Preparation method of four-functional alicyclic epoxy compound

Abstract

The invention discloses a preparation method of a tetra-functional alicyclic epoxy compound, which comprises the following steps: mixing pentaerythritol, 3-cyclohexene-1-formic acid, a catalyst and an organic solvent to obtain a solid-liquid mixture, dropwise adding a condensing agent into the solid-liquid mixture, dissolving the condensing agent into the organic solvent to obtain a first mixed solution, stirring until solids in the solid-liquid mixture are dissolved, reacting for 16-24 hours, filtering, washing, and drying to obtain the tetra-functional alicyclic epoxy compound. Washing and drying a reaction system after the reaction to obtain an organic phase, then carrying out reduced pressure distillation on the organic phase, and crystallizing residues of the organic phase obtained after the reduced pressure distillation to obtain pentaerythritol tetracyclohexene formate; the preparation method comprises the following steps: dissolving pentaerythritol tetracyclohexene formate into an organic solvent to obtain a second mixed solution, dissolving metachloroperbenzoic acid into the organic solvent to obtain a third mixed solution, dropwise adding the third mixed solution into the second mixed solution under the condition of ice bath, stirring, reacting for 16-24 hours, filtering, purifying the filtrate to obtain an organic phase, and drying to obtain the product. The method is mild in reaction condition, and the yield of the four-functional alicyclic epoxy compound is improved.

Description

Technical Field

[0001] The invention belongs to the technical field of photocurable materials, and in particular relates to a method for preparing a tetrafunctional alicyclic epoxy compound. Background Art

[0002] International patent application WO2018231804A1 discloses a method for preparing an ester containing cyclohexene oxide, the structural formula of the ester containing cyclohexene oxide is as follows:

[0003]

[0004] The method first uses a polyol and 3-cyclohexene-1-carboxylic acid to carry out an esterification reaction under an acid catalyst, and then uses peracetic acid to epoxidize the double bonds on the alicyclic ring to obtain an ester containing cyclohexene oxide. However, due to the low chemical equilibrium constant of the esterification reaction between the polyol and the organic acid, the above method needs to add an acid catalyst and react at a relatively high temperature and for a long time, and the esterification reaction conditions are harsh. At the same time, in order to increase the progress of the positive reaction, a dehydrating agent is added to remove the water generated by the esterification reaction from the reaction system. In addition, this method is a solvent-free reaction, the collision probability between the reactants is low, the reaction process takes a long time, and there is a possibility of side reactions, so the yield is low, and there are many unesterified hydroxyl groups. The epoxidation process is to epoxidize the double bonds of the alicyclic ring with peracetic acid at 60°C. Since peracetic acid contains water, the epoxy group may be opened at 60°C, reducing the number of its epoxy groups. Therefore, it is necessary to find a preparation method that can increase the yield of esters containing cyclohexene oxide. Summary of the invention

[0005] The first object of the present invention is to provide a method for preparing a tetrafunctional alicyclic epoxy compound to solve at least one of the above technical problems.

[0006] The first aspect of the present invention provides a method for preparing a tetrafunctional alicyclic epoxy compound, comprising the following steps:

[0007] S1, pentaerythritol, 3-cyclohexene-1-carboxylic acid, a catalyst and an organic solvent are mixed to obtain a solid-liquid mixture, a condensing agent is dissolved in an organic solvent to obtain a first mixed solution, the first mixed solution is added dropwise to the solid-liquid mixture and stirred until the solid in the solid-liquid mixture is dissolved in the organic solvent, the mixture is reacted for 16 to 24 hours, the reaction system after the reaction is washed and dried to obtain an organic phase, the organic phase is then subjected to reduced pressure distillation, and the residue of the organic phase after the reduced pressure distillation is crystallized to obtain pentaerythritol tetracyclohexene formate;

[0008] S2. Dissolve pentaerythritol tetracyclohexene carboxylate in an organic solvent to obtain a second mixed solution, dissolve meta-chloroperbenzoic acid in an organic solvent to obtain a third mixed solution, then dropwise add the third mixed solution to the second mixed solution under ice bath conditions, stir and react for 16 to 24 hours, filter, purify the filtered filtrate to obtain an organic phase, and dry to obtain.

[0009] Among them, the catalyst can be selected from at least one of 4-dimethylaminopyridine (DMAP), 1-hydroxybenzotriazole (HOBt), and 4-pyrrolidinopyridine (4-PPY), and the condensing agent can be selected from at least one of N,N-dicyclohexylcarbodiimide (DCC), N,N-diisopropylcarbodiimide (DIC), and 1-(3-dimethylaminopropyl)-3-ethylcarbodiimide (EDCI).

[0010] The preparation method of the tetrafunctional alicyclic epoxy compound of the present invention, pentaerythritol and 3-cyclohexene-1-carboxylic acid are first prepared by Steglich esterification reaction in an organic solvent to obtain pentaerythritol tetracyclohexene carboxylate, and then pentaerythritol tetracyclohexene carboxylate is epoxidized by meta-chloroperbenzoic acid to obtain a tetrafunctional alicyclic epoxy compound. Compared with the preparation method of WO2018231804A1, the preparation method of the present invention can react pentaerythritol and 3-cyclohexene-1-carboxylic acid to obtain pentaerythritol tetracyclohexene carboxylate at room temperature by selecting a catalyst and a condensing agent, and the reaction conditions are mild, and no dehydrating agent needs to be added. The preparation method of the present invention also improves the yield of pentaerythritol tetracyclohexene carboxylate. It is calculated that the yield of pentaerythritol tetracyclohexene carboxylate obtained by the preparation method of the present invention is not less than 85.07%. In addition, by selecting an oxidant in the epoxidation process, pentaerythritol tetracyclohexene carboxylate can be epoxidized to a tetrafunctional alicyclic epoxy compound at room temperature. Not only is the reaction condition mild, but the yield of the tetrafunctional alicyclic epoxy compound is also increased. The yield is calculated to be no less than 90.03%.

[0011] In some embodiments, the tetrafunctional alicyclic epoxy compound has the following structural formula:

[0012]

[0013] In some embodiments, the molar ratio of pentaerythritol, 3-cyclohexene-1-carboxylic acid, catalyst and condensing agent is 1:(4-4.12):(1-1.10):(4-4.10).

[0014] In some embodiments, the amount of the catalyst used may be 8-10% of the total mass of pentaerythritol, 3-cyclohexene-1-carboxylic acid and the condensing agent.

[0015] In some embodiments, the amount of the catalyst used may be 8-9% of the total mass of pentaerythritol, 3-cyclohexene-1-carboxylic acid and the condensation agent.

[0016] In some embodiments, the amount of the catalyst used may be 8.5% of the total mass of pentaerythritol, 3-cyclohexene-1-carboxylic acid and the condensing agent.

[0017] In some embodiments, the amount of the catalyst used may be 0.1% of the total mass of pentaerythritol, 3-cyclohexene-1-carboxylic acid and the condensing agent.

[0018] In some embodiments, the organic solvent may be selected from at least one of tetrahydrofuran and dichloromethane.

[0019] In some embodiments, in step S1, the amount of the organic solvent used may be 4 to 6 times the total mass of pentaerythritol, 3-cyclohexene-1-carboxylic acid and the condensation agent.

[0020] In some embodiments, in the first mixed liquid, the volume of the organic solvent required to dissolve the condensing agent may be 350-450 mL.

[0021] It should be noted that, in the present application, the purpose of adding an organic solvent to the solid-liquid mixture is to dissolve pentaerythritol in the organic solvent, and the purpose of adding an organic solvent to the first mixed liquid is to dissolve the condensation agent in the organic solvent. The organic solvent does not participate in the reaction. Therefore, the amount of the above-mentioned organic solvent is only one of the options and cannot be used as a limitation of the present application.

[0022] In some embodiments, in step S2, the amount of the organic solvent used can be 10 times the mass of m-chloroperbenzoic acid.

[0023] In some embodiments, in the second mixed solution, the volume of the organic solvent required to dissolve pentaerythritol tetracyclohexene carboxylate may be 50-70 mL.

[0024] In some embodiments, in the third mixed liquid, the volume of the organic solvent required to dissolve meta-chloroperbenzoic acid may be 180-220 mL.

[0025] It should be noted that, in the present application, the purpose of using an organic solvent in the second mixed liquid and the third mixed liquid is to dissolve pentaerythritol tetracyclohexene carboxylate and meta-chloroperbenzoic acid, and the amount of the above-mentioned organic solvent is only one of the options and cannot be used as a limitation of the present application.

[0026] In some embodiments, the molar ratio of pentaerythritol tetracyclohexene carboxylate to meta-chloroperbenzoic acid may be 1:(4-4.10).

[0027] In some embodiments, in step S1, the stirring and reaction time may be 18 hours.

[0028] In some embodiments, in step S1, the washing treatment method can be to transfer the reaction system after the reaction to a separatory funnel, first wash it 3 times with a hydrochloric acid solution with a mass fraction of 1%, then wash it 3 times with a saturated sodium bicarbonate solution, and then wash it 3 times with a saturated sodium chloride solution, and separate the liquids to obtain a lower organic phase. Specifically, hydrochloric acid and the catalyst can be combined to form a soluble salt that can be dissolved in water, and after washing, the excess catalyst in the reaction system can be removed; the saturated sodium bicarbonate solution is used to remove organic acids and hydrochloric acid, and adjust the pH of the reaction system to neutral; the saturated sodium chloride solution is used to remove water-soluble impurities in the organic phase.

[0029] In other embodiments, in step S1, the washing treatment method can be to transfer the reaction system after the reaction to a separatory funnel, wash it three times with a 1% hydrochloric acid solution, and then wash it three times with a saturated sodium chloride solution, and separate the liquids to obtain a lower organic phase.

[0030] In other embodiments, in step S1, the washing treatment method can be to transfer the reaction system after the reaction to a separatory funnel, wash the organic phase three times with a hydrochloric acid solution with a mass fraction of 1%, and separate the liquids to obtain a lower organic phase.

[0031] In some embodiments, in step S1, the drying treatment method may be to add a solid desiccant to the reaction system, filter and retain the filtered organic phase.

[0032] In some embodiments, in step S1, the treatment conditions of reduced pressure distillation are to distill the filtered organic phase under reduced pressure at a vacuum degree of -0.098 MPa and a water bath temperature of 30 to 40° C. for 1 to 3 hours.

[0033] In some embodiments, in step S2, the purification treatment method can be, first, add a saturated sodium sulfite solution to the filtrate, then wash the filtrate 3 times with a saturated sodium bicarbonate solution and a saturated sodium chloride solution respectively, separate the liquid to obtain a lower organic phase, add a solid desiccant to the washed organic phase, filter, and then remove the organic solvent in the organic phase by reduced pressure distillation. Specifically, the saturated sodium sulfite solution is used to remove excess meta-chloroperbenzoic acid, the saturated sodium bicarbonate solution is used to remove acidic impurities in the reaction system and adjust the pH of the reaction system to neutral, and the saturated sodium chloride solution is used in the reaction system to reduce the solubility of salt in the organic phase, so as to facilitate the removal of salt in the organic phase in the subsequent liquid separation.

[0034] In some embodiments, in step S2, the purification treatment method may be to further purify by column chromatography after reduced pressure distillation.

[0035] In some embodiments, the eluent used for column chromatography can be a mixture of petroleum ether and ethyl acetate, and the chromatography column used for column chromatography can be a silica gel column. The volume ratio of petroleum ether to ethyl acetate in the mixture can be (6-9):1.

[0036] In some embodiments, in step S2, the treatment conditions for reduced pressure distillation are to distill the filtered organic phase under reduced pressure at a vacuum degree of -0.098 MPa and a water bath temperature of 30 to 40° C. for 1 to 3 hours.

[0037] In some embodiments, in step S2, the stirring and reaction time may be 18 hours.

[0038] In some embodiments, the solid desiccant may be selected from at least one of anhydrous sodium sulfate or anhydrous magnesium sulfate.

[0039] The beneficial effects of the present invention are:

[0040] The invention improves the preparation method of tetrafunctional alicyclic epoxy compounds. By selecting a catalyst and a condensing agent, pentaerythritol and 3-cyclohexene-1-carboxylic acid can react at room temperature to obtain pentaerythritol tetracyclohexene carboxylate. No dehydrating agent needs to be added during the process, and the reaction conditions are mild and simple.

[0041] The preparation method of the present invention also improves the yields of pentaerythritol tetracyclohexene carboxylate and tetrafunctional alicyclic epoxy compounds. According to calculation, the yield of pentaerythritol tetracyclohexene carboxylate prepared by the preparation method of the present invention is not less than 85.07%, and the yield of tetrafunctional alicyclic epoxy compounds prepared by epoxidizing pentaerythritol tetracyclohexene carboxylate is not less than 90.03%. BRIEF DESCRIPTION OF THE DRAWINGS

[0042] Figure 1 The infrared spectra of 3-cyclohexene-1-carboxylic acid, intermediates and products of Example 1 of the present invention are shown;

[0043] Figure 2 The hydrogen nuclear magnetic resonance spectra of the intermediate product and the product of Example 1 of the present invention are shown in FIG. DETAILED DESCRIPTION

[0044] The present invention is further described in detail below in conjunction with the accompanying drawings, but the embodiments of the present invention are not limited thereto. The raw materials and reagents involved in the following examples can all be obtained from commercial channels.

[0045] Example 1

[0046] 6.8 g of pentaerythritol (0.05 mol), 25.23 g of 3-cyclohexene-1-carboxylic acid (0.2 mol), 6.13 g of DMAP (0.05 mol) and dichloromethane were added to a 500 mL three-necked flask in sequence to obtain a solid-liquid mixture, and 40.02 g of EDCI (0.2 mol) was dissolved in dichloromethane to obtain a first mixed solution; then the first mixed solution was added dropwise to the solid-liquid mixture, and after the addition was completed, it was stirred at room temperature until the solid in the solid-liquid mixture disappeared, and the reaction was reacted for 18 hours, and then the reaction system after the reaction was transferred to a separatory funnel, and dichloromethane was added to dilute it, and it was first washed with a 1% hydrochloric acid solution by mass, and then the reaction mixture was ... The mixture was washed three times, and then washed three times with saturated sodium bicarbonate solution and saturated sodium chloride solution respectively, and the lower organic phase was obtained by separation; the organic phase was dried with anhydrous sodium sulfate and filtered to obtain the organic phase, and the dichloromethane and trace water in the organic phase were removed by reduced pressure distillation for 2 hours at a vacuum degree of -0.098MPa and a water bath temperature of 30-40°C, and then column chromatography was performed on a silica gel column (the eluent was a mixture of petroleum ether and ethyl acetate, and the volume ratio of the two was 7:1) to obtain a colorless viscous liquid, and the intermediate product was obtained as a white crystal after standing and crystallizing. The yield of the intermediate product was calculated to be 92.02%.

[0047] Add dichloromethane to a 500mL three-necked flask, then weigh 5.68g of the intermediate product (0.01mol) and add it to the three-necked flask. Slowly drop m-chloroperbenzoic acid (6.88g, 0.04mol) dissolved in dichloromethane into the three-necked flask under ice bath conditions, then heat to room temperature and stir to react for 18h, filter to remove the intermediate product, and remove excess m-chloroperbenzoic acid from the filtrate with a saturated sodium sulfite solution, then rinse with a saturated sodium bicarbonate solution and saturated brine. The organic phase was washed three times with the solution, and the lower organic phase was obtained by separation; the organic phase was dried with anhydrous magnesium sulfate and filtered to obtain the organic phase, and the dichloromethane and trace water in the organic phase were removed by reduced pressure distillation for 2 hours at a vacuum degree of -0.098MPa and a water bath temperature of 30-40°C, and then column chromatography was performed using a silica gel column (the eluent was a mixture of petroleum ether and ethyl acetate, and the volume ratio of the two was 7:1) to obtain a colorless viscous liquid, and the colorless viscous liquid was allowed to stand for crystallization to obtain a white crystalline product. It was calculated that the yield of the intermediate product obtained by epoxidation was 91%.

[0048] The structures of the intermediate and product were confirmed by Fourier transform infrared spectroscopy (FT-IR) and hydrogen nuclear magnetic resonance (H-NMR) analysis. 3-cyclohexene-1-carboxylic acid, the intermediate and the product were analyzed by FT-IR. The results are as follows: Figure 1 As shown; the intermediate product and the product were analyzed by H-NMR, and the results are as follows Figure 2 shown.

[0049] from Figure 1It can be seen that the infrared spectrum of 3-cyclohexene-1-carboxylic acid is between 3500 and 3000 cm -1 A strong and broad -COOH stretching vibration peak can be observed between the intermediate and the final product, while no -COOH stretching vibration peak is observed in the infrared spectra of the intermediate and the final product. -1 The stretching vibration peak is attributed to C=CH and is at 1739 cm -1 There is an obvious C=O characteristic absorption peak at 3500cm -1 There is no -OH stretching vibration peak belonging to pentaerythritol, indicating that the four hydroxyl groups of pentaerythritol and 3-cyclohexene-1-carboxylic acid successfully synthesized pentaerythritol tetracyclohexene carboxylate through esterification reaction. In the infrared spectrum of the product, 797cm -1 There is an absorption peak attributed to COC at 3031cm -1 The C=CH stretching vibration peak disappears, indicating that the double bond of pentaerythritol tetracyclohexene carboxylate disappears under the oxidation of m-chloroperbenzoic acid, generating a product with an epoxidized structure, indicating the successful synthesis of the product tetrafunctional alicyclic epoxy compound.

[0050] from Figure 2 It can be seen that the chemical shift of the intermediate product (pentaerythritol tetracyclohexene carboxylate) is: 1H NMR (600MHz, Chloroform-d) δ5.68 (s, 8H), 4.18–4.12 (m, 8H), 2.62–2.55 (m, 4H), 2.28–2.20 (m, 8H), 2.13–2.05 (m, 8H), 2.01–1.94 (m, 4H), 1.68 (dddd, J=13.0, 11.2, 9.1, 6.8 Hz, 4H). The chemical shift of the product (tetrafunctional alicyclic epoxy compound) is: 1H NMR (600MHz, Chloroform-d) δ4.21–4.01 (m, 8H), 3.20 (ddd, J=57.2, 5.5, 3.2Hz, 8H), 2.58–2.47 (m, 2H), 2.32–1.53 (m, 26H). Comparing the H NMR spectra of the intermediate and the product, it can be found that the characteristic peak of the double bond on the six-membered ring of 3-cyclohexene-1-carboxylic acid at 5.68ppm in pentaerythritol tetracyclohexene carboxylate disappears in the spectrum of the tetrafunctional alicyclic epoxy compound, and two new characteristic peaks belonging to the epoxy group appear at 3.24-3.15ppm in the tetrafunctional alicyclic epoxy compound, further indicating the successful synthesis of the tetrafunctional alicyclic epoxy compound.

[0051] Example 2

[0052] This embodiment provides a method for preparing a tetrafunctional alicyclic epoxy compound, comprising the following steps:

[0053] 6.8 g of pentaerythritol (0.05 mol), 25.23 g of 3-cyclohexene-1-carboxylic acid (0.2 mol), 6.13 g of DMAP (0.05 mol) and dichloromethane were added to a 500 mL three-necked flask in sequence to obtain a solid-liquid mixture, and 40.03 g of EDCI (0.2 mol) was dissolved in dichloromethane to obtain a first mixed solution; then the first mixed solution was added dropwise to the solid-liquid mixture, and after the addition was completed, the mixture was stirred at room temperature until the solid in the solid-liquid mixture disappeared, and the reaction was continued for 18 h, and then the reacted The reaction system was transferred to a separatory funnel, washed three times with a 1% hydrochloric acid solution, separated to obtain a lower organic phase, dried with anhydrous sodium sulfate and filtered to obtain an organic phase, and distilled under reduced pressure for 2 hours at a vacuum degree of -0.098 MPa and a water bath temperature of 30 to 40°C to remove dichloromethane and trace amounts of water in the organic phase, and then column chromatography was performed using a silica gel column (the eluent was a mixture of petroleum ether and ethyl acetate, the volume ratio of the two being 7:1) to obtain a colorless viscous liquid, which was allowed to stand for crystallization to obtain a white crystalline intermediate product. The intermediate product weighed 24.16 g, and the yield of the intermediate product was calculated to be 85.07%.

[0054] First, add dichloromethane to a 500 ml three-necked flask, then weigh 5.68 g of the intermediate product (0.01 mol) and add it to the three-necked flask. Slowly drop m-chloroperbenzoic acid (83% activity, 8.28 g, 0.04 mol) dissolved in 250 mL of dichloromethane into the three-necked flask under ice bath conditions, then heat to room temperature and stir to react for 18 h, filter to remove the intermediate product, remove excess m-chloroperbenzoic acid from the filtered filtrate with a saturated sodium sulfite solution, and then add a saturated sodium bicarbonate solution. and saturated salt water solution for three times, and separated to obtain the lower organic phase; dried with anhydrous sodium sulfate and filtered to obtain the organic phase, and vacuum distilled for 2 hours at a vacuum degree of -0.098MPa and a water bath temperature of 30-40°C to remove dichloromethane and trace water in the organic phase, and then column chromatography was performed on a silica gel column (the eluent was a mixture of petroleum ether and ethyl acetate, and the volume ratio of the two was 7:1) to obtain a colorless viscous liquid, and the colorless viscous liquid was allowed to stand for crystallization to obtain a white crystalline product. The product weighed 5.69g, and the yield of the product obtained by epoxidation of the intermediate product was calculated to be 90.03%.

[0055] The structures of the intermediate product and the product were confirmed by Fourier transform infrared spectroscopy (FT-IR) and hydrogen nuclear magnetic resonance (H-NMR) analysis, respectively. The results were the same as those of Example 1, indicating that the intermediate product pentaerythritol tetracyclohexene carboxylate and the product tetrafunctional alicyclic epoxy compound were successfully synthesized.

[0056] The application of the tetrafunctional alicyclic epoxy compound of the present invention in the solder resist dry film is described in detail below. Specifically, the tetrafunctional alicyclic epoxy compound prepared in Example 1 and Example 2 is used to prepare the solder resist dry film resin composition.

[0057] In the application examples and comparative examples of the present invention, the alkali-soluble resin is an alkali-soluble resin synthesized with reference to Chinese patent CN118489087A, and its preparation method comprises the following steps:

[0058] Add 25g of glycidyl methacrylate and 53mL of propylene glycol monomethyl ether acetate to a three-necked flask, then add 17g of azobisisobutylnitrile, introduce nitrogen and heat to 80°C for reaction for 8h; add dropwise a mixed solution of 13.3g of acrylic acid, 0.25g of triphenylphosphine, 5mg of hydroquinone and 3.25mL of propylene glycol monomethyl ether acetate to the three-necked flask, heat to 100°C for reaction for 16h; after the reaction, add a mixed solution of 0.925g of succinic anhydride dissolved in 2.6mL of propylene glycol monomethyl ether acetate to the three-necked flask, cool to 65°C for reaction for 6h to obtain the product.

[0059] The solid content, weight average molecular weight and acid value of the obtained alkali-soluble resin are determined, wherein the solid content is determined by weighing a certain amount of mass sample, placing it in a 120°C oven for heating for 2 hours, and weighing the sample after cooling for 15 minutes. The weight average molecular weight is measured by GPC, and the acid value is measured by titration with a standard sodium hydroxide solution. After testing, the solid content of the alkali-soluble resin used in the embodiment of the present invention is 45%, the weight average molecular weight is 7000, and the acid value is 50 mgKOH / g.

[0060] It should be noted that the alkali-soluble resin can also be obtained from commercial channels, with a weight average molecular weight of 6000-9000, an acid value of 40-120 mgKOH / g, a solid content of 40-50%, and an alkali-soluble resin having a molecular structure containing at least one of a carboxyl group and a sulfonic acid group.

[0061] Application Example 1

[0062] This application example provides an application of the tetrafunctional alicyclic epoxy compound prepared in Example 1 in preparing a solder resist dry film resin composition, comprising the following steps:

[0063] According to the formula of the solder resist dry film resin composition shown in Table 1, an alkali-soluble resin, a photosensitive monomer, a photoinitiator, the tetrafunctional alicyclic epoxy compound prepared in Example 1, a thermal curing catalyst, an additive and a solvent are uniformly mixed to obtain a solder resist dry film resin composition.

[0064] Table 1 Formulation of solder resist dry film resin composition

[0065]

[0066] Application Example 2

[0067] This application example provides an application of the tetrafunctional alicyclic epoxy compound prepared in Example 2 in the preparation of a solder resist dry film resin composition, comprising the following steps:

[0068] According to the formula of the solder resist dry film resin composition shown in Table 2, the alkali-soluble resin, the photosensitive monomer, the photoinitiator, the thermosetting resin, the thermosetting catalyst, the additive and the solvent are uniformly mixed to obtain the solder resist dry film resin composition.

[0069] Table 2 Formulation of solder resist dry film resin composition

[0070]

[0071]

[0072] Comparative Example 1

[0073] This comparative example provides a method for preparing a solder resist dry film resin composition, comprising the following steps:

[0074] According to the formula of the solder resist dry film resin composition shown in Table 3, the alkali-soluble resin, the photosensitive monomer, the photoinitiator, the thermosetting resin, the thermosetting catalyst, the additive and the solvent are uniformly mixed to obtain the solder resist dry film resin composition.

[0075] Table 3 Formulation of solder resist dry film resin composition

[0076]

[0077] Experimental example

[0078] In this experimental example, the solder resist dry film resin compositions prepared in Application Example 1, Application Example 2 and Comparative Example 1 were subjected to performance tests to evaluate the comprehensive performance of the solder resist dry film of the present invention.

[0079] 1. Pre-treatment

[0080] (1) Preparation of photosensitive dry film: coating the mixed solder resist dry film resin composition on the surface of a PET support film with a thickness of 25 μm by a coating machine to obtain a photosensitive layer with a thickness of 25 μm, and covering the surface of the photosensitive layer with a PE protective film with a thickness of 25 μm;

[0081] (2) Laminating: The copper surface of the copper clad laminate is polished with a grinder, washed with water, and dried to obtain a bright and fresh copper surface, the PE protective film is peeled off to allow the solder resist dry film resin composition to contact the copper clad laminate, the solder resist dry film resin composition is laminated on the copper clad laminate using a laminating machine, and then placed in an oven at 100° C. for 5 min;

[0082] (3) Exposure: The test substrate obtained after film lamination was left to stand for 15 minutes, and then exposed using a laser direct imaging (LDI) exposure machine with a wavelength of 365 nm. Then, the photosensitivity test was performed using a stouffer 41-step exposure ruler. The number of exposure grids was controlled at 14-20 grids, and the exposure energy was 8-20 mJ / cm 2 ;

[0083] (4) Development: After exposure, the sample was allowed to stand for 20 min, the PET support film was peeled off, and an alkali developer was used for development. A 1% mass fraction of Na 2 CO 3 The aqueous solution is evenly sprayed onto the surface of the sample to be developed, and after development, it is washed with water and dried to obtain a substrate with a dry solder resist film for evaluation.

[0084] 2. Performance Test

[0085] (1) Sensitivity evaluation

[0086] A Stouffer 41-level step exposure scale was placed on the test substrate obtained after the above film lamination to conduct a sensitivity test. After exposure and development, a solder resist dry film obtained by curing the solder resist dry film resin composition was formed on the surface of the test substrate. The exposure energy (mJ / cm 2 ), the sensitivity of the photosensitive resin composition was evaluated, and the smaller the value, the better the sensitivity.

[0087] (2) Resolution evaluation

[0088] Exposure is performed using a mask having a wiring pattern with a width of 1:1 between the exposed part and the unexposed part. After development for twice the minimum development time, the minimum mask width at which a cured resist line is normally formed is taken as the resolution value and observation is performed using a two-dimensional imager or a scanning electron microscope (SEM).

[0089] (3) Adhesion evaluation

[0090] On the test substrate obtained after the above film lamination, the photomask data of the wiring pattern with L / S=n:400 (unit: μm) was used to expose the energy so that the number of residual stages after development of the Stouffer 41-stage exposure ruler reached 20. After the development process, the resist pattern was observed using an optical microscope, and the adhesion (μm) was evaluated by taking the minimum line width of the complete cured resist line as the adhesion value. The smaller the value, the better the adhesion.

[0091] (4) Hardness evaluation

[0092] The hardness of the solder resist dry film obtained after pretreatment is measured according to the test method of GB / T1730-93.

[0093] (5) Viscosity evaluation

[0094] The viscosity of the solder resist dry film resin compositions of Application Example 1, Application Example 2 and Comparative Example 1 was measured respectively according to the test method of GB / T10247-2008.

[0095] (6) Chemical resistance evaluation

[0096] Acid and alkali resistance test: The prepared solder resist dry film was immersed in 5% H2O at 50°C. 2 SO 4 Solution, 5% NaOH solution at 50℃, 5% NaCl solution at 50℃, the immersion time is 30min. The qualified standard is that there is no obvious change on the surface of the sample (such as no shedding, no bubbling).

[0097] (7) Flexibility evaluation

[0098] After lamination, exposure and development, the prepared solder mask dry film was folded 20 times from different angles to observe whether the dry film was cracked. The number of folding times when the dry film was cracked was counted. The larger the value, the better the flexibility of the dry film.

[0099] 3. Test Results

[0100] The above-mentioned properties of the solder resist dry film resin compositions prepared in Application Example 1, Application Example 2 and Comparative Example 1 were tested, and the test results are shown in Table 4.

[0101] Table 4 Performance test results of solder resist dry film resin composition

[0102] Application Example 1 Application Example 2 Comparative Example 1 <![CDATA[Exposure (mJ / cm 2 )]]> 25 25 27 Resolution(μm) 36 36 40 Adhesion(μm) 32 32 42 hardness 6H 6H 4H Viscosity (cps / 25℃) 16 16 28 Chemical resistance qualified qualified qualified Flexibility Cracking after 18 times Cracking after 18 times Cracking after 8 times

[0103] As can be seen from Table 4, the solder resist dry film resin composition prepared by using the tetrafunctional alicyclic epoxy compound of the present invention as a thermosetting resin is qualified in the chemical resistance test, and the test results of sensitivity and resolution are close to those of the solder resist dry film resin composition prepared by using ERL-4221 as a thermosetting resin, indicating that the solder resist dry film composition of the present invention can be used to prepare a solder resist dry film. Compared with the solder resist dry film prepared by using ERL-4221 as a thermosetting resin, the solder resist dry film of the present invention has slightly weaker test results in adhesion and viscosity, but the hardness and flexibility are significantly improved, the hardness evaluation result is 6H, and the dry film in the flexibility test cracks only after being folded in half 18 times. The above results show that the solder resist dry film prepared by the tetrafunctional alicyclic epoxy compound of the present invention has acid and alkali resistance, and is close to the solder resist dry film resin composition prepared by using ERL-4221 as a thermosetting resin in terms of sensitivity, resolution, adhesion, etc., and more effectively improves the hardness and flexibility of the solder resist dry film, so that it has better flexibility and hardness.

[0104] The above are only some embodiments of the present invention. For those skilled in the art, several modifications and improvements can be made without departing from the creative concept of the present invention, which all belong to the protection scope of the present invention.

Claims

1. A method for preparing a tetrafunctional alicyclic epoxy compound, characterized in that: The following steps are involved: S1, pentaerythritol, 3-cyclohexene-1-carboxylic acid, a catalyst and an organic solvent are mixed to obtain a solid-liquid mixture, a condensing agent is dissolved in an organic solvent to obtain a first mixed solution, the first mixed solution is added dropwise to the solid-liquid mixture and stirred until the solid in the solid-liquid mixture is dissolved in the organic solvent, the reaction is carried out for 16 to 24 hours, the reaction system after the reaction is washed and dried to obtain an organic phase, the organic phase is then subjected to reduced pressure distillation, and the residue of the organic phase after the reduced pressure distillation is crystallized to obtain pentaerythritol tetracyclohexene formate; S2, dissolving pentaerythritol tetracyclohexene carboxylate in an organic solvent to obtain a second mixed solution, dissolving m-chloroperbenzoic acid in an organic solvent to obtain a third mixed solution, then dropping the third mixed solution into the second mixed solution under ice bath conditions, stirring and reacting for 16 to 24 hours, filtering, purifying the filtered filtrate to obtain an organic phase, and crystallizing to obtain; The catalyst is selected from at least one of 4-dimethylaminopyridine, 1-hydroxybenzotriazole, and 4-pyrrolidinopyridine, and the condensing agent is selected from at least one of N,N-dicyclohexylcarbodiimide, N,N-diisopropylcarbodiimide, and 1-(3-dimethylaminopropyl)-3-ethylcarbodiimide.

2. The preparation method according to claim 1, characterized in that: The molar ratio of the pentaerythritol, 3-cyclohexene-1-carboxylic acid, catalyst and condensation agent is 1:(4-4.12):(1-1.10):(4-4.10), and the molar ratio of the pentaerythritol tetracyclohexene carboxylate to meta-chloroperbenzoic acid is 1:(4-4.10).

3. The preparation method according to claim 1 or 2, characterized in that: The amount of the catalyst used is 8-10% of the total mass of pentaerythritol, 3-cyclohexene-1-carboxylic acid and the condensation agent.

4. The preparation method according to claim 1, characterized in that: The organic solvent is selected from at least one of tetrahydrofuran and dichloromethane.

5. The preparation method according to claim 1, characterized in that: In step S1, the washing treatment method is to transfer the reaction system after the reaction to a separatory funnel, wash it three times with a 1% hydrochloric acid solution, and then wash it three times with a saturated sodium chloride solution, and separate the liquids to obtain a lower organic phase; Alternatively, the reaction system after the reaction is transferred to a separatory funnel, and first washed with a 1% hydrochloric acid solution for 3 times, then washed with a saturated sodium bicarbonate solution for 3 times, and then washed with a saturated sodium chloride solution for 3 times, and then separated to obtain a lower organic phase; Alternatively, the reaction system after the reaction is transferred to a separatory funnel, the organic phase is washed three times with a 1% by mass hydrochloric acid solution, and the lower organic phase is obtained by separation.

6. The preparation method according to claim 1, characterized in that: In step S1, the method of obtaining the organic phase by drying the reaction system after the reaction is to add a solid desiccant to the reaction system, filter and retain the filtered organic phase.

7. The preparation method according to claim 1, characterized in that: In step S2, the purification treatment method is to first add a saturated sodium sulfite solution to the filtrate, then wash the filtrate three times with a saturated sodium bicarbonate solution and a saturated sodium chloride solution, respectively, separate the liquids to obtain a lower organic phase, add a solid desiccant to the washed organic phase, filter, and remove the organic solvent in the organic phase by reduced pressure distillation.

8. The preparation method according to claim 1 or 7, characterized in that: The treatment method of reduced pressure distillation is to distill the organic phase under reduced pressure at a vacuum degree of -0.098 MPa and a water bath temperature of 30 to 40° C. for 1 to 3 hours.

9. The preparation method according to claim 6 or 7, characterized in that: The solid desiccant is selected from at least one of anhydrous sodium sulfate and anhydrous magnesium sulfate.

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