hours, then disperse in a sand mill, and collect the product to obtain ink.

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