Triazine acrylic acid epoxy resin as well as preparation method and application thereof

Abstract

The invention belongs to the technical field of high polymer materials, and particularly relates to triazine acrylic acid epoxy resin as well as a preparation method and application thereof. The epoxy resin composition comprises the following raw materials in parts by weight: 60-70 parts of epoxy resin, 3-10 parts of a triazine compound, 2-5 parts of a solvent, 10-15 parts of a bifunctional acrylate monomer, 0.05-0.50 part of a polymerization inhibitor, 0.02-0.08 part of a catalyst, 10-35 parts of xylene and 20-40 parts of anhydride. The triazine acrylic acid epoxy resin provided by the invention has excellent weather resistance, wear resistance, thermal stability, hardness, chemical resistance, adhesive force, photosensitivity, etching resistance, electroplating resistance, film stripping property, glossiness and the like, and is suitable for being applied to preparation of IC (integrated circuit) support plates.

Description

Technical Field

[0001] The invention belongs to the technical field of polymer materials, and in particular relates to a triazine acrylated epoxy resin and a preparation method and application thereof. Background Art

[0002] IC substrate is the basis of integrated circuit (IC) packaging and plays an important 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 them, solder mask ink, as a protective layer of IC substrates, is crucial to the stability and reliability of circuits.

[0003] Traditional PCB boards use epoxy resin substrates, and solder mask ink is used to cover the circuit surface during the preparation process to prevent short circuits or other problems during welding. With the continuous pursuit of performance and volume of electronic products, IC substrates require higher density, more complex wiring and stronger impedance control. Except for the solder joints on the IC substrate, the other parts of the board surface need to be covered with a layer of solder mask ink as a permanent protective coating to selectively mask the wire pattern from damage, prevent short circuits caused by solder bonding, increase insulation, and prevent circuit corrosion and disconnection. Compared with traditional PCB board solder mask ink, IC substrate solder mask ink has more stringent requirements on indicators such as photosensitivity, etching resistance, electroplating resistance, and film fading. Therefore, it is necessary to improve the formula of solder mask ink and further enhance its performance to meet the application requirements of IC substrates. Summary of the invention

[0004] The first object of the present invention is to provide a triazine acrylated epoxy resin, the second object of the present invention is to provide a method for preparing the triazine acrylated epoxy resin, and the third object of the present invention is to provide an application of the triazine acrylated epoxy resin.

[0005] According to a first aspect of the present invention, a triazine acrylated epoxy resin is provided, wherein the raw materials thereof comprise, in parts by weight, 60-70 parts of epoxy resin, 3-10 parts of triazine compounds, 2-5 parts of solvents, 10-15 parts of bifunctional acrylate monomers, 0.05-0.50 parts of polymerization inhibitors, 0.02-0.08 parts of catalysts, 10-35 parts of xylene, and 20-40 parts of acid anhydride.

[0006] The present invention firstly synthesizes a triazine acrylate solvent by a Michael addition reaction between a triazine compound and a bifunctional acrylate monomer. The solvent structure contains three acrylic groups, providing multiple reaction sites, thereby forming a higher crosslinking density; and the solvent structure contains an imide structure, which can significantly improve the heat resistance, chemical resistance and adhesion of the final resin; and the content of flexible groups in the molecular chain is increased. Then the triazine acrylate solvent is added to the epoxy resin system, and anhydride is used as a crosslinking agent of the epoxy resin to react with the epoxy resin to form a high molecular crosslinking structure, thereby improving the strength and stability of the resin.

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

[0008] In some embodiments, the triazine compound is selected from cyanuric acid and / or tris(hydroxyethyl)isocyanurate. These triazine compounds contain three reaction sites and can react with other monomers in the resin synthesis to form a high-density cross-linked structure. The high cross-linking density helps to enhance the mechanical strength, wear resistance and hardness of the resin. In addition, these triazine compounds can also improve the heat resistance and thermal stability of the resin, enhance chemical resistance, reduce hygroscopicity, enhance 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, tricyclo[5.2.1.0 2,6 ] At least one of 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-propylene glycol) diacrylate. These bifunctional acrylate monomers contain two reactive groups and can form a higher cross-linking density in the polymerization reaction. This high-density cross-linking structure helps to enhance the mechanical strength, hardness and wear resistance of the resin, thereby improving the durability and stability of the resin. In addition, these bifunctional acrylate monomers can also improve the thermal stability and chemical resistance of the resin, enhance dimensional stability and low hygroscopicity, 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 unnecessary polymerization reactions from occurring during the resin synthesis process, maintain the selectivity of the reaction, and prevent undesirable gelation or curing during the synthesis process.

[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 and promote the mixing and reaction of the reaction materials.

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

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

[0016] S1, first dissolving the triazine compound in a solvent, then adding a bifunctional acrylate monomer, raising the system temperature to 75-85°C and reacting for 7-9h to obtain a triazine acrylate solvent;

[0017] S2. Add xylene into the reaction kettle, raise the system temperature to 60-70°C, then add epoxy resin, raise the temperature to 80-100°C and dissolve for 1-2h. After dissolution, lower the system temperature to 60-70°C;

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

[0019] The present invention first uses triazine compounds as raw materials, and conducts Michael addition reaction with bifunctional acrylate monomers to synthesize triazine acrylate solvents containing imide structures. The solvent structure contains imide structures, which can significantly improve the heat resistance, chemical resistance and adhesion of the final resin; and the molecular chain contains multiple reaction sites and flexible groups. Then, epoxy resin and acid anhydride are added to carry out ring-opening reaction, and multiple acrylate groups and carboxyl groups are introduced, which play a role in regulating the performance and curing process of the final resin.

[0020] When the triazine compound is cyanuric acid, the synthesis route of the triazine acrylate solvent is as follows: Figure 1The bifunctional acrylate monomers of the present invention are 1,6-hexanediol diacrylate, neopentyl glycol diacrylate, tricyclo[5.2.1.0 2,6 ] At least one of 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-propylene glycol) diacrylate. In the figure, the structure of the group X depends on the selection of the bifunctional acrylate monomer and is not listed one by one in the figure.

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

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

[0023] According to a fifth aspect of the present invention, there is provided a use of the above-mentioned dry film in preparing an IC substrate.

[0024] The beneficial effects of the present invention include:

[0025] The triazine acrylated epoxy resin of the present invention has excellent weather resistance, wear resistance, thermal stability and hardness, chemical resistance, adhesion, photosensitivity, etching resistance, electroplating resistance, film fading and gloss, and is suitable for use in preparing IC substrates. BRIEF DESCRIPTION OF THE DRAWINGS

[0026] Figure 1 The present invention is a synthetic route diagram of the triazine acrylate solvent when the triazine compound is cyanuric acid. DETAILED DESCRIPTION

[0027] The present invention is further described in detail below. It is worth noting that the following examples are only for better explanation of the present invention and are not intended to limit the scope of the present invention. The undisclosed process steps in the examples are prior art. Unless otherwise specified, the following raw materials are commercially available.

[0028] For example, the phenolic epoxy resin can be selected from APU-20-52G of Peutectic Industries, Ltd.; DUREZ-29095 and DUREZ-29845 of Soli Enterprise Co., Ltd.; HR-1170, HR-1180 and HR-2116 of Guangdong Kemao Forestry Chemical Industry Co., Ltd., and the like.

[0029] The hydrogenated bisphenol A type epoxy resin can be selected from EP-4080E, EP-4081, EP-4085 of Adeka Corporation of Japan; NPST-3000, NPST-5100 of Nanya Plastics Industry Co., Ltd.; JET-300, JET-300s, JlET-3000 of Changshu Jiafa Chemical Co., Ltd.; I.ZY-40 of Shanghai Liyi Technology Development Co., Ltd., etc.

[0030] The bisphenol A type epoxy resin can be selected from EPIKOTE-1001, EPIKOTE-82, EPIKOTE-828L of Hexion Company of the Netherlands; EPON-1001F, EPON-1004F, EPON-1007F of Momentive Performance Materials Company of the United States, etc.

[0031] The bisphenol F type epoxy resin can be selected from NPEF-170, NPEF-164X, NPEF-175 of Nan Ya Plastics Industrial Co., Ltd.; DER-321, DER-324, DER-354 of Dow Chemical Group, USA.

[0032] The bisphenol S epoxy resin can be selected from the bisphenol S epoxy resin produced by Wuhan Kemik Biopharmaceutical Co., Ltd.

[0033] The cyanuric acid can be selected from the cyanuric acid of Guangdong Shengke Biochemical Technology Co., Ltd., Shanghai Gaoming Chemical Co., Ltd., Jinan Yunuo Chemical Co., Ltd. and the like.

[0034] The trihydroxyethyl isocyanurate can be selected from the trihydroxyethyl isocyanurate of Nantong Runfeng Petrochemical Co., Ltd., Seck Chemical (Shanghai) Co., Ltd., and the like.

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

[0036] Example 1

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

[0038] (1) First, 5.08 g of cyanuric acid was dissolved in 2.58 g of dimethylformamide, and then 12.84 g of 1,6-hexanediol diacrylate was added. The system temperature was raised to 80° C. and reacted for 8 h to obtain a triazine acrylate solvent.

[0039] (2) Add 32.34 g of p-xylene into the reaction kettle, raise the system temperature to 65°C, and then add 66.29 g of phenolic epoxy resin, raise the temperature to 90°C and dissolve for 1.5 hours. After dissolution, lower the system temperature to 65°C.

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

[0041] Example 2

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

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

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

[0045] (3) Add the triazine acrylate solvent obtained in step (1), 0.06 g of benzyldimethylamine and 0.11 g of p-tert-butylcatechol to the above reaction kettle, then raise the system temperature to 90° C. and stir to react for 4.5 hours. Then lower the system temperature to 65° C., add 37.90 g of benzophenonetetracarboxylic dianhydride, raise the system temperature to 93° C. and stir to react for 4 hours to obtain the product.

[0046] Example 3

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

[0048] (1) Dissolve 5.08 g of cyanuric acid in 2.58 g of dimethylformamide, then add 12.84 g of tricyclo[5.2.1.0 2,6 ] Sebacic acid diacrylate, raise the system temperature to 80°C and react for 8h to obtain a triazine acrylate solvent.

[0049] (2) Add 32.34 g of o-xylene into the reaction kettle, raise the system temperature to 65°C, and then add 66.29 g of bisphenol F epoxy resin, raise the temperature to 85°C and dissolve for 1.5 hours. 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 into the above reaction kettle, then raise the system temperature to 95° C. and stir to react for 4.5 hours. Then lower the system temperature to 68° C., add 37.90 g of tetrahydrophthalic anhydride, raise the system temperature to 94° C. and stir to react for 3.5 hours to obtain the product.

[0051] Example 4

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

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

[0054] (2) Add 32.34 g of p-xylene into the reaction kettle, raise the system temperature to 68°C, and then add 66.29 g of bisphenol S epoxy resin, raise the temperature to 95°C and dissolve for 1.5 hours. After dissolution, lower the system temperature to 62°C.

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

[0056] Example 5

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

[0058] (1) First, 5.08 g of tris(hydroxyethyl)isocyanurate was dissolved in 2.58 g of dimethylformamide, and then 12.84 g of triethylene glycol dimethacrylate was added. The system temperature was raised to 85° C. and reacted for 7 h to obtain a triazine acrylate solvent.

[0059] (2) Add 32.34 g of o-xylene into the reaction kettle, raise the system temperature to 70°C, and 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 into the above reaction kettle, then raise the system temperature to 100° C., stir and react 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., stir and react for 3 h, and obtain the product.

[0061] Example 6

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

[0063] (1) First, 5.08 g of cyanuric acid was dissolved in 2.58 g of dimethyl sulfoxide, and then 12.84 g of 1,3-butanediol dimethacrylate was added. The system temperature was raised to 75° C. and reacted for 9 hours to obtain a triazine acrylate solvent.

[0064] (2) Add 32.34 g of m-xylene into the reaction kettle, raise the system temperature to 60°C, and 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 into the above reaction kettle, then raise the system temperature to 80°C, stir and react for 5 hours, then lower the system temperature to 60°C, add 37.90 g of tetrahydrophthalic anhydride, raise the system temperature to 90°C, stir and react for 5 hours, and obtain the product.

[0066] Next, the performance of the triazine acrylated epoxy resins prepared in Examples 1-6 was tested, and the testing method was as follows:

[0067] (1) Photosensitivity: Print the resin on the copper clad laminate, bake at 75°C for 20 minutes, place a 21-level light gradient ruler on the film layer, expose and develop under an LED light source exposure machine, and use the time when 7 grids remain on the film layer as the standard.

[0068] (2) Minimum line spacing and line width: Tested in accordance with the method of GB / T 29846-2013 Photo-imaging electroplating resists for printed circuit boards.

[0069] (3) Etching resistance: The etching resistance is tested according to the method of GB / T 29846-2013 for photo-imaging electroplating resists for printed boards. After etching, the pattern is visually intact, the line edges are neat, and there is no wrinkling, shedding or dog-tooth shape. It is excellent. Wrinkling without shedding is good. Shedding is poor.

[0070] (4) Electroplating resistance: Electroplating resistance is tested according to the method of GB / T 29846-2013 Photo-imaging Electroplating Resist for Printed Boards. After electroplating, if the pattern has no seepage, bubbles, or shedding, it is excellent; if there is seepage but no shedding, it is good; if there is shedding, it is poor.

[0071] (5) Film fading property: The test specimens were placed in a 50°C, 3 wt% NaOH aqueous solution and the film fading performance was observed. The film fading performance was excellent if it completely shed within 60 seconds without any residue, good if it completely shed within 60-120 seconds without any residue, and poor if it shed after 120 seconds without any residue.

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

[0073] Table 1 Performance test results of triazine acrylated epoxy resin of Examples 1-6

[0074]

[0075] Photosensitivity: IC substrates generally require higher photosensitivity to ensure that the desired patterns and structures can be accurately formed during the exposure process. The test results in Table 1 show that the resin of the present invention performs well in terms of photosensitivity, which means that it can be cured quickly and accurately during the exposure process, which is conducive to forming high-precision patterns and structures.

[0076] Etching resistance: IC substrates require high etching resistance to ensure that good pattern clarity and edge retention can be maintained during the etching process. The test results in Table 1 show that the resin of the present invention has high etching resistance and can maintain pattern clarity and accuracy during the etching process.

[0077] Electroplating resistance: IC substrates need to have good electroplating resistance to ensure that the surface flatness and conductivity can be maintained 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 fading property: IC substrates require stable film fading properties to ensure that they can maintain stable performance and appearance for a long time during use. The test results in Table 1 show that the resin of the present invention has excellent film fading properties and can maintain stable performance and appearance during long-term use, 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-fading resistance, and is suitable for use in preparing IC substrates.

[0080] 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. Triazine acrylated epoxy resin, characterized in that: The raw material composition includes, by weight: 60-70 parts of epoxy resin, 3-10 parts of triazine compounds, 2-5 parts of solvents, 10-15 parts of bifunctional acrylate monomers, 0.05-0.50 parts of polymerization inhibitors, 0.02-0.08 parts of catalysts, 10-35 parts of xylene, and 20-40 parts of acid anhydride.

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

3. The triazine acrylated epoxy resin according to claim 1 or 2, characterized in that: The triazine compound is selected from cyanuric acid and / or tris(hydroxyethyl)isocyanurate.

4. The triazine acrylated epoxy resin according to claim 1 or 2, characterized in that: The solvent is selected from dimethylformamide and / or dimethyl sulfoxide; The bifunctional acrylate monomer is selected from 1,6-hexanediol diacrylate, neopentyl glycol diacrylate, tricyclo[5.2.1.0 2,6 ] At least one of 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-propylene glycol) 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 dianhydride, tetrahydrophthalic anhydride, hexahydrophthalic anhydride, and methyltetrahydrophthalic anhydride.

7. The method for preparing the triazine acrylated epoxy resin according to any one of claims 1 to 6, characterized in that: The steps include: S1, first dissolving the triazine compound in a solvent, then adding a bifunctional acrylate monomer, raising the system temperature to 75-85°C and reacting for 7-9h to obtain a triazine acrylate solvent; S2. Add xylene into the reaction kettle, raise the system temperature to 60-70°C, then add epoxy resin, raise the temperature to 80-100°C and dissolve for 1-2h. After dissolution, lower the system temperature to 60-70°C; S3. Add the triazine acrylate solvent, catalyst and polymerization inhibitor obtained in step S1 into the above-mentioned reaction kettle, then raise the system temperature to 80-100°C, stir and react for 4-5h, then lower the system temperature to 60-70°C, add acid anhydride, raise the system temperature to 90-95°C, stir and react for 3-5h, and obtain the product.

8. Use of the triazine acrylated epoxy resin according to any one of claims 1 to 6 as solder resist ink in the preparation of IC substrates.

9. A dry film, characterized in that: The invention is obtained by photocuring or thermal curing the triazine acrylated epoxy resin according to any one of claims 1 to 6.

10. Use of the dry film according to claim 9 in preparing an IC substrate.

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