A method for preparing a high-flow heat-resistant ink

Abstract

The application relates to the technical field of inks, and discloses a preparation method of high-flow heat-resistant ink, the ink comprising the following raw materials: acrylamide, methacrylic acid, methacryloyloxyethyl succinate, 3-methacryloxypropyl methyl dimethoxysilane, terminal alkenyl polybutadiene, modified mica powder, sodium dodecylbenzenesulfonate, an initiator, dimethyl silicone oil, pigments, deionized water; wherein the terminal alkenyl polybutadiene is obtained by reacting gallic acid modified polybutadiene with diallylaminocarbonyl chloride; the gallic acid modified polybutadiene is obtained by reacting terminal epoxy polybutadiene with gallic acid; and the modified mica powder is obtained by modifying the surface of 1-adamantane carboxylic acid on mica powder. The prepared ink has excellent wear resistance, heat resistance, oxidation resistance and adhesion, greatly expands the use field of the ink, and has a longer service life.

Description

TECHNICAL FIELD

[0001] The present application relates to the technical field of ink, in particular to a preparation method of high-flow heat-resistant ink. BACKGROUND

[0002] In today's rapidly changing printing technology, ink as the medium connecting creativity and reality in the printing process, the optimization of its performance is directly related to the quality and application field of printed matter. With the rapid development of modern industry and technology, the demand for high-quality printed matter in the market is increasing. The performance of traditional ink has been difficult to meet the requirements of the current development. The flowability of traditional ink is generally poor, which can easily lead to poor ink transmission during printing, causing printing equipment to be blocked, affecting printing speed and quality. At the same time, the adhesion of traditional ink is not strong, which can easily fall off and crack during use, affecting the aesthetics of the printed matter and greatly shortening the service life of the printed matter. In addition, the wear resistance of traditional ink is poor, which brings difficulties to the cleaning of printed matter. Moreover, the heat resistance of traditional ink is poor, which limits its use in electronic products, automobile parts and other fields.

[0003] In order to solve the above problems, the patent with publication number CN114672192B discloses a high-flow high-adhesion gravure printing ink and a preparation method thereof. The ink includes water-based polylactic acid emulsion, inorganic pigment, thickening agent, defoaming agent, leveling agent, polyacrylamide modified zeolite powder, coupling agent and deionized water. The high-flow high-adhesion gravure printing ink is obtained by mixing and stirring. The ink has excellent flowability and adhesion, can effectively ensure the printing quality and 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 use field. SUMMARY

[0004] The present application aims to provide a preparation method of high-flow heat-resistant ink, which solves the following technical problems: (1) the poor flowability and adhesion of traditional ink, which can easily fall off during use; (2) the wear resistance and heat resistance of traditional ink need to be improved.

[0005] The purpose of the present application can be achieved by the following technical solutions:

[0006] The application discloses a preparation method of a high-flow heat-resistant ink, and 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 alkenyl polybutadiene, 8-10 parts of modified mica powder, 2-6 parts of sodium dodecylbenzenesulfonate, 3-5 parts of an initiator, 1-3 parts of dimethyl silicone oil, 3-5 parts of pigment and 20-30 parts of deionized water; the terminal alkenyl polybutadiene is obtained by reacting gallic acid modified polybutadiene with diallyl aminocarbonyl chloride under the action of a catalyst; the gallic acid modified polybutadiene is obtained by reacting terminal epoxy polybutadiene with gallic acid under the action of tetrabutylammonium bromide; and the modified mica powder is obtained by modifying the surface of 1-adamantane carboxylic acid on mica powder.

[0007] Further, the initiator is any one of benzoyl peroxide and dicumyl peroxide; and the pigment is any one of carbon black, phthalocyanine blue, iron oxide red, iron black and titanium white powder.

[0008] Further, the preparation method of the terminal alkenyl polybutadiene comprises the following steps.

[0009] S1: the terminal epoxy polybutadiene is placed in toluene, gallic acid and tetrabutylammonium bromide are added, the reaction is carried out under temperature rising, the solvent is removed by distillation under reduced pressure, and the product is collected to obtain the gallic acid modified polybutadiene;

[0010] S2: the gallic acid modified polybutadiene is placed in N,N-dimethylformamide, is fully mixed and stirred, diallyl aminocarbonyl chloride and a catalyst are added, the temperature is raised to 60-65 DEG C and the reaction is carried out for 2-3 h, the product is collected after distillation under reduced pressure, and the terminal alkenyl polybutadiene is obtained.

[0011] By the above technical scheme, the ring-opening reaction occurs between the epoxy group in the structure of the terminal epoxy polybutadiene and the carboxyl group in the structure of the gallic acid under the action of tetrabutylammonium bromide, the gallic acid modified polybutadiene is obtained, the active hydroxyl group in the structure of the gallic acid modified polybutadiene reacts with the acyl chloride group in the structure of the diallyl aminocarbonyl chloride under the action of a catalyst, and the terminal alkenyl polybutadiene is obtained. The terminal alkenyl polybutadiene structure has multiple alkenyl groups at both ends, can participate in the preparation process of the ink, can produce cross-linking reaction between the ink matrix materials, can form a network structure, can effectively enhance the compactness of the ink matrix material, can improve the high-temperature resistance of the ink, the gallic acid structure in the terminal alkenyl polybutadiene structure has a pyrogallol structure, can effectively enhance the adhesion of the ink, can prevent the ink from falling off and being damaged during use, can effectively expand the use field of the ink, and can significantly prolong the service life of the ink.

[0012] Further, in step S1, the temperature of the temperature rising reaction is 85-95℃, and the time is 3-5h.

[0013] Further, in step S2, the catalyst is triethylamine.

[0014] Further, the preparation method of the modified mica powder comprises the following steps:

[0015] The mica powder is placed in anhydrous ethanol and ultrasonically dispersed for 10-15min, 1-adamantane carboxylic acid is added, and the temperature is raised for stirring, and the product is collected after filtration, washing and drying to obtain the modified mica powder.

[0016] By the above technical solution, the hydroxyl group on the surface of the mica powder interacts with the carboxyl group in the structure of 1-adamantane carboxylic acid, and the adamantane structure is modified on the surface of the mica powder to obtain a modified mica powder coated with an adamantane structure on the surface. The modified mica powder coated with an organic substance on the surface can effectively enhance the compatibility with the ink matrix material, effectively enhance the wear resistance of the ink, and through the unique lamellar structure of the mica powder, it can effectively block high temperature and improve the high temperature resistance of the ink. The adamantane structure coated on the surface can further enhance the wear resistance and high temperature resistance of the ink, which together enhances the wear resistance and heat resistance of the ink, so that the prepared ink can meet the use requirements in various environments, greatly expanding the use field of the ink.

[0017] Further, the temperature of the temperature rising stirring is 55-60℃, the stirring speed is 300-350r / min, and the time is 5-6h.

[0018] A preparation method of a high-flow heat-resistant ink comprises the following steps:

[0019] Step one, acrylamide, methacrylic acid, methacryloyloxyethyl succinate, 3-methacryloyloxypropyl methyl dimethoxy silane, terminal alkenyl polybutadiene, modified mica powder, sodium dodecylbenzenesulfonate, initiator, and dimethyl silicone oil are mixed, the temperature is raised to 45-55℃, and the mixture is stirred for 2-3h to obtain an ink base;

[0020] Step two, pigments and deionized water are added to the ink base, and the mixture is stirred for 1-2h and then dispersed in a sand mill to obtain the ink.

[0021] By the above technical scheme, the acrylamide, methacryloyloxyethyl succinate and 3-methacryloyloxypropyl methyl dimethoxy silane all have active alkenyl groups which can have a free radical polymerization reaction with the four active alkenyl groups at both ends of the terminal alkenyl polybutadiene to form a crosslinked network structure, effectively enhancing the adhesion and heat resistance of the ink, and the modified mica powder is added to have good compatibility with the matrix, further enhancing the heat resistance of the ink, and the added sodium dodecyl benzene sulfonate can effectively enhance the compatibility between the components, and the 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 to obtain more excellent printing effect. The scheme greatly improves the printing performance and quality of the ink through the coordination between the components.

[0022] Advantages of the present application:

[0023] The present application involves the preparation of terminal alkenyl polybutadiene and modified mica powder in the preparation process of the ink, so that the prepared ink has excellent wear resistance, heat resistance, oxidation resistance and adhesion, greatly expanding the use field of the ink and making it have a longer service life.

[0024] Of course, implementing any product of the present application does not necessarily require all the advantages described above. BRIEF DESCRIPTION OF DRAWINGS

[0025] In order to more clearly illustrate the technical solutions of the embodiments of the present application, the drawings needed for the embodiment description will be briefly introduced as follows. Obviously, the drawings in the following description are only some embodiments of the present application, and those skilled in the art can obtain other drawings according to these drawings without creative labor.

[0026] Figure 1 Preparation flow chart of the ink of the present application. DETAILED DESCRIPTION

[0027] The technical solutions in the embodiments of the present application will be described clearly and completely in combination with the drawings in the embodiments of the present application. Obviously, the described embodiments are only some embodiments of the present application, not all embodiments. Based on the embodiments in the present application, all other embodiments obtained by those skilled in the art without creative labor are within the scope of protection of the present application.

[0028] The preparation methods of the terminal alkenyl polybutadiene and modified mica powder in the following embodiments and comparative examples of the present application are as follows:

[0029] I. Preparation of terminal alkenyl polybutadiene

[0030] 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, and the temperature was raised to 85°C for 3 h. The solvent was removed by distillation under reduced pressure, and the product was collected to obtain gallic acid-modified polybutadiene;

[0031] S2: 3.5 g of gallic acid-modified polybutadiene was placed in 80 ml of N,N-dimethylformamide, and mixed well with stirring. 3 g of diallyl carbamoyl chloride and 0.5 g of triethylamine were added, and the temperature was raised to 60°C for 2 h. After distillation under reduced pressure, the product was collected to obtain an end-alkenyl polybutadiene.

[0032] II. Preparation of modified mica powder

[0033] 3 g of mica powder was placed in 100 ml of anhydrous ethanol and ultrasonically dispersed for 10 min. 3.2 g of 1-adamantane carboxylic acid was added, and the temperature was raised to 55°C for 5 h with stirring at 300 r / min. After filtration, washing and drying, the product was collected to obtain a modified mica powder. Example

[0034] Preparation of ink

[0035] Step 1: 15 parts of acrylamide, 20 parts of methacrylic acid, 12 parts of methacryloyloxyethyl succinate, 5 parts of 3-methacryloxypropyl methyl dimethoxy silane, 10 parts of end-alkenyl polybutadiene, 8 parts of modified mica powder, 2 parts of sodium dodecyl benzene sulfonate, 3 parts of benzoyl peroxide, and 1 part of dimethyl silicone oil were mixed, and the temperature was raised to 45°C for 2 h with stirring to obtain an ink base;

[0036] Step 2: 3 parts of carbon black and 20 parts of deionized water were added to the ink base, and mixed well with stirring for 1 h. The product was dispersed in a sand mill to obtain an ink. Example

[0037] Preparation of ink

[0038] Step 1: 18 parts of acrylamide, 23 parts of methacrylic acid, 13 parts of methacryloyloxyethyl succinate, 5.5 parts of 3-methacryloxypropyl methyl dimethoxy silane, 11 parts of end-alkenyl polybutadiene, 9 parts of modified mica powder, 4 parts of sodium dodecyl benzene sulfonate, 4 parts of dicumyl peroxide, and 2 parts of dimethyl silicone oil were mixed, and the temperature was raised to 50°C for 2.5 h with stirring to obtain an ink base;

[0039] Step 2: 4 parts of phthalocyanine blue and 25 parts of deionized water were added to the ink base, and mixed well with stirring for 1.5 h. The product was dispersed in a sand mill to obtain an ink. Example

[0040] Preparation of ink

[0041] Step one, 20 parts of acrylamide, 25 parts of methacrylic acid, 15 parts of methacryloyloxyethyl succinate, 6 parts of 3-methacryloxypropyl methyl dimethoxy silane, 12 parts of terminal alkenyl polybutadiene, 10 parts of modified mica powder, 6 parts of sodium dodecyl benzene sulfonate, 5 parts of benzoyl peroxide, 3 parts of dimethyl silicone oil were mixed, heated to 55°C and stirred for 3h to obtain an ink base;

[0042] Step two, 5 parts of iron oxide red and 30 parts of deionized water were added to the ink base, mixed and stirred for 2h, then dispersed in a sand mill to obtain an ink.

[0043] Comparative example 1

[0044] Preparation of ink

[0045] Step one, 18 parts of acrylamide, 23 parts of methacrylic acid, 13 parts of methacryloyloxyethyl succinate, 5.5 parts of 3-methacryloxypropyl methyl dimethoxy silane, 9 parts of modified mica powder, 4 parts of sodium dodecyl benzene sulfonate, 4 parts of dicumyl peroxide, 2 parts of dimethyl silicone oil were mixed, heated to 50°C and stirred for 2.5h to obtain an ink base;

[0046] Step two, 4 parts of phthalocyanine blue and 25 parts of deionized water were added to the ink base, mixed and stirred for 1.5h, then dispersed in a sand mill to obtain an ink.

[0047] Comparative example 2

[0048] Preparation of ink

[0049] Step one, 18 parts of acrylamide, 23 parts of methacrylic acid, 13 parts of methacryloyloxyethyl succinate, 5.5 parts of 3-methacryloxypropyl methyl dimethoxy silane, 11 parts of terminal alkenyl polybutadiene, 4 parts of sodium dodecyl benzene sulfonate, 4 parts of dicumyl peroxide, 2 parts of dimethyl silicone oil were mixed, heated to 50°C and stirred for 2.5h to obtain an ink base;

[0050] Step two, 4 parts of phthalocyanine blue and 25 parts of deionized water were added to the ink base, mixed and stirred for 1.5h, then dispersed in a sand mill to obtain an ink.

[0051] Comparative example 3

[0052] Preparation of ink

[0053] Step one, 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 dodecylbenzenesulfonate, 4 parts of dicumyl peroxide, 2 parts of dimethyl silicone oil were mixed, heated to 50°C and stirred for 2.5h to obtain an ink base;

[0054] Step two, 4 parts of phthalocyanine blue and 25 parts of deionized water were added to the ink base, mixed and stirred for 1.5h, then dispersed in a sand mill to obtain an ink.

[0055] Performance test

[0056] The inks prepared in Examples 1-3 and Comparative Examples 1-3 were used as samples, and the adhesion of the samples was tested according to the standard GB / T13217.7-2023; the disc flowability of the samples was tested according to the standard GB / T14624.3-2008; the samples were scraped onto the surface of PET and dried, then baked at a temperature of 150°C for 12h, and the surface of the sample was observed for cracking, bubbling, peeling, etc. to determine the heat resistance of the sample; the abrasion resistance of the sample was tested using an abrasion tester, the sample was cut into a size of 20cm×5cm and placed on the abrasion tester, and a 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 friction frequency was 150 times, and the surface of the blank A4 paper was observed after the test to determine the surface discoloration of the sample; the specific test results are shown in the table below:

[0057]

[0058] As shown in the above table, the samples prepared in Examples 1-3 all have excellent adhesion, flowability, heat resistance and abrasion resistance. The sample prepared in Comparative Example 1 does not contain end-vinyl polybutadiene and does not form a network structure, although modified mica powder is added, the adhesion of the sample is poor, and the heat resistance and abrasion resistance are not as good as the examples. The sample prepared in Comparative Example 2 does not contain modified mica powder, the adhesion of the sample is good, but the heat resistance and abrasion resistance are not as good as the examples. The sample prepared in Comparative Example 3 directly contains gallic acid modified polybutadiene and modified mica powder, although the phloroglucinol structure enhances the adhesion of the sample, the adhesion, heat resistance and abrasion resistance are not as good as the samples in the examples.

[0059] In the description of the specification, the description of the terms "one embodiment", "some embodiments", "an example", "a specific example", or "some examples" etc. means that the specific features, structures, materials or characteristics described in connection with the embodiment or example are included in at least one embodiment or example of the present application. In the specification, the illustrative description of the above terms does not necessarily refer to the same embodiment or example. Moreover, the specific features, structures, materials or characteristics described can be combined in any appropriate manner in any one or more embodiments or examples. In addition, the person skilled in the art can combine and combine the different embodiments or examples described in the specification and the features of the different embodiments or examples without contradiction.

[0060] The above is only an example and description of the concept of the present application, and those skilled in the art can make various modifications or supplements to the described specific embodiments or adopt similar ways to replace them without departing from the scope defined by the concept of the application.

Claims

1. A process for the preparation of 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 alkenyl polybutadiene, 8-10 parts of modified mica powder, 2-6 parts of sodium dodecyl benzene sulfonate, 3-5 parts of initiator, 1-3 parts of dimethyl silicone oil, 3-5 parts of pigment, 20-30 parts of deionized water; the terminal alkenyl polybutadiene is prepared by reacting gallic acid modified polybutadiene with diallyl aminocarbonyl 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 1-adamantane carboxylic acid on mica powder.

2. A process for the preparation of a high flow heat resistant ink as claimed in claim 1, wherein, The initiator is any one of benzoyl peroxide and dicumyl peroxide; the pigment is any one of carbon black, phthalocyanine blue, iron oxide red, iron black and titanium white powder.

3. A process for preparing a high flow heat resistant ink as claimed in claim 1, wherein, The preparation method of the terminal alkenyl polybutadiene comprises the following steps: S1: placing the terminal epoxy polybutadiene in toluene, adding gallic acid and tetrabutylammonium bromide, reacting under heating, removing the solvent by distillation under reduced pressure, and collecting the product to obtain gallic acid modified polybutadiene; S2: placing the gallic acid modified polybutadiene in N,N-dimethylformamide, fully mixing and stirring, adding diallyl aminocarbonyl chloride and a catalyst, reacting under heating to 60-65 DEG C for 2-3 h, collecting the product after distillation under reduced pressure, and obtaining terminal alkenyl polybutadiene.

4. A process for preparing a high flow heat resistant ink as claimed in claim 3, wherein, In step S1, the temperature of the reaction under heating is 85-95 DEG C, and the time is 3-5 h.

5. The method of claim 3, wherein the high flow heat resistant ink is prepared by adding 0.1 to 1.0 parts by weight of the compound of formula (I) to 100 parts by weight of the base ink. 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: placing mica powder in anhydrous ethanol, ultrasonic dispersion for 10-15 min, adding 1-adamantane carboxylic acid, stirring under heating, filtering, washing, drying, and collecting the product to obtain the modified mica powder.

7. A process for preparing a high flow heat resistant ink as claimed in claim 6, wherein, The temperature of the stirring under heating is 55-60 DEG C, the stirring speed is 300-350 r / min, and the time is 5-6 h.

8. A process for preparing a high flow heat resistant ink as claimed in claim 1, wherein, comprises the following steps: Step one, mixing acrylamide, methacrylic acid, methacryloyloxyethyl succinate, 3-methacryloxypropylmethyldimethoxysilane, terminal alkenyl polybutadiene, modified mica powder, sodium dodecyl benzene sulfonate, initiator, dimethyl silicone oil, heating to 45-55 DEG C, and fully stirring for 2-3 h to obtain an ink base; Step two, adding pigment and deionized water to the ink base, fully mixing and stirring for 1-2 h, dispersing in a sand mill, and collecting the product to obtain the ink.

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