A kind of high adhesion UV ink and preparation method thereof

Abstract

The invention discloses a high-adhesion UV ink and a preparation method thereof. The UV ink comprises the following raw materials in parts by weight: 50-60 parts of a modified resin, 40-50 parts of a modified monomer, 8-10 parts of a color paste and 5-10 parts of a photoinitiator. The modified resin contains a disulfide bond in its molecular structure, which is a dynamic covalent bond. During the curing process of the UV ink, the disulfide bond promotes the rearrangement of a cross-linked network through bond exchange, thereby dissipating the curing shrinkage stress of the system, thereby achieving an effect of increasing adhesion. The modified resin molecule contains a rigid group, which can reduce the double bond density and reduce volume shrinkage by cooperating with a methylphenyl silicone resin molecule of a side chain. The modified monomer contains a plurality of spirocyclic structures, which can generate volume expansion when the UV ink is cured, and the volume shrinkage generated is offset. The modified monomer contains a long-chain alkyl group, which can move into a gap to offset the volume shrinkage generated during light curing, thereby greatly improving the adhesion effect.

Description

Technical Field

[0001] The invention relates to the technical field of UV ink preparation, and in particular to a high-adhesion UV ink and a preparation method thereof. Background Art

[0002] UV ink refers to the ink that uses ultraviolet light of different wavelengths and energies to polymerize the monomers in the ink binder into polymers under ultraviolet light, so that the ink forms a film and dries. UV curing ink technology refers to the modern printing technology formed by integrating inkjet print heads, printing devices, light curing systems and light curing inks. It combines the advantages of UV curing ink and inkjet printing technology, and has both the economic and technical advantages of UV curing inks and the convenience of inkjet printing technology in use and operation. These advantages include: no volatile organic compounds; low energy consumption; fast curing; suitable for a variety of substrates; no clogging of the nozzle; constant ink composition; good printing quality; excellent comprehensive performance, etc. However, due to the limited adhesion of UV ink, it causes the problem of shedding and discoloration, which affects normal use. Summary of the invention

[0003] The purpose of the present invention is to provide a high-adhesion UV ink and a preparation method thereof, which solves the problem that the current UV ink has low adhesion and low hardness.

[0004] The purpose of the present invention can be achieved through the following technical solutions:

[0005] A method for preparing high-adhesion UV ink specifically comprises the following steps:

[0006] Step A1: isophorone diisocyanate, dibutyltin dilaurate and acetone are mixed uniformly, stirred for 15-20 minutes at a speed of 120-150 r / min and a temperature of 45-50° C., heated to 60-70° C., polyethylene glycol is added, reacted for 3-5 hours, castor oil is added, reacted for 3-5 hours, cystine is added, reacted for 2-3 hours, hydroxypropyl acrylate is added, reacted for 4-5 hours, and a pretreated resin is obtained; the pretreated resin, KH550, dicyclohexylcarbodiimide and DMF are mixed uniformly, reacted for 4-6 hours at a speed of 120-150 r / min and a temperature of 30-40° C., and a reinforced resin is obtained;

[0007] Step A2: Mix the reinforcing resin, methyltrimethoxysilane, dimethyldimethoxysilane, phenyltrimethoxysilane and ethanol, stir and add hydrochloric acid and deionized water at a speed of 120-150r / min and a temperature of 60-65°C, react for 3-5h, distill off the ethanol and deionized water, raise the temperature to 120-130°C, and keep warm for 1-1.5h to obtain a modified resin, weigh the following raw materials in parts by weight: 50-60 parts of modified resin, 40-50 parts of modified monomer, 8-10 parts of color paste and 5-10 parts of photoinitiator, mix the raw materials evenly, and obtain a high-adhesion UV ink.

[0008] Furthermore, the molar ratio of isophorone diisocyanate, polyethylene glycol, castor oil, cystine and hydroxypropyl acrylate in step A1 is 10:5:1:2:3.5, the amount of dibutyltin dilaurate is 1‰ of the sum of the mass of isophorone diisocyanate, polyethylene glycol, castor oil, cystine and hydroxypropyl acrylate, and the molar ratio of carboxyl, KH550 and dicyclohexylcarbodiimide on the pretreated resin is 1:1:1.2.

[0009] Furthermore, the mass ratio of the reinforcing resin, methyltrimethoxysilane, dimethyldimethoxysilane and phenyltrimethoxysilane described in step A2 is 15:3:6:2, and the amount of hydrochloric acid used is 1% of the total mass of methyltrimethoxysilane, dimethyldimethoxysilane and phenyltrimethoxysilane.

[0010] Further, the modified monomer comprises the following steps:

[0011] Step B1: (3-aminopropyl)dimethylethoxysilane, phthalic anhydride and acetonitrile are mixed, and the mixture is refluxed for 1-1.5 hours at a speed of 120-150 r / min and a temperature of 81-83° C., and the acetonitrile is distilled off, and deionized water is added, and the mixture is stirred for 3-5 minutes to obtain intermediate 1. Intermediate 1, n-butyl lithium and hexane are mixed, and the mixture is stirred for 1-1.5 hours at a speed of 120-150 r / min and a temperature of 25-30° C., and hexamethylcyclotrisiloxane is added to react for 5-7 hours, and diphenylchlorosilane is added to react for 10-15 hours, and the pH is adjusted to be neutral to obtain intermediate 2;

[0012] Step B2: Mix intermediate 2, hydrazine hydrate and ethanol, and reflux for reaction at a speed of 120-150 r / min and a temperature of 78-80° C. for 10-15 h, and adjust the pH value to 8-9 to obtain intermediate 3; mix intermediate 3, 1,2-epoxydodecane and DMF evenly, and react for 3-5 h at a speed of 120-150 r / min, a temperature of 50-60° C. and a pH value of 10-11 to obtain intermediate 4;

[0013] Step B3: terephthalaldehyde, pentaerythritol and isopropanol are mixed evenly, nitrogen is introduced for protection, p-toluenesulfonic acid monohydrate is added under stirring at a speed of 60-80 r / min and a temperature of 25-30° C., and the reaction is carried out for 10-15 hours, and then intermediate 4 is added, and the reaction is continued for 3-5 hours, and sodium bicarbonate is added, and the stirring treatment is carried out for 30-40 minutes to obtain intermediate 5, and intermediate 5, propenol and DMF are mixed evenly, and chloroplatinic acid is added under stirring at a speed of 150-200 r / min and a temperature of 50-60° C., and the reaction is carried out for 10-15 hours, and then acrylic acid and p-toluenesulfonic acid are added, and the temperature is raised to 110-120° C. and the reaction is carried out for 8-10 hours to obtain a modified monomer.

[0014] Furthermore, the amount ratio of (3-aminopropyl)dimethylethoxysilane, phthalic anhydride and deionized water in step B1 is 8mmo l:8mmo l:15mL, and the amount ratio of intermediate 1, n-butyl lithium, hexamethylcyclotrisiloxane and diphenylchlorosilane is 5mmo l:1.8mL:50mmo l:10mmo l.

[0015] Furthermore, the usage ratio of the intermediate 2, hydrazine hydrate and ethanol in step B2 is 1.5 g:2 mL:50 mL, and the molar ratio of the amino group on the intermediate 3 to 1,2-epoxydodecane is 1:2.

[0016] Furthermore, the molar ratio of terephthalaldehyde, pentaerythritol and intermediate 4 described in step B3 is 2:1:2, the amount of p-toluenesulfonic acid monohydrate is 5% of the mass of terephthalaldehyde, the amount of sodium bicarbonate is 3% of the mass of terephthalaldehyde, the molar ratio of Si-H bonds on intermediate 5, acrylol and acrylic acid is 1:1:1, the amount of chloroplatinic acid is 1‰ of the mass of acrylol, and the amount of p-toluenesulfonic acid is 2% of the mass of acrylic acid.

[0017] The beneficial effects of the present invention are as follows: a high-adhesion UV ink prepared by the present invention comprises the following raw materials: modified resin, modified monomer, color paste and photoinitiator; the modified resin is prepared by first reacting isophorone diisocyanate with polyethylene glycol, then reacting with castor oil to form a branched structure, then reacting with cystine, and finally end-capping with hydroxypropyl acrylate to obtain a pre-treated resin; the pre-treated resin and KH550 are subjected to the action of dicyclohexylcarbodiimide to make a dehydration reaction between the carboxyl group on the pre-treated resin and the amino group on the KH550 to obtain a reinforced resin; the reinforced resin, methyltrimethoxysilane, dimethyldimethoxysilane and phenyltrimethoxysilane are hydrolyzed and polymerized to form methylphenyl silicone resin molecules on the side chains of the reinforced resin to obtain a modified resin.

[0018] The modified monomer uses (3-aminopropyl)dimethylethoxysilane as a raw material and phthalic anhydride as a raw material for reaction protection, and then hydrolyzes to form silanol to obtain intermediate 1, ring-opening polymerization of hexamethylcyclotrisiloxane, and then capping with intermediate 1 and diphenylchlorosilane to form a polysiloxane structure to obtain intermediate 2, and deprotecting intermediate 2 with hydrazine hydrate to obtain intermediate 3, and reacting intermediate 3 with 1,2-epoxydodecane so that the amino group on intermediate 3 reacts with the amino group on 1,2-epoxydodecane to form a hydroxyl group to obtain intermediate 4, and reacting terephthalaldehyde and pentaerythritol to form an aldehyde group capping, and then adding intermediate 4 so that the hydroxyl group on intermediate 4 reacts with the aldehyde group diacetal to obtain intermediate 5, and reacting intermediate 5 with allyl alcohol so that Si-H on intermediate 5 and the double bond on allyl alcohol are grafted, and then esterification with acrylic acid to form a double bond capping to obtain the modified monomer.

[0019] The branched structure of the modified resin can increase the adhesion of UV ink. At the same time, the molecular structure contains disulfide bonds, which are dynamic covalent bonds. During the curing process of UV ink, the disulfide bonds promote the rearrangement of the cross-linked network through bond exchange, thereby dissipating the curing shrinkage stress of the system, thereby achieving the effect of increasing adhesion. The modified resin molecules contain rigid groups, which can reduce the double bond density and volume shrinkage when combined with the side chain methylphenyl silicone resin molecules. The modified monomer contains multiple spirocyclic structures, which will produce volume expansion when the UV ink is cured, offsetting the volume shrinkage. It also contains long-chain alkyl groups, which can move into the gaps to offset the volume shrinkage produced during light curing, thereby greatly improving the adhesion effect. DETAILED DESCRIPTION

[0020] The technical solutions in the embodiments of the present invention are described clearly and completely below. Obviously, the described embodiments are only part of the embodiments of the present invention, not all of them. 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] Example 1

[0022] A method for preparing high-adhesion UV ink specifically comprises the following steps:

[0023] Step A1: isophorone diisocyanate, dibutyltin dilaurate and acetone are mixed uniformly, stirred for 15 minutes at a speed of 120 r / min and a temperature of 45° C., heated to 60° C., polyethylene glycol is added, reacted for 3 hours, castor oil is added, reacted for 3 hours, cystine is added, reacted for 2 hours, hydroxypropyl acrylate is added, reacted for 4 hours to obtain a pretreated resin, the pretreated resin, KH550, dicyclohexylcarbodiimide and DMF are mixed uniformly, reacted for 4 hours at a speed of 120 r / min and a temperature of 30° C. to obtain a reinforced resin;

[0024] Step A2: Mix the reinforcing resin, methyltrimethoxysilane, dimethyldimethoxysilane, phenyltrimethoxysilane and ethanol, stir and add hydrochloric acid and deionized water at a speed of 120 r / min and a temperature of 60°C, react for 3 hours, distill off the ethanol and deionized water, raise the temperature to 120°C, and keep warm for 1 hour to obtain a modified resin, weigh the following raw materials in parts by weight: 50 parts of modified resin, 40 parts of modified monomer, 8 parts of color paste and 5 parts of photoinitiator, mix the raw materials evenly, and obtain a high-adhesion UV ink.

[0025] The molar ratio of isophorone diisocyanate, polyethylene glycol, castor oil, cystine and hydroxypropyl acrylate described in step A1 is 10:5:1:2:3.5, the molecular weight of polyethylene glycol is 200, the amount of dibutyltin dilaurate is 1‰ of the sum of the mass of isophorone diisocyanate, polyethylene glycol, castor oil, cystine and hydroxypropyl acrylate, and the molar ratio of carboxyl, KH550 and dicyclohexylcarbodiimide on the pretreated resin is 1:1:1.2.

[0026] The mass ratio of the reinforcing resin, methyltrimethoxysilane, dimethyldimethoxysilane and phenyltrimethoxysilane described in step A2 is 15:3:6:2, the amount of hydrochloric acid used is 1% of the total mass of methyltrimethoxysilane, dimethyldimethoxysilane and phenyltrimethoxysilane, and the photoinitiator is benzophenone.

[0027] The modified monomer is prepared by the following steps:

[0028] Step B1: (3-aminopropyl)dimethylethoxysilane, phthalic anhydride and acetonitrile are mixed, and refluxed for 1 hour at a speed of 120 r / min and a temperature of 81°C, and the acetonitrile is distilled off, deionized water is added, and the mixture is stirred for 3 minutes to obtain intermediate 1. Intermediate 1, n-butyl lithium and hexane are mixed, and the mixture is stirred for 1 hour at a speed of 120 r / min and a temperature of 25°C, and hexamethylcyclotrisiloxane is added to react for 5 hours, and diphenylchlorosilane is added to react for 10 hours, and the pH is adjusted to be neutral to obtain intermediate 2;

[0029] Step B2: Mix intermediate 2, hydrazine hydrate and ethanol, and reflux for reaction at a speed of 120 r / min and a temperature of 78° C. for 10 h, and adjust the pH value to 8 to obtain intermediate 3; mix intermediate 3, 1,2-epoxydodecane and DMF evenly, and react for reaction at a speed of 120 r / min, a temperature of 50° C. and a pH value of 10 for 3 h to obtain intermediate 4;

[0030] Step B3: terephthalaldehyde, pentaerythritol and isopropanol are mixed evenly, nitrogen is introduced for protection, p-toluenesulfonic acid monohydrate is added under stirring at a speed of 60 r / min and a temperature of 25°C, and the reaction is carried out for 10 hours, and intermediate 4 is added, and the reaction is continued for 3 hours, sodium bicarbonate is added, and the stirring treatment is carried out for 30 minutes to obtain intermediate 5, and intermediate 5, allyl alcohol and DMF are mixed evenly, and chloroplatinic acid is added under stirring at a speed of 150 r / min and a temperature of 50°C, and the reaction is carried out for 10 hours, and acrylic acid and p-toluenesulfonic acid are added, and the temperature is raised to 110°C, and the reaction is carried out for 8 hours to obtain a modified monomer.

[0031] The amount ratio of (3-aminopropyl)dimethylethoxysilane, phthalic anhydride and deionized water described in step B1 is 8mmo l:8mmo l:15mL, and the amount ratio of intermediate 1, n-butyl lithium, hexamethylcyclotrisiloxane and diphenylchlorosilane is 5mmo l:1.8mL:50mmo l:10mmo l.

[0032] The usage ratio of the intermediate 2, hydrazine hydrate and ethanol described in step B2 is 1.5 g:2 mL:50 mL, and the molar ratio of the amino group on the intermediate 3 to 1,2-epoxydodecane is 1:2.

[0033] The molar ratio of terephthalaldehyde, pentaerythritol and intermediate 4 described in step B3 is 2:1:2, the amount of p-toluenesulfonic acid monohydrate is 5% of the mass of terephthalaldehyde, the amount of sodium bicarbonate is 3% of the mass of terephthalaldehyde, the molar ratio of SiH bonds, acryl alcohol and acrylic acid on intermediate 5 is 1:1:1, the amount of chloroplatinic acid is 1‰ of the mass of acryl alcohol, and the amount of p-toluenesulfonic acid is 2% of the mass of acrylic acid.

[0034] Example 2

[0035] A method for preparing high-adhesion UV ink specifically comprises the following steps:

[0036] Step A1: isophorone diisocyanate, dibutyltin dilaurate and acetone are mixed uniformly, stirred for 18 minutes at a speed of 120 r / min and a temperature of 48° C., heated to 65° C., polyethylene glycol is added, reacted for 4 hours, castor oil is added, reacted for 4 hours, cystine is added, reacted for 2.5 hours, hydroxypropyl acrylate is added, reacted for 4 hours to obtain a pretreated resin, the pretreated resin, KH550, dicyclohexylcarbodiimide and DMF are mixed uniformly, reacted for 5 hours at a speed of 120 r / min and a temperature of 35° C. to obtain a reinforced resin;

[0037] Step A2: Mix the reinforcing resin, methyltrimethoxysilane, dimethyldimethoxysilane, phenyltrimethoxysilane and ethanol, stir and add hydrochloric acid and deionized water at a speed of 120 r / min and a temperature of 63°C, react for 4 hours, distill off the ethanol and deionized water, raise the temperature to 125°C, and keep warm for 1.5 hours to obtain a modified resin, weigh the following raw materials in parts by weight: 55 parts of modified resin, 45 parts of modified monomer, 9 parts of color paste and 8 parts of photoinitiator, mix the raw materials evenly, and obtain a high-adhesion UV ink.

[0038] The molar ratio of isophorone diisocyanate, polyethylene glycol, castor oil, cystine and hydroxypropyl acrylate described in step A1 is 10:5:1:2:3.5, the molecular weight of polyethylene glycol is 400, the amount of dibutyltin dilaurate is 1‰ of the sum of the mass of isophorone diisocyanate, polyethylene glycol, castor oil, cystine and hydroxypropyl acrylate, and the molar ratio of carboxyl, KH550 and dicyclohexylcarbodiimide on the pretreated resin is 1:1:1.2.

[0039] The mass ratio of the reinforcing resin, methyltrimethoxysilane, dimethyldimethoxysilane and phenyltrimethoxysilane described in step A2 is 15:3:6:2, the amount of hydrochloric acid used is 1% of the total mass of methyltrimethoxysilane, dimethyldimethoxysilane and phenyltrimethoxysilane, and the photoinitiator is benzophenone.

[0040] The modified monomer is prepared by the following steps:

[0041] Step B1: (3-aminopropyl)dimethylethoxysilane, phthalic anhydride and acetonitrile are mixed, and the mixture is refluxed for 1.3 hours at a speed of 120 r / min and a temperature of 82° C., and the acetonitrile is distilled off, and deionized water is added, and the mixture is stirred for 4 minutes to obtain intermediate 1. Intermediate 1, n-butyl lithium and hexane are mixed, and the mixture is stirred for 1.3 hours at a speed of 120 r / min and a temperature of 28° C., and hexamethylcyclotrisiloxane is added to react for 6 hours, and diphenylchlorosilane is added to react for 13 hours, and the pH is adjusted to be neutral to obtain intermediate 2;

[0042] Step B2: Intermediate 2, hydrazine hydrate and ethanol were mixed, and the mixture was refluxed for 13 hours at a speed of 120 r / min and a temperature of 79° C., and the pH value was adjusted to 9 to obtain intermediate 3; intermediate 3, 1,2-epoxydodecane and DMF were mixed evenly, and the mixture was reacted for 4 hours at a speed of 120 r / min, a temperature of 55° C. and a pH value of 11 to obtain intermediate 4;

[0043] Step B3: terephthalaldehyde, pentaerythritol and isopropanol are mixed evenly, nitrogen is introduced for protection, p-toluenesulfonic acid monohydrate is added under stirring at a speed of 60 r / min and a temperature of 28°C, and the reaction is carried out for 10 hours, and intermediate 4 is added, and the reaction is continued for 4 hours, sodium bicarbonate is added, and the stirring treatment is carried out for 35 minutes to obtain intermediate 5, intermediate 5, allyl alcohol and DMF are mixed evenly, and chloroplatinic acid is added under stirring at a speed of 150 r / min and a temperature of 55°C, and the reaction is carried out for 13 hours, and acrylic acid and p-toluenesulfonic acid are added, and the temperature is raised to 115°C, and the reaction is carried out for 9 hours to obtain a modified monomer.

[0044] The amount ratio of (3-aminopropyl)dimethylethoxysilane, phthalic anhydride and deionized water described in step B1 is 8mmo l:8mmo l:15mL, and the amount ratio of intermediate 1, n-butyl lithium, hexamethylcyclotrisiloxane and diphenylchlorosilane is 5mmo l:1.8mL:50mmo l:10mmo l.

[0045] The usage ratio of the intermediate 2, hydrazine hydrate and ethanol described in step B2 is 1.5 g:2 mL:50 mL, and the molar ratio of the amino group on the intermediate 3 to 1,2-epoxydodecane is 1:2.

[0046] The molar ratio of terephthalaldehyde, pentaerythritol and intermediate 4 described in step B3 is 2:1:2, the amount of p-toluenesulfonic acid monohydrate is 5% of the mass of terephthalaldehyde, the amount of sodium bicarbonate is 3% of the mass of terephthalaldehyde, the molar ratio of SiH bonds, acryl alcohol and acrylic acid on intermediate 5 is 1:1:1, the amount of chloroplatinic acid is 1‰ of the mass of acryl alcohol, and the amount of p-toluenesulfonic acid is 2% of the mass of acrylic acid.

[0047] Example 3

[0048] A method for preparing high-adhesion UV ink specifically comprises the following steps:

[0049] Step A1: isophorone diisocyanate, dibutyltin dilaurate and acetone are mixed uniformly, stirred for 20 minutes at a speed of 150 r / min and a temperature of 50° C., heated to 70° C., polyethylene glycol is added, reacted for 5 hours, castor oil is added, reacted for 5 hours, cystine is added, reacted for 3 hours, hydroxypropyl acrylate is added, reacted for 5 hours, and a pretreated resin is obtained; the pretreated resin, KH550, dicyclohexylcarbodiimide and DMF are mixed uniformly, reacted for 6 hours at a speed of 150 r / min and a temperature of 40° C., and a reinforced resin is obtained;

[0050] Step A2: The reinforcing resin, methyltrimethoxysilane, dimethyldimethoxysilane, phenyltrimethoxysilane and ethanol are mixed, stirred at a speed of 150 r / min and a temperature of 65°C, and hydrochloric acid and deionized water are added. After reacting for 5 hours, the ethanol and deionized water are distilled off, the temperature is raised to 130°C, and the temperature is kept for 1.5 hours to obtain a modified resin. The following raw materials are weighed in parts by weight: 60 parts of modified resin, 50 parts of modified monomer, 10 parts of color paste and 10 parts of photoinitiator, the raw materials are mixed evenly, and a high-adhesion UV ink is obtained.

[0051] The molar ratio of isophorone diisocyanate, polyethylene glycol, castor oil, cystine and hydroxypropyl acrylate described in step A1 is 10:5:1:2:3.5, the molecular weight of polyethylene glycol is 600, the amount of dibutyltin dilaurate is 1‰ of the sum of the mass of isophorone diisocyanate, polyethylene glycol, castor oil, cystine and hydroxypropyl acrylate, and the molar ratio of carboxyl, KH550 and dicyclohexylcarbodiimide on the pretreated resin is 1:1:1.2.

[0052] The mass ratio of the reinforcing resin, methyltrimethoxysilane, dimethyldimethoxysilane and phenyltrimethoxysilane described in step A2 is 15:3:6:2, the amount of hydrochloric acid used is 1% of the total mass of methyltrimethoxysilane, dimethyldimethoxysilane and phenyltrimethoxysilane, and the photoinitiator is one of benzophenone and 4-methylbenzophenone.

[0053] The modified monomer is prepared by the following steps:

[0054] Step B1: (3-aminopropyl)dimethylethoxysilane, phthalic anhydride and acetonitrile are mixed, and the mixture is refluxed for 1.5 hours at a speed of 150 r / min and a temperature of 83°C, and the acetonitrile is distilled off, and deionized water is added, and the mixture is stirred for 5 minutes to obtain intermediate 1. Intermediate 1, n-butyl lithium and hexane are mixed, and the mixture is stirred for 1.5 hours at a speed of 150 r / min and a temperature of 30°C, and hexamethylcyclotrisiloxane is added to react for 7 hours, and diphenylchlorosilane is added to react for 15 hours, and the pH is adjusted to be neutral to obtain intermediate 2;

[0055] Step B2: Mix intermediate 2, hydrazine hydrate and ethanol, and reflux for reaction at a speed of 150 r / min and a temperature of 80° C. for 15 h, and adjust the pH value to 9 to obtain intermediate 3; mix intermediate 3, 1,2-epoxydodecane and DMF evenly, and react for reaction at a speed of 150 r / min, a temperature of 60° C. and a pH value of 11 for 5 h to obtain intermediate 4;

[0056] Step B3: terephthalaldehyde, pentaerythritol and isopropanol are mixed evenly, nitrogen is introduced for protection, p-toluenesulfonic acid monohydrate is added under stirring at a speed of 80 r / min and a temperature of 30°C, and the reaction is carried out for 15 hours, and intermediate 4 is added, and the reaction is continued for 5 hours, sodium bicarbonate is added, and the stirring treatment is carried out for 40 minutes to obtain intermediate 5, and intermediate 5, allyl alcohol and DMF are mixed evenly, and chloroplatinic acid is added under stirring at a speed of 200 r / min and a temperature of 60°C, and the reaction is carried out for 15 hours, and acrylic acid and p-toluenesulfonic acid are added, and the temperature is raised to 120°C, and the reaction is carried out for 10 hours to obtain a modified monomer.

[0057] The amount ratio of (3-aminopropyl)dimethylethoxysilane, phthalic anhydride and deionized water described in step B1 is 8mmo l:8mmo l:15mL, and the amount ratio of intermediate 1, n-butyl lithium, hexamethylcyclotrisiloxane and diphenylchlorosilane is 5mmo l:1.8mL:50mmo l:10mmo l.

[0058] The usage ratio of the intermediate 2, hydrazine hydrate and ethanol described in step B2 is 1.5 g:2 mL:50 mL, and the molar ratio of the amino group on the intermediate 3 to 1,2-epoxydodecane is 1:2.

[0059] The molar ratio of terephthalaldehyde, pentaerythritol and intermediate 4 described in step B3 is 2:1:2, the amount of p-toluenesulfonic acid monohydrate is 5% of the mass of terephthalaldehyde, the amount of sodium bicarbonate is 3% of the mass of terephthalaldehyde, the molar ratio of Si-H bonds on intermediate 5, acrylol and acrylic acid is 1:1:1, the amount of chloroplatinic acid is 1‰ of the mass of acrylol, and the amount of p-toluenesulfonic acid is 2% of the mass of acrylic acid.

[0060] Comparative Example 1

[0061] Compared with Example 1, in this comparative example, isophorone diisocyanate, dibutyltin dilaurate and acetone were uniformly mixed, stirred for 15 minutes at a speed of 120 r / min and a temperature of 45° C., the temperature was raised to 60° C., polyethylene glycol was added, and the reaction was carried out for 3 hours, castor oil was added, and the reaction was carried out for 3 hours, hydroxypropyl acrylate was added, and the reaction was carried out for 4 hours, the obtained product replaced the modified resin, and the remaining steps were the same.

[0062] Comparative Example 2

[0063] Compared with Example 1, this comparative example uses a reinforcing resin instead of a modified resin, and the remaining steps are the same.

[0064] Comparative Example 3

[0065] Compared with Example 1, this comparative example uses trimethylsilanol, n-butyl lithium and hexane to mix, and stirs for 1 hour at a speed of 120 r / min and a temperature of 25°C, adds hexamethylcyclotrisiloxane, and reacts for 5 hours, adds diphenylchlorosilane, and continues to react for 10 hours, adjusts the pH to neutral, and replaces intermediate 5 with the obtained product, and the remaining steps are the same.

[0066] The UV inks prepared in Examples 1-3 and Comparative Examples 1-3 were tested for adhesion performance by the cross-cut method according to the standard of GB / T13217.7-2023, and the hardness was tested by the strength of 9B-9H and the pushing speed of 1 mm / s according to the standard of GB / T6739-2006. The test results are shown in the following table.

[0067] Example 1 Example 2 Example 3 Comparative Example 1 Comparative Example 2 Comparative Example 3 Adhesion level 0 0 0 3 1 2 Pencil hardness 5H 5H 5H 3H 4H 4H

[0068] From the above table, we can see that this application has very good adhesion and hardness.

[0069] The above contents are merely examples and explanations of the concept 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 concept of 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 method for preparing high adhesion UV ink, characterized in that: The specific steps include: Step A1: after mixing isophorone diisocyanate, dibutyltin dilaurate and acetone, heating and adding polyethylene glycol to react, adding castor oil to react, adding cystine to react, adding hydroxypropyl acrylate to react, to obtain a pretreated resin, and mixing the pretreated resin, KH550, dicyclohexylcarbodiimide and DMF to react to obtain a reinforced resin; Step A2: a reinforcing resin, methyltrimethoxysilane, dimethyldimethoxysilane, phenyltrimethoxysilane and ethanol are mixed and stirred, and hydrochloric acid and deionized water are added. After the reaction, the ethanol and deionized water are distilled off, and the temperature is increased and kept to obtain a modified resin. The following raw materials are weighed in parts by weight: 50-60 parts of a modified resin, 40-50 parts of a modified monomer, 8-10 parts of a color paste and 5-10 parts of a photoinitiator. The raw materials are evenly mixed to obtain a high-adhesion UV ink. The modified monomer is prepared by the following steps: Step B1: (3-aminopropyl)dimethylethoxysilane, phthalic anhydride and acetonitrile are mixed and refluxed for reaction, the acetonitrile is distilled off, deionized water is added, and the mixture is stirred to obtain intermediate 1, intermediate 1, n-butyl lithium and hexane are mixed and stirred, hexamethylcyclotrisiloxane is added, and the mixture is reacted, diphenylchlorosilane is added, the reaction is continued, and the pH is adjusted to be neutral to obtain intermediate 2; Step B2: Mix intermediate 2, hydrazine hydrate and ethanol for reflux reaction, adjust the pH value to be alkaline, and obtain intermediate 3; Mix intermediate 3, 1,2-epoxydodecane and DMF for reaction, and obtain intermediate 4; Step B3: terephthalaldehyde, pentaerythritol and isopropanol are mixed and stirred, and p-toluenesulfonic acid monohydrate is added. After reaction, intermediate 4 is added, the reaction is continued, sodium bicarbonate is added, and stirring is performed to obtain intermediate 5. Intermediate 5, allyl alcohol and DMF are mixed and stirred, and chloroplatinic acid is added. After reaction, acrylic acid and p-toluenesulfonic acid are added, and the temperature is increased to react to obtain a modified monomer.

2. The method for preparing a high adhesion UV ink according to claim 1, characterized in that: The molar ratio of isophorone diisocyanate, polyethylene glycol, castor oil, cystine and hydroxypropyl acrylate in step A1 is 10:5:1:2:3.5, and the molar ratio of carboxyl group, KH550 and dicyclohexylcarbodiimide on the pretreated resin is 1:1:1.

2.

3. The method for preparing a high adhesion UV ink according to claim 1, characterized in that: The mass ratio of the reinforcing resin, methyltrimethoxysilane, dimethyldimethoxysilane and phenyltrimethoxysilane described in step A2 is 15:3:6:

2.

4. The method for preparing a high adhesion UV ink according to claim 1, characterized in that: The amount ratio of (3-aminopropyl)dimethylethoxysilane, phthalic anhydride and deionized water in step B1 is 8mmol:8mmol:15mL, and the amount ratio of intermediate 1, n-butyl lithium, hexamethylcyclotrisiloxane and diphenylchlorosilane is 5mmol:1.8mL:50mmol:10mmol.

5. The method for preparing a high adhesion UV ink according to claim 1, characterized in that: The usage ratio of the intermediate 2, hydrazine hydrate and ethanol described in step B2 is 1.5 g:2 mL:50 mL, and the molar ratio of the amino group on the intermediate 3 to 1,2-epoxydodecane is 1:

2.

6. The method for preparing a high adhesion UV ink according to claim 1, characterized in that: The molar ratio of terephthalaldehyde, pentaerythritol and intermediate 4 in step B3 is 2:1:2, the amount of sodium bicarbonate used is 3% of the mass of terephthalaldehyde, and the molar ratio of Si-H bonds on intermediate 5, acryl alcohol and acrylic acid is 1:1:

1.

7. A high adhesion UV ink, characterized by: Prepared according to any one of claims 1 to 6.