Triazine acrylic epoxy resin, its preparation method and application

Abstract

This invention belongs to the field of polymer materials technology, specifically relating to a triazine acrylate epoxy resin, its preparation method, and its applications. By weight, its raw material composition includes: 60-70 parts epoxy resin, 3-10 parts triazine compound, 2-5 parts solvent, 10-15 parts difunctional acrylate monomer, 0.05-0.50 parts polymerization inhibitor, 0.02-0.08 parts catalyst, 10-35 parts xylene, and 20-40 parts acid anhydride. The triazine acrylate epoxy resin of this invention possesses excellent weather resistance, abrasion resistance, thermal stability, and hardness; as well as excellent chemical resistance, adhesion, photosensitivity, etching resistance, electroplating resistance, peeling resistance, and gloss, making it suitable for use in the preparation of IC substrates.

Description

Technical Field

[0001] This invention belongs to the field of polymer materials technology, specifically relating to a triazine acrylated epoxy resin, its preparation method, and its application. Background Technology

[0002] IC substrates are the foundation of integrated circuit (IC) packaging, playing a crucial role in connecting and supporting chips. With the rapid development of electronic technology, IC substrates have made significant progress in manufacturing processes and materials. Among these advancements, solder resist ink, as a protective layer of the IC substrate, is essential for the stability and reliability of the circuit.

[0003] Traditional PCBs use epoxy resin substrates, and during the manufacturing process, solder resist ink is used to cover the circuit surface to prevent short circuits or other problems during soldering. With the increasing demands for performance and size in electronic products, IC substrates require higher density, more complex wiring, and stronger impedance control. Except for solder joints, all other parts of the IC substrate surface need to be covered with a layer of solder resist ink as a permanent protective coating to selectively mask the conductor patterns from damage, prevent short circuits caused by solder bridging, increase insulation, and prevent circuit corrosion and breakage. Compared to traditional PCB solder resist inks, IC substrate solder resist inks have more stringent requirements in terms of photosensitivity, etching resistance, electroplating resistance, and peel resistance. Therefore, it is necessary to improve the formulation of solder resist inks to further enhance their performance and meet the application requirements of IC substrates. Summary of the Invention

[0004] The first objective of this invention is to provide a triazine acrylated epoxy resin; the second objective of this invention is to provide a method for preparing the triazine acrylated epoxy resin; and the third objective of this invention is to provide applications of the triazine acrylated epoxy resin.

[0005] According to a first aspect of the present invention, a triazine acrylated epoxy resin is provided, comprising, by weight, 60-70 parts epoxy resin, 3-10 parts triazine compound, 2-5 parts solvent, 10-15 parts bifunctional acrylate monomer, 0.05-0.50 parts polymerization inhibitor, 0.02-0.08 parts catalyst, 10-35 parts xylene, and 20-40 parts acid anhydride.

[0006] This invention first synthesizes a triazine acrylate solvent by Michael addition reaction of a triazine compound with a bifunctional acrylate monomer. This solvent structure contains three acrylic groups, providing multiple reaction sites and thus achieving a higher crosslinking density. Furthermore, the presence of an imide structure significantly improves the heat resistance, chemical resistance, and adhesion of the final resin, and increases the content of flexible groups in the molecular chain. The triazine acrylate solvent is then added to an epoxy resin system, using an anhydride as a crosslinking agent to react with the epoxy resin, forming a high-molecular-weight crosslinked structure, thereby enhancing the resin's strength and stability.

[0007] In some embodiments, the epoxy resin is selected from at least one of phenolic epoxy resin, hydrogenated bisphenol A type epoxy resin, bisphenol A type epoxy resin, bisphenol S type epoxy resin, and bisphenol F type epoxy resin.

[0008] In some embodiments, the triazine compounds are selected from cyanuric acid and / or trihydroxyethyl isocyanurate. These triazine compounds contain three reaction sites, enabling them to react with other monomers during resin synthesis to form a high-density cross-linked structure. This high cross-linking density helps enhance the mechanical strength, abrasion resistance, and hardness of the resin. Furthermore, these triazine compounds can also improve the resin's heat resistance and thermal stability, enhance chemical resistance, reduce hygroscopicity, improve light stability, and improve adhesion.

[0009] In some embodiments, the solvent is selected from dimethylformamide (DMF) and / or dimethyl sulfoxide (DMSO).

[0010] In some embodiments, the bifunctional acrylate monomer is selected from 1,6-hexanediol diacrylate, neopentyl glycol diacrylate, and tricyclic [5.2.1.0]. 2,6 At least one of the following: sebacic acid diacrylate, ethylene glycol dimethacrylate, triethylene glycol dimethacrylate, 1,3-butanediol dimethacrylate, diethylene glycol diacrylate, dipropylene glycol diacrylate, dithiodiethanol diacrylate, and trimer(1,3-propanediol) diacrylate. These bifunctional acrylate monomers contain two reactive groups, enabling them to form a higher crosslink density during polymerization. This high-density crosslinking structure helps enhance the mechanical strength, hardness, and abrasion resistance of the resin, thereby improving its durability and stability. Furthermore, these bifunctional acrylate monomers can also improve the resin's thermal stability and chemical resistance, enhance dimensional stability and reduce moisture absorption, and improve adhesion and light aging resistance.

[0011] In some embodiments, the polymerization inhibitor is selected from at least one of hydroquinone, p-tert-butylcatechol, and catechol. The polymerization inhibitor can prevent unwanted polymerization reactions during resin synthesis, maintain reaction selectivity, and prevent undesirable gelation or curing during synthesis.

[0012] In some embodiments, the catalyst is selected from at least one of benzyltriethylammonium chloride, benzyldimethylamine, triethylamine, diethylamine, and triphenylphosphine.

[0013] In some embodiments, xylene is selected from at least one of p-xylene, m-xylene, and o-xylene. Xylene, as a solvent, can fully dissolve the epoxy resin, promoting the mixing and reaction of the reactants.

[0014] In some embodiments, the acid anhydride is selected from at least one of pyromellitic dianhydride, benzophenone tetracarboxylic acid dianhydride, tetrahydrophthalic anhydride, hexahydrophthalic anhydride, and methyltetrahydrophthalic anhydride.

[0015] According to a second aspect of the present invention, a method for preparing the above-described triazine acrylated epoxy resin is provided, comprising the following steps:

[0016] S1. First, dissolve the triazine compound in a solvent, then add the bifunctional acrylate monomer, raise the system temperature to 75-85℃ and react for 7-9 hours to obtain the triazine acrylate solvent.

[0017] S2. Add xylene to the reactor and raise the system temperature to 60-70℃. Then add epoxy resin and raise the temperature to 80-100℃ to dissolve for 1-2 hours. After dissolution, lower the system temperature to 60-70℃.

[0018] S3. Add the triazine acrylate solvent, catalyst and polymerization inhibitor obtained in step S1 to the above reaction vessel, then raise the system temperature to 80-100℃ and stir for 4-5 hours. Then lower the system temperature to 60-70℃, add acid anhydride, raise the system temperature to 90-95℃ and stir for 3-5 hours to obtain the product.

[0019] This invention first uses triazine compounds as raw materials and performs a Michael addition reaction with bifunctional acrylate monomers to synthesize triazine acrylate solvents containing imide structures. The presence of imide structures in this solvent significantly improves the heat resistance, chemical resistance, and adhesion of the final resin; furthermore, the molecular chain contains multiple reaction sites and flexible groups. Subsequently, epoxy resin and acid anhydride are added to perform a ring-opening reaction, introducing multiple acrylate groups and carboxyl groups, which regulate the performance of the final resin and the curing process.

[0020] When the triazine compound is cyanuric acid, the synthetic route for the triazine acrylate solvent is as follows: Figure 1As shown. The bifunctional acrylate monomers of this invention are 1,6-hexanediol diacrylate, neopentyl glycol diacrylate, and tricyclic [5.2.1.0]. 2,6 At least one of the following: sebacic acid diacrylate, ethylene glycol dimethacrylate, triethylene glycol dimethacrylate, 1,3-butanediol dimethacrylate, diethylene glycol diacrylate, dipropylene glycol diacrylate, dithiodiethanol diacrylate, and trimer(1,3-propanediol) diacrylate. In the figure, the structure of group X depends on the selection of the bifunctional acrylate monomer, and they are not listed one by one in the figure.

[0021] According to a third aspect of the present invention, the above-described triazine acrylated epoxy resin is provided as a solder resist ink in the preparation of IC substrates.

[0022] According to a fourth aspect of the present invention, a dry film is provided, which is obtained by photocuring or thermocuring the above-described triazine acrylated epoxy resin.

[0023] According to a fifth aspect of the present invention, the application of the above-described dry film in the preparation of IC substrates is provided.

[0024] The beneficial effects of this invention include:

[0025] The triazine acrylate epoxy resin of the present invention has excellent weather resistance, abrasion resistance, thermal stability and hardness, as well as excellent chemical resistance, adhesion, photosensitivity, etching resistance, electroplating resistance, film removal resistance and gloss, making it suitable for use in the preparation of IC substrates. Attached Figure Description

[0026] Figure 1 This is a synthetic route diagram of the triazine acrylate solvent of the present invention when the triazine compound is cyanuric acid. Detailed Implementation

[0027] The present invention will now be described in further detail. It is worth noting that the following embodiments are merely for better explanation of the invention and do not limit the scope of protection of the invention. Process steps not disclosed in the embodiments are prior art. Unless otherwise specified, all raw materials are commercially available.

[0028] For example, phenolic epoxy resins can be selected from APU-20-52G of Piyo Industrial Co., Ltd.; DUREZ-29095 and DUREZ-29845 of Shouli Enterprise Co., Ltd.; HR-1170, HR-1180 and HR-2116 of Guangdong Kemao Forest Products Chemical Co., Ltd., etc.

[0029] Hydrogenated bisphenol A type epoxy resins can be selected from Adeka Corporation of Japan's EP-4080E, EP-4081, and EP-4085; Nan Ya Plastics Industrial Co., Ltd.'s NPST-3000 and NPST-5100; Changshu Jiafa Chemical Co., Ltd.'s JET-300, JET-300s, and JlET-3000; and Shanghai Liyi Technology Development Co., Ltd.'s I.ZY-40, etc.

[0030] Bisphenol A type epoxy resins can be selected from EPIKOTE-1001, EPIKOTE-82, and EPIKOTE-828L from Hexion (Netherlands); and EPON-1001F, EPON-1004F, and EPON-1007F from Momentive Performance Materials (USA).

[0031] Bisphenol F type epoxy resins can be selected from NPEF-170, NPEF-164X, and NPEF-175 from Nan Ya Plastics Industrial Co., Ltd.; and DER-321, DER-324, and DER-354 from Dow Chemical Company, USA.

[0032] Bisphenol S type epoxy resin can be selected from bisphenol S type epoxy resin of Wuhan Kemike Biomedical Co., Ltd.

[0033] Cyanide can be selected from Guangdong Shengke Biochemical Technology Co., Ltd., Shanghai Gaoming Chemical Co., Ltd., Jinan Yuno Chemical Co., Ltd., etc.

[0034] Trihydroxyethyl isocyanurate can be selected from trihydroxyethyl isocyanurate of companies such as Nantong Runfeng Petrochemical Co., Ltd. and Sek Chemical (Shanghai) Co., Ltd.

[0035] In the following examples, the stirring speed is 550 rpm.

[0036] Example 1

[0037] The preparation method of the triazine acrylated epoxy resin in this embodiment includes the following steps:

[0038] (1) First, dissolve 5.08g of cyanuric acid in 2.58g of dimethylformamide, then add 12.84g of 1,6-hexanediol diacrylate, raise the temperature of the system to 80℃ and react for 8h to obtain triazine acrylate solvent.

[0039] (2) Add 32.34g of p-xylene to the reactor, raise the system temperature to 65℃, then add 66.29g of phenolic epoxy resin, raise the temperature to 90℃ and dissolve for 1.5h. After dissolution, lower the system temperature to 65℃.

[0040] (3) Add the triazine acrylate solvent obtained in step (1), 0.06 g benzyltriethylammonium chloride and 0.11 g hydroquinone to the above reaction vessel, then raise the system temperature to 90°C and stir the reaction for 4.5 h. Then lower the system temperature to 65°C, add 37.90 g pyromellitic dianhydride, raise the system temperature to 92°C and stir the reaction for 4 h to obtain the final product.

[0041] Example 2

[0042] The preparation method of the triazine acrylated epoxy resin in this embodiment includes the following steps:

[0043] (1) First, 5.08g of trihydroxyethyl isocyanurate was dissolved in 2.58g of dimethyl sulfoxide, and then 12.84g of neopentyl glycol diacrylate was added. The system temperature was raised to 80℃ and reacted for 8h to obtain triazine acrylate solvent.

[0044] (2) Add 32.34 g of m-xylene to the reactor, raise the system temperature to 65°C, then add 66.29 g of hydrogenated bisphenol A epoxy resin, raise the temperature to 90°C and dissolve for 1.5 h. After dissolution, lower the system temperature to 65°C.

[0045] (3) Add the triazine acrylate solvent obtained in step (1), 0.06 g benzyl dimethylamine and 0.11 g p-tert-butylcatechol to the above reaction vessel, then raise the system temperature to 90°C and stir for 4.5 h. Then lower the system temperature to 65°C, add 37.90 g benzophenone tetracarboxylic acid dianhydride, raise the system temperature to 93°C and stir for 4 h to obtain the product.

[0046] Example 3

[0047] The preparation method of the triazine acrylated epoxy resin in this embodiment includes the following steps:

[0048] (1) First, dissolve 5.08g of cyanuric acid in 2.58g of dimethylformamide, then add 12.84g of tricyclo[5.2.1.0]. 2,6 Sebacic acid diacrylate was reacted at 80°C for 8 hours to obtain triazine acrylate solvent.

[0049] (2) Add 32.34 g of o-xylene to the reactor, raise the system temperature to 65°C, then add 66.29 g of bisphenol F epoxy resin, raise the temperature to 85°C and dissolve for 1.5 h. After dissolution, lower the system temperature to 68°C.

[0050] (3) Add the triazine acrylate solvent obtained in step (1), 0.06 g of triethylamine and 0.11 g of catechol to the above reaction vessel, then raise the system temperature to 95°C and stir the reaction for 4.5 h. Then lower the system temperature to 68°C, add 37.90 g of tetrahydrophthalic anhydride, raise the system temperature to 94°C and stir the reaction for 3.5 h to obtain the final product.

[0051] Example 4

[0052] The preparation method of the triazine acrylated epoxy resin in this embodiment includes the following steps:

[0053] (1) First, 5.08g of trihydroxyethyl isocyanurate was dissolved in 2.58g of dimethyl sulfoxide, and then 12.84g of ethylene glycol dimethacrylate was added. The system temperature was raised to 78℃ and reacted for 8.5h to obtain triazine acrylate solvent.

[0054] (2) Add 32.34g of p-xylene to the reactor and raise the system temperature to 68℃. Then add 66.29g of bisphenol S-type epoxy resin and raise the temperature to 95℃ to dissolve for 1.5h. After dissolution, lower the system temperature to 62℃.

[0055] (3) Add the triazine acrylate solvent obtained in step (1), 0.06 g of diethylamine and 0.11 g of hydroquinone to the above reaction vessel, then raise the system temperature to 85°C and stir the reaction for 4.5 h. Then lower the system temperature to 63°C, add 37.90 g of hexahydrophthalic anhydride, raise the system temperature to 91°C and stir the reaction for 4.5 h to obtain the final product.

[0056] Example 5

[0057] The preparation method of the triazine acrylated epoxy resin in this embodiment includes the following steps:

[0058] (1) First, dissolve 5.08g of trihydroxyethyl isocyanurate in 2.58g of dimethylformamide, then add 12.84g of triethylene glycol dimethacrylate, raise the temperature of the system to 85℃ and react for 7h to obtain triazine acrylate solvent.

[0059] (2) Add 32.34 g of o-xylene to the reactor, raise the system temperature to 70°C, then add 66.29 g of phenolic epoxy resin, raise the temperature to 100°C and dissolve for 1 hour. After dissolution, lower the system temperature to 70°C.

[0060] (3) Add the triazine acrylate solvent obtained in step (1), 0.06 g of triphenylphosphine and 0.11 g of p-tert-butylcatechol to the above reaction vessel, then raise the system temperature to 100°C and stir for 4 h, then lower the system temperature to 70°C, add 37.90 g of methyltetrahydrophthalic anhydride, raise the system temperature to 95°C and stir for 3 h to obtain the product.

[0061] Example 6

[0062] The preparation method of the triazine acrylated epoxy resin in this embodiment includes the following steps:

[0063] (1) First, dissolve 5.08g of cyanuric acid in 2.58g of dimethyl sulfoxide, then add 12.84g of 1,3-butanediol dimethacrylate, raise the temperature of the system to 75℃ and react for 9h to obtain triazine acrylate solvent.

[0064] (2) Add 32.34 g of m-xylene to the reactor, raise the system temperature to 60°C, then add 66.29 g of bisphenol A epoxy resin, raise the temperature to 80°C and dissolve for 2 hours. After dissolution, lower the system temperature to 60°C.

[0065] (3) Add the triazine acrylate solvent obtained in step (1), 0.06 g of triethylamine and 0.11 g of hydroquinone to the above reaction vessel, then raise the system temperature to 80°C and stir for 5 h, then lower the system temperature to 60°C, add 37.90 g of tetrahydrophthalic anhydride, raise the system temperature to 90°C and stir for 5 h to obtain the product.

[0066] The performance of the triazine acrylic epoxy resins prepared in Examples 1-6 is tested below, and the test methods are as follows:

[0067] (1) Photosensitivity: The resin is printed on the copper-clad board and baked at 75°C for 20 minutes. A 21-level optical gradient ruler is placed above the film layer and exposed and developed under an LED light source exposure machine. The time when 7 grids remain in the film layer is used as the standard.

[0068] (2) Minimum line spacing and line width: Tested according to GB / T 29846-2013 Method for photolithography resist of electroplating for printed circuit boards.

[0069] (3) Etching resistance: The etching resistance is tested according to the method of photo-imaging electroplating resist for printed circuit boards in GB / T 29846-2013. After etching, the pattern is complete, the line edges are neat, and there is no wrinkling, peeling or jagged shape. The pattern is good, the wrinkling without peeling is good, and the peeling is poor.

[0070] (4) Electroplating resistance: The electroplating resistance is tested according to the method of photo-imaging electroplating resist for printed circuit boards in GB / T 29846-2013. After electroplating, the pattern is considered excellent if there is no plating penetration, bubbles, or peeling. If there is plating penetration but no peeling, it is considered good. If peeling occurs, it is considered poor.

[0071] (5) Removal property: The test sample was placed in a 3wt% NaOH aqueous solution at 50℃ and the removal property was observed. The sample that completely peeled off without any residue within 60s was considered excellent, the sample that completely peeled off without any residue within 60-120s was considered good, and the sample that peeled off without any residue after 120s was considered poor.

[0072] The test results are shown in Table 1.

[0073] Table 1. Performance test results of triazine acrylated epoxy resins in Examples 1-6

[0074]

[0075] Photosensitivity: IC substrates typically require higher photosensitivity to ensure accurate formation of the desired patterns and structures during exposure. The test results in Table 1 show that the resin of this invention exhibits excellent photosensitivity, meaning it can cure quickly and accurately during exposure, which is beneficial for forming high-precision patterns and structures.

[0076] Etching resistance: IC substrates require high etching resistance to ensure good pattern clarity and edge retention during etching. The test results in Table 1 show that the resin of this invention has high etching resistance, maintaining pattern clarity and accuracy during etching.

[0077] Electroplating resistance: IC substrates need to have good electroplating resistance to ensure that they can maintain surface smoothness and conductivity during the electroplating process. The test results in Table 1 show that the resin of the present invention has good electroplating resistance and can effectively prevent adverse reactions and defects during the electroplating process.

[0078] Film removal performance: IC substrates require stable film removal performance to ensure consistent performance and appearance over long-term use. The test results in Table 1 show that the resin of this invention exhibits excellent film removal performance, maintaining stable performance and appearance during long-term use, thus meeting the requirements of IC substrates.

[0079] Therefore, the triazine acrylated epoxy resin of the present invention has excellent properties such as photosensitivity, etching resistance, electroplating resistance, and film removal resistance, and is suitable for use in the preparation of IC substrates.

[0080] The above embodiments are preferred embodiments of the present invention, but the embodiments of the present invention are not limited to the above embodiments. Any changes, modifications, substitutions, combinations, or simplifications made without departing from the spirit and principle of the present invention shall be considered equivalent substitutions and shall be included within the protection scope of the present invention.

Claims

1. A triazine acrylated epoxy resin, characterized in that, The raw material composition, by weight, is as follows: 60-70 parts epoxy resin, 3-10 parts triazine compound, 2-5 parts solvent, 10-15 parts difunctional acrylate monomer, 0.05-0.50 parts polymerization inhibitor, 0.02-0.08 parts catalyst, 10-35 parts xylene, and 20-40 parts acid anhydride; the solvent is selected from dimethylformamide and / or dimethyl sulfoxide. Its preparation method includes the following steps: S1. First, dissolve the triazine compound in a solvent, then add the bifunctional acrylate monomer, raise the system temperature to 75-85℃ and react for 7-9 hours to obtain the triazine acrylate solvent. S2. Add xylene to the reactor and raise the system temperature to 60-70℃. Then add epoxy resin and raise the temperature to 80-100℃ to dissolve for 1-2 hours. After dissolution, lower the system temperature to 60-70℃. S3. Add the triazine acrylate solvent, catalyst and polymerization inhibitor obtained in step S1 to the above reaction vessel, then raise the system temperature to 80-100℃ and stir for 4-5 hours. Then lower the system temperature to 60-70℃, add acid anhydride, raise the system temperature to 90-95℃ and stir for 3-5 hours to obtain the product.

2. The triazine acrylated epoxy resin according to claim 1, characterized in that, The epoxy resin is selected from at least one of phenolic epoxy resin, hydrogenated bisphenol A type epoxy resin, bisphenol A type epoxy resin, bisphenol S type epoxy resin, and bisphenol F type epoxy resin.

3. The triazine acrylated epoxy resin according to claim 1 or 2, characterized in that, The triazine compounds are selected from cyanuric acid and / or trihydroxyethyl isocyanurate.

4. The triazine acrylated epoxy resin according to claim 1 or 2, characterized in that, The bifunctional acrylate monomers are selected from 1,6-hexanediol diacrylate, neopentyl glycol diacrylate, and tricyclic [5.2.1.0]. 2,6 At least one of the following: sebacic acid diacrylate, ethylene glycol dimethacrylate, triethylene glycol dimethacrylate, 1,3-butanediol dimethacrylate, diethylene glycol diacrylate, dipropylene glycol diacrylate, dithiodiethanol diacrylate, and tripoly(1,3-propanediol) diacrylate.

5. The triazine acrylated epoxy resin according to claim 1 or 2, characterized in that, The polymerization inhibitor is selected from at least one of hydroquinone, p-tert-butylcatechol, and catechol. The catalyst is selected from at least one of benzyltriethylammonium chloride, benzyldimethylamine, triethylamine, diethylamine, and triphenylphosphine.

6. The triazine acrylated epoxy resin according to claim 1 or 2, characterized in that, The xylene is selected from at least one of p-xylene, m-xylene, and o-xylene; The acid anhydride is selected from at least one of pyromellitic dianhydride, benzophenone tetracarboxylic acid dianhydride, tetrahydrophthalic anhydride, hexahydrophthalic anhydride, and methyltetrahydrophthalic anhydride.

7. The use of the triazine acrylated epoxy resin according to any one of claims 1-6 as a solder resist ink in the preparation of IC substrates.

8. A dry film, characterized in that, It is obtained by photocuring or thermocuring the triazine acrylated epoxy resin according to any one of claims 1-6.

9. The application of the dry film according to claim 8 in the preparation of IC substrates.

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