Glycerol carbonate modified epoxy resin and preparation method and application thereof

Abstract

The present invention belongs to the technical field of polymer materials, and specifically relates to a glycerol carbonate modified epoxy resin and a preparation method and application thereof. In parts by weight, the raw material composition includes: 60-70 parts of epoxy resin, 10-15 parts of glycerol carbonate monomers, 10-15 parts of acrylate monomers, 20-30 parts of anhydride, 0.10-0.50 parts of polymerization inhibitors, 0.10-0.50 parts of solid base catalysts, and 10-35 parts of xylene. The glycerol carbonate modified epoxy resin of the present invention has strong adhesion, high glass transition temperature and low thermal expansion coefficient, and has excellent properties such as photosensitivity, etching resistance, electroplating resistance, and film-fading resistance, and is suitable for use in the preparation of IC carriers.

Description

Technical Field

[0001] The invention belongs to the technical field of polymer materials, and in particular relates to a glycerol carbonate modified 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 glycerol carbonate modified epoxy resin. The second object of the present invention is to provide a method for preparing the glycerol carbonate modified epoxy resin. The third object of the present invention is to provide an application of the glycerol carbonate modified epoxy resin.

[0005] According to a first aspect of the present invention, a glycerol carbonate modified epoxy resin is provided, and its raw material composition comprises, by weight: 60-70 parts of epoxy resin, 10-15 parts of glycerol carbonate monomer, 10-15 parts of acrylate monomer, 20-30 parts of acid anhydride, 0.10-0.50 parts of inhibitor, 0.10-0.50 parts of solid base catalyst, and 10-35 parts of xylene.

[0006] The present invention uses epoxy resin as the main basic material to provide the main structure and the basis for the reaction; more alcohol hydroxyl groups are introduced into the resin by adding glycerol carbonate monomers to facilitate subsequent modification and structural adjustment; acrylate monomers are added to participate in the polymerization reaction to introduce acrylate groups, which play a regulating role on the performance and curing process of the resin; acid anhydride is used as the crosslinking agent of the epoxy resin to react with the epoxy resin to form a high molecular crosslinking structure, while increasing the strength and stability of the resin.

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

[0008] In some embodiments, the glycerol carbonate monomer is selected from 4-(hydroxymethyl)-1,3-dioxolan-2-one (i.e., 4-(Hydroxymethyl)-1,3-dioxolan-2-one, CAS No.: 931-40-8) and / or 5-hydroxy-1,3-dioxan-2-one (i.e., 5-Hydroxy-1,3-dioxan-2-one, CAS No.: 86629-67-6). 4-(Hydroxymethyl)-1,3-dioxolan-2-one and 5-hydroxy-1,3-dioxan-2-one have stable molecular structures, high thermal stability and chemical stability, and can react more effectively with raw materials such as epoxy resin to form stable chemical bonds, thereby improving the high temperature resistance and chemical stability of the resin solder resist ink. In addition, the molecular structures of 4-(hydroxymethyl)-1,3-dioxolane-2-one and 5-hydroxy-1,3-dioxane-2-one are also more compatible with other formulation ingredients, which is beneficial to the processing and performance regulation of resin solder mask inks, thereby improving the quality and stability of the products.

[0009] In some embodiments, the acrylic acid ester monomer is selected from at least one of hydroxyethyl acrylate, hydroxyethyl methacrylate, hydroxypropyl acrylate, and hydroxypropyl methacrylate.

[0010] In some embodiments, the acid anhydride is selected from at least one of pyromellitic dianhydride, benzophenonetetracarboxylic dianhydride, tetrahydrophthalic anhydride, hexahydrophthalic anhydride, and methyltetrahydrophthalic anhydride.

[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 solid base catalyst is selected from at least one of magnesium oxide, calcium oxide, magnesium hydroxide, and synthetic hydrotalcite. The solid base catalyst can promote the synthesis rate of the resin and improve the performance of the resin, such as improving the hardness and heat resistance of the resin.

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

[0014] According to a second aspect of the present invention, there is provided a method for preparing the above-mentioned glycerol carbonate modified epoxy resin, comprising the following steps:

[0015] S1. Add xylene to the reaction kettle, raise the system temperature to 60-70°C, then add epoxy resin and stir for 2-3h; then add glycerol carbonate monomer and solid base catalyst to the reaction kettle, after adding, raise the temperature to 90-100°C, and continue stirring and reacting for 6-8h;

[0016] S2. Lower the system temperature to 60-70°C, then add acrylate monomer, acid anhydride and polymerization inhibitor into the reaction kettle, raise the system temperature to 80-100°C after adding, stir and react for 2-3h, then lower the system temperature to 60-70°C to obtain.

[0017] The present invention first uses glycerol carbonate monomers to react with epoxy resin under alkaline catalysis conditions to introduce more alcohol hydroxyl groups on the resin, which will provide more room for subsequent modification and facilitate subsequent modification and structural adjustment. The reaction generates carbon dioxide, and the catalyst is a solid base that is recyclable, and the technical route is green and safe. Then, acrylate monomers and acid anhydrides are added to the epoxy resin for a ring-opening reaction, and acrylate groups and carboxyl groups are introduced to regulate the performance and curing process of the resin. The photocuring crosslinking density, alkali development efficiency, and post-bake curing performance of the glycerol carbonate modified epoxy resin finally obtained are easier to control.

[0018] According to a third aspect of the present invention, there is provided a use of the above-mentioned glycerol carbonate modified epoxy resin as solder resist ink in the preparation of an IC substrate.

[0019] According to a fourth aspect of the present invention, there is provided a dry film obtained by photocuring or thermal curing the above-mentioned glycerol carbonate modified epoxy resin.

[0020] 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.

[0021] The beneficial effects of the present invention include:

[0022] The glycerol carbonate modified epoxy resin of the present invention has strong adhesion, high glass transition temperature (Tg) and low thermal expansion coefficient, and has excellent properties such as photosensitivity, etching resistance, electroplating resistance and film-fading resistance, and is suitable for use in preparing IC substrates. DETAILED DESCRIPTION

[0023] 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.

[0024] 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.

[0025] 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.

[0026] 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.

[0027] 4-(Hydroxymethyl)-1,3-dioxolan-2-one can be purchased from Sigma-Aldrich Company, Weifang Energy Storage Biotechnology Co., Ltd., Jinan Haode Biotechnology Co., Ltd., Shijiazhuang Chirui Chemical Technology Co., Ltd., etc.

[0028] 5-Hydroxy-1,3-dioxane-2-one can be purchased from Zibo Hangyu Biotechnology Development Co., Ltd.

[0029] The magnesium oxide can be selected from 243388 (ACS Reagent) and 203718 (99.99% trace metal basis) of Sigma-Aldrich Company of the United States; active magnesium oxide of Xingtai Kaimei New Material Technology Co., Ltd.; light magnesium oxide (analytical grade AR) of Xilong Science Co., Ltd., etc.

[0030] Calcium oxide can be selected from 248568 (Reagent grade), 229539 (99.995% trace metal basis), 208159 ( 99.99% trace metal basis); YHG-001 from Hebei Huakai Environmental Protection Materials Co., Ltd.; calcium oxide (analytical grade AR) from Xilong Science Co., Ltd., etc.

[0031] The magnesium hydroxide can be selected from 310093 (reagent grade, 95%) of Sigma-Aldrich Company of the United States; XY2500 of Dongguan Xingyuan Chemical Co., Ltd.; magnesium hydroxide (analytical grade AR) of Xilong Scientific Co., Ltd., etc.

[0032] The synthetic hydrotalcite can be selected from 652288 from Sigma-Aldrich Company of the United States; HI-TAL P1, HI-TAL P2, HI-TAL P3 from SINWON Company of South Korea, and the like.

[0033] In the following examples, the stirring speed is 550 rpm.

[0034] Example 1

[0035] The preparation method of the glycerol carbonate modified epoxy resin of this embodiment comprises the following steps:

[0036] (1) Add 33.50 g of p-xylene to the reaction kettle, raise the system temperature to 60°C, and then add 66.86 g of phenolic epoxy resin and stir vigorously for about 2 hours; then, slowly add 12.28 g of 4-(hydroxymethyl)-1,3-dioxolan-2-one and 0.34 g of magnesium oxide to the reaction kettle. After the addition is complete, raise the temperature to 95°C and continue to stir vigorously for about 7 hours.

[0037] (2) The system temperature was lowered to 60°C, and then 11.41 g of hydroxyethyl acrylate, 22.07 g of pyromellitic anhydride and 0.34 g of hydroquinone were slowly added to the reaction kettle. After the addition, the system temperature was raised to 90°C, and the reaction was vigorously stirred for about 2.5 hours, and then the system temperature was lowered to 60°C to obtain the product.

[0038] Example 2

[0039] The preparation method of the glycerol carbonate modified epoxy resin of this embodiment comprises the following steps:

[0040] (1) Add 33.50 g of m-xylene to the reaction kettle, raise the system temperature to 60°C, then add 66.86 g of hydrogenated bisphenol A epoxy resin, and stir vigorously for about 2 hours; then, slowly add 12.28 g of 5-hydroxy-1,3-dioxane-2-one and 0.34 g of calcium oxide to the reaction kettle. After the additions are complete, raise the temperature to 95°C, and continue to stir vigorously for about 7 hours.

[0041] (2) The system temperature was lowered to 60°C, and then 11.41 g of hydroxyethyl methacrylate, 22.07 g of benzophenone tetracarboxylic dianhydride and 0.34 g of p-tert-butylcatechol were slowly added to the reaction kettle. After the addition, the system temperature was raised to 90°C, and the reaction was vigorously stirred for about 2.5 hours, and then the system temperature was lowered to 60°C to obtain the product.

[0042] Example 3

[0043] The preparation method of the glycerol carbonate modified epoxy resin of this embodiment comprises the following steps:

[0044] (1) Add 33.50 g of o-xylene to the reaction kettle, raise the system temperature to 60°C, and then add 66.86 g of bisphenol A epoxy resin and stir vigorously for about 2 hours; then, slowly add 12.28 g of 4-(hydroxymethyl)-1,3-dioxolan-2-one and 0.34 g of magnesium hydroxide to the reaction kettle. After the addition is complete, raise the temperature to 95°C and continue to stir vigorously for about 7 hours.

[0045] (2) The system temperature was lowered to 60°C, and then 11.41 g of hydroxypropyl acrylate, 22.07 g of tetrahydrophthalic anhydride and 0.34 g of catechol were slowly added to the reaction kettle. After the addition, the system temperature was raised to 90°C, and the reaction was stirred vigorously for about 2.5 hours, and then the system temperature was lowered to 60°C to obtain the product.

[0046] Example 4

[0047] The preparation method of the glycerol carbonate modified epoxy resin of this embodiment comprises the following steps:

[0048] (1) Add 33.50 g of m-xylene to a reaction kettle, raise the system temperature to 60°C, then add 66.86 g of phenolic epoxy resin and stir vigorously for about 2 h; then, slowly add 12.28 g of 5-hydroxy-1,3-dioxane-2-one and 0.34 g of synthetic hydrotalcite to the reaction kettle. After the additions are complete, raise the temperature to 95°C and continue to stir vigorously for about 7 h.

[0049] (2) The system temperature was lowered to 60°C, and then 11.41 g of hydroxypropyl acrylate, 22.07 g of hexahydrophthalic anhydride and 0.34 g of catechol were slowly added to the reaction kettle. After the addition, the system temperature was raised to 90°C, and the reaction was stirred vigorously for about 2.5 hours, and then the system temperature was lowered to 60°C to obtain the product.

[0050] Example 5

[0051] The preparation method of the glycerol carbonate modified epoxy resin of this embodiment comprises the following steps:

[0052] (1) Add 33.50 g of m-xylene to the reaction kettle, raise the system temperature to 60°C, then add 66.86 g of hydrogenated bisphenol A epoxy resin, and stir vigorously for about 2 hours; then, slowly add 12.28 g of 4-(hydroxymethyl)-1,3-dioxolan-2-one and 0.34 g of magnesium oxide to the reaction kettle. After the addition is complete, raise the temperature to 95°C, and continue to stir vigorously for about 7 hours.

[0053] (2) The system temperature was lowered to 60°C, and then 11.41 g of hydroxypropyl methacrylate, 22.07 g of methyltetrahydrophthalic anhydride and 0.34 g of p-tert-butylcatechol were slowly added to the reaction kettle. After the addition, the system temperature was raised to 90°C, and the reaction was stirred vigorously for about 2.5 hours, and then the system temperature was lowered to 60°C to obtain the product.

[0054] Example 6

[0055] The preparation method of the glycerol carbonate modified epoxy resin of this embodiment comprises the following steps:

[0056] (1) Add 33.50 g of p-xylene to the reaction kettle, raise the system temperature to 60°C, and then add 66.86 g of bisphenol A epoxy resin and stir vigorously for about 2 hours; then, slowly add 12.28 g of 5-hydroxy-1,3-dioxane-2-one and 0.34 g of magnesium hydroxide to the reaction kettle. After the addition is complete, raise the temperature to 95°C and continue to stir vigorously for about 7 hours.

[0057] (2) The system temperature was lowered to 60°C, and then 11.41 g of hydroxyethyl acrylate, 22.07 g of pyromellitic anhydride and 0.34 g of hydroquinone were slowly added to the reaction kettle. After the addition, the system temperature was raised to 90°C, and the reaction was vigorously stirred for about 2.5 hours, and then the system temperature was lowered to 60°C to obtain the product.

[0058] Next, the performance of the glycerol carbonate modified epoxy resin obtained in Examples 1-6 was tested, and the testing method was as follows:

[0059] (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.

[0060] (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.

[0061] (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.

[0062] (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.

[0063] (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.

[0064] The test results are shown in Table 1.

[0065] Table 1 Performance test results of glycerol carbonate modified epoxy resin of Examples 1-6

[0066]

[0067] 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.

[0068] 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.

[0069] 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.

[0070] 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.

[0071] Therefore, the glycerol carbonate modified 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.

[0072] 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. Glycerol carbonate modified epoxy resin, characterized in that, The raw material composition includes, by weight: 60-70 parts of epoxy resin, 10-15 parts of glycerol carbonate monomer, 10-15 parts of acrylate monomer, 20-30 parts of acid anhydride, 0.10-0.50 parts of polymerization inhibitor, 0.10-0.50 parts of solid base catalyst, and 10-35 parts of xylene; The epoxy resin is selected from at least one of phenolic epoxy resin, hydrogenated bisphenol A epoxy resin and bisphenol A epoxy resin; The acrylic acid ester monomer is selected from at least one of hydroxyethyl acrylate, hydroxyethyl methacrylate, hydroxypropyl acrylate and hydroxypropyl methacrylate; The preparation method of the glycerol carbonate modified epoxy resin comprises the following steps: S1. Add xylene to the reaction kettle, raise the system temperature to 60-70°C, then add epoxy resin and stir for 2-3h; then add glycerol carbonate monomer and solid base catalyst to the reaction kettle, after adding, raise the temperature to 90-100°C, and continue stirring and reacting for 6-8h; S2. Lower the system temperature to 60-70°C, then add acrylate monomer, acid anhydride and polymerization inhibitor into the reaction kettle, raise the system temperature to 80-100°C after adding, stir and react for 2-3h, then lower the system temperature to 60-70°C to obtain.

2. The glycerol carbonate modified epoxy resin according to claim 1, characterized in that The glycerol carbonate monomer is selected from 4-(hydroxymethyl)-1,3-dioxolan-2-one and / or 5-hydroxy-1,3-dioxane-2-one.

3. The glycerol carbonate modified epoxy resin according to claim 1 or 2, characterized in that: The acid anhydride is selected from at least one of pyromellitic dianhydride, benzophenone tetracarboxylic dianhydride, tetrahydrophthalic anhydride, hexahydrophthalic anhydride, and methyltetrahydrophthalic anhydride.

4. The glycerol carbonate modified 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 solid base catalyst is selected from at least one of magnesium oxide, calcium oxide, magnesium hydroxide and synthetic hydrotalcite; The xylene is selected from at least one of p-xylene, m-xylene and o-xylene.

5. Use of the glycerol carbonate modified epoxy resin according to any one of claims 1 to 4 as solder resist ink in the preparation of IC substrates.

6. A dry film, characterized in that: The epoxy resin is obtained by photocuring or thermal curing the glycerol carbonate modified epoxy resin according to any one of claims 1 to 4.

7. Use of the dry film according to claim 6 in preparing an IC substrate.

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