Eugenol-modified alkali-soluble photocurable epoxy resin, preparation method and application thereof

Abstract

The application provides a eugenol-modified alkali-soluble photocuring epoxy resin and a preparation method and application thereof, the preparation method is as follows: first, using mercaptoalkanol as a chain extender to chain-extend eugenol and introduce alcohol hydroxyl, then performing an epoxidation reaction with epichlorohydrin to obtain an epoxy intermediate monomer, then performing an open ring polymerization reaction modification on the epoxy intermediate monomer with acrylic acid, and finally performing an esterification reaction with an unsaturated anhydride, so that the eugenol-modified alkali-soluble photocuring epoxy resin is obtained. In the synthesis path, the first step is to chain-extend eugenol and introduce alcohol hydroxyl by using mercaptoalkanol, and a designed amount of epoxy units is introduced through an epoxidation reaction. Different lengths of mercaptoalkanol can be selected to introduce different alkane chain intermediate connection structures in the phenolic hydroxyl and alcohol hydroxyl, and a series of epoxy molecules containing a bio-based benzene ring structure are synthesized, and the flexible alkane chain has a significant promoting effect on the withstand voltage of the direct current voltage breakdown strength of the cured film formed by curing the ink product.

Description

TECHNICAL FIELD

[0001] The present application relates to the technical field of modified photocurable epoxy resin and application, and in particular to a eugenol-modified alkali-soluble photocurable epoxy resin, a preparation method and application thereof. BACKGROUND

[0002] Photocurable resins are widely used in the semiconductor industry, such as integrated circuits, electronic packaging and photoresists, due to their high-precision manufacturing and excellent performance in rapid prototyping, and are manufactured into customized materials with solid and complex structures.

[0003] With the development of advanced chip manufacturing technology towards multi-level, multi-dimensional and multi-functionalization, to match the performance indicators of high-density integrated circuits, more stringent standards are put forward for the solder resist coating of the corresponding semiconductor component printed circuit board (PCB). For example, to meet the high-speed, low-latency and anti-interference communication capabilities of 5G communication technology, electronic packaging coatings need to have excellent heat resistance and mechanical strength and reliable electrical insulation capability to ensure safe and accurate data transmission. In addition, under the driving of the expanding industrial market demand, the design of the coating tends to be flexible and customizable, such as ductility, low surface energy, interface compatibility, etc., and traditional resin-based materials are difficult to meet the use requirements of diversified scenarios. Epoxy resin is the most widely used thermosetting resin including PCB substrates due to its diverse performance characteristics, and epoxy resin is also the most commonly used photocurable precursor for electronic packaging coatings, and the design and optimization of epoxy monomer structure are particularly critical. Many studies have integrated existing materials to further synthesize and improve functional epoxy resins with simple and effective means.

[0004] For example, the Chinese invention patent application "Method for modifying epoxy resin composite material with nano-inorganic filler" (CN109943021A) of the University of Electronic Science and Technology discloses a method for modifying epoxy resin composite material with nano-inorganic filler, which uses high-pressure microparticulation device for micron particle nanocrystallization for the dispersion of inorganic filler in epoxy resin liquid, greatly improves the problem of nano-particle agglomeration due to its high surface energy affecting the performance of the composite material, and greatly improves the dispersibility of inorganic filler in epoxy resin.

[0005] For example, Chinese invention patent "A rigid acrylate UV photocurable modified tung oil resin, its preparation method and application" (CN111909075B) discloses a high double bond content rigid acrylate UV photocurable modified tung oil resin, its preparation method and application. The high double bond content rigid acrylate UV photocurable modified tung oil resin contains a rigid ring-shaped tetra / hexahydrophthalimide group and a large number of (methyl) acrylate structures in its structure. When UV radiation is performed, a plurality of acrylate double bonds are polymerized to form a crosslinked network; at the same time, a plurality of hydroxyl groups generated after the consumption of the epoxy group of glycidyl (methyl) acrylate and the polar tetra / hexahydrophthalimide structure enhance the intermolecular force between the cured film and the substrate surface.

[0006] However, the biggest problem is that in the prior art including the above patent documents, almost all the epoxy resins are derived from petroleum-based raw materials, which largely violates the environmental protection and sustainable consideration factors. Developing value-added chemicals based on biomass resources to replace non-renewable energy is extremely attractive in this regard, and is also an important way to convert green renewable raw materials other than fuel.

[0007] Therefore, it is necessary to provide a method for preparing high-performance photocurable epoxy resin from renewable raw materials, and to optimize and improve the functional bio-based photocurable solder resist ink with high temperature resistance, strong toughness, and DC voltage breakdown resistance. SUMMARY

[0008] The present application provides a eugenol-modified alkali-soluble photocurable epoxy resin and its preparation method and application according to the problems raised by the prior art. In the synthesis path, the first step uses mercaptoalkanol to chain extend eugenol and introduce alcohol hydroxyl groups, and a designed amount of epoxy units are introduced through epoxidation reaction. Different lengths of mercaptoalkanol can be selected to introduce different alkane chain intermediate connection structures in the phenolic hydroxyl and alcohol hydroxyl groups, and a series of epoxy molecules containing bio-based benzene ring structures are synthesized. The flexible alkane chain has a significant promoting effect on the DC voltage breakdown resistance of the cured film formed by the curing of the ink product.

[0009] To achieve the above-mentioned purpose, the present application is realized by adopting the technical scheme composed of the following technical measures.

[0010] In one aspect, the present application provides a eugenol-modified alkali-soluble photocurable epoxy resin, whose chemical structural formula is as follows:

[0011]

[0012] Or is:

[0013]

[0014] wherein R is any one of the following structures:

[0015]

[0016] In the above chemical structure, "…" represents the position connected by a chemical bond.

[0017] In another aspect, the present application also provides a preparation method of the eugenol-modified alkali-soluble photocuring epoxy resin, which comprises the following steps: firstly, using mercaptoalkanol as a chain extender to chain-extend eugenol (CAS: 97-53-0) and introduce alcohol hydroxyl group, then performing an epoxidation reaction with epichlorohydrin to obtain an epoxy intermediate monomer, then performing an open ring polymerization reaction modification with acrylic acid, and finally performing an esterification reaction with an unsaturated anhydride, so as to obtain the eugenol-modified alkali-soluble photocuring epoxy resin. It should be noted that the skilled in the art can obtain the specific preparation steps according to the above-mentioned reaction sequence, especially the open ring polymerization reaction modification with acrylic acid and the esterification reaction with an unsaturated anhydride, which is a conventional synthesis route for preparing alkali-soluble photocuring epoxy resin in the art; therefore, the technical solutions provided below of the present application do not mean the only designation or limitation of the preparation method of the eugenol-modified alkali-soluble photocuring epoxy resin.

[0018] In a preferred technical solution, the preparation method of the eugenol-modified alkali-soluble photocuring epoxy resin mainly comprises the following steps:

[0019] (1) under an air atmosphere, adding eugenol (EU), mercaptoalkanol and a photo initiator for thiol-ene click chemistry reaction into a reaction container, and performing stirring reaction under the condition of ultraviolet light irradiation at the wavelength of the photo initiation of the photo initiator for thiol-ene click chemistry reaction for 12-24 h, so as to obtain a dihydroxyl compound modified by eugenol;

[0020] wherein the mercaptoalkanol is an alkyl chain compound with a hydroxyl group at one end of the molecular structure and a mercapothyl group at the other end, and the molar ratio of eugenol to mercaptoalkanol is 1:(1-1.1);

[0021] (2) adding epichlorohydrin and a catalyst for epoxidation reaction into the dihydroxyl compound modified by eugenol obtained in step (1), fully mixing and dissolving, and then performing stirring reaction at a temperature of 60-80℃ for 8-24 h, so as to obtain an epoxy intermediate monomer;

[0022] wherein the reaction is performed at a temperature of 60-80℃ for 8-24 h, and a ring closure reaction is performed during the reaction process or after the reaction time reaches;

[0023] the molar ratio of the dihydroxyl compound modified by eugenol to epichlorohydrin is 1:(5-12);

[0024] (3) under air atmosphere, the epoxy intermediate monomer, acrylic acid and solvent obtained in step (2) are added into a reaction vessel, a ring ester ring-opening polymerization catalyst and a polymerization inhibitor are added, after being mixed thoroughly, the temperature is adjusted to 100-125℃, and then the reaction is stirred for 8-16 hours to obtain an acrylic-modified epoxy intermediate monomer;

[0025] (4) the acrylic-modified epoxy intermediate monomer obtained in step (3) is cooled to 70-80℃, and then an unsaturated acid anhydride is added, and the reaction is continued to be stirred at 85-100℃ for 6-12 hours to obtain a eugenol-modified alkali-soluble photocuring epoxy resin.

[0026] In this article, the "eugenol" (CAS: 97-53-0) in step (1) is a lignin-derived monomer, which can be commercially available or self-made, and the purity is usually chemical raw material grade.

[0027] In one of the technical solutions, the mercapto alkanol in step (1) is selected from at least one of mercapto methanol, 2-mercaptoethanol, 3-mercapto propanol, 4-mercapto butanol, 5-mercapto pentanol, 6-mercapto hexanol, 7-mercapto heptanol, 8-mercapto octanol, 9-mercapto nonanol, 10-mercapto decanol, 11-mercapto undecanol, 12-mercapto dodecanol, 13-mercapto tridecanol, 14-mercapto tetradecanol, 15-mercapto pentadecanol, 16-mercapto hexadecanol, 17-mercapto heptadecanol or 18-mercapto octadecanol.

[0028] In this article, the photo initiator for thiol-ene click chemistry reaction in step (1) is a photo initiator commonly used in the field of thiol-ene click chemistry reaction, and the person skilled in the art can select a suitable photo initiator for thiol-ene click chemistry reaction according to the actual needs, and determine the appropriate amount of addition and the best wavelength of ultraviolet light according to the existing technical information such as the sales instruction / manual of operation of the photo initiator for thiol-ene click chemistry reaction.

[0029] In one of the technical solutions, the photo initiator for thiol-ene click chemistry reaction in step (1) is selected from any one of 2-hydroxy-2-methylpropiophenone, 2-hydroxy-2-methylpropiophenone, benzophenone, benzophenone, (2,4,6-trimethylbenzoyl) diphenyl phosphine oxide.

[0030] In order to better illustrate the present application, and to provide a technical solution for reference, when the photo initiator for thiol-ene click chemistry reaction in step (1) is selected as 2-hydroxy-2-methylpropiophenone, 395 nm wavelength ultraviolet light should be used for irradiation, and the amount of addition is 2.5-3.5 wt% of the total mass of eugenol and mercapto alkanol in step (1).

[0031] In the present text, the catalyst used in the epoxidation reaction in step (2) is a catalyst commonly used in the epoxidation reaction in the technical field, and a person skilled in the art can select a suitable catalyst for the epoxidation reaction according to actual needs.

[0032] In one of the technical solutions, the catalyst used in the epoxidation reaction in step (2) is selected from any one of tetrabutylammonium bromide, tetramethylammonium bromide, and benzyltriethylammonium chloride; and the addition amount of the catalyst used in the epoxidation reaction is 8-12% of the molar amount of the eugenol-modified dihydroxy compound in step (2).

[0033] In the present text, the ring-closing reaction treatment in step (2) is a conventional process selected during the epoxidation reaction, and a person skilled in the art can directly select a suitable ring-closing reaction treatment according to the common knowledge of the epoxidation reaction or the conventional epoxidation reaction process in the art.

[0034] In order to better illustrate the present application, and to provide a technical solution for reference, the reaction in step (2) is carried out at a temperature of 60-80°C for 8-24h, and the ring-closing reaction treatment is carried out during the reaction, specifically, a NaOH aqueous solution with a mass of 3-5 times that of the dihydroxy compound and a mass concentration of 20-40wt% is further added to the reaction liquid (eugenol-modified dihydroxy compound, epichlorohydrin, and catalyst for the epoxidation reaction), and the reaction is carried out at a temperature of 60-80°C for 8-24h.

[0035] In order to better illustrate the present application, and to provide a technical solution for reference, the reaction in step (2) is carried out at a temperature of 60-80°C for 8-24h, and the ring-closing reaction treatment is carried out after the reaction time reaches, specifically, after the product is cooled to room temperature, a NaOH aqueous solution with a mass of 3-5 times that of the dihydroxy compound and a mass concentration of 20-40wt% is added under stirring, and the stirring is continued for 15h.

[0036] In one of the technical solutions, the epoxy intermediate monomer obtained by separation in step (2) is separated by rotary evaporation, because epichlorohydrin is used as a reactant and a solvent, and the reaction product is also a liquid.

[0037] It should be noted that, during the separation in step (2), conventional process operations such as liquid separation and washing are usually accompanied, which are common knowledge in the technical field and will not be described here.

[0038] In the present text, the ring ester ring-opening polymerization catalyst in step (3) is a ring ester ring-opening polymerization catalyst commonly used in the art for the ring-opening polymerization of epoxy resins, and a person skilled in the art can select a suitable ring ester ring-opening polymerization catalyst according to actual needs.

[0039] In one of the technical solutions, the ring ester ring-opening polymerization catalyst in step (3) is selected from one of triethylamine, triethanolamine, 4-dimethylaminopyridine, tetrabutylammonium bromide, tetramethylammonium chloride, N,N-dimethylbenzylamine and triphenylphosphine; and the addition amount of the ring ester ring-opening polymerization catalyst is 0.5-1.0 wt% of the total mass of the epoxy intermediate monomer and the acrylic acid in step (3).

[0040] In the present text, the solvent in step (3) is a conventional solvent in the art, which can be a conventional solvent for inks.

[0041] In one of the technical solutions, the solvent in step (3) is at least one of divalent acid ester high-boiling environmentally friendly solvents, ethylene glycol ethyl ether acetate, ethylene glycol butyl ether acetate, diethylene glycol ethyl ether acetate, diethylene glycol butyl ether acetate, propylene glycol methyl ether acetate, propylene glycol methyl ether propionate, dipropylene glycol methyl ether, propylene glycol methyl ether, mesitylene and tetramethylbenzene; and the addition amount of the solvent can refer to the conventional amount in the preparation process of the alkali-soluble photocurable epoxy resin in the art, or refer to the following preferred mode: in step (1), the mass of the solvent: the mass of the epoxy intermediate monomer = (0.5-4): 1.

[0042] In the present text, the polymerization inhibitor in step (3) is a conventional polymerization inhibitor in the art, which can be a conventional polymerization inhibitor in the ink process.

[0043] In one of the technical solutions, the polymerization inhibitor in step (3) is at least one of hydroquinone, o-methyl hydroquinone, p-hydroxyanisole, p-benzoquinone and 2,6-di-tert-butyl-4-methylphenol. Preferably, the two added polymerization inhibitors are the same polymerization inhibitor; and the addition amount of the polymerization inhibitor in step (3) is 0.3-1.0 wt% of the total mass of the epoxy intermediate monomer and the acrylic acid in step (3).

[0044] In the present text, the addition amount of the acrylic acid in step (3) is consistent with the addition amount of the acrylic acid in the conventional synthesis process for preparing the alkali-soluble photocurable epoxy resin in the art, which is usually calculated according to the stoichiometric molar amount, for example, the molar amount of the acrylic acid: the molar amount of the epoxy intermediate monomer = (2-2.1): 1.

[0045] In the present application, the unsaturated anhydride in step (4) is a conventional choice of unsaturated anhydride in the preparation of alkali-soluble photocuring epoxy resin in the art, and a person skilled in the art can directly select a suitable unsaturated anhydride by referring to the relevant technical literature in the art.

[0046] In the present application, the amount of the unsaturated anhydride added in step (4) is preferably consistent with the amount of the unsaturated anhydride added in the conventional synthesis process for preparing alkali-soluble photocuring epoxy resin in the art, but it can also be selected to be only half of the esterification reaction with the hydroxyl groups, so that the molar ratio of the unsaturated anhydride to the molar amount of the epoxy intermediate monomer is (1-2.1):1.

[0047] In one of the technical solutions, the unsaturated anhydride in step (4) is selected from at least one of tetrahydrophthalic anhydride, itaconic anhydride, maleic anhydride, succinic anhydride, methyltetrahydrophthalic anhydride, hexahydrophthalic anhydride and methylhexahydrophthalic anhydride.

[0048] In the present application, the stirring reaction is a conventional stirring reaction used in the art, including magnetic stirring or mechanical stirring, and a person skilled in the art can select a suitable stirring reaction mode according to the production scale or the current process conditions. In one of the technical solutions, the stirring reaction can be carried out at a stirring rate of 100-300 rpm.

[0049] On the other hand, based on the above-mentioned eugenol-modified alkali-soluble photocuring epoxy resin, the present application also provides a high-performance photosensitive solder resist ink using the above-mentioned alkali-soluble photocuring epoxy resin as the main component, the raw materials of which mainly include, by weight fraction:

[0050] eugenol-modified alkali-soluble photocuring epoxy resin 100 parts,

[0051] photoinitiator 1-5 parts.

[0052] In the present application, the photoinitiator is a conventional photoinitiator selected for preparing photosensitive solder resist ink in the art, and a person skilled in the art can select a suitable photoinitiator based on the current process conditions or the existing technical literature in the art.

[0053] In one preferred technical solution, the high performance photosensitive solder resist ink further comprises, by weight fraction:

[0054] In one preferred technical solution, the high performance photosensitive solder resist ink further comprises, by weight fraction:

[0055] Filler 20-50 parts,

[0056] Additive 1-25 parts.

[0057] In order to improve the physical strength of the coating film after the use of the solder resist ink, the solder resist ink component comprises a filler, which is a commonly known inorganic or organic filler, preferably one or several of titanium white, bentonite, barium sulfate, spherical silica, nano calcium carbonate, talc, and further preferably a commonly known metal oxide as both a filler and a pigment.

[0058] The additive is one or a combination of a pigment, a thermal polymerization inhibitor, an adhesion promoter, an antifoaming agent, a leveling agent, a coupling agent, an antioxidant, and a rust inhibitor. The pigment, the thermal polymerization inhibitor, the adhesion promoter, the antifoaming agent, the leveling agent, the coupling agent, the antioxidant, and the rust inhibitor are commonly known.

[0059] The preparation method of the high performance photosensitive solder resist ink can refer to the prior art to mix all the components to prepare. For example, after the components are pre-mixed in a blender, they are mixed by a three-roll mill to obtain the high performance photosensitive solder resist ink.

[0060] When the solder resist ink is used, it is applied to a substrate, dried appropriately (at about 60 to 90°C), exposed through a pattern film or the like, and a cured coating film is obtained by developing the unexposed portion. At the time of development, solvent development can be performed using the above-described solvent or a halogen-based solvent such as trichloroethylene, which is generally known, but since the carboxyl group is introduced in the alkynyl active monomer-modified alkali-soluble photocurable epoxy resin, the unexposed portion is dissolved in an alkaline aqueous solution, and thus, alkaline development is preferably performed. The alkaline solvent developer can be selected from an alkali metal compound such as sodium carbonate, potassium carbonate, sodium hydroxide, potassium hydroxide, or the like; an alkaline earth metal compound such as calcium hydroxide, or the like; an alkaline solution such as aqueous ammonia; and a water-soluble organic amine such as monomethylamine, dimethylamine, trimethylamine, monoethylamine, diethylamine, triethylamine, monopropylamine, dipropylamine, dimethylpropylamine, monoethanolamine, diethanolamine, triethanolamine, ethylenediamine, diethylenetriamine, dimethylaminoethyl methacrylate, polyethyleneimine, or the like.

[0061] After development, heat treatment at about 120 to 160°C for 1 hour is preferably performed to further thermally cure the photocured coating film.

[0062] Generally, the above-described high-performance photosensitive solder resist ink can be used in a state in which a solder resist layer dry film is formed by previously applying and drying the solder resist ink on a film of PET or the like, in addition to a method in which the solder resist ink is directly applied to a substrate in a liquid state.

[0063] The present application has the following advantageous effects:

[0064] 1. The present application provides a eugenol-modified alkali-soluble photocurable epoxy resin and a preparation method and application thereof. In the synthesis path thereof, a mercaptoalkanol is used to chain-extend eugenol and introduce an alcohol hydroxyl group in the first step, and a designed amount of an epoxy unit is introduced through an epoxidation reaction. Different lengths of mercaptoalkanols can be selected to introduce different alkane chain intermediate connection structures in the phenolic hydroxyl group and the alcohol hydroxyl group, and a series of epoxy molecules containing a bio-based benzene ring structure are synthesized. The flexible alkane chain has a significant promoting effect on the withstand voltage breakdown strength of the cured film formed by curing the ink product.

[0065] 2. According to the test results, the alkane chain chain-extended connection unit in the designed amount endows the bio-based high-crosslinking system with excellent mechanical property adjustment ability, achieving high tensile strain and high toughness.

[0066] 3. In the second half of the synthesis path of the present application, a large number of double bonds and hydroxyl groups are introduced through acrylic acid in the ring-opening reaction, and the esterification reaction of the hydroxyl group with an unsaturated acid anhydride. In some embodiments, the prepared alkali-soluble photocurable epoxy resin has a high double bond density and intermolecular force, and the cured film has a high glass transition temperature and the ability to adhere to a substrate.

[0067] 4. The alkali-soluble photocurable epoxy resin prepared by this invention has the ability to be eluted by alkali, that is, it has alkali development properties, and it can be quickly and completely detached by direct immersion and rinsing in concentrated alkali solution without damaging the substrate.

[0068] 5. Comparative experiments have shown that the alkali-soluble photocurable epoxy resin prepared based on eugenol exhibits excellent performance in terms of mechanical properties, solderability, solvent resistance, dielectric properties, voltage breakdown resistance, chemical resistance, resistance to electroless gold plating, resistance to electroless tin plating, and electrical insulation properties. Attached Figure Description

[0069] Fig. 1 The above is the 1H NMR spectrum of the eugenol-modified dihydroxy compound obtained in step (1) of Example 1 of this invention.

[0070] Fig. 2 The above is the 1H NMR spectrum of the eugenol-modified dihydroxy compound obtained in step (1) of Example 2 of this invention.

[0071] Fig. 3 The figures show the 1H NMR spectra of the intermediate and final products of Synthesis Examples 1-2 and Comparative Synthesis Example 1. In Figure (a), from top to bottom, are the 1H NMR spectra of the vanillin-modified alkali-soluble photocurable epoxy resin (EAAT), the intermediate product acrylic acid-modified epoxy intermediate monomer (DGEVA / AA), and the intermediate product epoxy intermediate monomer (DGEVA) prepared in Comparative Synthesis Example 1. In Figure (b), from top to bottom, are the 1H NMR spectra of the eugenol-modified alkali-soluble photocurable epoxy resin (2-EMAT), the intermediate product acrylic acid-modified epoxy intermediate monomer (2-DGEEM / AA), and the intermediate product epoxy intermediate monomer (2-DGEEM) prepared in Synthesis Example 1. In Figure (c), from top to bottom, are the 1H NMR spectra of the eugenol-modified alkali-soluble photocurable epoxy resin (6-EMAT), the intermediate product acrylic acid-modified epoxy intermediate monomer (6-DGEEM / AA), and the intermediate product epoxy intermediate monomer (6-DGEEM) prepared in Synthesis Example 2.

[0072] Fig. 4 Figure 1 shows the stress-strain curves and photographs of the cured film samples obtained in Application Examples 1 and 2 of the present invention, and Comparative Application Example 1. Figure (a) shows the stress-strain curve of the comparative cured film sample obtained in Application Example 1, with the smaller figures being photographs taken during the stress-strain test; Figure (b) shows the stress-strain curve of the cured film sample obtained in Application Example 1; and Figure (c) shows the stress-strain curve of the cured film sample obtained in Application Example 2.

[0073] Fig. 5The dynamic mechanical thermal test results of the cured film samples obtained in application examples 1-2 and comparative application example 1 are shown in the figures. Figure (a) is a tan(δ) result comparison chart of the cured film samples obtained in application examples 1-2 and comparative application example 1, and figure (b) is a storage modulus result comparison chart of the cured film samples obtained in application examples 1-2 and comparative application example 1. In the figures, 6-EMAT corresponds to the cured film sample obtained in application example 2, 2-EMAT corresponds to the cured film sample obtained in application example 1, and EAAT corresponds to the cured film comparative sample obtained in comparative application example 1.

[0074] Fig. 6 The direct current voltage breakdown strength comparison chart of the cured film samples obtained in application examples 1-2 and comparative application example 1 is shown in the figure. In the figure, 6-EMAT corresponds to the cured film sample obtained in application example 2, 2-EMAT corresponds to the cured film sample obtained in application example 1, and EAAT corresponds to the cured film comparative sample obtained in comparative application example 1. DETAILED DESCRIPTION

[0075] In order to further understand the present application, the preferred embodiments of the present application are described below in conjunction with the examples, but it should be understood that these descriptions are only intended to further illustrate the features and advantages of the present application, and are not intended to limit the claims of the present application. Those skilled in the art can modify the process parameters according to the content herein. It should be particularly pointed out that all similar replacements and modifications are obvious to those skilled in the art, and are considered to be included in the present application. The methods and applications of the present application have been described by the preferred embodiments, and those skilled in the art can obviously modify or appropriately change and combine the methods and applications described herein to realize and apply the present application technology without departing from the content, spirit and scope of the present application. Although the following terms are believed to be well understood by those skilled in the art, the following definitions are set forth to facilitate the explanation of the subject matter disclosed herein.

[0076] In one aspect, the present application provides a eugenol-modified alkali-soluble photocurable epoxy resin, which has the following chemical structure:

[0077]

[0078] or is:

[0079]

[0080] In the above chemical structure, "…" indicates the position connected by a chemical bond.

[0081]

[0082] In the above chemical structure, "…" indicates the position connected by a chemical bond.

[0083] In another aspect, the present application also provides a preparation method of the eugenol-modified alkali-soluble photocuring epoxy resin, which comprises the following steps: firstly, chain extending eugenol (CAS: 97-53-0) with mercaptoalkanol as a chain extender to introduce alcohol hydroxyl groups, then performing an epoxidation reaction with epichlorohydrin to obtain an epoxy intermediate monomer, then modifying the epoxy intermediate monomer by performing an open ring polymerization reaction with acrylic acid, and finally performing an esterification reaction with an unsaturated anhydride to obtain the eugenol-modified alkali-soluble photocuring epoxy resin. It should be noted that the skilled in the art can obtain specific preparation steps according to the above-mentioned reaction sequence, especially the open ring polymerization reaction with acrylic acid and the esterification reaction with an unsaturated anhydride, which are conventional synthesis routes for preparing alkali-soluble photocuring epoxy resins in the art; therefore, the embodiments provided below of the present application do not mean the only specification or limitation of the preparation method of the eugenol-modified alkali-soluble photocuring epoxy resin.

[0084] In a preferred embodiment, the preparation method of the eugenol-modified alkali-soluble photocuring epoxy resin mainly comprises the following steps:

[0085] (1) under an air atmosphere, adding eugenol (EU), mercaptoalkanol and a photo initiator for thiol-ene click chemistry reaction into a reaction vessel, and performing stirring reaction under the irradiation of ultraviolet light at a wavelength of the photo initiation of the photo initiator for thiol-ene click chemistry reaction for 12-24 hours to obtain a dihydroxyl compound modified by eugenol;

[0086] wherein the mercaptoalkanol is an alkyl chain compound with a hydroxyl group at one end of the molecular structure and a mercapto group at the other end, and the molar ratio of eugenol to mercaptoalkanol is 1:(1-1.1);

[0087] (2) adding epichlorohydrin and a catalyst for epoxidation reaction into the dihydroxyl compound modified by eugenol obtained in step (1), fully mixing and dissolving, and then performing stirring reaction at a temperature of 60-80°C for 8-24 hours to obtain an epoxy intermediate monomer;

[0088] wherein the reaction is performed at a temperature of 60-80°C for 8-24 hours, and a ring closure reaction is performed during the reaction process or after the reaction time reaches;

[0089] the molar ratio of the dihydroxyl compound modified by eugenol to epichlorohydrin is 1:(5-12);

[0090] (3) under an air atmosphere, adding the epoxy intermediate monomer obtained in step (2), acrylic acid and a solvent into a reaction vessel, adding a ring ester open ring polymerization catalyst and a polymerization inhibitor, fully mixing, then adjusting the temperature to 100-125°C, and performing stirring reaction for 8-16 hours to obtain an acrylic acid-modified epoxy intermediate monomer;

[0091] (4) The acrylic modified epoxy intermediate monomer obtained in step (3) is cooled to 70-80℃, then the unsaturated acid anhydride is added, and the reaction is continued at 85-100℃ for 6-12 hours to obtain the eugenol modified alkali-soluble photo-curable epoxy resin.

[0092] In this context, the "eugenol" (CAS: 97-53-0) in step (1) is a lignin-derived structural monomer, which can be commercially available or self-made, and the purity is generally required to be chemical raw material grade.

[0093] In one embodiment, the mercaptoalkanol in step (1) is selected from at least one of mercaptomethanol, 2-mercaptoethanol, 3-mercapto-1-propanol, 4-mercapto-1-butanol, 5-mercapto-1-pentanol, 6-mercapto-1-hexanol, 7-mercapto-1-heptanol, 8-mercapto-1-octanol, 9-mercapto-1-nonanol, 10-mercapto-1-decanol, 11-mercapto-1-undecanol, 12-mercapto-1-dodecanol, 13-mercapto-1-tridecanol, 14-mercapto-1-tetradecanol, 15-mercapto-1-pentadecanol, 16-mercapto-1-hexadecanol, 17-mercapto-1-heptadecanol, or 18-mercapto-1-octadecanol.

[0094] In this context, the photo-initiator for the thiol-ene click chemistry reaction in step (1) is a photo-initiator commonly used in the thiol-ene click chemistry reaction in the technical field, and a person skilled in the art can select a suitable photo-initiator for the thiol-ene click chemistry reaction according to actual needs, and determine the appropriate amount of addition and the optimal wavelength of ultraviolet light according to the existing technical information such as the commercial instruction / manual of the photo-initiator for the thiol-ene click chemistry reaction.

[0095] In one embodiment, the photo-initiator for the thiol-ene click chemistry reaction in step (1) is selected from any one of 2-hydroxy-2-methylpropiophenone, 2-hydroxy-2-methylpropiophenone, benzophenone, benzophenone, and (2,4,6-trimethylbenzoyl) diphenyl phosphine oxide.

[0096] In order to better illustrate the present application, and to provide an embodiment for reference, when the photo-initiator for the thiol-ene click chemistry reaction in step (1) is selected as 2-hydroxy-2-methylpropiophenone, 395 nm wavelength ultraviolet light should be used for irradiation, and the amount of addition is 2.5-3.5wt% of the total mass of eugenol and mercaptoalkanol in step (1).

[0097] In this context, the catalyst for the epoxidation reaction in step (2) is a catalyst commonly used in the epoxidation reaction in the technical field, and a person skilled in the art can select a suitable catalyst for the epoxidation reaction according to actual needs.

[0098] In one embodiment, the catalyst used in the epoxidation reaction in step (2) is selected from any one of tetrabutylammonium bromide, tetramethylammonium bromide, benzyltriethylammonium chloride; and the amount of the catalyst used in the epoxidation reaction is 8-12% of the molar amount of the eugenol-modified dihydroxy compound in step (2).

[0099] In this context, the ring-closing reaction in step (2) is a conventional process selected during the epoxidation reaction, and those skilled in the art can directly select a suitable ring-closing reaction process according to the common knowledge of the epoxidation reaction or the conventional epoxidation reaction process in the art.

[0100] In order to better illustrate the present application, and to provide an embodiment for reference, the reaction in step (2) is carried out at a temperature of 60-80°C for 8-24 hours, and the ring-closing reaction is carried out during the reaction, specifically, a NaOH aqueous solution with a mass of 3-5 times that of the dihydroxy compound and a mass concentration of 20-40 wt% is added to the reaction liquid (eugenol-modified dihydroxy compound, epichlorohydrin, and catalyst for the epoxidation reaction), and the reaction is carried out at a temperature of 60-80°C for 8-24 hours.

[0101] In order to better illustrate the present application, and to provide an embodiment for reference, the reaction in step (2) is carried out at a temperature of 60-80°C for 8-24 hours, and the ring-closing reaction is carried out during the reaction, specifically, a NaOH aqueous solution with a mass of 3-5 times that of the dihydroxy compound and a mass concentration of 20-40 wt% is added to the reaction liquid (eugenol-modified dihydroxy compound, epichlorohydrin, and catalyst for the epoxidation reaction), and the reaction is carried out at a temperature of 60-80°C for 8-24 hours.

[0102] In one embodiment, the intermediate epoxy monomer obtained in step (2) is separated by rotary evaporation, because epichlorohydrin is used as a solvent and the reaction product is also a liquid.

[0103] It should be noted that during the separation in step (2), the conventional process operations such as liquid-liquid separation and washing are usually accompanied, which are common knowledge in the technical field and will not be described here.

[0104] In this context, the ring-closing reaction in step (2) is a conventional process selected during the epoxidation reaction, and those skilled in the art can directly select a suitable ring-closing reaction process according to the common knowledge of the epoxidation reaction or the conventional epoxidation reaction process in the art.

[0105] In one embodiment, the ring ester ring-opening polymerization catalyst in step (3) is selected from one of triethylamine, triethanolamine, 4-dimethylaminopyridine, tetrabutylammonium bromide, tetramethylammonium chloride, N,N-dimethylbenzylamine and triphenylphosphine; the ring ester ring-opening polymerization catalyst is added in an amount of 0.5-1.0 wt% of the total mass of the epoxy intermediate monomer and acrylic acid in step (3).

[0106] In this context, the solvent in step (3) is selected from conventional solvents in the technical field, which can be conventional solvents for inks.

[0107] In one embodiment, the solvent in step (3) is selected from at least one of divalent acid ester high-boiling environmentally friendly solvents, ethylene glycol ethyl ether acetate, ethylene glycol butyl ether acetate, diethylene glycol ethyl ether acetate, diethylene glycol butyl ether acetate, propylene glycol methyl ether acetate, propylene glycol methyl ether propionate, dipropylene glycol methyl ether, propylene glycol methyl ether, mesitylene and tetramethylbenzene; the amount of solvent added can be determined according to the conventional amount in the preparation of alkali-soluble photo-curable epoxy resin in the technical field, or according to the following preferred method: in step (1), the mass of solvent: the mass of epoxy intermediate monomer = (0.5-4):1.

[0108] In this context, the polymerization inhibitor in step (3) is selected from conventional polymerization inhibitors in the technical field, which can be conventional polymerization inhibitors in the ink process.

[0109] In one embodiment, the polymerization inhibitor in step (3) is selected from at least one of hydroquinone, o-methyl hydroquinone, p-hydroxyanisole, p-benzoquinone and 2,6-di-tert-butyl-4-methylphenol. Preferably, the two added polymerization inhibitors are the same; the amount of polymerization inhibitor added in step (3) is 0.3-1.0 wt% of the total mass of the epoxy intermediate monomer and acrylic acid in step (3).

[0110] In this context, the amount of acrylic acid added in step (3) is consistent with the amount of acrylic acid added in the conventional synthesis process for preparing alkali-soluble photo-curable epoxy resin in the technical field, which is usually calculated according to the stoichiometric molar amount of the chemical reaction formula; in one embodiment, for example, the molar amount of acrylic acid is (2-2.1):1 of the molar amount of the epoxy intermediate monomer.

[0111] In this context, the unsaturated acid anhydride in step (4) is a conventional selection of unsaturated acid anhydride in the preparation of alkali-soluble photo-curable epoxy resin in the technical field, which can be directly selected by a person skilled in the art through the relevant technical literature in the prior art for preparing alkali-soluble photo-curable epoxy resin.

[0112] In the present application, the amount of the unsaturated anhydride added in step (4) is preferably consistent with the amount of the unsaturated anhydride added in the conventional synthesis process for preparing the alkali-soluble photocurable epoxy resin in the art, but can also be selected to esterify only half of the hydroxyl groups. In one embodiment, the molar ratio of the unsaturated anhydride to the epoxy intermediate monomer is (1-2.1): 1.

[0113] In one embodiment, the unsaturated anhydride in step (4) is selected from at least one of tetrahydrophthalic anhydride, itaconic anhydride, maleic anhydride, succinic anhydride, methyltetrahydrophthalic anhydride, hexahydrophthalic anhydride, and methylhexahydrophthalic anhydride.

[0114] In the present application, the stirring reaction is a conventional stirring reaction used in the art, including magnetic stirring or mechanical stirring, and a person skilled in the art can select an appropriate stirring reaction mode according to the production scale or the current process conditions. In one embodiment, the stirring reaction can be carried out at a stirring rate of 100-300 rpm.

[0115] On the other hand, based on the above-mentioned eugenol-modified alkali-soluble photocurable epoxy resin, the present application also provides a high-performance photosensitive solder resist ink using the above-mentioned alkali-soluble photocurable epoxy resin as the main component, the raw materials of which mainly include, by weight fraction:

[0116] eugenol-modified alkali-soluble photocurable epoxy resin 100 parts,

[0117] photoinitiator 1-5 parts.

[0118] In the present application, the photoinitiator is a conventional photoinitiator selected for preparing the photosensitive solder resist ink in the art, and a person skilled in the art can select an appropriate photoinitiator based on the current process conditions or the existing technical literature in the art.

[0119] In one embodiment, the photoinitiator is preferably at least one of 2,4,6-(trimethylbenzoyl)diphenylphosphine oxide, 2-methyl-1-(4-methylthiophenyl)-2-morpholinopropanone, 2-hydroxy-4-(2-hydroxyethoxyphenyl)-2-methylpropiophenone, 2-isopropylthioxanthone (2,4 isomer), 2-hydroxy-2-methyl-1-phenylpropanone, 1-hydroxycyclohexyl phenylmethanol, benzoin ethyl ether, benzil dimethyl ketal, 1-hydroxyphenylhexyl phenyl ketone, benzophenone / triethanolamine, and benzophenone / acrylate active amine.

[0120] In one preferred embodiment, the high-performance photosensitive solder resist ink further includes, by weight fraction:

[0121] filler 20-50 parts,

[0122] additive 1-25 parts.

[0123] In order to improve the physical strength of the coating film after the solder resist ink is used, the solder resist ink composition includes a filler, which is a commonly known inorganic or organic filler. In one embodiment, titanium white, bentonite, barium sulfate, spherical silica, nano calcium carbonate, talc, or one or more of the above are preferred. Further, a commonly known metal oxide is preferably used as both a filler and a pigment.

[0124] The additive is one or more of a pigment, a thermal inhibitor, an adhesion promoter, a defoamer, a leveling agent, a coupling agent, an antioxidant, and a rust inhibitor. The pigment, the thermal inhibitor, the adhesion promoter, the defoamer, the leveling agent, the coupling agent, the antioxidant, and the rust inhibitor are commonly known.

[0125] The high-performance photosensitive solder resist ink can be prepared by mixing all the components according to the prior art. For example, the components are mixed in a blender, and then mixed by three-roll milling to obtain the high-performance photosensitive solder resist ink.

[0126] When the solder resist ink is used, it is applied to a substrate, dried appropriately (at about 60-90°C), exposed to a pattern film, and the like, to obtain a cured coating film. The unexposed portion is developed. During development, solvent development can be performed using the solvent described above or a commonly known halogen-based solvent such as trichloroethylene. However, since the alkynyl active monomer-modified alkali-soluble photocurable epoxy resin contains a carboxyl group, the unexposed portion is dissolved in an alkaline aqueous solution, and thus alkaline development is preferred. The alkaline solvent for development can be an alkali metal compound such as sodium carbonate, potassium carbonate, sodium hydroxide, potassium hydroxide, and the like; an alkaline earth metal compound such as calcium hydroxide, and the like; an aqueous ammonia solution; or a water-soluble organic amine such as monomethylamine, dimethylamine, trimethylamine, monoethylamine, diethylamine, triethylamine, monopropylamine, dipropylamine, dimethylpropylamine, monoethanolamine, diethanolamine, triethanolamine, ethylene diamine, diethylene triamine, dimethylaminoethyl methacrylate, polyethylene imine, and the like.

[0127] After development, the photocured coating film is preferably heat-treated at about 120-160°C for 1 hour to further thermally cure the photocured coating film.

[0128] In general, the high-performance photosensitive solder resist ink described above can be used in the form of a solder resist layer dry film formed by previously applying and drying the solder resist ink on a film such as a PET film, in addition to the method of directly applying the solder resist ink in a liquid state to a substrate.

[0129] The present application will be further explained in detail with reference to the following examples. However, those skilled in the art will appreciate that the examples are provided for illustrative purposes only and are not intended to limit the scope of the present application.

[0130] Examples

[0131] The embodiments of the present application will be described in detail with reference to the following examples. However, those skilled in the art will appreciate that the examples are provided for illustrative purposes only and are not intended to limit the scope of the present application. Unless otherwise indicated, the conditions in the examples are conventional or those recommended by the manufacturer. Unless otherwise indicated, the reagents or instruments used are conventional products available commercially. The present application should not be construed as being limited to the specific examples described.

[0132] 1. Raw materials

[0133] Eugenol (EU), Benzyltriethylammonium chloride (TEBAC) were provided by Shanghai Titan Science and Technology Co., Ltd;

[0134] 2-(2-Ethoxyethoxy)ethyl acetate (DCAC), 2-Mercaptoethanol (2-MCH), 6-Mercaptohexanol (6-MCH), Hydroquinone (HQ), Triphenylphosphine (TPP) were provided by Chengdu Huaxia Chemical Reagent Co., Ltd;

[0135] Vanillyl alcohol (VA) was purchased from Shanghai McLean Biochemical Science and Technology Co., Ltd;

[0136] Epichlorohydrin (ECH), Sodium hydroxide (NaOH), 2-Hydroxy-2-methylpropiophenone (HMPP) were provided by Chengdu Kolon Chemical Co., Ltd;

[0137] 2-Isopropylthioxanthone (Photoinitiator ITX), Acrylic acid (AA), Tetrahydrophthalic anhydride (THPA) were provided by Sinopharm Chemical Reagent Co., Ltd;

[0138] Phthalocyanine green, Pentaerythritol triacrylate (PETA) were produced by Aladdin Reagent (Shanghai) Co., Ltd;

[0139] Epoxy-functionalized silica and barium sulfate nanoparticles were prepared by Shenzhen Haiyang Powder Technology Co., Ltd;

[0140] Thermosetting epoxy resin (NC3000) was provided by Nippon Kayaku Co., Ltd.

[0141] Synthesis Example 1

[0142] (1) Under air atmosphere, 32.8 g of eugenol (EU), 15.6 g of 2-mercaptoethanol (2-MCH) and 1.5 g of 2-hydroxy-2-methylpropiophenone (HMPP) were added to a reaction vessel, and the reaction was stirred for 15 h under irradiation of 395 nm UV light to obtain a dihydroxy compound modified with eugenol;

[0143] (2) 185.0 g of epichlorohydrin (ECH) and 4.5 g of benzyltriethylammonium chloride (TEBAC) were added to the dihydroxy compound modified with eugenol obtained in step (1), and the mixture was dissolved and stirred for 15 h at 80°C to obtain a pink solution;

[0144] Then, the pink solution was completely cooled at room temperature, 133 g of 30 wt% NaOH aqueous solution was added, and the stirring was continued for 15 h to obtain a mixed solution after a ring closure reaction;

[0145] The mixed solution was subjected to liquid separation to obtain an organic phase, which was washed to neutrality, and then the solvent was removed by vacuum distillation to obtain an epoxy intermediate monomer;

[0146] (3) Under air atmosphere, 53.2 g of the epoxy intermediate monomer obtained in step (2), 21.6 g of acrylic acid and 24.9 g of 2-(2-ethoxyethoxy)ethyl acetate (DCAC) were added to a reaction vessel, 0.6 g of triphenylphosphine (TPP) and 0.4 g of hydroquinone (HQ) were added, and the mixture was stirred for 12 h after being adjusted to 105°C to obtain an acrylic acid-modified epoxy intermediate monomer;

[0147] (4) The acrylic acid-modified epoxy intermediate monomer obtained in step (3) was cooled to 70°C, and then 22.8 g of tetrahydrophthalic anhydride (THPA) was added, and the stirring was continued for 6 h at 95°C to obtain an eugenol-modified alkali-soluble photocurable epoxy resin.

[0148] Synthesis Example 2

[0149] (1) Under air atmosphere, 32.8 g of eugenol (EU), 15.6 g of 2-mercaptoethanol (2-MCH) and 1.5 g of 2-hydroxy-2-methylpropiophenone (HMPP) were added to a reaction vessel, and the reaction was stirred for 15 h under irradiation of 395 nm UV light to obtain a dihydroxy compound modified with eugenol;

[0150] (2) 185.0 g of epichlorohydrin (ECH) and 4.5 g of benzyltriethylammonium chloride (TEBAC) were added to the dihydroxy compound modified with eugenol obtained in step (1), and the mixture was dissolved and stirred for 15 h at 80°C to obtain a pink solution;

[0151] Then, after the pink solution was completely cooled at room temperature, 133 g of a 30 wt% aqueous NaOH solution was added, and stirring was continued for 20 h to obtain a mixed solution after a ring-closing reaction treatment;

[0152] The mixed solution was separated into an organic phase, washed to neutrality, and then the solvent was removed by vacuum distillation to obtain an epoxy intermediate monomer;

[0153] (3) Under an air atmosphere, 61.6 g of the epoxy intermediate monomer obtained in step (2), 21.6 g of acrylic acid, and 27.7 g of 2-(2-ethoxyethoxy)ethyl acetate (DCAC) were added to a reaction vessel, 0.7 g of triphenylphosphine (TPP) and 0.4 g of hydroquinone (HQ) were added, and after being thoroughly mixed, the temperature was adjusted to 105°C, and stirring was continued for 12 h to obtain an acrylic acid-modified epoxy intermediate monomer;

[0154] (4) The acrylic acid-modified epoxy intermediate monomer obtained in step (3) was cooled to 70°C, and then 22.8 g of tetrahydrophthalic anhydride (THPA) was added, and stirring was continued at 95°C for 6 h to obtain a eugenol-modified alkali-soluble photocurable epoxy resin.

[0155] Comparative Synthesis Example 1

[0156] (1) Under an air atmosphere, 46.2 g of vanillyl alcohol (VA), 277.6 g of epichlorohydrin (ECH), and 6.8 g of benzyltriethylammonium chloride (TEBAC) were added to a reaction vessel, and after being thoroughly mixed and dissolved, stirring was continued at 80°C for 8 h to obtain a pink solution;

[0157] Then, after the pink solution was completely cooled at room temperature, 133 g of a 30 wt% aqueous NaOH solution was added, and stirring was continued for 20 h to obtain a mixed solution after a ring-closing reaction treatment;

[0158] The mixed solution was separated into an organic phase, washed to neutrality, and then the solvent was removed by vacuum distillation to obtain an epoxy intermediate monomer;

[0159] (3) Under an air atmosphere, 61.6 g of the epoxy intermediate monomer obtained in step (2), 21.6 g of acrylic acid, and 27.7 g of 2-(2-ethoxyethoxy)ethyl acetate (DCAC) were added to a reaction vessel, 0.7 g of triphenylphosphine (TPP) and 0.4 g of hydroquinone (HQ) were added, and after being thoroughly mixed, the temperature was adjusted to 105°C, and stirring was continued for 12 h to obtain an acrylic acid-modified epoxy intermediate monomer;

[0160] (4) The acrylic-modified epoxy intermediate monomer obtained in step (3) is cooled to 70°C, and then 22.8 g of tetrahydrophthalic anhydride (THPA) is added, and the reaction is continued at 95°C for 6 hours, to obtain a vanillyl alcohol-modified alkali-soluble photocurable epoxy resin.

[0161] Application Example 1

[0162] The vanillyl alcohol-modified alkali-soluble photocurable epoxy resin prepared in Synthesis Example 1 is used as a raw material, and the following raw materials are prepared in parts by weight:

[0163] Vanillyl alcohol-modified alkali-soluble photocurable epoxy resin 100 parts,

[0164] Photoinitiator ITX 3 parts;

[0165] The prepared components are mixed in a blender, and then mixed by three-roll milling, to obtain a high-performance photosensitive solder resist ink.

[0166] The obtained high-performance photosensitive solder resist ink is then coated on a substrate, dried at 75°C for 30 min for curing, and finally the cured film formed after curing is tested as a sample.

[0167] Application Example 2

[0168] The vanillyl alcohol-modified alkali-soluble photocurable epoxy resin prepared in Synthesis Example 2 is used as a raw material, and the following raw materials are prepared in parts by weight:

[0169] Vanillyl alcohol-modified alkali-soluble photocurable epoxy resin 100 parts,

[0170] Photoinitiator ITX 3 parts;

[0171] The prepared components are mixed in a blender, and then mixed by three-roll milling, to obtain a high-performance photosensitive solder resist ink.

[0172] The obtained high-performance photosensitive solder resist ink is then coated on a substrate, dried at 75°C for 30 min for curing, and finally the cured film formed after curing is tested as a sample.

[0173] Comparative Application Example 1

[0174] The vanillyl alcohol-modified alkali-soluble photocurable epoxy resin prepared in Comparative Synthesis Example 1 is used as a raw material, and the following raw materials are prepared in parts by weight:

[0175] Vanillyl alcohol-modified alkali-soluble photocurable epoxy resin 100 parts,

[0176] Photoinitiator ITX 3 parts;

[0177] The prepared components are mixed in a blender, and then mixed by three-roll mill to obtain the photosensitive solder resist contrast ink.

[0178] The obtained photosensitive solder resist contrast ink is coated on a substrate, dried at 75°C for 30 min for curing, and the cured film formed after curing is finally tested as a contrast sample.

[0179] Application Example 3

[0180] The eugenol-modified alkali-soluble photocurable epoxy resin prepared in Synthesis Example 1 is used as a raw material, and the following raw materials are prepared by weight fraction:

[0181]

[0182]

[0183] The prepared components are mixed in a blender, and then mixed by three-roll mill to obtain the high-performance photosensitive solder resist ink.

[0184] 3. Test method

[0185] (1) Infrared test: The infrared spectrum (FT-IR) test is measured by Nicolet is50 Fourier transform infrared spectrometer with a resolution of 4 cm -1 -1, and a scanning range of 400-4000 cm -1 -1. Among them, the solid sample is measured by potassium bromide tabletting method, and the liquid sample is measured by smearing method on potassium bromide tablet.

[0186] (2) Nuclear magnetic resonance hydrogen spectrum test: Nuclear magnetic resonance hydrogen spectrum test uses tetramethylsilane (TMS) as internal standard, and Bruker AV-400 spectrometer is used for 1 H NMR analysis, and the concentration of test sample is 10 mg / ml.

[0187] (3) Stress-strain test: Dynamic mechanical thermal analyzer (DMTA, TA Instruments Q850) is used to obtain the stress-strain curve of the cured film. The stress-strain test is carried out at 25°C constant temperature condition with a rate of 0.2 Nmin -1 . The mechanical properties of the sample at room temperature are measured, and the sample size is 30 mm x 3 mm x 0.05 mm.

[0188] (4) Dynamic mechanical thermal test: Dynamic mechanical thermal analyzer (DMTA, TA Instruments Q850) has thermal characteristics. Under the controlled force mode with pre-tightening force of 0.001 N and rate of 5°Cmin -1 , the stability of the sample with temperature change is measured, and the temperature range is 25-150°C, and the sample size is 30 mm x 3 mm x 0.05 mm.

[0189] (5) Breakdown strength: recorded by breakdown voltage tester (Beijing Guan measurement precision electrical instrument equipment Co. Ltd.), the maximum electric field is 100 kV.

[0190] The test results are shown in the following table. Figs. 1-6

[0191] The above examples are the preferred embodiments of the present application, but the embodiments of the present application are not limited to the above examples, and any changes, modifications, substitutions, combinations, simplifications made without departing from the spirit and principles of the present application should be equivalent replacement methods, and are all included in the protection scope of the present application.​

Claims

1. An eugenol-modified alkali-soluble photocurable epoxy resin, characterized by The chemical structural formula is as follows: ， Or is: ， In the formula, R is any one of the following structures: 、 、 、 。 2. A process for the preparation of eugenol-modified alkali-soluble photocurable epoxy resin according to claim 1, characterized by Mainly including the following steps: (1) Under the air atmosphere, adding eugenol, mercapto alkanol and thiol-ene click chemistry reaction photo initiator in the reaction container, under the condition of ultraviolet light irradiation of the wavelength of the photo initiation of the thiol-ene click chemistry reaction photo initiator, with stirring reaction for 12-24h, the eugenol modified dihydroxyl compound is obtained; Wherein, the mercapto alkanol is an alkyl chain compound with one end of the molecular structure being a hydroxyl group and the other end being a mercapto group, and the molar ratio of the eugenol to the mercapto alkanol is 1:(1-1.1); (2) Adding epichlorohydrin and an epoxidation catalyst in the eugenol modified dihydroxyl compound obtained in step (1), fully mixing and dissolving, and then stirring and reacting at a temperature of 60-80℃ for 8-24h, an epoxy intermediate monomer is obtained by separation; Wherein, the reaction is carried out at a temperature of 60-80℃ for 8-24h, and a ring closing reaction is carried out during the reaction process or after the reaction time reaches; The reaction is carried out at a temperature of 60-80℃ for 8-24h, and a ring closing reaction is carried out during the reaction process, specifically, a NaOH aqueous solution with a mass of 3-5 times that of the dihydroxyl compound and a mass concentration of 20-40wt% is further added in the reaction liquid, and the reaction is carried out at a temperature of 60-80℃ for 8-24h; The reaction is carried out at a temperature of 60-80℃ for 8-24h, and a ring closing reaction is carried out after the reaction time reaches, specifically, after the product is cooled to room temperature, a NaOH aqueous solution with a mass of 3-5 times that of the dihydroxyl compound and a mass concentration of 20-40wt% is added under stirring, and stirring is continued for 15h; The molar ratio of the eugenol modified dihydroxyl compound to the epichlorohydrin is 1:(5-12); (3) Under the air atmosphere, adding the epoxy intermediate monomer obtained in step (2), acrylic acid and a solvent in the reaction container, adding a ring-opening polymerization catalyst for cyclic ester and a polymerization inhibitor, fully mixing, then adjusting the temperature to 100-125℃, and stirring and reacting for 8-16h, an acrylic acid modified epoxy intermediate monomer is obtained; (4) The acrylic acid modified epoxy intermediate monomer obtained in step (3) is cooled to 70-80℃, then an unsaturated acid anhydride is added, and stirring and reacting at 85-100℃ for 6-12h, an eugenol modified alkali-soluble photo-curable epoxy resin is obtained.

3. The method of claim 2, wherein: The mercapto alkanol in step (1) includes at least one of 2-mercaptoethanol and 6-mercaptohexanol.

4. The method of claim 2, wherein: The thiol-ene click chemistry reaction photo initiator in step (1) includes any one of 2-hydroxy-2-methylpropiophenone, 2-hydroxy-2-methylpropiophenone, benzophenone, benzophenone, (2,4,6-trimethylbenzoyl) diphenyl phosphine oxide.

5. The method of claim 2, wherein: The catalyst used in the epoxidation reaction in step (2) includes any one of tetrabutylammonium bromide, tetramethylammonium bromide, and benzyltriethylammonium chloride; and the addition amount of the catalyst used in the epoxidation reaction is 8-12% of the molar amount of the eugenol-modified dihydroxy compound in step (2).

6. The method of claim 2, wherein: The unsaturated acid anhydride in step (4) is at least one of tetrahydrophthalic anhydride, methyltetrahydrophthalic anhydride, hexahydrophthalic anhydride, and methylhexahydrophthalic anhydride.

7. The method of claim 2, wherein: The molar amount ratio of the unsaturated acid anhydride to the molar amount of the epoxy intermediate monomer in step (4) is (1-2.1):

1.

8. A high performance photosensitive solder resist ink using the eugenol-modified alkali-soluble photocurable epoxy resin of claim 1 as a main component, characterized by The raw materials thereof include, by weight fraction: eugenol-modified alkali-soluble photocurable epoxy resin 100 parts, photoinitiator 1-5 parts.

9. The high performance photosensitive solder resist ink according to claim 8, characterized in that: The raw materials thereof further include, by weight fraction: filler 20-50 parts, additive 1-25 parts.

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