Modified epoxy resin composition, prepreg, laminate, and printed wiring board

Abstract

The application discloses a modified epoxy resin composition, which comprises the following components in parts by weight: modified hydantoin epoxy resin 30-70 parts, base epoxy resin 30-70 parts, curing agent 10-30 parts, phosphorus-based flame retardant 5-20 parts, dispersing agent 0.1-1 part, filler 50-100 parts, accelerator 0.01-0.1 part and solvent 50-200 parts; the modified hydantoin epoxy resin with a specific structure is used, the benzene ring and the Schiff base structure in the modified hydantoin epoxy resin are both rigid structures, and the benzene ring and the Schiff base structure can improve the thermal stability of a cured product, improve the carbon residue rate of the cured product during high-temperature decomposition, and the carbon-nitrogen double bond in the Schiff base structure can also have an addition reaction with phosphorus hydrogen; when the phosphorus-based flame retardant is added into the reaction system, phosphorus is introduced into the molecular structure, the synergistic flame-retardant effect of phosphorus and nitrogen is realized, the flame-retardant effect is further improved, halogen-free flame retardation can be realized under the condition that the addition amount of the phosphorus-containing flame retardant is small, UL 94V-0 level is reached, and the green environmental protection requirement is met.

Description

TECHNICAL FIELD

[0001] The present application relates to the field of circuit board technology, in particular to a modified epoxy resin composition, prepreg, laminated board and printed circuit board. BACKGROUND

[0002] Halogen refers to the halogen elements in the periodic table, including fluorine, chlorine, bromine, iodine. At present, the flame-retardant base material FR4, CEM-3 and the like, the flame retardant is mostly brominated epoxy resin, and in the brominated epoxy resin, tetrabromobisphenol A, polymeric polybrominated biphenyl, polymeric polybrominated biphenyl ether and polybrominated diphenyl ether are the main flame-retardant materials of the copper-clad plate, which has low cost and is compatible with the epoxy resin. But the relevant agencies research shows that the halogen-containing flame-retardant material (polymeric polybrominated biphenyl PBB; polymeric polybrominated biphenyl ether PBDE) is ignited and burns when it is discarded, and emits dioxin (dioxin TCDD), benzofuran (Benzfuran), etc. The smoke emission is large, the smell is bad, there is a high toxic gas, it is carcinogenic, and it cannot be discharged after being taken into the human body, which seriously affects health. Therefore, the European Union law prohibits the use of six substances such as PBB and PBDE. The Ministry of Information Industry of China also requires that electronic information products put into the market cannot contain lead, mercury, hexavalent chromium, polymeric polybrominated biphenyl or polymeric polybrominated biphenyl ether and other substances.

[0003] At the same time, with the gradual penetration of electronic products into all aspects of people's daily work and life, and the continuous improvement of the environmental protection consciousness of the international community, the environmental protection problems of various electronic products and household appliances are becoming increasingly serious, and the green environmental protection requirements of the electronic industry promote the halogen-free of the copper-clad plate industry. Therefore, the current method of realizing halogen-free flame retardation is mostly by adding phosphorus element flame retardant, although the addition of phosphorus element flame retardant can make the laminated board made has flame retardant performance, due to the limitation of the characteristics of these materials, it is difficult to meet the requirements of the flame retardancy of the halogen-free composite laminated board material by adding a small amount of phosphorus element flame retardant, and if a large amount of phosphorus element flame retardant is added, it will affect the properties such as immersion welding and glass transition temperature of the laminated board, therefore, it is necessary to propose a new scheme to solve the above problems. SUMMARY

[0004] Therefore, the present application aims at the defects in the prior art, and the main purpose is to provide a modified epoxy resin composition, prepreg, laminated board and printed circuit board, which only needs to add a small amount of phosphorus element flame retardant to meet the requirements of the flame retardancy of the halogen-free composite laminated board material.

[0005] In order to achieve the above purpose, the technical scheme adopted by the present application is as follows:

[0006] A modified epoxy resin composition comprises, by weight parts, the following components: modified hydantoin epoxy resin 30-70 parts, base epoxy resin 30-70 parts, curing agent 10-30 parts, phosphorus-based flame retardant 5-20 parts, dispersing agent 0.1-1 part, filler 50-100 parts, accelerator 0.01-0.1 part, and solvent 50-200 parts; wherein the modified hydantoin epoxy resin has the structural formula

[0007]

[0008] As a preferred solution, the base epoxy resin is one or more of bisphenol A type epoxy resin, bisphenol F type epoxy resin, bisphenol A type novolac epoxy resin, bisphenol F type novolac epoxy resin, bisphenol A type phenoxy resin, or bisphenol F type phenoxy resin, and the weight ratio of modified hydantoin epoxy resin to base epoxy resin is 1:(1-2).

[0009] As a preferred solution, the curing agent is one or more of amine compound, amide compound, acid anhydride compound, phenolic compound, or active ester compound, and preferably, the curing agent is selected from one or more of dicyandiamide, linear phenol formaldehyde resin, or active aliphatic resin.

[0010] As a preferred solution, the phosphorus-based flame retardant is one or more of DOPO, DOPO-HQ, DOPO-NQ, melamine polyphosphate, cresyl diphenyl phosphate, trichloropropyl phosphate, hexaphenoxy cyclotriphosphazene, 1,3-phenylene phosphate (2,6-xylyl) tetraester, or modified diphenyl phosphate.

[0011] As a preferred solution, the dispersing agent is one or more of silane coupling agent, titanate coupling agent, and aluminate coupling agent.

[0012] As a preferred solution, the filler is one or more of basalt flake, magnesium carbonate, barium sulfate, zinc borate, talc powder, silicon dioxide, boron nitride, calcium carbonate, aluminum oxide, aluminum hydroxide, or silicon micro powder.

[0013] As a preferred solution, the accelerator is one or more of 2-methyl imidazole, 2-ethyl-4-methyl imidazole, 2-phenyl imidazole, 2-phenyl-4-methyl imidazole, or 1-cyanoethyl-2-methyl imidazole; and the solvent is one or more of methanol, ethanol, acetone, butanone, cyclohexanone, propylene glycol methyl ether, ethylene glycol methyl ether, and dibutyl ether.

[0014] A prepreg is prepared from the aforementioned modified epoxy resin composition.

[0015] A laminate is characterized in that it comprises at least one prepreg as described above and a metal foil on one or both sides of the prepreg.

[0016] A printed circuit board comprising at least one of the aforementioned laminated boards.

[0017] Compared with the prior art, the present application has obvious advantages and beneficial effects, and specifically, the above technical solution can know that:

[0018] The present application uses a specific structure of modified hydantoin epoxy resin, in which the benzene ring and the Schiff base structure are both rigid structures, which can improve the thermal stability of the cured product and increase the carbon residue rate of the cured product at high temperature decomposition. In addition, the carbon-nitrogen double bond in the Schiff base structure can also undergo an addition reaction with phosphorus hydrogen. When a phosphorus-based combustion improver is added to the reaction system, phosphorus is introduced into the molecular structure, realizing the synergistic flame-retardant effect of phosphorus and nitrogen, further improving the flame-retardant effect, and achieving halogen-free flame retardation with less phosphorus-containing flame retardant addition amount, reaching the UL 94V-0 level, and meeting the green environmental protection requirements.

[0019] In order to more clearly illustrate the effects of the present application, the present application will be described in detail below in combination with specific examples. DETAILED DESCRIPTION

[0020] The present application discloses a modified epoxy resin composition, which comprises the following components by weight parts: modified hydantoin epoxy resin 30-70 parts, base epoxy resin 30-70 parts, curing agent 10-30 parts, phosphorus-based flame retardant 5-20 parts, dispersing agent 0.1-1 part, filler 50-100 parts, accelerator 0.01-0.1 part and solvent 50-200 parts; wherein the structural formula of the modified hydantoin epoxy resin is

[0021] The base epoxy resin is one or more of bisphenol A type epoxy resin, bisphenol F type epoxy resin, bisphenol A type phenolic epoxy resin, bisphenol F type phenolic epoxy resin, bisphenol A type phenoxy resin or bisphenol F type phenoxy resin, preferably, the weight ratio of modified hydantoin epoxy resin to base epoxy resin is 1:(1-2).

[0022] The curing agent is one or more of amine compounds, amide compounds, acid anhydride compounds, phenolic compounds or active ester compounds, preferably, the curing agent is selected from one or more of dicyandiamide, linear phenolic resin or active aliphatic resin.

[0023] The phosphorus-based flame retardant is one or more of DOPO, DOPO-HQ, DOPO-NQ, melamine polyphosphate, toluene diphenyl phosphate, trichloropropyl phosphate, hexaphenoxy cyclotriphosphazene, 1,3-phenylene phosphate (2,6-dimethylphenyl) tetraester or modified diphenyl phosphate.

[0024] The dispersant is one or more of a silane coupling agent, a titanate coupling agent, and an aluminate coupling agent.

[0025] The filler is one or more of basalt flakes, magnesium carbonate, barium sulfate, zinc borate, talc powder, silicon dioxide, boron nitride, calcium carbonate, aluminum oxide, aluminum hydroxide, or silicon powder.

[0026] The promoter is one or more of 2-methylimidazole, 2-ethyl-4-methylimidazole, 2-phenylimidazole, 2-phenyl-4-methylimidazole, or 1-cyanoethyl-2-methylimidazole; and the solvent is one or more of methanol, ethanol, acetone, butanone, cyclohexanone, propylene glycol methyl ether, ethylene glycol methyl ether, and dibutyl ether.

[0027] The present application also discloses a prepreg prepared from the modified epoxy resin composition, and the preparation process is as follows: mixing the raw materials according to the components, and then mixing uniformly by stirring to obtain the modified epoxy resin composition; then, immersing 7628, 2116, 1080, 106 or 1017 glass fiber cloth into the modified epoxy resin composition; and then baking in a 171℃ oven for 3-6 min to obtain the prepreg.

[0028] The present application also discloses a laminate comprising at least one prepreg and a metal foil on one or both sides of the prepreg, and the preparation process is as follows: covering one 12μm-thick HTE copper foil on each of the upper and lower sides of the prepreg prepared from three 7628 glass fiber cloths, and then hot-pressing in a laminating machine, wherein the temperature of the high-temperature section is 230℃ and the forming time is 90 min to obtain the laminate; in subsequent examples, the laminate is prepared by the above method and the performance of the obtained laminate is tested. It should be noted that, in the preparation of the laminate, the thickness of the laminate can be in the range of 0.03-2.0mm, the metal foil can be one or more of 12μm, 18μm, 35μm or 70μm copper foil, the forming temperature of the high-temperature section is above 200℃, and the forming time is above 90 min to ensure complete curing of the resin.

[0029] The present application also discloses a printed circuit board comprising at least one laminate.

[0030] The raw materials used in the following examples and comparative examples are shown in Table 1.

[0031] Material Manufacturer Code Modified hydantoin epoxy resin Self-made A Bisphenol A type epoxy resin Shandong Shengqun New Material Co., Ltd. B Linear phenol-formaldehyde resin Shandong Shengqun New Material Co., Ltd. C Melamine polyphosphate Xusen Flame Retardant Co., Ltd. D Silane coupling agent Jianghan New Material Co., Ltd. E 2-Ethyl-4-methylimidazole Shikoku Chemicals Corporation F Aluminum hydroxide Ji New Material Co., Ltd. G Butanone Columan Chemical Co., Ltd. H

[0032] Table 1

[0033] The preparation method of the modified hydantoin epoxy resin is as follows:

[0034] The benzaldehyde is mixed with the amine group-containing styrene oxide to generate an intermediate with a Schiff base, then a hydantoin ring is added, under the catalysis of lithium chloride, the ethylene oxide on the intermediate reacts with the amino group on the hydantoin to generate a diol, then, epichlorohydrin is added, under the catalysis of tetraethylammonium chloride, the diol reacts with the epoxide to generate a halogen alcohol ether, finally, sodium hydroxide is added to remove chlorine to generate the modified hydantoin epoxy resin. The preparation process is as follows:

[0035]

[0036] The component ratio of each embodiment and the comparative example is shown in Table 2.

[0037] Example 1 Example 2 Example 3 Example 4 Example 5 Example 6 Comparative Example 1 Comparative Example 2 Comparative Example 3 Comparative Example 4 A 20 30 40 20 30 40 B 40 40 40 40 40 40 40 40 40 40 C 20 20 20 20 20 20 20 20 20 20 D 20 20 20 10 10 10 30 20 10 10 E 0.25 0.25 0.25 0.25 0.25 0.25 0.25 0.25 0.25 0.25 F 0.05 0.05 0.05 0.05 0.05 0.05 0.05 0.05 0.05 0.05 G 50 50 50 50 50 50 50 50 50 100 H 100 100 100 100 100 100 100 100 100 100

[0038] Table 2 tests the performance of the above embodiments and comparative examples, and the test results are shown in Table 3.

[0039] Example 1 Example 2 Example 3 Example 4 Example 5 Example 6 Comparative Example 1 Comparative Example 2 Comparative Example 3 Comparative Example 4 Tg (℃) 183 191 199 187 197 206 161 166 172 171 T288 (Min) >60 >60 >60 >60 >60 >60 >60 >60 >60 35 Flame Retardancy V-0 V-0 V-0 V-1 V-0 V-0 V-1 V-2 V-3 V-2

[0040] Table 3

[0041] Through analysis of the above data, the metal-clad foil laminated board prepared from the modified epoxy resin composition of the present application has high glass transition temperature and good flame retardancy, and the flame retardant level can meet the V-0 level, while the comparative examples cannot meet the V-0 level of flame retardant performance; compared with Example 1, Comparative Example 2, under the condition that the amount of other components is the same, the modified hydantoin epoxy resin is added, which greatly improves the flame retardant performance of the resin composition, and by comparing Comparative Example 1, Comparative Example 2 and Comparative Example 3, it can be seen that the more the amount of the flame retardant, the better the flame retardant performance of the resin composition, but even if a large amount of phosphorus-based flame retardant is added in the reaction system without the modified hydantoin epoxy resin, it is difficult to achieve the V-0 level of flame retardant performance; in addition, compared with Example 2 and Example 5, and Example 3 and Example 6, under the condition that the amount of other components is the same, even if the amount of phosphorus-based flame retardant is greatly reduced, the flame retardant performance of V-0 level can still be achieved, and from Examples 4-6, it can be seen that under the condition that the amount of phosphorus-based flame retardant is the same, the more the modified hydantoin epoxy resin added, the better the flame retardancy, and the flame retardant performance of Example 4 is V-1 level, which is because the amount of modified hydantoin epoxy resin and phosphorus-based flame retardant is the least, but compared with Comparative Example 1, the amount of phosphorus-based flame retardant of Comparative Example 1 is 3 times of that of Example 4, but the flame retardant performance is the same, which shows that the modified hydantoin epoxy resin with a specific structure in the present application and the phosphorus in the phosphorus-based flame retardant produce a synergistic effect, further improving the flame retardant effect and greatly improving the flame retardancy of the resin composition.

[0042] The above merely describes preferred embodiments of the present application, and is not intended to limit the technical scope of the present application in any way. Any minor modification, equivalent change and modification made to the above embodiments according to the technical essence of the present application shall still fall within the technical scope of the present application.

Claims

1. A modified epoxy resin composition, characterized by: The modified hydantoin epoxy resin is 30-70 parts by weight, the base epoxy resin is 30-70 parts by weight, the curing agent is 10-30 parts by weight, the phosphorus-based flame retardant is 5-20 parts by weight, the dispersant is 0.1-1 part by weight, the filler is 50-100 parts by weight, the accelerator is 0.01-0.1 part by weight, and the solvent is 50-200 parts by weight.

2. The modified epoxy resin composition according to claim 1, characterized by: The base epoxy resin is one or more of bisphenol A type epoxy resin, bisphenol F type epoxy resin, bisphenol A type phenolic epoxy resin, bisphenol F type phenolic epoxy resin, bisphenol A type phenoxy resin or bisphenol F type phenoxy resin, and the weight ratio of the modified hydantoin epoxy resin to the base epoxy resin is 1:(1-2).

3. The modified epoxy resin composition according to claim 1, characterized by: The curing agent is one or more of amine compound, amide compound, acid anhydride compound, phenolic compound or active ester compound.

4. The modified epoxy resin composition according to claim 1, characterized by: The phosphorus-based flame retardant is one or more of DOPO, DOPO-HQ, DOPO-NQ, melamine polyphosphate, toluene diphenyl phosphate, trichloropropyl phosphate, hexaphenoxy cyclotriphosphazene, 1,3-phenylene phosphate (2,6-dimethylphenyl) tetraester or modified diphenyl phosphate.

5. The modified epoxy resin composition according to claim 1, characterized by: The dispersant is one or more of silane coupling agent, titanate coupling agent and aluminate coupling agent.

6. The modified epoxy resin composition according to claim 1, characterized by: The filler is one or more of basalt flake, magnesium carbonate, barium sulfate, zinc borate, talc powder, silicon dioxide, boron nitride, calcium carbonate, aluminum oxide, aluminum hydroxide or silicon powder.

7. The modified epoxy resin composition according to claim 1, characterized by: The accelerator is one or more of 2-methylimidazole, 2-ethyl-4-methylimidazole, 2-phenylimidazole, 2-phenyl-4-methylimidazole or 1-cyanoethyl-2-methylimidazole, and the solvent is one or more of methanol, ethanol, acetone, butanone, cyclohexanone, propylene glycol methyl ether, ethylene glycol methyl ether and dibutyl ether.

8. A prepreg, characterized by: It is made of the modified epoxy resin composition according to any one of claims 1-7.

9. A laminate characterized by: It comprises at least one prepreg according to claim 8 and a metal foil covering one or both sides of the prepreg.

10. A printed circuit board, characterized by: It comprises at least one laminate according to claim 9.

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