Ball-point pen ink with high and low temperature resistance and high stability and preparation method of ball-point pen ink

Abstract

The invention relates to ball-point pen ink with high and low temperature resistance and high stability and a preparation method thereof, and belongs to the technical field of ink, the ball-point pen ink comprises the following raw materials: 15-25 parts of a modified polyurethane prepolymer, 50-60 parts of a solvent, 8-10 parts of a dispersant, 3-5 parts of a plasticizer, 4-6 parts of an antioxidant and 2-4 parts of a leveling agent; according to the technical scheme, the composite material is obtained by combining a natural compound with 4-vinyl benzyl glycidyl ether; combining the composite material with a silanized pigment compound to obtain a reinforced material; mixing a reinforcing material, polyethylene glycol and isocyanate to obtain a modified polyurethane prepolymer; and mixing the modified polyurethane prepolymer, a solvent, a dispersing agent, a plasticizer, an antioxidant and a flatting agent to finally prepare the ball-point pen ink with high and low temperature resistance and high stability. The high temperature resistance, low temperature resistance, weather resistance, stability and adhesion performance of the ball-point pen ink are integrally improved, the service life of the ball-point pen ink is prolonged, and the comprehensive performance of the ball-point pen ink is good.

Description

Technical Field

[0001] The invention belongs to the technical field of inks, and in particular relates to a ballpoint pen ink with high stability and high temperature resistance and a preparation method thereof. Background Art

[0002] Ballpoint pens are popular among consumers for their clear writing, convenient use and low price. As a key component of ballpoint pens, ballpoint pen inks can be divided into oil-based inks, water-based inks and neutral inks between the two. Ballpoint pen inks are widely used in daily office, study and life scenes due to their smooth writing experience, quick drying and good water resistance. With the rapid development of modern office, industrial marking and outdoor signage, the performance requirements for ballpoint pen inks are also constantly increasing. However, traditional ballpoint pen inks have significant limitations in performance in extreme temperature environments and long-term exposure to natural conditions, which limits their use in certain special application scenarios. Therefore, it is urgent to develop a ballpoint pen ink with high and low temperature resistance and high stability.

[0003] In the prior art, the resin in traditional ballpoint pen ink is easy to soften, flow, or even decompose at high temperatures, resulting in uneven writing, blurred ink or discoloration, and becomes too viscous at low temperatures, resulting in difficulty in writing, broken lines or no ink, affecting the user experience; the pigment in traditional ballpoint pen ink is prone to oxidative degradation when exposed to ultraviolet rays, moisture and oxygen for a long time, resulting in color fading and decreased adhesion; traditional ballpoint pen ink has weak adhesion on certain substrates (such as plastics, metals, etc.), and the written text is easily erased or peeled off, so it is necessary to prepare a ballpoint pen ink with good high temperature resistance, low temperature resistance, stability and adhesion. Summary of the invention

[0004] The object of the present invention is to provide a ballpoint pen ink with high stability and high temperature resistance and a preparation method thereof. A composite material is obtained by combining a natural compound with 4-vinylbenzyl glycidyl ether; maleopimaric acid and ferulic acid not only have good binding force with 4-vinylbenzyl glycidyl ether, but also can provide reaction sites for subsequent reactions, thereby improving the stability and adhesion of polyurethane; the benzene ring structure in 4-vinylbenzyl glycidyl ether can increase the heat resistance of polyurethane and increase the binding force between natural compounds and isocyanate; the composite material is combined with a silanized pigment compound to obtain to the reinforcing material; the silanized pigment compound is prepared by combining a silane coupling agent with a pigment compound, which can not only increase the color intensity of the ink, but also enhance the stability, weather resistance and high and low temperature resistance of the ink, and can also improve the compatibility between the pigment compound and polyurethane; the reinforcing material, polyethylene glycol and isocyanate are mixed to obtain a modified polyurethane prepolymer; the modified polyurethane prepolymer, solvent, dispersant, plasticizer, antioxidant and leveling agent are mixed to finally obtain a ballpoint pen ink with high and low temperature resistance and high stability, which generally improves the comprehensive performance of the ballpoint pen ink and extends its service life.

[0005] Technical problems to be solved by the present invention: In the prior art, the resin in traditional ballpoint pen ink is easy to soften, flow, or even decompose at high temperatures, resulting in unsmooth writing, blurred ink or discoloration, and becomes too viscous at low temperatures, resulting in difficulty in writing, broken lines or no ink, affecting the user experience; the pigment in traditional ballpoint pen ink is prone to oxidative degradation when exposed to ultraviolet rays, moisture and oxygen for a long time, resulting in color fading and decreased adhesion; traditional ballpoint pen ink has weak adhesion on certain substrates (such as plastics, metals, etc.), and the written text is easily erased or peeled off, so it is necessary to prepare a ballpoint pen ink with good high temperature resistance, low temperature resistance, stability and adhesion.

[0006] The purpose of the present invention can be achieved through the following technical solutions:

[0007] A ballpoint pen ink with high and low temperature resistance and high stability, comprising the following raw materials in parts by weight: 15-25 parts of modified polyurethane prepolymer, 50-60 parts of solvent, 8-10 parts of dispersant, 3-5 parts of plasticizer, 4-6 parts of antioxidant and 2-4 parts of leveling agent;

[0008] The preparation method of the modified polyurethane prepolymer comprises the following steps:

[0009] S1: A composite material is obtained by combining a natural compound with 4-vinylbenzyl glycidyl ether;

[0010] S2: combining the composite material with the silanized pigment compound to obtain a reinforced material;

[0011] S3: Mix the reinforcing material, polyethylene glycol and isocyanate to obtain a modified polyurethane prepolymer.

[0012] Furthermore, step S1 is specifically as follows:

[0013] The natural compound is mixed with N,N-dimethylformamide, and then tetrabutylammonium bromide is added to obtain component A. 4-vinylbenzyl glycidyl ether and 4-methoxyphenol are added to N,N-dimethylformamide and mixed evenly to obtain component B. Component B is added to component A and reacted at 105-115°C for 4-6h. After the reaction is completed, it is cooled to room temperature, filtered, and then added to deionized water. After the product is precipitated and the supernatant is removed, it is vacuum dried at 40-50°C to obtain a composite material.

[0014] In the above reaction process, the natural compound has a carboxyl group and 4-vinylbenzyl glycidyl ether has an epoxy group. The carboxyl group in the natural compound can be combined with the epoxy group in 4-vinylbenzyl glycidyl ether through a ring-opening reaction, and 4-vinylbenzyl glycidyl ether is combined with the natural compound to finally obtain a composite material.

[0015] Furthermore, the mass ratio of the natural compound, N,N-dimethylformamide and tetrabutylammonium bromide is 4.5-5.5:50-60:0.1-0.2.

[0016] Furthermore, the natural compound is composed of maleopimaric acid and ferulic acid mixed in a mass ratio of 0.8-0.9:0.5-0.6.

[0017] Furthermore, the mass ratio of 4-vinylbenzyl glycidyl ether, 4-methoxyphenol, and N,N-dimethylformamide is 1.5-1.6: 0.01-0.02: 50-60.

[0018] Furthermore, the preparation method of maleopimaric acid comprises the following steps:

[0019] Abietic acid, maleic anhydride, p-toluenesulfonic acid and acetic acid are uniformly mixed, and then stirred for reaction at 180-190° C. for 1.5-2.5 hours, cooled to room temperature, and recrystallized with acetic acid at 75-85° C. to finally obtain maleopimaric acid.

[0020] In the above reaction process, the two carbon-carbon double bonds of abietic acid are conjugated to generate levorotatory pimaric acid through an isomerization reaction, levorotatory pimaric acid acts as a conjugated diene, and maleic anhydride acts as a dienophile. Levorotatory pimaric acid and maleic anhydride undergo a Diels-Alder reaction to finally obtain maleopimaric acid.

[0021] Furthermore, the mass ratio of abietic acid, maleic anhydride, p-toluenesulfonic acid and acetic acid is 19-21:6-7:0.2-0.3:30-40.

[0022] Furthermore, step S2 is specifically as follows:

[0023] The composite material in step S1 is mixed with the silanized pigment compound, and then a photoinitiator is added and stirred evenly, and then the mixture is irradiated with ultraviolet light from a mercury lamp in an ice water bath for 6-8 hours. After the irradiation, ethyl acetate is added for dilution, and the mixture is washed with deionized water and a saturated sodium chloride solution in turn, and then dried with magnesium sulfate. The ethyl acetate is removed by rotary evaporation, and finally vacuum dried at 50-60° C. to obtain a reinforced material.

[0024] In the above reaction process, the composite material has a carbon-carbon double bond, and the silylated pigment compound has a thiol group. The carbon-carbon double bond in the composite material can be combined with the thiol group in the silylated pigment compound through a thiol-ene click reaction, and the silylated pigment compound is grafted onto the composite material to finally obtain a reinforced material.

[0025] Furthermore, the mass ratio of the composite material, the silanized pigment compound, and the photoinitiator 1173 is 9-9.5:5.5-6:0.25-0.35.

[0026] Furthermore, the photoinitiator is photoinitiator 1173 or photoinitiator 651.

[0027] Furthermore, the preparation method of the silanized pigment compound comprises the following steps:

[0028] The pigment compound is added to an ethanol solution and ultrasonically treated for 25-35 minutes, then a silane coupling agent is added, and then a hydrochloric acid solution is added, and the pH value of the system is adjusted to 3.5-4.5, and the reaction is carried out at 40-50°C for 4-6 hours, filtered, washed with ethanol, and then vacuum dried at 55-65°C to finally obtain a silanized pigment compound.

[0029] During the above reaction process, the silane coupling agent is hydrolyzed to generate silanol groups. The pigment compound has hydroxyl groups. The silanol groups in the silane coupling agent can react and combine with the hydroxyl groups in the pigment compound, and the silane coupling agent is grafted onto the pigment compound to obtain a silanized pigment compound.

[0030] Furthermore, the mass ratio of the pigment compound, the ethanol solution and the silane coupling agent is 0.8-1.2:10-15:1-1.5.

[0031] Furthermore, the silane coupling agent is composed of 3-mercaptopropyltrimethoxysilane and 3-isocyanatepropyltriethoxysilane mixed in a mass ratio of 0.7-0.8:0.3-0.4.

[0032] Furthermore, the pigment compound is composed of carbon black, black iron oxide and nano silicon dioxide in a mass ratio of 0.7-0.8:0.4-0.5:0.2-0.3.

[0033] Furthermore, step S3 is specifically as follows:

[0034] The reinforcing material in step S2 and polyethylene glycol are mixed and stirred at 55-65° C. for 8-12 minutes, then isocyanate is added, the temperature is raised to 80-90° C. after mixing, and stirred for reaction for 2-4 hours under a nitrogen atmosphere, then a chain extender is added, the reaction is stirred at 55-65° C. for 0.5-1 hour, and vacuum degassing is performed for 25-35 minutes to obtain a modified polyurethane prepolymer.

[0035] In the above reaction process, both the reinforcing material and the polyethylene glycol have hydroxyl groups, and the isocyanate has isocyanate groups. The hydroxyl groups in the reinforcing material and the polyethylene glycol can combine with the isocyanate groups in the isocyanate, and the reinforcing material, the polyethylene glycol and the isocyanate are combined together to finally obtain a modified polyurethane prepolymer.

[0036] Furthermore, the mass ratio of the reinforcing material, polyethylene glycol and isocyanate is 0.3-0.4:0.9-1.1:1.4-1.6.

[0037] Furthermore, the isocyanate is a mixture of 4,4-diisocyanate dicyclohexylmethane and triphenylmethane triisocyanate in a mass ratio of 0.8-0.9:0.4-0.5.

[0038] Furthermore, the chain extender is trimethylolpropane.

[0039] A method for preparing ballpoint pen ink with high stability and high temperature resistance comprises the following steps:

[0040] Weigh the raw materials by mass, mix the modified polyurethane elastomer, solvent, dispersant, plasticizer, antioxidant and leveling agent, and stir at 30-40°C for 30-40 minutes, then add the catalyst and continue stirring for 0.5-1 hour, dry at 55-65°C for 1-2 hours, and continue drying at 80-85°C for 25-35 minutes, and finally obtain a ballpoint pen ink with high and low temperature resistance and high stability.

[0041] Furthermore, the solvent is composed of benzyl alcohol and ethylene glycol monobutyl ether mixed in a mass ratio of 2-3:1.

[0042] Furthermore, the dispersant is polyoxyethylene lauryl ether or tributyl phosphate.

[0043] Furthermore, the plasticizer is at least one of dibutyl phthalate, triethyl citrate, and epoxidized soybean oil.

[0044] Furthermore, the antioxidant is at least one of triphenyl phosphite, 2,6-di-tert-butyl-p-cresol, and butylated hydroxyanisole.

[0045] Furthermore, the leveling agent is polydimethylsiloxane or polyacrylate.

[0046] Furthermore, the catalyst is dibutyltin dilaurate.

[0047] Beneficial effects of the present invention:

[0048] (1) In the technical scheme of the present invention, a composite material is obtained by combining a natural compound with 4-vinylbenzyl glycidyl ether; the natural compound is composed of a mixture of maleopimaric acid and ferulic acid; both maleopimaric acid and ferulic acid have good biodegradability and biocompatibility, maleopimaric acid and ferulic acid not only have good binding force with 4-vinylbenzyl glycidyl ether, but also can provide reaction sites for subsequent reactions, and ferulic acid also has good antioxidant properties, further improving the stability and adhesion of polyurethane, the benzene ring structure in 4-vinylbenzyl glycidyl ether can increase the heat resistance of polyurethane, and the carbon-carbon double bond therein can also provide reaction sites for subsequent reactions, and can The bonding force between the natural compound and the isocyanate is increased; the composite material is combined with the silanized pigment compound to obtain a reinforced material; the silanized pigment compound is prepared by combining a silane coupling agent with a pigment compound, wherein the pigment compound is a mixture of carbon black, black iron oxide and nano-silicon dioxide, which can not only increase the color intensity of the ink, but also enhance the stability, weather resistance and high and low temperature resistance of the ink; the silane coupling agent can not only enhance the bonding force between the pigment compound and the natural compound, but also improve the dispersibility of the pigment compound in polyurethane, improve its compatibility with polyurethane, and further improve the mechanical properties, weather resistance, high and low temperature resistance and stability of the polyurethane.

[0049] (2) In the technical scheme of the present invention, a modified polyurethane prepolymer is obtained by mixing a reinforcing material, polyethylene glycol and isocyanate; the reinforcing material, polyethylene glycol and isocyanate have good bonding strength, which not only makes the polyurethane have good weather resistance, high and low temperature resistance and stability, but also increases the bonding strength of the polyurethane, further improving the adhesion performance of the ink; after the modified polyurethane prepolymer, solvent, dispersant, plasticizer, antioxidant and leveling agent are mixed, a ballpoint pen ink with high and low temperature resistance and high stability is finally prepared, and the modified polyurethane prepolymer has better improved the high temperature resistance, low temperature resistance, weather resistance, stability and adhesion of the ballpoint pen ink.

[0050] (3) In the technical scheme of the present invention, a natural compound is combined with 4-vinylbenzyl glycidyl ether, then combined with a silanized pigment compound, and then mixed with polyethylene glycol and isocyanate to obtain a modified polyurethane prepolymer; the modified polyurethane prepolymer, solvent, dispersant, plasticizer, antioxidant and leveling agent are mixed to finally obtain a ballpoint pen ink with high and low temperature resistance and high stability; the weather resistance, high temperature resistance, low temperature resistance, stability and adhesion performance of the ballpoint pen ink are improved as a whole, and its service life is extended, and the overall comprehensive performance is good. DETAILED DESCRIPTION

[0051] The following will be combined with 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.

[0052] The specific parameters of the raw materials used in the present invention are as follows:

[0053] Ferulic acid, CAS No.: 1135-24-6, provided by Shanghai Aladdin Biochemical Technology Co., Ltd.; 4-vinylbenzyl glycidyl ether, CAS No.: 113538-80-0, provided by Shanghai Bid Pharmaceutical Technology Co., Ltd.; carbon black, CAS No.: 1333-86-4, product No.: C914875, particle size of 100nm, provided by Shanghai McLean Biochemical Technology Co., Ltd.; iron oxide black, CAS No.: 1317-61-9, product No.: I861679, particle size of 100nm, provided by Shanghai McLean Biochemical Technology Co., Ltd.; nano-silica, particle size of 100nm, provided by Luoyang Tongrun Nanotechnology Co., Ltd.; triphenylmethane triisocyanate, CAS: 2422-91-5, provided by Shanghai Yien Chemical Technology Co., Ltd.; 4,4-diisocyanate dicyclohexylmethane, CAS No.: 5124-30-1, provided by Shanghai McLean Biochemical Technology Co., Ltd.

[0054] Example 1

[0055] Preparation of ballpoint pen ink with high stability and high temperature resistance, the specific steps are:

[0056] S1: According to the mass ratio of natural compound, N,N-dimethylformamide and tetrabutylammonium bromide being 4.5:50:0.1, the natural compound and N,N-dimethylformamide are mixed, and then tetrabutylammonium bromide is added to obtain component A. According to the mass ratio of 4-vinylbenzyl glycidyl ether, 4-methoxyphenol and N,N-dimethylformamide being 1.5:0.01:50, 4-vinylbenzyl glycidyl ether and 4-methoxyphenol are added to N,N-dimethylformamide, and mixed evenly. The components B are mixed to obtain component B, and the mass ratio of component B to component A is 2:1. Component B is added to component A, and the mixture is reacted at 105°C for 4 hours. After the reaction is completed, the mixture is cooled to room temperature, filtered, and then added into deionized water (the mass of deionized water is equal to that of N,N-dimethylformamide). After the product is precipitated and the supernatant is removed, the mixture is vacuum dried at 40°C for 24 hours to obtain a composite material, wherein the natural compound is composed of maleopimaric acid and ferulic acid mixed at a mass ratio of 0.8:0.5.

[0057] The preparation method of maleopimaric acid comprises the following steps:

[0058] According to the mass ratio of abietic acid, maleic anhydride, p-toluenesulfonic acid and acetic acid being 19:6:0.2:30, abietic acid, maleic anhydride, p-toluenesulfonic acid and acetic acid are uniformly mixed, and then stirred for reaction at 180°C for 1.5 hours, cooled to room temperature, and recrystallized with acetic acid at 75°C for 3 times (the mass of acetic acid each time is equal to the mass of the above acetic acid), and finally maleopimaric acid is obtained;

[0059] S2: According to the mass ratio of composite material, silanized pigment compound and photoinitiator 1173 being 9:5.5:0.25, the composite material in step S1 is mixed with the silanized pigment compound, and then the photoinitiator 1173 is added and stirred evenly, and then the mixture is irradiated with ultraviolet light of a mercury lamp for 6 hours in an ice water bath at 0°C (the power of the mercury lamp is 50W). After the irradiation, ethyl acetate is added for dilution (the mass of ethyl acetate is 3 times the mass of the composite material), and the mixture is washed with deionized water and saturated sodium chloride solution for 3 times each (the mass of deionized water each time is 2 times the mass of the composite material, and the mass of the saturated sodium chloride solution each time is 1.5 times the mass of the composite material), and then dried with magnesium sulfate, and the ethyl acetate is removed by rotary evaporation, and finally vacuum dried at 50°C for 24 hours to obtain a reinforced material;

[0060] Wherein, the preparation method of the silanized pigment compound comprises the following steps:

[0061] According to the mass ratio of the pigment compound, the ethanol solution and the silane coupling agent being 0.8:10:1, the pigment compound is added to a 20wt% ethanol solution and ultrasonically treated for 25 minutes (ultrasonic power is 100W, ultrasonic frequency is 40kHz), then the silane coupling agent is added, and then a 1mol / L hydrochloric acid solution is added, and the pH value of the system is adjusted to 3.5, and the mixture is reacted at 40°C for 4 hours, filtered, washed with ethanol 3 times (the mass of ethanol each time is 10 times the mass of the pigment compound), and then vacuum dried at 55°C for 3 hours to finally obtain a silanized pigment compound, wherein the silane coupling agent is composed of 3-mercaptopropyltrimethoxysilane and 3-isocyanatepropyltriethoxysilane mixed in a mass ratio of 0.7:0.3; the pigment compound is composed of carbon black, black iron oxide and nano-silicon dioxide mixed in a mass ratio of 0.7:0.4:0.2;

[0062] S3: According to the mass ratio of reinforcing material, polyethylene glycol and isocyanate being 0.3:0.9:1.4, the reinforcing material and polyethylene glycol in step S2 are mixed, and stirred at 55°C for 8 minutes, and then isocyanate is added, and the temperature is raised to 80°C after mixing, and stirred for reaction for 2 hours under a nitrogen atmosphere, and then trimethylolpropane (the mass of trimethylolpropane is 5% of the mass of polyethylene glycol) is added, and the reaction is stirred at 55°C for 0.5 hours, and vacuum degassing is carried out for 25 minutes to obtain a modified polyurethane prepolymer, wherein the isocyanate is composed of 4,4-diisocyanate dicyclohexylmethane and triphenylmethane triisocyanate mixed in a mass ratio of 0.8:0.4;

[0063] A ballpoint pen ink with high and low temperature resistance and high stability, comprising the following raw materials in parts by weight: 15 parts of modified polyurethane prepolymer, 50 parts of solvent, 8 parts of polyoxyethylene lauryl ether, 3 parts of dibutyl phthalate, 4 parts of triphenyl phosphite and 2 parts of polydimethylsiloxane;

[0064] The preparation method comprises the following steps:

[0065] Weigh the raw materials by mass, mix the modified polyurethane elastomer, solvent, polyoxyethylene lauryl ether, dibutyl phthalate, triphenyl phosphite and polydimethylsiloxane, and stir at 30°C at a speed of 500 rpm for 40 minutes, then add dibutyl tin dilaurate (the mass of dibutyl tin dilaurate is 0.5% of the mass of the modified polyurethane elastomer), and continue stirring for 0.5 hours, dry at 55°C for 1 hour, and continue drying at 80°C for 25 minutes, and finally obtain a ballpoint pen ink with high and low temperature resistance and high stability, wherein the solvent is a mixture of benzyl alcohol and ethylene glycol monobutyl ether in a mass ratio of 2:1.

[0066] Example 2

[0067] Preparation of ballpoint pen ink with high stability and high temperature resistance, the specific steps are:

[0068] S1: According to the mass ratio of natural compound, N,N-dimethylformamide and tetrabutylammonium bromide being 5:55:0.15, the natural compound is mixed with N,N-dimethylformamide, and then tetrabutylammonium bromide is added to obtain component A. According to the mass ratio of 4-vinylbenzyl glycidyl ether, 4-methoxyphenol and N,N-dimethylformamide being 1.55:0.015:55, 4-vinylbenzyl glycidyl ether and 4-methoxyphenol are added to N,N-dimethylformamide and mixed evenly. The components B are mixed to obtain component B, and the mass ratio of component B to component A is 2:1. Component B is added to component A, and the mixture is reacted at 110°C for 5 hours. After the reaction is completed, the mixture is cooled to room temperature, filtered, and then added into deionized water (the mass of deionized water is equal to that of N,N-dimethylformamide). After the product is precipitated and the supernatant is removed, the mixture is vacuum dried at 45°C for 24 hours to obtain a composite material, wherein the natural compound is composed of maleopimaric acid and ferulic acid mixed at a mass ratio of 0.85:0.55.

[0069] The preparation method of maleopimaric acid comprises the following steps:

[0070] According to the mass ratio of abietic acid, maleic anhydride, p-toluenesulfonic acid and acetic acid being 20:6.5:0.25:35, abietic acid, maleic anhydride, p-toluenesulfonic acid and acetic acid are uniformly mixed, and then stirred for reaction at 185° C. for 2 hours, cooled to room temperature, and recrystallized with acetic acid at 80° C. for 3 times (the mass of acetic acid each time is equal to the mass of the above acetic acid), and finally maleopimaric acid is obtained;

[0071] S2: According to the mass ratio of composite material, silanized pigment compound and photoinitiator 651 being 9.3:5.8:0.3, the composite material in step S1 is mixed with the silanized pigment compound, and then the photoinitiator 651 is added and stirred evenly, and then the mixture is irradiated with ultraviolet light of a mercury lamp for 7 hours in an ice water bath at 2°C (the power of the mercury lamp is 50W). After the irradiation, ethyl acetate is added for dilution (the mass of ethyl acetate is 3 times the mass of the composite material), and the mixture is washed with deionized water and saturated sodium chloride solution for 3 times each (the mass of deionized water each time is 2 times the mass of the composite material, and the mass of the saturated sodium chloride solution each time is 1.5 times the mass of the composite material), and then dried with magnesium sulfate, and the ethyl acetate is removed by rotary evaporation, and finally vacuum dried at 55°C for 24 hours to obtain a reinforced material;

[0072] Wherein, the preparation method of the silanized pigment compound comprises the following steps:

[0073] According to the mass ratio of pigment compound, ethanol solution and silane coupling agent being 1:12:1.3, the pigment compound is added to 20wt% ethanol solution and ultrasonically treated for 30min (ultrasonic power is 100W, ultrasonic frequency is 40kHz), then the silane coupling agent is added, and then 1mol / L hydrochloric acid solution is added, and the pH value of the system is adjusted to 4, and the mixture is reacted at 45°C for 5h, filtered, washed with ethanol 3 times (the mass of ethanol each time is 10 times the mass of the pigment compound), and then vacuum dried at 60°C for 4h to finally obtain a silylated pigment compound, wherein the silane coupling agent is composed of 3-mercaptopropyltrimethoxysilane and 3-isocyanatepropyltriethoxysilane mixed in a mass ratio of 0.75:0.35; the pigment compound is composed of carbon black, black iron oxide and nano silicon dioxide mixed in a mass ratio of 0.75:0.45:0.25;

[0074] S3: According to the mass ratio of reinforcing material, polyethylene glycol and isocyanate being 0.35:1:1.5, the reinforcing material and polyethylene glycol in step S2 are mixed, and stirred at 60°C for 10 minutes, and then isocyanate is added, and the temperature is raised to 85°C after mixing, and stirred for reaction for 3 hours under a nitrogen atmosphere, and then trimethylolpropane (the mass of trimethylolpropane is 5% of the mass of polyethylene glycol) is added, and the reaction is stirred at 60°C for 0.8 hours, and vacuum degassing is performed for 30 minutes to obtain a modified polyurethane prepolymer, wherein the isocyanate is composed of 4,4-diisocyanate dicyclohexylmethane and triphenylmethane triisocyanate mixed in a mass ratio of 0.85:0.45;

[0075] A ballpoint pen ink with high and low temperature resistance and high stability, comprising the following raw materials in parts by weight: 20 parts of modified polyurethane prepolymer, 55 parts of solvent, 9 parts of tributyl phosphate, 4 parts of triethyl citrate, 5 parts of 2,6-di-tert-butyl-p-cresol and 3 parts of polyacrylate;

[0076] The preparation method comprises the following steps:

[0077] Weigh the raw materials by mass, mix the modified polyurethane elastomer, solvent, tributyl phosphate, triethyl citrate, 2,6-di-tert-butyl-p-cresol and polyacrylate, and stir at 35°C at a speed of 600 rpm for 35 minutes, then add dibutyltin dilaurate (the mass of dibutyltin dilaurate is 0.5% of the mass of the modified polyurethane elastomer), and continue stirring for 0.8 hours, dry at 60°C for 1.5 hours, and continue drying at 82°C for 30 minutes, and finally obtain a ballpoint pen ink with high and low temperature resistance and high stability, wherein the solvent is a mixture of benzyl alcohol and ethylene glycol monobutyl ether in a mass ratio of 2.5:1.

[0078] Example 3

[0079] Preparation of ballpoint pen ink with high stability and high temperature resistance, the specific steps are:

[0080] S1: According to the mass ratio of natural compound, N,N-dimethylformamide and tetrabutylammonium bromide of 5.5:60:0.2, the natural compound and N,N-dimethylformamide are mixed, and then tetrabutylammonium bromide is added to obtain component A. According to the mass ratio of 4-vinylbenzyl glycidyl ether, 4-methoxyphenol and N,N-dimethylformamide of 1.6:0.02:60, 4-vinylbenzyl glycidyl ether and 4-methoxyphenol are added to N,N-dimethylformamide, and mixed evenly. The components B are mixed to obtain component B, and the mass ratio of component B to component A is 2:1. Component B is added to component A, and the mixture is reacted at 115°C for 6 hours. After the reaction is completed, the mixture is cooled to room temperature, filtered, and then added into deionized water (the mass of deionized water is equal to that of N,N-dimethylformamide). After the product is precipitated and the supernatant is removed, the mixture is vacuum dried at 50°C for 24 hours to obtain a composite material, wherein the natural compound is composed of maleopimaric acid and ferulic acid mixed at a mass ratio of 0.9:0.6;

[0081] The preparation method of maleopimaric acid comprises the following steps:

[0082] According to the mass ratio of abietic acid, maleic anhydride, p-toluenesulfonic acid and acetic acid being 21:7:0.3:40, abietic acid, maleic anhydride, p-toluenesulfonic acid and acetic acid are uniformly mixed, and then stirred for reaction at 190° C. for 2.5 hours, cooled to room temperature, and recrystallized with acetic acid at 85° C. for 3 times (the mass of acetic acid each time is equal to the mass of the above acetic acid), and finally maleopimaric acid is obtained;

[0083] S2: According to the mass ratio of the composite material, the silanized pigment compound and the photoinitiator 1173 being 9.5:6:0.35, the composite material in step S1 is mixed with the silanized pigment compound, and the photoinitiator 1173 is added, and stirred evenly, and then the mixture is irradiated with ultraviolet light of a mercury lamp for 8 hours in an ice water bath at 4°C (the power of the mercury lamp is 50W). After the irradiation, ethyl acetate is added for dilution (the mass of ethyl acetate is 3 times the mass of the composite material), and the mixture is washed with deionized water and saturated sodium chloride solution for 3 times each (the mass of deionized water each time is 2 times the mass of the composite material, and the mass of the saturated sodium chloride solution each time is 1.5 times the mass of the composite material), and then dried with magnesium sulfate, and the ethyl acetate is removed by rotary evaporation, and finally vacuum dried at 60°C for 24 hours to obtain a reinforced material;

[0084] Wherein, the preparation method of the silanized pigment compound comprises the following steps:

[0085] According to the mass ratio of the pigment compound, the ethanol solution and the silane coupling agent being 1.2:15:1.5, the pigment compound is added to a 20wt% ethanol solution and ultrasonically treated for 35 minutes (ultrasonic power is 100W, ultrasonic frequency is 40kHz), then the silane coupling agent is added, and then a 1mol / L hydrochloric acid solution is added, and the pH value of the system is adjusted to 4.5, and the mixture is reacted at 50°C for 6 hours, filtered, washed with ethanol 3 times (the mass of ethanol each time is 10 times the mass of the pigment compound), and then vacuum dried at 65°C for 5 hours to finally obtain a silanized pigment compound, wherein the silane coupling agent is composed of 3-mercaptopropyltrimethoxysilane and 3-isocyanatepropyltriethoxysilane mixed in a mass ratio of 0.8:0.4; the pigment compound is composed of carbon black, black iron oxide and nano-silicon dioxide mixed in a mass ratio of 0.8:0.5:0.3;

[0086] S3: According to the mass ratio of reinforcing material, polyethylene glycol and isocyanate being 0.4:1.1:1.6, the reinforcing material and polyethylene glycol in step S2 are mixed, and stirred at 65°C for 12 minutes, and then isocyanate is added, and the temperature is raised to 90°C after mixing, and stirred for reaction for 4 hours under a nitrogen atmosphere, and then trimethylolpropane (the mass of trimethylolpropane is 5% of the mass of polyethylene glycol) is added, and the reaction is stirred at 65°C for 1 hour, and vacuum degassing is performed for 35 minutes to obtain a modified polyurethane prepolymer, wherein the isocyanate is composed of 4,4-diisocyanate dicyclohexylmethane and triphenylmethane triisocyanate mixed in a mass ratio of 0.9:0.5;

[0087] A ballpoint pen ink with high and low temperature resistance and high stability, comprising the following raw materials in parts by weight: 25 parts of modified polyurethane prepolymer, 60 parts of solvent, 10 parts of polyoxyethylene lauryl ether, 5 parts of epoxy soybean oil, 6 parts of butylated hydroxyanisole and 4 parts of polydimethylsiloxane;

[0088] The preparation method comprises the following steps:

[0089] Weigh the raw materials by mass, mix the modified polyurethane elastomer, solvent, polyoxyethylene lauryl ether, epoxy soybean oil, butyl hydroxyanisole and polydimethylsiloxane, and stir at 40°C at a speed of 700 rpm for 30 minutes, then add dibutyltin dilaurate (the mass of dibutyltin dilaurate is 0.5% of the mass of the modified polyurethane elastomer), and continue stirring for 1 hour, dry at 65°C for 2 hours, and continue drying at 85°C for 35 minutes, and finally obtain a ballpoint pen ink with high and low temperature resistance and high stability, wherein the solvent is a mixture of benzyl alcohol and ethylene glycol monobutyl ether in a mass ratio of 3:1.

[0090] Comparative Example 1

[0091] The difference between this comparative example and Example 3 is that when preparing the ballpoint pen ink with high stability and high temperature resistance, the natural compound in step S1 is replaced by maleopimaric acid, and the remaining steps and raw materials are the same as those in Example 3;

[0092] S1: Maleopimaric acid and N,N-dimethylformamide were mixed in a mass ratio of 5.5:60:0.2, and tetrabutylammonium bromide was added to obtain component A. 4-vinylbenzyl glycidyl ether, 4-methoxyphenol and N,N-dimethylformamide were added in a mass ratio of 1.6:0.02:60 to N,N-dimethylformamide, and the mixture was uniformly mixed to obtain component B. Component B was added to component A in a mass ratio of 2:1 to component A, and the mixture was reacted at 115°C for 6h. After the reaction was completed, the mixture was cooled to room temperature, filtered, and added to deionized water (the mass of deionized water was equal to the mass of N,N-dimethylformamide). The product was precipitated and the supernatant was removed, and then vacuum dried at 50°C for 24h to obtain a composite material.

[0093] Comparative Example 2

[0094] The difference between this comparative example and Example 3 is that when preparing the ballpoint pen ink with high stability and high temperature resistance, the mass of the natural compound in step S1 is replaced by ferulic acid, and the remaining steps and raw materials are synchronized with Example 3;

[0095] S1: According to the mass ratio of ferulic acid, N,N-dimethylformamide and tetrabutylammonium bromide being 5.5:60:0.2, ferulic acid and N,N-dimethylformamide are mixed, and tetrabutylammonium bromide is added to obtain component A. According to the mass ratio of 4-vinylbenzyl glycidyl ether, 4-methoxyphenol and N,N-dimethylformamide being 1.6:0.02:60, 4-vinylbenzyl glycidyl ether and 4-methoxyphenol are added to N,N-dimethylformamide and mixed evenly to obtain component B. According to the mass ratio of component B to component A being 2:1, component B is added to component A, and the mixture is reacted at 115°C for 6h. After the reaction is completed, the mixture is cooled to room temperature, filtered, and then added into deionized water (the mass of deionized water is equal to the mass of N,N-dimethylformamide). After the product is precipitated and the supernatant is removed, the mixture is vacuum dried at 50°C for 24h to obtain a composite material.

[0096] Comparative Example 3

[0097] The difference between this comparative example and Example 3 is that when preparing the ballpoint pen ink with high and low temperature resistance and high stability, the mass of 4-vinylbenzyl glycidyl ether in step S1 is replaced by glycidyl methacrylate, and the remaining steps and raw materials are synchronized with Example 3;

[0098] S1: According to the mass ratio of natural compound, N,N-dimethylformamide and tetrabutylammonium bromide being 5.5:60:0.2, the natural compound is mixed with N,N-dimethylformamide, and then tetrabutylammonium bromide is added to obtain component A. According to the mass ratio of glycidyl methacrylate, 4-methoxyphenol and N,N-dimethylformamide being 1.6:0.02:60, glycidyl methacrylate and 4-methoxyphenol are added to N,N-dimethylformamide and mixed evenly. Component B is obtained, and component B is added to component A according to a mass ratio of component B to component A of 2:1, and the reaction is carried out at 115°C for 6 hours. After the reaction is completed, it is cooled to room temperature, filtered, and then added into deionized water (the mass of deionized water is equal to the mass of N,N-dimethylformamide), the product is precipitated and the supernatant is removed, and then vacuum dried at 50°C for 24 hours to obtain a composite material, wherein the natural compound is composed of maleopimaric acid and ferulic acid mixed in a mass ratio of 0.9:0.6.

[0099] Comparative Example 4

[0100] The difference between this comparative example and Example 3 is that when preparing the ballpoint pen ink with high stability and high temperature resistance, the composite material and the silanized pigment compound in step S2 are directly mixed, and the remaining steps and raw materials are synchronized with Example 3;

[0101] S2: According to the mass ratio of the composite material to the silanized pigment compound being 9.5:6, the composite material in step S1 is mixed with the silanized pigment compound, stirred evenly, and finally vacuum dried at 60° C. for 24 hours to obtain a reinforced material.

[0102] Comparative Example 5

[0103] The difference between this comparative example and Example 3 is that when preparing the ballpoint pen ink with high stability and high temperature resistance, the pigment compound in step S2 is composed of a mixture of carbon black and nano-silicon dioxide, and the remaining steps and raw materials are the same as those in Example 3;

[0104] The preparation method of the silanized pigment compound comprises the following steps:

[0105] According to the mass ratio of pigment compound, ethanol solution and silane coupling agent of 1.2:15:1.5, the pigment compound is added to 20wt% ethanol solution and ultrasonically treated for 35min (ultrasonic power of 100W, ultrasonic frequency of 40kHz), then the silane coupling agent is added, and then 1mol / L hydrochloric acid solution is added, and the pH value of the system is adjusted to 4.5, and the reaction is carried out at 50°C for 6h, filtered, washed with ethanol 3 times (the mass of ethanol each time is 10 times the mass of the pigment compound), and then vacuum dried at 65°C for 5h to finally obtain a silylated pigment compound, wherein the silane coupling agent is composed of 3-mercaptopropyltrimethoxysilane and 3-isocyanatepropyltriethoxysilane mixed in a mass ratio of 0.8:0.4; the pigment compound is composed of carbon black and nano-silicon dioxide mixed in a mass ratio of 1.3:0.3.

[0106] Comparative Example 6

[0107] The difference between this comparative example and Example 3 is that when preparing the ballpoint pen ink with high and low temperature resistance and high stability, the pigment compound in step S2 is composed of a mixture of black iron oxide and nano silicon dioxide, and the remaining steps and raw materials are the same as those in Example 3;

[0108] The preparation method of the silanized pigment compound comprises the following steps:

[0109] According to the mass ratio of pigment compound, ethanol solution and silane coupling agent of 1.2:15:1.5, the pigment compound is added to 20wt% ethanol solution and ultrasonically treated for 35min (ultrasonic power of 100W, ultrasonic frequency of 40kHz), then the silane coupling agent is added, and then 1mol / L hydrochloric acid solution is added, and the pH value of the system is adjusted to 4.5, and the reaction is carried out at 50°C for 6h, filtered, washed with ethanol 3 times (the mass of ethanol each time is 10 times the mass of the pigment compound), and then vacuum dried at 65°C for 5h to finally obtain a silylated pigment compound, wherein the silane coupling agent is composed of 3-mercaptopropyltrimethoxysilane and 3-isocyanatepropyltriethoxysilane mixed in a mass ratio of 0.8:0.4; the pigment compound is composed of black iron oxide and nano silicon dioxide mixed in a mass ratio of 1.3:0.3.

[0110] Comparative Example 7

[0111] The difference between this comparative example and Example 3 is that when preparing the ballpoint pen ink with high stability and high temperature resistance, the pigment compound in step S2 is composed of a mixture of carbon black and black iron oxide, and the remaining steps and raw materials are the same as those in Example 3;

[0112] The preparation method of the silanized pigment compound comprises the following steps:

[0113] According to the mass ratio of pigment compound, ethanol solution and silane coupling agent of 1.2:15:1.5, the pigment compound is added to 20wt% ethanol solution and ultrasonically treated for 35min (ultrasonic power of 100W, ultrasonic frequency of 40kHz), then the silane coupling agent is added, and then 1mol / L hydrochloric acid solution is added, and the pH value of the system is adjusted to 4.5, and the reaction is carried out at 50°C for 6h, filtered, washed with ethanol 3 times (the mass of ethanol each time is 10 times the mass of the pigment compound), and then vacuum dried at 65°C for 5h to finally obtain a silylated pigment compound, wherein the silane coupling agent is composed of 3-mercaptopropyltrimethoxysilane and 3-isocyanatepropyltriethoxysilane mixed in a mass ratio of 0.8:0.4; the pigment compound is composed of carbon black and iron oxide black mixed in a mass ratio of 0.8:0.8.

[0114] The high temperature resistance, low temperature resistance, stability and writing performance tests are now conducted on the ballpoint pen inks with high and low temperature resistance and high stability prepared in Examples 1-3 and Comparative Examples 1-7; High temperature resistance test: a section of diffusion graded writing test paper is cut off, and the same text is written on the paper using the ballpoint pen inks with high and low temperature resistance and high stability prepared in Examples 1-3 and Comparative Examples 1-7, and then placed in boiling water at 100°C, immersed and boiled for 5 minutes, then taken out, dried naturally, and compared with the comparison color standard to observe whether the handwriting fades and diffuses, and whether the traces are clear. If the handwriting does not fade and diffuse, and the traces are clearly visible, the high temperature resistance is good; Low temperature resistance test: The embodiment 1-3 and Comparative Examples 1-7 are placed in a boiling water at 100°C, and the writing is written on the paper. The writing is written on the paper. The writing is written on the paper. The writing is written on the paper. The writing is written on the paper. The ballpoint pen ink with high and low temperature resistance and high stability prepared in Example 1-3 and Comparative Example 1-7 is used to print black text with the same font and size on the same printing paper with a printer, and four copies are printed respectively. The ink writing is allowed to dry completely, and placed in the freezer of Hualing BCD-205W refrigerator, and other items are emptied. It is frozen for 24 hours at 1, 2, 3, and 4 levels respectively, and then curled after being taken out, and then hit with a hammer with the same force. The crease is observed under a microscope to see if the surface of the writing changes color, becomes hard and brittle, and breaks after being hit. If the surface of the writing does not change color, become hard and brittle, and does not break or breaks slightly after being hit, the low temperature resistance is good; Stability test: According to GB / T 26714-2019 stability test, test method: the high and low temperature resistant and high stability ballpoint pen ink prepared in Examples 1-3 and Comparative Examples 1-7 are divided into 10 500ml ground-mouth bottles, placed in a constant temperature box at (60±2℃) for 10 days, taken out and naturally cooled, placed in a refrigerator at -20℃ for 3 days, and immediately observed under a microscope after taking out to see if there is agglomeration, flocculation, floating oil, or stratification. Immediately after observation, the refill is made to see if the ink is normal, whether the handwriting has obvious line breaks or fades, and then the viscosity is tested. The difference with the viscosity before high and low temperature damage is within 5% to be qualified;

[0115] Writing performance test:

[0116] 1) Low-temperature writing performance test: The high-low temperature resistant and high-stability ballpoint pen inks prepared in Examples 1-3 and Comparative Examples 1-7 were made into pen refills, and one refill with normal initial stroke was taken from each of them. After being covered with a sheath, it was placed horizontally in a low-temperature storage box at -20°C for 240 hours. After that, the sheath was removed in a -20°C environment. The quantitative specification of GB / T 12654-2008 was 70g / m 2 Draw a line on the writing paper to check whether the ink is flowing normally. The low-temperature writing performance is determined according to the following conditions: if the ink flows normally within 100mm, the low-temperature writing performance is qualified; if the ink flows abnormally within 100mm, the low-temperature writing performance is unqualified;

[0117] 2) High temperature writing performance test: The high and low temperature resistant and high stability ballpoint pen inks prepared in Examples 1-3 and Comparative Examples 1-7 were made into pen refills, and one refill with normal initial stroke was taken from each of them. After being covered with a sheath, it was placed horizontally in a high temperature storage box at 60°C for 240 hours. After that, the sheath was removed at 60°C. The quantitative specification of GB / T 12654-2008 was 70g / m 2 Draw a line on the writing paper to check whether the ink is flowing out normally. The low-temperature writing performance is determined according to the following conditions: if the ink is flowing out normally within 100mm, the low-temperature writing performance is qualified; if the ink is flowing out abnormally within 100mm, the low-temperature writing performance is unqualified.

[0118] The test results are shown in Table 1 below:

[0119] Table 1 Performance parameters of ballpoint pen inks with high and low temperature resistance and high stability prepared in Examples 1-3 and Comparative Examples 1-7

[0120]

[0121] It can be seen from the data in Table 1 above that, by comparing Comparative Examples 1-3 with Example 3, it can be seen that the natural compound in step S1 is replaced by maleopimaric acid or ferulic acid, or the 4-vinylbenzyl glycidyl ether in step S1 is replaced by glycidyl methacrylate to prepare a ballpoint pen ink with high and low temperature resistance and high stability. The test results are worse than those in Example 3, indicating that the natural compound composed of a mixture of maleopimaric acid and ferulic acid not only has a good antioxidant effect, but also has a good binding force with 4-vinylbenzyl glycidyl ether, thereby improving the stability and adhesion of the polyurethane; the benzene ring structure in 4-vinylbenzyl glycidyl ether can increase the heat resistance of the polyurethane, and can increase the binding force between the natural compound and the isocyanate, further improving the stability, high temperature resistance, low temperature resistance and writing performance of the ballpoint pen ink;

[0122] By comparing Comparative Examples 4-7 with Example 3, it can be seen that the composite material in step S2 is directly mixed with the silanized pigment compound, or the pigment compound is composed of a mixture of carbon black and nano-silicon dioxide, or the pigment compound is composed of a mixture of black iron oxide and nano-silicon dioxide, or the pigment compound is composed of a mixture of carbon black and black iron oxide to prepare a ballpoint pen ink with high and low temperature resistance and high stability. The test results are worse than those of Example 3, indicating that combining the composite material with the silanized pigment compound through a thiol-ene click reaction can better disperse the pigment compound, improve the compatibility between the pigment compound and polyurethane, and improve the weather resistance and stability of the polyurethane; the pigment compound composed of a mixture of carbon black, black iron oxide and nano-silicon dioxide has good color intensity, and improves the stability, weather resistance and high and low temperature resistance of the ink, further improving the high temperature resistance, low temperature resistance, stability and writing performance of the ballpoint pen ink.

[0123] As can be seen from Table 1 above, the ballpoint pen ink with high and low temperature resistance and high stability prepared in Examples 1-3 is compared with the ballpoint pen ink with high and low temperature resistance and high stability prepared in Comparative Examples 1-7. The natural compound is combined with 4-vinylbenzyl glycidyl ether, and then combined with a silanized pigment compound, and then mixed with polyethylene glycol and isocyanate to obtain a modified polyurethane prepolymer; the modified polyurethane prepolymer, solvent, dispersant, plasticizer, antioxidant and leveling agent are mixed to finally obtain a ballpoint pen ink with high and low temperature resistance and high stability, which meets the test performance requirements, while the ballpoint pen ink with high and low temperature resistance and high stability prepared in Comparative Examples 1-7 does not meet the performance requirements. The ballpoint pen ink with high and low temperature resistance and high stability prepared by the present invention not only has good high temperature resistance, low temperature resistance, stability, weather resistance and adhesion performance, but also has good writing performance and a long service life, and its comprehensive performance is good.

[0124] In the description of the specification, the description with reference to the terms "one embodiment", "example", "specific example", 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 representation 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 one or more embodiments or examples in a suitable manner.

[0125] The above contents are merely examples and explanations of the present invention. Those skilled in the art 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 invention or exceed the scope defined by the claims, they shall all fall within the protection scope of the present invention.

Claims

1. A ballpoint pen ink with high stability and high temperature resistance, characterized in that: The method comprises the following raw materials in parts by weight: 15-25 parts of modified polyurethane prepolymer, 50-60 parts of solvent, 8-10 parts of dispersant, 3-5 parts of plasticizer, 4-6 parts of antioxidant and 2-4 parts of leveling agent; The preparation method of the modified polyurethane prepolymer comprises the following steps: S1: A composite material is obtained by combining a natural compound with 4-vinylbenzyl glycidyl ether; S2: combining the composite material with the silanized pigment compound to obtain a reinforced material; S3: Mix the reinforcing material, polyethylene glycol and isocyanate to obtain a modified polyurethane prepolymer.

2. The ballpoint pen ink with high stability and high temperature resistance according to claim 1, characterized in that: Step S1 is specifically as follows: The natural compound is mixed with N,N-dimethylformamide, and then tetrabutylammonium bromide is added to obtain component A. 4-vinylbenzyl glycidyl ether and 4-methoxyphenol are added to N,N-dimethylformamide and mixed evenly to obtain component B. Component B is added to component A and reacted at 105-115°C for 4-6h. After the reaction is completed, it is cooled to room temperature, filtered, and then added to deionized water. After the product is precipitated and the supernatant is removed, it is vacuum dried at 40-50°C to obtain a composite material.

3. The ballpoint pen ink with high stability and high temperature resistance according to claim 2, characterized in that: The natural compound is composed of maleopimaric acid and ferulic acid mixed in a mass ratio of 0.8-0.9:0.5-0.

6.

4. The ballpoint pen ink with high stability and high temperature resistance according to claim 1, characterized in that: Step S2 is specifically as follows: The composite material in step S1 is mixed with the silanized pigment compound, and then a photoinitiator is added and stirred evenly, and then the mixture is irradiated with ultraviolet light from a mercury lamp in an ice water bath for 6-8 hours. After the irradiation, ethyl acetate is added for dilution, and the mixture is washed with deionized water and a saturated sodium chloride solution in turn, and then dried with magnesium sulfate. The ethyl acetate is removed by rotary evaporation, and finally vacuum dried at 50-60° C. to obtain a reinforced material.

5. The ballpoint pen ink with high stability and high temperature resistance according to claim 4, characterized in that: The preparation method of the silanized pigment composite comprises the following steps: The pigment compound is added to an ethanol solution and ultrasonically treated for 25-35 minutes, then a silane coupling agent is added, and then a hydrochloric acid solution is added, and the pH value of the system is adjusted to 3.5-4.5, and the reaction is carried out at 40-50°C for 4-6 hours, filtered, washed with ethanol, and then vacuum dried at 55-65°C to finally obtain a silanized pigment compound.

6. The ballpoint pen ink with high stability and high temperature resistance according to claim 5, characterized in that: The silane coupling agent is composed of 3-mercaptopropyltrimethoxysilane and 3-isocyanatepropyltriethoxysilane mixed in a mass ratio of 0.7-0.8:0.3-0.

4.

7. The ballpoint pen ink with high stability and high temperature resistance according to claim 5, characterized in that: The pigment compound is composed of carbon black, black iron oxide and nano silicon dioxide mixed in a mass ratio of 0.7-0.8:0.4-0.5:0.2-0.

3.

8. The ballpoint pen ink with high stability and high temperature resistance according to claim 1, characterized in that: Step S3 is specifically as follows: The reinforcing material in step S2 and polyethylene glycol are mixed and stirred at 55-65° C. for 8-12 minutes, then isocyanate is added, the temperature is raised to 80-90° C. after mixing, and stirred for reaction for 2-4 hours under a nitrogen atmosphere, then a chain extender is added, the reaction is stirred at 55-65° C. for 0.5-1 hour, and vacuum degassing is performed for 25-35 minutes to obtain a modified polyurethane prepolymer.

9. The ballpoint pen ink with high stability and high temperature resistance according to claim 1, characterized in that: The solvent is composed of benzyl alcohol and ethylene glycol monobutyl ether mixed in a mass ratio of 2-3:

1.

10. A method for preparing a ballpoint pen ink having high stability and high temperature resistance according to any one of claims 1 to 9, characterized in that: The following steps are involved: Weigh the raw materials by mass, mix the modified polyurethane elastomer, solvent, dispersant, plasticizer, antioxidant and leveling agent, and stir at 30-40°C for 30-40 minutes, then add the catalyst and continue stirring for 0.5-1 hour, dry at 55-65°C for 1-2 hours, and continue drying at 80-85°C for 25-35 minutes, and finally obtain a ballpoint pen ink with high and low temperature resistance and high stability.

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