High-performance photocurable solder resist ink based on biomass soy extract and preparation method thereof

Abstract

The present invention provides a high-performance photocurable solder resist ink based on biomass soybean daidzein and a preparation method thereof. The preparation method comprises modifying soybean daidzein diglycidyl ether by ring-opening polymerization with acrylic acid, followed by esterification with an unsaturated acid anhydride to obtain the biomass soybean daidzein-based alkali-soluble photocurable resin. The technical solution utilizes soybean daidzein, a daidzein derivative with liquid crystal properties, as the main structure. Then, soybean daidzein diglycidyl ether is synthesized using epichlorohydrin. The alkali-soluble photocurable resin is then synthesized by grafting acrylic acid and an unsaturated acid anhydride to produce a high-performance photocurable solder resist ink. The cured film formed by curing the alkali-soluble photocurable resin exhibits the advantageous properties of high heat resistance and high toughness.

Description

Technical Field

[0001] The present invention relates to the technical field of photocurable solder resist inks, and in particular to a high-performance photocurable solder resist ink based on biomass soy extract and a preparation method thereof. The cured film formed by the cured solder resist ink has the advantageous properties of high heat resistance and high toughness. Background Art

[0002] Printed circuit boards (PCBs), the substrates used to mount and connect electronic components in modern electrical appliances, are essential components in the electronics industry. Light-curing solder resist ink is a key PCB material. It's a protective coating applied to the copper wires of printed circuits. It prevents corrosion and breakage, prevents short circuits caused by excessive solder joints, regulates solder adhesion, reduces copper dissolution contamination in welds, conserves solder, reduces instrument weight, increases wiring density, avoids cold solder joints, and speeds up inspections.

[0003] As data transmission evolves toward high-capacity, high-speed, and low-latency, high-frequency signal bands are expected to meet the requirements of fifth-generation (5G) communications technology. Electronic packaging and high-frequency communications are placing higher demands on solder mask layers for heat resistance, such as a glass transition temperature (Tg) of 160-190°C. However, traditional PCB packaging technologies based on bisphenol A, biphenyl, and cresol novolac epoxy resin backbones typically have Tgs between 120 and 150°C, far from meeting these requirements. Furthermore, increasingly complex electronic devices require PCBs that are no longer simply flat, but incorporate curves and angles, requiring solder mask inks to possess both excellent heat resistance and flexibility. Photocurable resin films obtained from these traditional epoxy resins exhibit elongation at break between 2 and 6%. Furthermore, when formulated as photosensitive inks, the inclusion of inorganic nanoparticles reduces the Tg of the cured film to between 0.5 and 3%. This Tg is far below the ideal Tg of 4% or higher.

[0004] Furthermore, these epoxy resins are all derived from non-renewable petroleum-based derivatives, which will undoubtedly exacerbate the environmental, energy, and ecological crises. Therefore, the development of renewable bio-based materials and derivatives from biological resources, such as cardanol, vanillin, tannic acid, gallic acid, and daidzein, is an effective way to achieve sustainability.

[0005] Therefore, how to combine bio-based materials with high heat resistance and high toughness, and how to compete with fossil fuel-derived materials without losing out (price, performance, and processability) is the research focus of all bio-based materials, and it is ultimately hoped that high-heat-resistant and high-toughness solder mask inks can be obtained. Summary of the Invention

[0006] In response to the problems raised by the above-mentioned prior art, the present invention provides a high-performance photocurable solder resist ink based on biomass soybean extract and a preparation method thereof. In its technical solution, soybean extract, a daidzein derivative with liquid crystal properties, is used as the main structure, followed by synthesizing soybean extract diglycidyl ether using epichlorohydrin, and then synthesizing an alkali-soluble photocurable resin by grafting acrylic acid and unsaturated acid anhydride to obtain a high-performance photocurable solder resist ink. The cured film formed by curing has the advantageous characteristics of high heat resistance and high toughness.

[0007] To achieve the above objectives, the present invention is implemented by adopting a technical solution consisting of the following technical measures.

[0008] In one aspect, the present invention provides an alkali-soluble photocurable resin based on biomass soy bean extract, the chemical structure of which is as follows:

[0009]

[0010] Wherein, R is any of the following structures:

[0011]

[0012] In the above chemical structural formula, “…” indicates the position where the chemical bonds are connected.

[0013] On the other hand, the present invention also provides a method for preparing the above-mentioned biomass soy bean-based alkali-soluble photocurable resin, which is modified by ring-opening polymerization of soy bean diglycidyl ether with acrylic acid, and finally esterified with an unsaturated acid anhydride to obtain the biomass soy bean-based alkali-soluble photocurable resin. It should be noted that those skilled in the art can derive specific preparation steps based on the reaction sequence shown above, especially the modification by ring-opening polymerization with acrylic acid and the esterification with an unsaturated acid anhydride, which are conventional synthetic routes for preparing alkali-soluble photocurable epoxy resins in the art; therefore, the technical solutions provided below in the present invention do not mean the sole designation or limitation of the preparation method of the biomass soy bean-based alkali-soluble photocurable resin.

[0014] The present invention also provides a method for preparing an alkali-soluble photocurable resin based on biomass soy extract, comprising the following steps:

[0015] (1) In an air atmosphere, daidzein diglycidyl ether, acrylic acid, and solvent A are added to a reaction vessel, a cyclic ester ring-opening polymerization catalyst and a polymerization inhibitor are added, and after thorough mixing, the temperature is adjusted to 100-125° C. and stirred for reaction for 8-16 hours to obtain daidzein diglycidyl ether grafted with acrylic acid;

[0016] (2) Cooling the daidzein diglycidyl ether grafted with acrylic acid obtained in step (1) to 90-100° C., then adding unsaturated acid anhydride, and continuing to stir and react at 85-100° C. for 6-12 hours to obtain an alkali-soluble photocurable resin based on biomass daidzein.

[0017] In this article, the "daidzein diglycidyl ether" described in step (1) is synthesized using commercially available daidzein (daidzein, CAS: 486-66-8) as a raw material, and its chemical structure is as follows:

[0018]

[0019] It should be noted that the "daidzein diglycidyl ether" is prepared by synthesizing daidzein by epoxidation of the terminal hydroxyl groups on daidzein. Those skilled in the art can obtain specific preparation steps based on the reaction principle shown above, or directly customize and purchase the finished product of daidzein diglycidyl ether. For example, daidzein diglycidyl ether is prepared by synthesizing daidzein by epichlorohydrin, which is a conventional synthetic route for preparing diglycidyl ether derivatives in this field.

[0020] In order to better illustrate the present invention and provide a technical solution for reference, the preparation method of soybean diglycidyl ether in step (1) mainly comprises the following steps:

[0021] Solvent B, daidzein, epichlorohydrin, and a phase transfer catalyst are added to a reaction vessel, fully mixed and dissolved, and stirred at 40-100° C. for 1-4 hours. After the reaction time is up, a ring-closing reaction reagent is added to carry out a ring-closing reaction treatment to separate and obtain daidzein diglycidyl ether;

[0022] Or for,

[0023] Add solvent B, daidzein, epichlorohydrin and a ring-closing reaction reagent into a reaction vessel, mix and dissolve them thoroughly, and then stir and react at 40-100° C. for 1-4 hours to separate and obtain daidzein diglycidyl ether;

[0024] The molar ratio of soymilk to epichlorohydrin is 1:(5-15);

[0025] The ring-closing reaction reagent is a NaOH aqueous solution in which the molar amount of the solute NaOH is 2.2 to 3.5 times that of daidzein and the mass concentration is 20 to 40 wt%.

[0026] In the above technical solution, the phase transfer catalyst is a catalyst commonly used in epoxidation reactions in this technical field. Those skilled in the art can select a suitable phase transfer catalyst according to actual needs.

[0027] Preferably, the phase transfer catalyst is selected from any one of benzyltriethylammonium chloride, hexadecyltrimethylammonium bromide, tetraethylammonium bromide, polyethylene glycol 500, CW-2 catalyst, CW-4 catalyst, and tetrabutylammonium bromide catalyst; and the added amount of the phase transfer catalyst is 8 to 12% of the molar amount of soybean extract.

[0028] In the above technical solution, the ring-closure reaction treatment is a conventional process selection during the epoxidation reaction process. Those skilled in the art can directly select an appropriate method for the ring-closure reaction treatment based on the common knowledge of the epoxidation reaction or the conventional epoxidation reaction process in the art.

[0029] In order to better illustrate the present invention and provide a technical solution for reference, after the reaction time is reached, a ring-closing reaction reagent is added to carry out a ring-closing reaction treatment, specifically, after adding the ring-closing reaction reagent, stirring the reaction at a temperature of 40 to 60° C. for 1 to 2 hours.

[0030] In the above technical solution, the solvent B is an organic solvent capable of dissolving soybean extract, and can be selected from any one of ethanol, isopropyl alcohol, dimethyl sulfoxide, and N-methylpyrrolidone. It should be noted that, generally speaking, solvent A and solvent B are different solvents.

[0031] In the above technical solution, the separated daidzein diglycidyl ether is dissolved in the reaction solution, and a non-solvent is usually added for precipitation to obtain the product. For example, the reaction solution is added into a large amount of petroleum ether and stirred to precipitate the product.

[0032] It should be noted that the separation process is usually accompanied by conventional process operations such as liquid separation and washing, which are common knowledge in the technical field and will not be repeated here.

[0033] Herein, the cyclic ester ring-opening polymerization catalyst in step (1) is a cyclic ester ring-opening polymerization catalyst commonly used in epoxy resin ring-opening polymerization reactions in this technical field. Technicians in this technical field can select a suitable cyclic ester ring-opening polymerization catalyst according to actual needs.

[0034] In one of the technical solutions, the cyclic ester ring-opening polymerization catalyst in step (1) is selected from one of triethylamine, triethanolamine, 4-dimethylaminopyridine, tetrabutylammonium bromide, tetramethylammonium chloride, N,N-dimethylbenzylamine and triphenylphosphine; the amount of the cyclic ester ring-opening polymerization catalyst added is 0.5 to 1.0 wt% of the total mass of the daidzein diglycidyl ether and acrylic acid in step (1).

[0035] In this article, the solvent A in step (1) is selected from conventional solvents in this technical field, and can be a conventional solvent for ink.

[0036] In one of the technical solutions, the solvent A in step (1) is selected from at least one of a divalent acid ester high-boiling point environmentally friendly solvent, 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, trimethylbenzene and tetramethylbenzene; the amount of solvent added can refer to the conventional amount used in the process for preparing alkali-soluble light-curing epoxy resin in the present technical field, or refer to the following preferred embodiment: in step (1), the mass of solvent A: the mass of soymilk diglycidyl ether = (0.5~4): 1.

[0037] In this article, the polymerization inhibitor in step (1) is selected from conventional polymerization inhibitors in this technical field, and can be a polymerization inhibitor commonly used in ink technology.

[0038] In one of the technical solutions, the polymerization inhibitor selected in step (1) includes at least one of hydroquinone, o-methyl hydroquinone, p-hydroxyanisole, p-benzoquinone and 2,6-di-tert-butyl-4-methylphenol; the amount of the polymerization inhibitor added in step (1) is 0.3 to 1.0 wt% of the total mass of daidzein diglycidyl ether and acrylic acid in step (1).

[0039] In this article, the amount of acrylic acid added in step (1) should be consistent with the amount of acrylic acid added in the conventional synthesis process for preparing alkali-soluble light-curing epoxy resins in the art, and is usually calculated based on the balanced molar amount of the chemical reaction formula. For example, the molar amount of acrylic acid and the molar amount of daidzein diglycidyl ether are (2 to 2.1):1.

[0040] Herein, the unsaturated anhydride in step (2) is a conventional choice of unsaturated anhydride in the process of preparing alkali-soluble light-curing epoxy resin in the art. Those skilled in the art can directly select a suitable unsaturated anhydride through the relevant technical literature on the preparation of alkali-soluble light-curing epoxy resin in the prior art.

[0041] In this article, the amount of unsaturated acid anhydride added in step (2) should be consistent with the amount of unsaturated acid anhydride added in the conventional synthesis process for preparing alkali-soluble light-curing epoxy resins in the art, but it is also possible to choose to esterify with only half of the hydroxyl groups, so the molar ratio of the unsaturated acid anhydride to the molar ratio of the soymilk diglycidyl ether is (1 to 1.8):1.

[0042] In one technical solution, the unsaturated acid anhydride in step (2) is selected from at least one of tetrahydrophthalic anhydride, itaconic anhydride, maleic anhydride, succinic anhydride, methyltetrahydrophthalic anhydride, hexahydrophthalic anhydride and methylhexahydrophthalic anhydride.

[0043] Herein, the stirring reaction is a stirring reaction conventionally used in the art, including magnetic stirring or mechanical stirring. Those skilled in the art can select an appropriate stirring reaction method according to the production scale or process conditions. In one technical solution, the stirring reaction can be carried out at a stirring rate of 100 to 300 rpm.

[0044] On the other hand, based on the above-mentioned biomass soybean extract-based alkali-soluble photocurable resin, the present invention also provides a high-performance photocurable solder resist ink using the above-mentioned alkali-soluble photocurable resin as a main component, and its raw materials mainly include, by weight:

[0045] 100 parts of alkali-soluble light-curing resin based on biomass soy bean extract,

[0046] 1 to 5 parts of photoinitiator.

[0047] Herein, the photoinitiator is a photoinitiator conventionally selected for preparing photocurable solder resist ink in the art. Those skilled in the art can select a suitable photoinitiator based on the current process conditions or existing technical literature in the art.

[0048] In one of the technical solutions, the photoinitiator is preferably at least one of 2,4,6-(trimethylbenzoyl)diphenylphosphine oxide, 2-methyl-1-(4-methylthiophenyl)-2-morpholinyl-1-propanone, 2-hydroxy-4-(2-hydroxyethoxyphenyl)-2-methylpropiophenone, 2-isopropylthioxanthone (2,4 isomers), 2-hydroxy-2-methyl-1-phenylpropiophenone, 1-hydroxycyclohexylphenylmethanol, benzoin ethyl ether, benzil dimethyl ketal, 1-hydroxyphenylhexylacetophenone, benzophenone / triethanolamine and benzophenone / acrylate active amine.

[0049] During the actual research and development process, the inventors further discovered that by further compounding the prepared biomass soybean alkali-soluble photocurable resin with soybean alkali diglycidyl ether to obtain a photocurable solder resist ink, the cured film obtained by curing has better heat resistance and mechanical properties. In one of the more preferred technical solutions, the present invention also provides a high-performance photocurable solder resist ink compounded with the above-mentioned alkali-soluble photocurable resin, and its raw materials mainly include, by weight:

[0050] 70-90 parts of alkali-soluble photocurable resin based on biomass soybean extract,

[0051] 10-30 parts of soybean diglycidyl ether,

[0052] 1 to 5 parts of photoinitiator,

[0053] The biomass soy bean extract-based alkali-soluble photocurable resin and soy bean extract diglycidyl ether are in a total of 100 parts.

[0054] It should be noted that when preparing the above formula, if the daidzein diglycidyl ether does not dissolve, 5 to 15 parts of solvent A should be added to assist in dissolving the daidzein diglycidyl ether.

[0055] In one preferred technical solution, the high-performance light-curable solder resist ink further comprises, by weight, the following raw materials:

[0056] 20 to 50 parts of filler,

[0057] 1 to 25 parts of additives.

[0058] In order to improve the physical strength of the coating film after the solder resist ink is used, the solder resist ink component includes a filler, and the filler is a well-known inorganic or organic filler, preferably one or more of titanium dioxide, bentonite, barium sulfate, spherical silica, nano-calcium carbonate, and talc. Furthermore, well-known metal oxides are preferably used as both fillers and pigments.

[0059] The additives are one or more combinations of pigments, thermal polymerization inhibitors, tackifiers, defoamers, leveling agents, coupling agents, antioxidants, and rust inhibitors. Typically, the pigments, thermal polymerization inhibitors, tackifiers, defoamers, leveling agents, coupling agents, antioxidants, and rust inhibitors are well-known and commonly used.

[0060] The high-performance light-curable solder resist ink can be prepared by mixing all components in accordance with existing techniques. For example, the components can be pre-mixed in a blender and then kneaded in a three-roll mill to obtain the high-performance light-curable solder resist ink.

[0061] When using the solder resist ink described above, it is applied to a substrate, dried appropriately (approximately 60-90°C), and then exposed through a patterned film to form a cured coating, allowing the unexposed portions to be developed. Development can be performed using the aforementioned solvents or conventionally used halogen-based solvents such as trichloroethylene. However, since carboxyl groups are introduced into alkali-soluble photocurable resins, the unexposed portions will dissolve in alkaline aqueous solutions, so alkaline development is preferred. Alkaline solvent development can include alkali metal compounds such as sodium carbonate, potassium carbonate, sodium hydroxide, and potassium hydroxide; alkaline earth metal compounds such as calcium hydroxide; alkaline aqueous ammonia; or water-soluble organic amines such as monomethylamine, dimethylamine, trimethylamine, monoethylamine, diethylamine, triethylamine, monopropylamine, dipropylamine, dimethylpropylamine, monoethanolamine, diethanolamine, triethanolamine, ethylenediamine, diethylenetriamine, dimethylaminoethyl methacrylate, and polyethyleneimine.

[0062] After development, it is preferred to perform heat treatment at approximately 120 to 160° C. for 1 hour to further heat cure the photocured coating film.

[0063] Generally, the high-performance photocurable solder resist ink can be directly applied to a substrate in a liquid state or can be used in a state where a solder resist layer is formed by applying and drying the solder resist layer on a film such as PET.

[0064] The present invention has the following beneficial effects:

[0065] 1. This invention provides a high-performance, photocurable solder mask ink based on biomass-derived daidzein and a method for its preparation. This technical solution utilizes daidzein, a daidzein derivative with liquid crystal properties, as the main structural component. Daidzein diglycidyl ether is then prepared using daidzein diglycidyl ether, which is then reacted with acrylic acid and tetrahydrophthalic anhydride to synthesize an alkali-soluble, photocurable resin. The use of sustainable bio-based materials reduces the solder mask ink industry's reliance on fossil fuel-derived compounds.

[0066] 2. In the present invention, soybean extract has a rigid structure with a large aspect ratio, which makes the derived photocurable resin have liquid crystal properties. It can enhance the mechanical properties of the material through specific arrangement and orientation, thereby improving the toughness of the material. At the same time, the rigid structure has a strong restraining effect on the movement of the chain segments, thereby obtaining an excellent glass transition temperature.

[0067] 3. In this invention, a large number of carboxyl groups are introduced by the reaction of acid anhydride with hydroxyl groups, giving the product excellent alkali developability. Direct immersion in a weak alkaline solution allows for rapid and complete release without damaging the substrate. Furthermore, the strong polarity of the carboxyl groups ensures excellent adhesion to the substrate and prevents it from falling off.

[0068] 4. The high-performance photocurable solder resist ink in the preferred technical solution provided by the present invention has been tested and has excellent properties in terms of mechanical properties, resistance to soldering heat, solvent resistance, chemical resistance, electroless gold plating resistance, electroless tin plating resistance, and electrical properties. BRIEF DESCRIPTION OF THE DRAWINGS

[0069] Figure 1 The infrared spectra of the raw materials, intermediates, and final products used in Synthesis Example 1 of the present invention are shown. In the figure, DDAT is the biomass-based daidzein-based alkali-soluble photocurable resin prepared in Synthesis Example 1; DDDE-AA is daidzein diglycidyl ether grafted onto acrylic acid in Synthesis Example 1; DDDE is daidzein diglycidyl ether in Synthesis Example 1; and DD is the daidzein raw material used in Synthesis Example 1.

[0070] Figure 2 1 is the H NMR spectrum of the raw materials, intermediate products and final products used in Synthesis Example 1 of the present invention.

[0071] In the figure, DDAT is the biomass daidzein-based alkali-soluble photocurable resin finally prepared in Synthesis Example 1; DDDE-AA is daidzein diglycidyl ether grafted with acrylic acid in Synthesis Example 1; DDDE is daidzein diglycidyl ether in Synthesis Example 1; DD is the raw material daidzein used in Synthesis Example 1.

[0072] Figure 3 This is a graph comparing the double bond conversion rate and time of the high-performance photocurable solder resist inks prepared in Examples 1 to 4 of the present invention during the photocuring process.

[0073] Figure 4 The storage modulus versus temperature curves of the cured film samples obtained in Examples 1 to 8 of the present invention are shown in Figure (a). The storage modulus versus temperature curves of the cured film samples obtained in Examples 1 to 4 of the present invention are shown in Figure (b).

[0074] Figure 5 The tangent loss spectrum of the cured film samples obtained in Examples 1 to 8 of the present invention is compared. Figure (a) corresponds to the cured film samples obtained in Examples 1 to 4 of the present invention; Figure (b) corresponds to the cured film samples obtained in Examples 5 to 8 of the present invention; the T g The value is recorded as the temperature at which the maximum Tanδ signal is obtained. g The value is greater than 190℃, which is much higher than the 120-140℃ of ordinary epoxy resins; the T g The temperatures were further improved to 212℃, 222℃, 227℃ and 219℃ respectively.

[0075] Figure 6 The figures are stress-strain curve comparisons and strength, strain, and toughness statistical column comparisons of the cured film samples obtained in Examples 1 to 8 of the present invention. Figure (a) is a stress-strain curve comparison of the cured film samples obtained in Examples 1 to 4 of the present invention, Figure (b) is a strength statistical column comparison of the cured film samples obtained in Examples 1 to 4 of the present invention, Figure (c) is a strain statistical column comparison of the cured film samples obtained in Examples 1 to 4 of the present invention, Figure (d) is a toughness statistical column comparison of the cured film samples obtained in Examples 1 to 4 of the present invention, Figure (e) is a stress-strain curve comparison of the cured film samples obtained in Examples 5 to 8 of the present invention, Figure (f) is a strength statistical column comparison of the cured film samples obtained in Examples 5 to 8 of the present invention, Figure (g) is a strain statistical column comparison of the cured film samples obtained in Examples 5 to 8 of the present invention, and Figure (h) is a toughness statistical column comparison of the cured film samples obtained in Examples 5 to 8 of the present invention. DETAILED DESCRIPTION

[0076] In order to further understand the present invention, preferred embodiments of the present invention are described below in conjunction with examples, but it should be understood that these descriptions are only for further illustrating the features and advantages of the present invention, rather than for limiting the claims of the invention. Those skilled in the art can refer to the contents of this article and appropriately improve the process parameters for implementation. It is particularly important to point out that all similar replacements and modifications are obvious to those skilled in the art, and they are all considered to be included in the present invention. The methods and applications of the present invention have been described through preferred embodiments, and relevant personnel can obviously modify or appropriately change and combine the methods and applications described herein without departing from the content, spirit and scope of the present invention to implement and apply the technology of the present invention. Although it is believed that those of ordinary skill in the art fully understand the following terms, the following definitions are still stated to help illustrate the subject matter disclosed by the present invention.

[0077] In one aspect, the present invention provides an alkali-soluble photocurable resin based on biomass soy bean extract, the chemical structure of which is as follows:

[0078]

[0079] Wherein, R is any of the following structures:

[0080]

[0081] In the above chemical structural formula, “…” indicates the position where the chemical bonds are connected.

[0082] On the other hand, the present invention also provides a method for preparing the above-mentioned biomass soy bean-based alkali-soluble photocurable resin, which is modified by ring-opening polymerization of soy bean diglycidyl ether with acrylic acid, and finally esterified with an unsaturated acid anhydride to obtain the biomass soy bean-based alkali-soluble photocurable resin. It should be noted that those skilled in the art can derive specific preparation steps based on the reaction sequence shown above, especially the modification by ring-opening polymerization with acrylic acid and the esterification with an unsaturated acid anhydride, which are conventional synthetic routes for preparing alkali-soluble photocurable epoxy resins in the art; therefore, the technical solutions provided below in the present invention do not mean the sole designation or limitation of the preparation method of the biomass soy bean-based alkali-soluble photocurable resin.

[0083] The present invention also provides a method for preparing an alkali-soluble photocurable resin based on biomass soy extract, comprising the following steps:

[0084] (1) In an air atmosphere, daidzein diglycidyl ether, acrylic acid, and solvent A are added to a reaction vessel, a cyclic ester ring-opening polymerization catalyst and a polymerization inhibitor are added, and after thorough mixing, the temperature is adjusted to 100-125° C. and stirred for reaction for 8-16 hours to obtain daidzein diglycidyl ether grafted with acrylic acid;

[0085] (2) Cooling the daidzein diglycidyl ether grafted with acrylic acid obtained in step (1) to 90-100° C., then adding unsaturated acid anhydride, and continuing to stir and react at 85-100° C. for 6-12 hours to obtain an alkali-soluble photocurable resin based on biomass daidzein.

[0086] In this article, the "daidzein diglycidyl ether" described in step (1) is synthesized using commercially available daidzein (daidzein, CAS: 486-66-8) as a raw material, and its chemical structure is as follows:

[0087]

[0088] It should be noted that the "daidzein diglycidyl ether" is prepared by synthesizing daidzein by epoxidation of the terminal hydroxyl groups on daidzein. Those skilled in the art can obtain specific preparation steps based on the reaction principle shown above, or directly customize and purchase the finished product of daidzein diglycidyl ether. For example, daidzein diglycidyl ether is prepared by synthesizing daidzein by epichlorohydrin, which is a conventional synthetic route for preparing diglycidyl ether derivatives in this field.

[0089] In order to better illustrate the present invention and provide an embodiment for reference, the preparation method of soybean diglycidyl ether in step (1) mainly comprises the following steps:

[0090] Solvent B, daidzein, epichlorohydrin, and a phase transfer catalyst are added to a reaction vessel, fully mixed and dissolved, and stirred at 40-100° C. for 1-4 hours. After the reaction time is up, a ring-closing reaction reagent is added to carry out a ring-closing reaction treatment to separate and obtain daidzein diglycidyl ether;

[0091] Or for,

[0092] Add solvent B, daidzein, epichlorohydrin and a ring-closing reaction reagent into a reaction vessel, mix and dissolve them thoroughly, and then stir and react at 40-100° C. for 1-4 hours to separate and obtain daidzein diglycidyl ether;

[0093] The molar ratio of soymilk to epichlorohydrin is 1:(5-15);

[0094] The ring-closing reaction reagent is a NaOH aqueous solution in which the molar amount of the solute NaOH is 2.2 to 3.5 times that of daidzein and the mass concentration is 20 to 40 wt%.

[0095] In the above embodiment, the phase transfer catalyst is a catalyst commonly used in epoxidation reactions in the technical field. Those skilled in the art can select a suitable phase transfer catalyst according to actual needs.

[0096] Preferably, the phase transfer catalyst is selected from any one of benzyltriethylammonium chloride, hexadecyltrimethylammonium bromide, tetraethylammonium bromide, polyethylene glycol 500, CW-2 catalyst, CW-4 catalyst, and tetrabutylammonium bromide catalyst; and the added amount of the phase transfer catalyst is 8 to 12% of the molar amount of soybean extract.

[0097] In the above embodiment, the ring-closure reaction treatment is a conventional process selection during the epoxidation reaction process. Those skilled in the art can directly select an appropriate method for the ring-closure reaction treatment based on the common knowledge of the epoxidation reaction or the conventional epoxidation reaction process in the art.

[0098] In order to better illustrate the present invention and provide an embodiment for reference, after the reaction time is reached, a ring-closing reaction reagent is added to carry out a ring-closing reaction treatment, specifically, after adding the ring-closing reaction reagent, stirring the reaction at a temperature of 40 to 60° C. for 1 to 2 hours.

[0099] In the above embodiment, the molar ratio of daidzein to epichlorohydrin is 1:(5-15), for example, 1:5, 1:6, 1:7, 1:8, 1:9, 1:10, 1:11, 1:12, 1:13, 1:14, 1:15 or any range or point value therebetween.

[0100] In the above embodiment, the solvent B is an organic solvent capable of dissolving soybean extract, and can be selected from any one of ethanol, isopropyl alcohol, dimethyl sulfoxide, and N-methylpyrrolidone. It should be noted that, generally speaking, solvent A and solvent B are different solvents.

[0101] In the above embodiment, the separated daidzein diglycidyl ether is dissolved in the reaction solution, and a non-solvent is usually added for precipitation to obtain the product. For example, the reaction solution is added to a large amount of petroleum ether and stirred to precipitate the product.

[0102] It should be noted that the separation process is usually accompanied by conventional process operations such as liquid separation and washing, which are common knowledge in the technical field and will not be repeated here.

[0103] Herein, the cyclic ester ring-opening polymerization catalyst in step (1) is a cyclic ester ring-opening polymerization catalyst commonly used in epoxy resin ring-opening polymerization reactions in this technical field. Technicians in this technical field can select a suitable cyclic ester ring-opening polymerization catalyst according to actual needs.

[0104] In one embodiment, the cyclic ester ring-opening polymerization catalyst in step (1) is selected from one of triethylamine, triethanolamine, 4-dimethylaminopyridine, tetrabutylammonium bromide, tetramethylammonium chloride, N,N-dimethylbenzylamine and triphenylphosphine; the amount of the cyclic ester ring-opening polymerization catalyst added is 0.5-1.0 wt% of the total mass of the daidzein diglycidyl ether and acrylic acid in step (1), for example, 0.5 wt%, 0.6 wt%, 0.7 wt%, 0.8 wt%, 0.9 wt%, 1.0 wt% or any range or point value therebetween.

[0105] In this article, the solvent A in step (1) is selected from conventional solvents in the art, and can be conventional solvents used in inks.

[0106] In one embodiment, the solvent A in step (1) is selected from at least one of a divalent acid ester high-boiling point environmentally friendly solvent, 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, trimethylbenzene and tetramethylbenzene; the amount of solvent added can refer to the conventional amount used in the process for preparing alkali-soluble light-curing epoxy resin in the present technical field, or refer to the following preferred embodiment: in step (1), the mass of solvent A: the mass of soymilk diglycidyl ether = (0.5-4): 1, for example, 0.5:1, 0.6:1, 0.8:1, 1:1, 1.2:1, 1.5:1, 2:1, 2.5:1, 3:1, 3.5:1, 3.8:1, 4:1 or any range or point value therebetween.

[0107] In this article, the polymerization inhibitor in step (1) is selected from conventional polymerization inhibitors in this technical field, and can be a polymerization inhibitor commonly used in ink technology.

[0108] In one embodiment, the polymerization inhibitor selected in step (1) includes at least one of hydroquinone, o-methyl hydroquinone, p-hydroxyanisole, p-benzoquinone and 2,6-di-tert-butyl-4-methylphenol; the amount of the polymerization inhibitor added in step (1) is 0.3 to 1.0 wt% of the total mass of daidzein diglycidyl ether and acrylic acid in step (1), for example, 0.3 wt%, 0.4 wt%, 0.5 wt%, 0.6 wt%, 0.7 wt%, 0.8 wt%, 0.9 wt%, 1.0 wt% or any range or point value therebetween.

[0109] In this article, the amount of acrylic acid added in step (1) should be consistent with the amount of acrylic acid added in the conventional synthesis process for preparing alkali-soluble light-curing epoxy resins in the art, and is usually calculated based on the balanced molar amount of the chemical reaction formula. For example, the molar amount of acrylic acid and the molar amount of daidzein diglycidyl ether are (2 to 2.1):1.

[0110] Herein, the unsaturated anhydride in step (2) is a conventional choice of unsaturated anhydride in the process of preparing alkali-soluble light-curing epoxy resin in the art. Those skilled in the art can directly select a suitable unsaturated anhydride through the relevant technical literature on the preparation of alkali-soluble light-curing epoxy resin in the prior art.

[0111] Herein, the amount of unsaturated anhydride added in step (2) should be consistent with the amount of unsaturated anhydride added in the conventional synthesis process for preparing alkali-soluble light-curing epoxy resins in the art, but it is also possible to choose to esterify with only half of the hydroxyl groups. In one embodiment, the molar amount of the unsaturated anhydride and the molar amount of the soymilk diglycidyl ether are (1 to 1.8):1, for example, 1:1, 1.1:1, 1.2:1, 1.3:1, 1.4:1, 1.5:1, 1.6:1, 1.7:1, 1.8:1 or any range or point value therebetween.

[0112] In one embodiment, the unsaturated acid anhydride in step (2) is selected from at least one of tetrahydrophthalic anhydride, itaconic anhydride, maleic anhydride, succinic anhydride, methyltetrahydrophthalic anhydride, hexahydrophthalic anhydride and methylhexahydrophthalic anhydride.

[0113] Herein, the stirring reaction is a stirring reaction conventionally used in the art, including magnetic stirring or mechanical stirring. Those skilled in the art can select an appropriate stirring reaction method according to the production scale or process conditions. In one embodiment, the stirring reaction can be carried out at a stirring rate of 100 to 300 rpm.

[0114] On the other hand, based on the above-mentioned biomass soybean extract-based alkali-soluble photocurable resin, the present invention also provides a high-performance photocurable solder resist ink using the above-mentioned alkali-soluble photocurable resin as a main component, and its raw materials mainly include, by weight:

[0115] 100 parts of alkali-soluble light-curing resin based on biomass soy bean extract,

[0116] 1 to 5 parts of photoinitiator.

[0117] Herein, the photoinitiator is a photoinitiator conventionally selected for preparing photocurable solder resist ink in the art. Those skilled in the art can select a suitable photoinitiator based on the current process conditions or existing technical literature in the art.

[0118] In one embodiment, the photoinitiator is preferably at least one of 2,4,6-(trimethylbenzoyl)diphenylphosphine oxide, 2-methyl-1-(4-methylthiophenyl)-2-morpholinyl-1-propanone, 2-hydroxy-4-(2-hydroxyethoxyphenyl)-2-methylpropiophenone, 2-isopropylthioxanthone (2,4 isomers), 2-hydroxy-2-methyl-1-phenylpropiophenone, 1-hydroxycyclohexylphenylmethanol, benzoin ethyl ether, benzil dimethyl ketal, 1-hydroxyphenylhexylacetophenone, benzophenone / triethanolamine and benzophenone / acrylate reactive amine.

[0119] During the actual research and development process, the inventors further discovered that by further compounding the prepared biomass soybean alkali-soluble photocurable resin with soybean alkali diglycidyl ether to obtain a photocurable solder resist ink, the cured film obtained by curing has better heat resistance and mechanical properties. In one of the more preferred embodiments, the present invention also provides a high-performance photocurable solder resist ink compounded with the above-mentioned alkali-soluble photocurable resin, and its raw materials mainly include, by weight:

[0120] 70-90 parts of alkali-soluble photocurable resin based on biomass soybean extract,

[0121] 10-30 parts of soybean diglycidyl ether,

[0122] 1 to 5 parts of photoinitiator,

[0123] The biomass soy bean extract-based alkali-soluble photocurable resin and soy bean extract diglycidyl ether are in a total of 100 parts.

[0124] It should be noted that when preparing the above formula, if the daidzein diglycidyl ether does not dissolve, 5 to 15 parts of solvent A should be added to assist in dissolving the daidzein diglycidyl ether.

[0125] In one preferred embodiment, the high-performance light-curable solder resist ink further comprises, by weight, the following raw materials:

[0126] 20 to 50 parts of filler,

[0127] 1 to 25 parts of additives.

[0128] In order to improve the physical strength of the coating film after the solder resist ink is used, the solder resist ink component includes a filler, and the filler is a well-known inorganic or organic filler, preferably one or more of titanium dioxide, bentonite, barium sulfate, spherical silica, nano-calcium carbonate, and talc. Furthermore, well-known metal oxides are preferably used as both fillers and pigments.

[0129] The additives are one or more combinations of pigments, thermal polymerization inhibitors, tackifiers, defoamers, leveling agents, coupling agents, antioxidants, and rust inhibitors. Typically, the pigments, thermal polymerization inhibitors, tackifiers, defoamers, leveling agents, coupling agents, antioxidants, and rust inhibitors are well-known and commonly used.

[0130] The high-performance light-curable solder resist ink can be prepared by mixing all components in accordance with existing techniques. For example, the components can be pre-mixed in a blender and then kneaded in a three-roll mill to obtain the high-performance light-curable solder resist ink.

[0131] When using the solder resist ink described above, it is applied to a substrate, dried appropriately (approximately 60-90°C), and then exposed through a patterned film to form a cured coating, allowing the unexposed portions to be developed. Development can be performed using the aforementioned solvents or conventionally used halogen-based solvents such as trichloroethylene. However, since carboxyl groups are introduced into alkali-soluble photocurable resins, the unexposed portions will dissolve in alkaline aqueous solutions, so alkaline development is preferred. Alkaline solvent development can include alkali metal compounds such as sodium carbonate, potassium carbonate, sodium hydroxide, and potassium hydroxide; alkaline earth metal compounds such as calcium hydroxide; alkaline aqueous ammonia; or water-soluble organic amines such as monomethylamine, dimethylamine, trimethylamine, monoethylamine, diethylamine, triethylamine, monopropylamine, dipropylamine, dimethylpropylamine, monoethanolamine, diethanolamine, triethanolamine, ethylenediamine, diethylenetriamine, dimethylaminoethyl methacrylate, and polyethyleneimine.

[0132] After development, it is preferred to perform heat treatment at approximately 120 to 160° C. for 1 hour to further heat cure the photocured coating film.

[0133] Generally, the high-performance photocurable solder resist ink can be directly applied to a substrate in a liquid state or can be used in a state where a solder resist layer is formed by applying and drying the solder resist layer on a film such as PET.

[0134] The present invention will be further explained in detail below with reference to the examples. However, it will be appreciated by those skilled in the art that these examples are provided for illustrative purposes only and are not intended to limit the present invention.

[0135] Example

[0136] The embodiments of the present application will be described in detail below in conjunction with the examples, but it will be appreciated by those skilled in the art that the following examples are merely illustrative of the present application and should not be considered as limiting the scope of the present application. In the examples, if no specific conditions are indicated, the conditions are carried out according to normal conditions or manufacturer recommendations. The reagents used or the instruments that are not indicated by the manufacturer are conventional products that can be obtained commercially. The application should not be construed as being limited to the specific examples described.

[0137] 1. Raw materials

[0138] Soybean extract (DD), catalyst triphenylphosphine (TPP), inhibitor hydroquinone (HQ) and photoinitiator 2-isopropylthioxanthone (ITX) were purchased from Chengdu Huaxia Chemical Reagent Co., Ltd.

[0139] Epichlorohydrin, dichloromethane, isopropyl alcohol, diethylene glycol ethyl ether acetate (DCAC), and tetrabutylammonium bromide were provided by Chengdu Kelon Chemical Engineering Reagent Factory.

[0140] 1,2,5,6-Tetrahydrophthalic anhydride (THPA), acrylic acid (AA), petroleum ether, and sodium hydroxide were provided by Chengdu Best Reagent Co., Ltd.

[0141] 2. Test Method

[0142] (1) Infrared test: Infrared spectrum (FT-IR) test is measured by Nicolet 560 Fourier transform infrared spectrometer with a resolution of 4cm -1 , scanning range is 400-4000cm -1 Among them, solid samples are measured by potassium bromide tablet method, and liquid samples are measured by smearing method on potassium bromide tablets.

[0143] (2) H NMR test: H NMR test was performed using a Bruker ARX600 NMR spectrometer from Bruker Corporation of the United States, using deuterated dimethyl sulfoxide (DMSO-d6) as the solvent, and the test sample concentration was 10 mg / ml.

[0144] (3) Thermogravimetric analysis: A TG 209F1 thermogravimetric analyzer (Netzsch, Germany) was used to determine the thermal stability of the samples. The test conditions were as follows: the cured films (4–6 mg) were heated from 30°C to 700°C at a heating rate of 10°C / min under a nitrogen atmosphere (flow rate of 20 ml / min).

[0145] (4) Room temperature broadband dielectric test: At room temperature, use Concept-50 broadband dielectric tester (Novocontrol, Germany) at 10-10 7The dielectric spectrum was measured in the frequency range of Hz. The size of the sample was 12 mm × 12 mm × 0.02 mm.

[0146] (5) Water contact angle test: The water contact angle test was performed using a DSA 25 (KRUSS, Germany) instrument using deionized water at room temperature. The thickness of the sample was 0.02 mm.

[0147] (6) Dynamic mechanical thermal test: Dynamic mechanical thermal analyzer (DMTA, TA Instruments Q850) has thermal characteristics. -1 The stability of the sample with temperature change was measured in the controlled force mode, the temperature range was 30 ~ 250 ° C, and the sample size was 12mm × 4mm × 0.05mm.

[0148] Synthesis example 1

[0149] In an air atmosphere, 100 g of daidzein (DD), 300 g of epichlorohydrin, 300 g of isopropyl alcohol, and 10 g of tetrabutylammonium bromide were added to a 1 L three-necked flask equipped with a mechanical stirrer. After mixing well, the mixture was stirred at 300 rpm at 90 °C for 4 hours.

[0150] The temperature was then lowered to 40°C, and 100 g of a 40 wt% aqueous sodium hydroxide solution was added dropwise over 1 hour. After reacting for another hour, the mixture was added to a large amount of petroleum ether and stirred to precipitate the product. Finally, the product was washed multiple times with water and methanol, respectively, and dried to obtain daidzein diglycidyl ether with a yield of 84%, which was designated as DDDE.

[0151] In an air atmosphere, 100 g of daidzein diglycidyl ether and 50 g of diethylene glycol ethyl ether acetate (DCAC) were added to a 500 ml three-necked flask equipped with a mechanical stirrer, followed by the addition of 40 g of acrylic acid, 3 g of triphenylphosphine, and 1.5 g of hydroquinone. After thorough mixing, the mixture was heated to 110°C for thorough dissolution and stirring, and the mixture was stirred at 110°C for 12 hours to obtain a daidzein diglycidyl ether grafted acrylic acid mixture, designated as DDDE-AA.

[0152] Then, the mixture of daidzein diglycidyl ether grafted with acrylic acid was cooled to 100°C, 41.53 g of 1,2,5,6-tetrahydrophthalic anhydride (THPA) was added, and the reaction was stirred at 100°C for 8 hours to obtain an alkali-soluble light-curable resin based on biomass daidzein, which was recorded as DDAT.

[0153] Synthesis example 2

[0154] Synthesis Example 2 follows the steps of Synthesis Example 1, except that 1,2,5,6-tetrahydrophthalic anhydride (THPA) is replaced by an equimolar amount of itaconic anhydride.

[0155] Synthesis example 3

[0156] Synthesis Example 3 follows the steps of Synthesis Example 1, except that 1,2,5,6-tetrahydrophthalic anhydride (THPA) is replaced by an equimolar amount of maleic anhydride.

[0157] Synthesis example 4

[0158] Synthesis Example 4 follows the steps of Synthesis Example 1, except that 1,2,5,6-tetrahydrophthalic anhydride (THPA) is replaced by an equal molar amount of succinic anhydride.

[0159] Synthesis example 5

[0160] Synthesis Example 5 follows the steps of Synthesis Example 1, except that 1,2,5,6-tetrahydrophthalic anhydride (THPA) is replaced by an equal molar amount of methyltetrahydrophthalic anhydride.

[0161] Synthesis example 6

[0162] Synthesis Example 6 follows the steps of Synthesis Example 1, except that 1,2,5,6-tetrahydrophthalic anhydride (THPA) is replaced by an equimolar amount of hexahydrophthalic anhydride.

[0163] Synthesis Example 7

[0164] Synthesis Example 7 follows the steps of Synthesis Example 1, except that 1,2,5,6-tetrahydrophthalic anhydride (THPA) is replaced by an equal molar amount of methylhexahydrophthalic anhydride.

[0165] Synthesis example 8

[0166] Synthesis Example 8 follows the steps of Synthesis Example 1, except that the amount of 1,2,5,6-tetrahydrophthalic anhydride (THPA) added is 74.75 g.

[0167] Example 1

[0168] Example 1 is a high-performance photocurable solder resist ink using the biomass soybean extract-based alkali-soluble photocurable resin obtained in Synthesis Example 1 as a main component. The raw materials thereof mainly include, by weight:

[0169] 100 parts of alkali-soluble light-curing resin based on biomass soy bean extract,

[0170] 2-Isopropylthioxanthone (ITX) 2.5 parts.

[0171] The components of the prepared material are pre-mixed in a blender and then kneaded using a three-roll mill to obtain a high-performance light-curable solder resist ink, which is referred to as DDATs.

[0172] The obtained high-performance light-curable solder resist ink was then coated on a substrate, light-cured under 395nm wavelength ultraviolet light for 30 minutes, and then placed in an oven at 120-160°C for thermal curing for 1 hour. Finally, the cured film formed after curing was used as a sample for testing.

[0173] Example 2

[0174] Example 2 is a high-performance photocurable solder resist ink compounded with the biomass soybean extract-based alkali-soluble photocurable resin obtained in Synthesis Example 1. The raw materials thereof mainly include, by weight:

[0175] 90 parts of alkali-soluble photocurable resin based on biomass soy bean extract,

[0176] 10 parts of soybean extract diglycidyl ether,

[0177] 2.25 parts of photoinitiator.

[0178] After the components of the prepared material are pre-mixed in a blender, they are kneaded using a three-roll mill to obtain a high-performance light-curing solder resist ink, with a ratio of 9:1.

[0179] The obtained high-performance light-curable solder resist ink was then coated on a substrate, light-cured under 395nm wavelength ultraviolet light for 30 minutes, and then placed in an oven at 120-160°C for thermal curing for 1 hour. Finally, the cured film formed after curing was used as a sample for testing.

[0180] Example 3

[0181] Example 3 is a high-performance photocurable solder resist ink compounded with the biomass soybean extract-based alkali-soluble photocurable resin obtained in Synthesis Example 1. The raw materials thereof mainly include, by weight:

[0182] 80 parts of alkali-soluble photocurable resin based on biomass soy bean extract,

[0183] 20 parts of soybean extract diglycidyl ether,

[0184] 2 parts of photoinitiator.

[0185] After the components of the prepared material are pre-mixed in a blender, they are kneaded using a three-roll mill to obtain a high-performance light-curable solder resist ink, with a ratio of 8:2.

[0186] The obtained high-performance light-curable solder resist ink was then coated on a substrate, light-cured under 395nm wavelength ultraviolet light for 30 minutes, and then placed in an oven at 120-160°C for thermal curing for 1 hour. Finally, the cured film formed after curing was used as a sample for testing.

[0187] Example 4

[0188] Example 4 is a high-performance photocurable solder resist ink compounded with the biomass soybean extract-based alkali-soluble photocurable resin obtained in Synthesis Example 1. The raw materials thereof mainly include, by weight:

[0189] 70 parts of alkali-soluble photocurable resin based on biomass soy bean extract,

[0190] 30 parts of soybean extract diglycidyl ether,

[0191] 1.75 parts of photoinitiator.

[0192] After the components of the prepared material are pre-mixed in a blender, they are kneaded using a three-roll mill to obtain a high-performance light-curing solder resist ink, with a ratio of 7:3.

[0193] The obtained high-performance light-curable solder resist ink was then coated on a substrate, light-cured under 395nm wavelength ultraviolet light for 30 minutes, and then placed in an oven at 120-160°C for thermal curing for 1 hour. Finally, the cured film formed after curing was used as a sample for testing.

[0194] Example 5

[0195] The high-performance photocurable solder resist ink provided in Example 5 is prepared by adding 2.4 g of epoxidized nano-silica, 7.2 g of epoxidized barium sulfate, 1.44 g of active diluent pentaerythritol triacrylate, and 0.48 g of phthalocyanine green to 60 g of the high-performance photocurable solder resist ink obtained in Example 1.

[0196] The components of the prepared material are pre-mixed in a blender and then kneaded using a three-roll mill to obtain a high-performance light-curable solder resist ink, which is designated as CDDAT.

[0197] The obtained high-performance light-curable solder resist ink was then coated on a substrate, light-cured under 395nm wavelength ultraviolet light for 30 minutes, and then placed in an oven at 120-160°C for thermal curing for 1 hour. Finally, the cured film formed after curing was used as a sample for testing.

[0198] Example 6

[0199] The high-performance photocurable solder resist ink provided in Example 6 is prepared by adding 2.3 g of epoxidized nano-silica, 6.9 g of epoxidized barium sulfate, 1.38 g of active diluent pentaerythritol triacrylate, and 0.46 g of phthalocyanine green to 60 g of the high-performance photocurable solder resist ink obtained in Example 2.

[0200] After the components of the prepared material are pre-mixed in a blender, they are kneaded using a three-roll mill to obtain a high-performance light-curable solder resist ink, which is denoted as C9:1.

[0201] The obtained high-performance light-curable solder resist ink was then coated on a substrate, light-cured under 395nm wavelength ultraviolet light for 30 minutes, and then placed in an oven at 120-160°C for thermal curing for 1 hour. Finally, the cured film formed after curing was used as a sample for testing.

[0202] Example 7

[0203] The high-performance photocurable solder resist ink provided in Example 7 is prepared by adding 2.15 g of epoxidized nano-silica, 6.45 g of epoxidized barium sulfate, 1.29 g of active diluent pentaerythritol triacrylate, and 0.43 g of phthalocyanine green to 60 g of the high-performance photocurable solder resist ink obtained in Example 3.

[0204] The components of the prepared material were pre-mixed in a blender and then kneaded using a three-roll mill to obtain a high-performance light-curing solder resist ink, which was designated as C8:2.

[0205] The obtained high-performance light-curable solder resist ink was then coated on a substrate, light-cured under 395nm wavelength ultraviolet light for 30 minutes, and then placed in an oven at 120-160°C for thermal curing for 1 hour. Finally, the cured film formed after curing was used as a sample for testing.

[0206] Example 8

[0207] The high-performance photocurable solder resist ink provided in Example 8 is prepared by adding 2 grams of epoxidized nano-silica, 6 grams of epoxidized barium sulfate, 1.2 grams of active diluent pentaerythritol triacrylate, and 0.4 grams of phthalocyanine green to 60 grams of the high-performance photocurable solder resist ink obtained in Example 4.

[0208] The components of the prepared material were pre-mixed in a blender and then kneaded using a three-roll mill to obtain a high-performance light-curing solder resist ink, which was designated as C7:3.

[0209] The obtained high-performance light-curable solder resist ink was then coated on a substrate, light-cured under 395nm wavelength ultraviolet light for 30 minutes, and then placed in an oven at 120-160°C for thermal curing for 1 hour. Finally, the cured film formed after curing was used as a sample for testing.

[0210] The test results are as attached Figures 1 to 6 As shown, Figure 6 Provided are stress-strain curve comparison charts and strength, strain, and toughness statistical bar charts of the cured film samples obtained in Examples 1 to 8.

[0211] The tensile strengths of the cured film samples obtained in Examples 1 to 4 were 58.74±6.36 MPa, 71.46±3.87 MPa, 85.40±8.30 MPa, and 74.46±5.62 MPa, respectively; the elongations at break were 5.13±1.22%, 8.37±0.56%, 9.58±1.72%, and 11.66±1.27%, respectively; and the toughness was 1.82±0.74 MJ m -3 、3.87±0.18MJ m -3 , 5.50±1.41MJ m -3 and 6.00±1.29MJ m -3 .

[0212] The tensile strengths of the cured film samples obtained in Examples 5 to 8 were 46.47±5.96 MPa, 50.78±3.10 MPa, 53.67±1.41 MPa, and 72.54±5.37 MPa, respectively; the elongations at break were 3.42±0.60%, 3.63±0.32%, 4.11±0.23%, and 5.52±0.59%, respectively; and the toughness was 1.03±0.51 MJ m -3 、1.14±0.24MJ m -3 、1.34±0.06MJ m -3 and 2.39 ± 0.61 MJ m -3 .

[0213] It can be seen that with the increase in the proportion of soymilk diglycidyl ether in the compound, the mechanical properties of the cured film formed by the prepared high-performance light-curing solder mask ink show a significant increase.

[0214] The above embodiments are preferred implementation modes of the present invention, but the implementation modes of the present invention are not limited to the above embodiments. Any other changes, modifications, substitutions, combinations, and simplifications that do not deviate from the spirit and principles of the present invention should be considered as equivalent replacement methods and are included in the scope of protection of the present invention.

Claims

1. An alkali-soluble photocurable resin based on biomass soybean extract, characterized in that The chemical structure is as follows: ， Wherein, R is the following structure: ； "..." indicates the location where the chemical bonds are connected.

2. The method for preparing the alkali-soluble light-curing resin according to claim 1, characterized in that The following steps are involved: (1) In an air atmosphere, daidzein diglycidyl ether, acrylic acid, and solvent A are added to a reaction vessel, and a cyclic ester ring-opening polymerization catalyst and a polymerization inhibitor are added. After thorough mixing, the temperature is adjusted to 100-125°C, and the mixture is stirred and reacted for 8-16 hours to obtain daidzein diglycidyl ether grafted with acrylic acid. The chemical structural formula of the soymilk diglycidyl ether is as follows: ； (2) The daidzein diglycidyl ether grafted with acrylic acid obtained in step (1) is cooled to 90-100°C, and then 1,2,5,6-tetrahydrophthalic anhydride is added, and the mixture is stirred and reacted at 85-100°C for 6-12 hours to obtain an alkali-soluble photocurable resin based on biomass daidzein.

3. The preparation method according to claim 2, characterized in that: The preparation method of soybean diglycidyl ether in step (1) mainly comprises the following steps: Solvent B, daidzein, epichlorohydrin, and a phase transfer catalyst are added to a reaction vessel, fully mixed and dissolved, and stirred at 40-100° C. for 1-4 hours. After the reaction time is up, a ring-closing reaction reagent is added to carry out a ring-closing reaction treatment to separate and obtain daidzein diglycidyl ether; Or for, Add solvent B, daidzein, epichlorohydrin and a ring-closing reaction reagent into a reaction vessel, mix and dissolve them thoroughly, and stir the mixture at 40-100° C. for 1-4 hours to separate and obtain daidzein diglycidyl ether. The molar ratio of soymilk to epichlorohydrin is 1:(5-15); The ring-closing reaction reagent is a NaOH aqueous solution in which the molar amount of the solute NaOH is 2.2 to 3.5 times that of daidzein and the mass concentration is 20 to 40 wt%.

4. The preparation method according to claim 3, characterized in that: The phase transfer catalyst is selected from any one of benzyltriethylammonium chloride, hexadecyltrimethylammonium bromide, tetraethylammonium bromide, polyethylene glycol 500, CW-2 catalyst, CW-4 catalyst, and tetrabutylammonium bromide catalyst; and the added amount of the phase transfer catalyst is 8-12% of the molar amount of soybean extract.

5. The preparation method according to claim 3, characterized in that: The solvent B is selected from any one of ethanol, isopropanol, dimethyl sulfoxide, and N-methylpyrrolidone.

6. The preparation method according to claim 2, characterized in that: The cyclic ester ring-opening polymerization catalyst in step (1) is selected from one of triethylamine, triethanolamine, 4-dimethylaminopyridine, tetrabutylammonium bromide, tetramethylammonium chloride, N,N-dimethylbenzylamine and triphenylphosphine; the amount of the cyclic ester ring-opening polymerization catalyst added is 0.5~1.0 wt% of the total mass of daidzein diglycidyl ether and acrylic acid in step (1).

7. The preparation method according to claim 2, characterized in that: The solvent A in step (1) is selected from at least one of 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, trimethylbenzene and tetramethylbenzene.

8. The preparation method according to claim 2, characterized in that: The molar ratio of the 1,2,5,6-tetrahydrophthalic anhydride to the daidzein diglycidyl ether is (1-1.8):

1.

9. A high-performance photocurable solder resist ink using the alkali-soluble photocurable resin according to claim 1 as a main component, characterized in that The raw materials mainly include: 100 parts of alkali-soluble light-curing resin based on biomass soy bean extract, 1~5 parts of photoinitiator.

10. A high-performance photocurable solder resist ink using the alkali-soluble photocurable resin according to claim 1 as a main component, characterized in that The raw materials mainly include: 70~90 parts of alkali-soluble photocurable resin based on biomass soy extract, 10-30 parts of soybean diglycidyl ether, 1~5 parts of photoinitiator, The biomass soy bean extract-based alkali-soluble photocurable resin and soy bean extract diglycidyl ether are in a total of 100 parts.

Images