High-performance photocuring solder resist ink based on biomass daidzein and preparation method of high-performance photocuring solder resist ink

Abstract

The invention provides biomass daidzein-based high-performance light-cured solder resist ink and a preparation method thereof, and the preparation method comprises the following steps: carrying out ring-opening polymerization reaction modification on daidzein diglycidyl ether and acrylic acid, and finally carrying out esterification reaction with unsaturated anhydride to obtain biomass daidzein-based alkali-soluble light-cured resin. According to the technical scheme, daidzein derivative daidzein with liquid crystal characteristics is adopted as a main body structure, then daidzein diglycidyl ether is synthesized through epichlorohydrin, and then the alkali-soluble light-cured resin is synthesized and prepared through grafting acrylic acid and unsaturated anhydride. And a cured film formed by curing the high-performance light-cured solder resist ink formed by compounding the high-performance light-cured solder resist ink with daidzein diglycidyl ether has the advantages and characteristics 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 bean extract and a preparation method thereof. The cured film formed by the cured solder resist ink has the advantageous characteristics of high heat resistance and high toughness. Background Art

[0002] Printed circuit board (PCB) is a substrate for modern electrical appliances to install and connect electronic components, and is an important basic assembly in the electronics industry. Among them, light-curing solder resist ink is one of the key materials of PCB. It refers to the protective coating covering the copper wire of the printed circuit to prevent circuit corrosion and disconnection, prevent short circuits between wires caused by too many welding points, adjust the amount of solder adhesion, reduce the dissolution contamination of copper in the weld, save solder, reduce the weight of the instrument, increase the density of wiring, avoid cold solder joints and increase the inspection speed.

[0003] As data transmission develops towards large capacity, high speed and low latency, high-frequency signal bands are expected to meet the requirements of the fifth generation (5G) communication technology. In terms of electronic packaging, high-frequency communication and other aspects, higher heat resistance requirements are put forward for the solder mask layer, such as the glass transition temperature must reach 160-190°C. However, the PCB packaging technology based on the main chain of traditional bisphenol A, biphenyl and cresol novolac epoxy resin generally has a glass transition temperature between 120 and 150°C, which is far from meeting the above requirements. At the same time, the PCB required by more and more complex electronic devices is no longer just a traditional flat plate form, but also has curvature or angles, which requires that the solder mask ink must have good flexibility while having excellent heat resistance. The photocurable resin film obtained by these traditional epoxy resins shows an elongation at break between 2 and 6%. Moreover, when formulated into a photosensitive ink, due to the introduction of inorganic nanoparticles, the elongation at break of the cured film will drop to between 0.5 and 3%. The elongation at break is far lower than the ideal elongation at break of more than 4%.

[0004] In addition, all of these epoxy resins are derived from non-renewable petroleum-based derivatives, which will undoubtedly aggravate the environmental crisis, energy crisis and ecological crisis. Therefore, the development of renewable bio-based materials and derivative materials from biological resources, such as cardanol, vanillin, tannic acid, gallic acid, daidzein, etc., 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 not lose out in the competition with fossil fuel-derived materials (price, performance, and processability) is the research focus of all bio-based materials, and it is ultimately expected that highly heat-resistant and highly tough solder mask inks will be obtained. Summary of the invention

[0006] The present invention provides a high-performance photocurable solder resist ink based on biomass soybean extract and a preparation method thereof. In the technical scheme, soybean extract, a daidzein derivative with liquid crystal properties, is used as the main structure, and then soybean extract diglycidyl ether is synthesized by epichlorohydrin, and then an alkali-soluble photocurable resin is synthesized by grafting acrylic acid and unsaturated acid anhydride, and a high-performance photocurable solder resist ink is prepared by compounding the daidzein extract with soybean extract diglycidyl ether. The cured film formed by curing has the advantages 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 soybean element, and its chemical structure is as follows:

[0009]

[0010] In the formula, 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 alkali-soluble photocurable resin based on biomass soy bean extract, which is modified by ring-opening polymerization of soy bean extract diglycidyl ether with acrylic acid, and finally esterification with unsaturated acid anhydride to obtain the alkali-soluble photocurable resin based on biomass soy bean extract. It should be noted that those skilled in the art can obtain specific preparation steps according to the reaction sequence shown above, especially the modification by ring-opening polymerization with acrylic acid and the esterification with unsaturated acid anhydride, which is a conventional synthetic route for preparing alkali-soluble photocurable epoxy resins in the art; therefore, the technical scheme provided below in the present invention does not mean the sole designation or limitation of the preparation method of the alkali-soluble photocurable resin based on biomass soy bean extract.

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

[0015] (1) In an air atmosphere, add soymilk diglycidyl ether, acrylic acid and solvent A into a reaction container, add a cyclic ester ring-opening polymerization catalyst and a polymerization inhibitor, mix thoroughly, adjust the temperature to 100-125° C., stir and react for 8-16 hours, and obtain soymilk diglycidyl ether grafted with acrylic acid;

[0016] (2) Cooling the soy bean extract 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 soy bean extract.

[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 "diglycidyl ether of soy bean" is prepared by synthesizing soy bean by epoxidation of the terminal hydroxyl groups on soy bean. 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 soy bean diglycidyl ether. For example, soy bean diglycidyl ether is prepared by synthesizing soy bean diglycidyl ether using epichlorohydrin, which is a conventional synthetic route for preparing diglycidyl ether derivatives in the art.

[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] Add solvent B, daidzein, epichlorohydrin and a phase transfer catalyst into a reaction vessel, mix and dissolve them thoroughly, stir and react at 40 to 100° C. for 1 to 4 hours, add a ring-closing reaction reagent after the reaction time is up, and perform a ring-closing reaction 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, stir and react at 40 to 100° C. for 1 to 4 hours, and separate and obtain daidzein diglycidyl ether;

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

[0025] The ring-closing reaction reagent is a NaOH aqueous solution whose molar amount of solute NaOH is 2.2 to 3.5 times of that of soybean extract and whose 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 the 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 soy bean extract.

[0028] In the above technical scheme, the ring-closing reaction treatment is a conventional process selection during the epoxidation reaction. Those skilled in the art can directly select an appropriate method for the ring-closing 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, the reaction is stirred 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, isopropanol, dimethyl sulfoxide, and N-methylpyrrolidone. It should be noted that, generally speaking, the solvent A and the solvent B are different solvents.

[0031] In the above technical solution, the separated soymilk 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 reaction in the technical field. Technicians in the 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 soymilk diglycidyl ether and acrylic acid in step (1).

[0035] 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.

[0036] In one of the technical schemes, the solvent A in step (1) is selected from at least one of a dibasic 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 technical field of this invention, 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 the art, and can be polymerization inhibitors conventionally 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 soymilk 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 photocurable 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 the acrylic acid to the molar amount of the soymilk diglycidyl ether is (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 photocurable epoxy resin in the art. Those skilled in the art can directly select a suitable unsaturated anhydride from the relevant technical literature on preparing alkali-soluble photocurable epoxy resin in the prior art.

[0041] In this article, the amount of unsaturated acid anhydride added in step (2) is preferably consistent with the amount of unsaturated acid anhydride added in the conventional synthesis process for preparing alkali-soluble photocurable epoxy resin 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 soymilk diglycidyl ether is (1 to 1.8):1.

[0042] In one of the technical solutions, 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, and those skilled in the art can select a suitable stirring reaction mode according to the production scale or the current 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 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 photocurable resin based on biomass soybean element,

[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, and 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] In the actual research and development process, the inventors further found that the photocurable solder resist ink obtained by further compounding the prepared alkali-soluble photocurable resin based on biomass soybean extract with soybean extract diglycidyl ether 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 element,

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

[0052] 1 to 5 parts of photoinitiator,

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

[0054] It should be noted that when preparing the above formula, if the soymilk diglycidyl ether is insoluble, 5 to 15 parts of solvent A should be added to assist in dissolving the soymilk diglycidyl ether.

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

[0056] 20 to 50 parts of filler,

[0057] 1 to 25 parts of additives.

[0058] Among them, in order to improve the physical strength of the coating 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, it is preferred that well-known metal oxides are used as both fillers and pigments.

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

[0060] The preparation method of the high-performance light-curable solder resist ink can be prepared by mixing all components in accordance with the prior art. For example, the components are preliminarily mixed in a blender and then kneaded in a three-roll mill to obtain the high-performance light-curable solder resist ink.

[0061] When the above solder resist ink is used, it is applied to the substrate, dried appropriately (about 60 to 90°C), and then exposed through a pattern film to obtain a cured coating film, and the unexposed portion is developed. When developing, the above solvent or a well-known halogen solvent such as trichloroethylene can be used for solvent development, but since carboxyl groups are introduced into the alkali-soluble photocurable resin, the unexposed portion will dissolve in an alkaline aqueous solution, so alkaline development is preferably performed. For alkaline solvent development, alkali metal compounds such as sodium carbonate, potassium carbonate, sodium hydroxide, potassium hydroxide, etc. can be selected; alkaline earth metal compounds such as calcium hydroxide can also be selected; alkaline solution ammonia water can also be selected; water-soluble organic amines such as monomethylamine, dimethylamine, trimethylamine, monoethylamine, diethylamine, triethylamine, monopropylamine, dipropylamine, dimethylpropylamine, monoethanolamine, diethanolamine, triethanolamine, ethylenediamine, diethylenetriamine, dimethylaminoethyl methacrylate, polyethyleneimine, etc. can also be selected.

[0062] After development, it is preferred that a heat treatment be performed at about 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 used in a state of a solder resist layer dry film formed by applying and drying on a film such as PET in advance.

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

[0065] 1. The present invention provides a high-performance photocurable solder resist ink based on biomass soy bean extract and a preparation method thereof. The technical solution adopts soy bean extract, a daidzein derivative with liquid crystal properties, as the main structure, and utilizes it to prepare soy bean extract diglycidyl ether, which is then successively reacted with acrylic acid and tetrahydrophthalic anhydride to synthesize an alkali-soluble photocurable resin. The use of sustainable bio-based materials reduces the dependence of the solder resist ink field on fossil fuel-derived compounds.

[0066] 2. In the present invention, soybean protein has a rigid structure with a large aspect ratio, so that the photocurable resin derived from it has liquid crystal properties, which 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 the present invention, a large number of carboxyl groups are introduced by the reaction of acid anhydride and hydroxyl groups, so that the product has good alkali developability, and can be quickly and completely detached by direct immersion in weak alkali solution without damaging the substrate. In addition, due to the strong polarity of the carboxyl group, the product has good adhesion on the substrate and is not easy to fall 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, intermediate products and final products used in Synthesis Example 1 of the present invention are shown in FIG. DDAT is the alkali-soluble photocurable resin based on biomass soybean extract finally prepared in Synthesis Example 1; DDDE-AA is soybean extract diglycidyl ether grafted with acrylic acid in Synthesis Example 1; DDDE is soybean extract diglycidyl ether in Synthesis Example 1; and DD is the raw soybean extract used in Synthesis Example 1.

[0070] Figure 2 The following are the H-NMR spectra 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 soybean protein-based alkali-soluble photocurable resin finally prepared in Synthesis Example 1; DDDE-AA is soybean protein diglycidyl ether grafted with acrylic acid in Synthesis Example 1; DDDE is soybean protein diglycidyl ether in Synthesis Example 1; DD is the raw soybean protein used in Synthesis Example 1.

[0072] Figure 3 The graph is a comparison of 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 and temperature comparison curves of the cured film samples obtained in Examples 1 to 8 of the present invention are shown in Figure (a). The storage modulus and temperature comparison curves of the cured film samples obtained in Examples 1 to 4 of the present invention are shown in Figure (b). The storage modulus and temperature comparison curves of the cured film samples obtained in Examples 5 to 8 of the present invention are shown in Figure (a).

[0074] Figure 5 The loss tangent comparison spectra of the cured film samples obtained in Examples 1 to 8 of the present invention are shown in Figure (a) corresponding to the cured film samples obtained in Examples 1 to 4 of the present invention; Figure (b) corresponding 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 It was further improved to 212℃, 222℃, 227℃ and 219℃ respectively.

[0075] Figure 6 The stress-strain curve comparison diagram and strength, strain, and toughness statistical column comparison diagram of the cured film samples obtained in Examples 1 to 8 of the present invention are shown. Among them, Figure (a) is a stress-strain curve comparison diagram of the cured film samples obtained in Examples 1 to 4 of the present invention, Figure (b) is a strength statistical column comparison diagram of the cured film samples obtained in Examples 1 to 4 of the present invention, Figure (c) is a strain statistical column comparison diagram of the cured film samples obtained in Examples 1 to 4 of the present invention, Figure (d) is a toughness statistical column comparison diagram of the cured film samples obtained in Examples 1 to 4 of the present invention, Figure (e) is a stress-strain curve comparison diagram of the cured film samples obtained in Examples 5 to 8 of the present invention, Figure (f) is a strength statistical column comparison diagram of the cured film samples obtained in Examples 5 to 8 of the present invention, Figure (g) is a strain statistical column comparison diagram of the cured film samples obtained in Examples 5 to 8 of the present invention, and Figure (h) is a toughness statistical column comparison diagram 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, the 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 limiting the claims of the invention. Those skilled in the art can refer to the content of this article and appropriately improve the process parameters to achieve it. It is particularly important to point out that all similar substitutions 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 change 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 soybean element, and its chemical structure is as follows:

[0078]

[0079] In the formula, 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 alkali-soluble photocurable resin based on biomass soy bean extract, which is modified by ring-opening polymerization of soy bean extract diglycidyl ether with acrylic acid, and finally esterification with unsaturated acid anhydride to obtain the alkali-soluble photocurable resin based on biomass soy bean extract. It should be noted that those skilled in the art can obtain specific preparation steps according to the reaction sequence shown above, especially the modification by ring-opening polymerization with acrylic acid and the esterification with unsaturated acid anhydride, which is a conventional synthetic route for preparing alkali-soluble photocurable epoxy resins in the art; therefore, the technical scheme provided below in the present invention does not mean the sole designation or limitation of the preparation method of the alkali-soluble photocurable resin based on biomass soy bean extract.

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

[0084] (1) In an air atmosphere, add soymilk diglycidyl ether, acrylic acid and solvent A into a reaction container, add a cyclic ester ring-opening polymerization catalyst and a polymerization inhibitor, mix thoroughly, adjust the temperature to 100-125° C., stir and react for 8-16 hours, and obtain soymilk diglycidyl ether grafted with acrylic acid;

[0085] (2) Cooling the soy bean extract 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 soy bean extract.

[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 "diglycidyl ether of soy bean" is prepared by synthesizing soy bean by epoxidation of the terminal hydroxyl groups on soy bean. 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 soy bean diglycidyl ether. For example, soy bean diglycidyl ether is prepared by synthesizing soy bean diglycidyl ether using epichlorohydrin, which is a conventional synthetic route for preparing diglycidyl ether derivatives in the art.

[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] Add solvent B, daidzein, epichlorohydrin and a phase transfer catalyst into a reaction vessel, mix and dissolve them thoroughly, stir and react at 40 to 100° C. for 1 to 4 hours, add a ring-closing reaction reagent after the reaction time is up, and perform a ring-closing reaction 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, stir and react at 40 to 100° C. for 1 to 4 hours, and separate and obtain daidzein diglycidyl ether;

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

[0094] The ring-closing reaction reagent is a NaOH aqueous solution whose molar amount of solute NaOH is 2.2 to 3.5 times of that of soybean extract and whose 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 soy bean extract.

[0097] In the above embodiment, the ring-closing reaction treatment is a conventional process selection during the epoxidation reaction. Those skilled in the art can directly select an appropriate method for the ring-closing 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 implementation method 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, the reaction is stirred at a temperature of 40 to 60° C. for 1 to 2 hours.

[0099] In the above embodiment, the molar ratio of soy bean curd 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 is selected from any one of ethanol, isopropanol, dimethyl sulfoxide, and N-methylpyrrolidone. It should be noted that, generally speaking, the solvent A and the solvent B are different solvents.

[0101] In the above embodiment, the soy bean diglycidyl ether is separated and obtained. Since the product is dissolved in the reaction solution, it is usually necessary to add a non-solvent 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.

[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 reaction in the technical field. Technicians in the 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 0.5-1.0wt% of the total mass of the soymilk diglycidyl ether and acrylic acid in step (1), for example, 0.5wt%, 0.6wt%, 0.7wt%, 0.8wt%, 0.9wt%, 1.0wt% 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 dibasic 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 technical field of this invention, 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 the art, and can be polymerization inhibitors conventionally used in ink technology.

[0108] In one embodiment, the polymerization inhibitor in step (1) is selected from 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 0.3-1.0wt% of the total mass of the soymilk diglycidyl ether and acrylic acid in step (1), for example, 0.3wt%, 0.4wt%, 0.5wt%, 0.6wt%, 0.7wt%, 0.8wt%, 0.9wt%, 1.0wt% 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 photocurable 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 the acrylic acid to the molar amount of the soymilk diglycidyl ether is (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 photocurable epoxy resin in the art. Those skilled in the art can directly select a suitable unsaturated anhydride from the relevant technical literature on preparing alkali-soluble photocurable epoxy resin in the prior art.

[0111] Herein, the amount of unsaturated anhydride added in step (2) is preferably consistent with the amount of unsaturated anhydride added in the conventional synthesis process for preparing alkali-soluble photocurable epoxy resin 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 to the molar amount of the soymilk diglycidyl ether is (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, and those skilled in the art can select a suitable 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 to 300 rpm.

[0114] On the other hand, based on the above-mentioned biomass soybean 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 photocurable resin based on biomass soybean element,

[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, and 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 active amine.

[0119] In the actual research and development process, the inventors further found that the photocurable solder resist ink obtained by further compounding the prepared biomass soybean alkali-soluble photocurable resin with soybean alkali diglycidyl ether 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 element,

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

[0122] 1 to 5 parts of photoinitiator,

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

[0124] It should be noted that when preparing the above formula, if the soymilk diglycidyl ether is insoluble, 5 to 15 parts of solvent A should be added to assist in dissolving the soymilk diglycidyl ether.

[0125] In one preferred embodiment, the high performance light curing solder resist ink further comprises, by weight:

[0126] 20 to 50 parts of filler,

[0127] 1 to 25 parts of additives.

[0128] Among them, in order to improve the physical strength of the coating 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, it is preferred that well-known metal oxides are used as both fillers and pigments.

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

[0130] The preparation method of the high-performance light-curable solder resist ink can be prepared by mixing all components in accordance with the prior art. For example, the components are preliminarily mixed in a blender and then kneaded in a three-roll mill to obtain the high-performance light-curable solder resist ink.

[0131] When the above solder resist ink is used, it is applied to the substrate, dried appropriately (about 60 to 90°C), and then exposed through a pattern film to obtain a cured coating, and the unexposed portion is developed. When developing, the above solvent or a well-known halogen solvent such as trichloroethylene can be used for solvent development, but since carboxyl groups are introduced into the alkali-soluble photocurable resin, the unexposed portion will dissolve in an alkaline aqueous solution, so alkaline development is preferably performed. For alkaline solvent development, alkali metal compounds such as sodium carbonate, potassium carbonate, sodium hydroxide, potassium hydroxide, etc. can be selected; alkaline earth metal compounds such as calcium hydroxide can also be selected; alkaline solution ammonia water can also be selected; water-soluble organic amines such as monomethylamine, dimethylamine, trimethylamine, monoethylamine, diethylamine, triethylamine, monopropylamine, dipropylamine, dimethylpropylamine, monoethanolamine, diethanolamine, triethanolamine, ethylenediamine, diethylenetriamine, dimethylaminoethyl methacrylate, polyethyleneimine, etc. can also be selected.

[0132] After development, it is preferred that a heat treatment be performed at about 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 used in a state of a solder resist layer dry film formed by applying and drying on a film such as PET in advance.

[0134] The present invention will be further explained in detail with reference to the following examples. However, it should be understood 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 only used to illustrate the present application and should not be considered as limiting the scope of the present application. The specific conditions not specified in the examples are carried out according to the conditions recommended by normal conditions or manufacturers. The reagents used or the instruments not specified by the manufacturer are all 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 acetate (DCAC) and tetrabutylammonium bromide were provided by Chengdu Kelong 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 4 cm -1 , scanning range is 400-4000cm -1 Among them, the solid sample is measured by potassium bromide tablet method, and the liquid sample is measured by smearing method on potassium bromide tablet.

[0143] (2) Nuclear Magnetic Resonance (H 2 NMR) Spectroscopy Test: The H 2 NMR spectroscopy test was measured using a Bruker ARX600 nuclear magnetic resonance spectrometer from Bruker Corporation of the United States, and deuterated dimethyl sulfoxide (DMSO-d6) was used as the solvent. 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 film (4-6 mg) was heated from 30°C to 700°C in a nitrogen environment (flow rate of 20 ml / min) at a heating rate of 10°C / min.

[0145] (4) Room temperature broadband dielectric test: At room temperature, use the 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 conducted using a DSA 25 (KRUSS, Germany) instrument using deionized water at room temperature, wherein 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 temperature stability of the sample was measured in the controlled force mode, with a temperature range of 30 to 250 °C and a sample size of 12 mm × 4 mm × 0.05 mm.

[0148] Synthesis example 1

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

[0150] Then the temperature was lowered to 40°C, 100 g of 40 wt% sodium hydroxide aqueous solution was added dropwise within 1 hour, and after reacting for another 1 hour, a large amount of petroleum ether was added and stirred to precipitate the product; finally, the product was washed with water and methanol for several times; and dried to obtain daidzein diglycidyl ether with a yield of 84%, which was recorded as DDDE.

[0151] In an air atmosphere, 100 g of soymilk 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, and then 40 g of acrylic acid, 3 g of triphenylphosphine and 1.5 g of hydroquinone were added. After fully mixing, the mixture was heated to 110° C. to fully dissolve and stir evenly, and the mixture was stirred at 110° C. for 12 hours to prepare a soymilk diglycidyl ether grafted acrylic acid mixed solution, which was recorded as DDDE-AA.

[0152] Then, the mixture of soy bean extract 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 photocurable resin based on biomass soy bean extract, 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 with 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 with 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 with 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 with 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 with an equal molar amount of methylhexahydrophthalic anhydride.

[0165] Synthesis example 8

[0166] Synthesis Example 8 follows the procedure of Synthesis Example 1, but 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 element-based alkali-soluble photocurable resin obtained in the above-mentioned Synthesis Example 1 as a main component, and its raw materials mainly include, by weight:

[0169] 100 parts of alkali-soluble photocurable resin based on biomass soybean element,

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

[0171] After the components of the prepared materials are pre-mixed in a blender, they are kneaded with 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 photocurable solder resist ink is then coated on a substrate, photocured under 395 nm wavelength ultraviolet light for 30 min, then placed in an oven for thermal curing at 120-160° C. for 1 h, and finally the cured film formed after curing is 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 element-based alkali-soluble photocurable resin obtained in the above-mentioned Synthesis Example 1. The raw materials thereof mainly include, by weight:

[0175] 90 parts of alkali-soluble photocurable resin based on biomass soybean element,

[0176] 10 parts of soybean extract diglycidyl ether,

[0177] 2.25 parts of photoinitiator.

[0178] After the components of the prepared materials are pre-mixed in a blender, they are kneaded with a three-roll mill to obtain a high-performance light-curable solder resist ink, which is recorded as 9:1.

[0179] The obtained high-performance photocurable solder resist ink is then coated on a substrate, photocured under 395 nm wavelength ultraviolet light for 30 min, then placed in an oven for thermal curing at 120-160° C. for 1 h, and finally the cured film formed after curing is 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 element-based alkali-soluble photocurable resin obtained in the above-mentioned Synthesis Example 1. The raw materials thereof mainly include, by weight:

[0182] 80 parts of alkali-soluble photocurable resin based on biomass soybean element,

[0183] 20 parts of soybean extract diglycidyl ether,

[0184] 2 parts of photoinitiator.

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

[0186] The obtained high-performance photocurable solder resist ink is then coated on a substrate, photocured under 395 nm wavelength ultraviolet light for 30 min, then placed in an oven for thermal curing at 120-160° C. for 1 h, and finally the cured film formed after curing is 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 element-based alkali-soluble photocurable resin obtained in the above-mentioned Synthesis Example 1. The raw materials thereof mainly include, by weight:

[0189] 70 parts of alkali-soluble photocurable resin based on biomass soybean element,

[0190] 30 parts of soybean extract diglycidyl ether,

[0191] 1.75 parts of photoinitiator.

[0192] After the components of the prepared materials are pre-mixed in a blender, they are kneaded with a three-roll mill to obtain a high-performance light-curable solder resist ink, which is recorded as 7:3.

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

[0194] Example 5

[0195] A 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] After the components of the prepared materials are pre-mixed in a blender, they are kneaded in a three-roll mill to obtain a high-performance light-curable solder resist ink, which is denoted as CDDAT.

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

[0198] Example 6

[0199] A 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 materials are pre-mixed in a blender, they are kneaded with 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 photocurable solder resist ink is then coated on a substrate, photocured under 395 nm wavelength ultraviolet light for 30 min, then placed in an oven for thermal curing at 120-160° C. for 1 h, and finally the cured film formed after curing is used as a sample for testing.

[0202] Example 7

[0203] A 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] After the components of the prepared materials are pre-mixed in a blender, they are kneaded with a three-roll mill to obtain a high-performance light-curable solder resist ink, which is denoted as C8:2.

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

[0206] Example 8

[0207] A 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] After the components of the prepared materials are pre-mixed in a blender, they are kneaded with a three-roll mill to obtain a high-performance light-curable solder resist ink, which is denoted as C7:3.

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

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

[0211] The tensile strengths of the cured film samples obtained in Examples 1 to 4 were 58.74±6.36MPa, 71.46±3.87MPa, 85.40±8.30MPa, and 74.46±5.62MPa, 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±0.74MJ 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±5.96MPa, 50.78±3.10MPa, 53.67±1.41MPa, and 72.54±5.37MPa, 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±0.51MJ m -3 , 1.14±0.24MJ m -3 , 1.34±0.06MJ m -3 and 2.39±0.61MJ m -3 .

[0213] It can be seen that with the increase in the proportion of soy bean diglycidyl ether in the compound, the mechanical properties of the cured film formed by the prepared high-performance photocurable solder resist ink showed 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 equivalent replacement methods and are included in the protection scope of the present invention.

Claims

1. An alkali-soluble photocurable resin based on biomass soybean element, characterized in that The chemical structure is as follows: In the formula, R is any of the following structures:

2. A method for preparing an alkali-soluble photocurable resin based on biomass soybean extract, characterized in that The following steps are involved: (1) In an air atmosphere, add soymilk diglycidyl ether, acrylic acid and solvent A into a reaction container, add a cyclic ester ring-opening polymerization catalyst and a polymerization inhibitor, mix thoroughly, adjust the temperature to 100-125° C., stir and react for 8-16 hours, and obtain soymilk diglycidyl ether grafted with acrylic acid; (2) Cooling the soy bean extract 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 soy bean extract.

3. The preparation method according to claim 2, characterized in that: The preparation method of soybean extract diglycidyl ether in step (1) mainly comprises the following steps: Add solvent B, daidzein, epichlorohydrin and a phase transfer catalyst into a reaction vessel, mix and dissolve them thoroughly, stir and react at 40 to 100° C. for 1 to 4 hours, add a ring-closing reaction reagent after the reaction time is up, and perform a ring-closing reaction 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, stir and react at 40 to 100° C. for 1 to 4 hours, and separate and obtain daidzein diglycidyl ether; The molar ratio of soy bean extract to epichlorohydrin is 1:(5-15); The ring-closing reaction reagent is a NaOH aqueous solution whose molar amount of solute NaOH is 2.2 to 3.5 times of that of soybean extract and whose mass concentration is 20 to 40 wt %.

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

5. The preparation method according to claim 3, characterized in that: The solvent B includes 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) includes 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 soymilk 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) comprises 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.

8. The preparation method according to claim 2, characterized in that: The molar ratio of the unsaturated acid anhydride to the soymilk diglycidyl ether is (1-1.8):

1.

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

10. The high performance light curing solder resist ink according to claim 9, characterized in that The raw materials mainly include: 70-90 parts of alkali-soluble photocurable resin based on biomass soybean element, 10-30 parts of soybean diglycidyl ether, The alkali-soluble photocurable resin based on biomass soy bean extract and soy bean extract diglycidyl ether are 100 parts in total.

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