阅读说明：本技术 环氧树脂组合物及由其制备的半固化片和层压板 (Epoxy resin composition and prepreg and laminated board prepared from same ) 是由 刘传富 刘传海 于 2020-12-31 设计创作，主要内容包括：本发明属于电子材料技术领域。一种环氧树脂组合物,包括以下按重量份数计算的组分：环氧树脂40-60份,氨基二苯醚树脂30-50份、端氨基丁晴橡胶30-40份、改性填料1-80份、咪唑类固化促进剂0.1-5份。本发明环氧树脂组合物具有良好的耐热性和介电性能,由其制备的半固化片和层压板具有良好的耐热性、介电性能和机械性能。(The invention belongs to the technical field of electronic materials. An epoxy resin composition comprises the following components in parts by weight: 40-60 parts of epoxy resin, 30-50 parts of amino diphenyl ether resin, 30-40 parts of amino terminated butadiene acrylonitrile rubber, 1-80 parts of modified filler and 0.1-5 parts of imidazole curing accelerator. The epoxy resin composition has good heat resistance and dielectric property, and prepregs and laminated plates prepared from the epoxy resin composition have good heat resistance, dielectric property and mechanical property.)

1. The epoxy resin composition is characterized by comprising the following components in parts by weight: 40-60 parts of epoxy resin, 30-50 parts of amino diphenyl ether resin, 30-40 parts of amino terminated butadiene acrylonitrile rubber, 1-80 parts of modified filler and 0.1-5 parts of imidazole curing accelerator.

2. The epoxy resin composition according to claim 1, wherein the epoxy resin is at least one of a bisphenol A epoxy resin, a bisphenol F epoxy resin, an o-cresol novolac epoxy resin, a bisphenol A novolac epoxy resin, a phenol novolac epoxy resin, a trifunctional phenol type epoxy resin, a tetraphenylethane epoxy resin, a biphenyl type epoxy resin, a naphthalene type epoxy resin, a dicyclopentadiene type epoxy resin, an isocyanate type epoxy resin, an aralkyl novolac epoxy resin, an alicyclic type epoxy resin, a glycidylamine type epoxy resin, a glycidyl ester type epoxy resin, and a phosphorus-containing epoxy resin.

3. The epoxy resin composition according to claim 1, wherein the preparation method of the aminodiphenyl ether resin comprises the following steps: diphenyl ether resin and ethanilide are mixed according to a molar ratio of 1: 1-2, adding 1-5wt% of p-toluenesulfonic acid, reacting at constant temperature of 120 ℃ for 1-2h, adding 10% hydrochloric acid/ethanol solution with volume ratio of the reaction product of 3-5:1, heating and stirring until the solution is completely dissolved, reacting at constant temperature for 4-6h, and distilling ethanol under reduced pressure to obtain the amino diphenyl ether resin.

4. The epoxy resin composition of claim 1, wherein the amino terminated butadiene nitrile rubber comprises an amino terminated butadiene-acrylonitrile copolymer.

5. The epoxy resin composition as claimed in claim 1, wherein the modified filler is prepared by mixing an inorganic filler and a surface modifier according to a mass ratio of 100: 15-18; the inorganic filler is prepared from the following components in a mass ratio of 1: 1-3 of sepiolite velvet powder and mica powder; the surface modifier is amino functional group silane, ethanol, acetone and barium hydroxide in a mass ratio of 1-3:40-50:1-2: 1.

6. The epoxy resin composition according to claim 1, wherein the imidazole-based curing accelerator is at least one of 2-methylimidazole, 2-ethyl-4-methylimidazole, 2-phenylimidazole, 2-undecylimidazole, 1-benzyl-2-methylimidazole, 2-heptadecylimidazole, 2-isopropylimidazole, 2-phenyl-4-methylimidazole, 2-dodecylimidazole, and 1-cyanoethyl-2-methylimidazole.

7. A prepreg prepared from the epoxy resin composition according to any one of claims 1 to 6, characterized in that the preparation method comprises the steps of: dissolving the epoxy resin composition with a solvent to prepare a glue solution, soaking a reinforcing material in the glue solution, and heating and drying.

8. Prepreg according to claim 7, characterized in that the reinforcement material comprises glass fibre cloth, non-woven fabric or carbon fibre.

9. A laminate prepared from the prepreg according to claim 7, wherein the preparation method comprises the steps of: and covering at least one surface of the prepreg with a metal foil, or covering at least one surface of the prepreg with a metal foil after laminating at least two prepregs, and performing hot press molding.

10. The laminate of claim 9, wherein the metal foil is copper foil.

Technical Field

The invention belongs to the technical field of electronic materials, and particularly relates to an epoxy resin composition, and a prepreg and a laminated board prepared from the epoxy resin composition.

Background

With the development of electronic components toward miniaturization, light weight, thinness, high performance, and multi-functionalization, high-frequency and high-speed signal transmission is accompanied. This requires that the electronic material have low dielectric constant and low dielectric loss ratios, which are related to the structure of the material, while low dielectric constant, low dielectric loss resins generally have: large free volume, low polarizability, low water absorption, low dielectric constant structure, and the like. In the reaction process of phenolic resin curing epoxy resin and epoxy, secondary hydroxyl is generated, so that the problems of poor water absorption and dielectric property of a system are caused, and the brittleness is high. During the reaction process of the active ester and the epoxy resin, no secondary hydroxyl is generated, the active ester has low water absorption, wet heat resistance and quite good dielectric property, but the cost is high, and the glass transition temperature of the system is low when the active ester is used as a single curing agent. Therefore, it is desirable to provide an epoxy resin material having good heat resistance, moist heat resistance and toughness, a low dielectric loss value and a low water absorption rate.

Disclosure of Invention

The technical problem to be solved by the invention is to provide an epoxy resin composition, the composition has good heat resistance and dielectric property, and prepregs and laminated plates prepared from the composition have good heat resistance, dielectric property and mechanical property.

The technical scheme of the invention is as follows:

an epoxy resin composition comprises the following components in parts by weight: 40-60 parts of epoxy resin, 30-50 parts of amino diphenyl ether resin, 30-40 parts of amino terminated butadiene acrylonitrile rubber, 1-80 parts of modified filler and 0.1-5 parts of imidazole curing accelerator.

Further, the epoxy resin is at least one of bisphenol a epoxy resin, bisphenol F epoxy resin, o-cresol novolac epoxy resin, bisphenol a novolac epoxy resin, phenol novolac epoxy resin, trifunctional phenol type epoxy resin, tetraphenylethane epoxy resin, biphenyl type epoxy resin, naphthalene ring type epoxy resin, dicyclopentadiene type epoxy resin, isocyanate type epoxy resin, aralkyl novolac epoxy resin, alicyclic epoxy resin, glycidylamine type epoxy resin, glycidyl ester type epoxy resin, and phosphorus-containing epoxy resin.

Further, the preparation method of the amino diphenyl ether resin comprises the following steps: diphenyl ether resin and ethanilide are mixed according to a molar ratio of 1: 1-2, adding 1-5wt% of p-toluenesulfonic acid, reacting at constant temperature of 120 ℃ for 1-2h, adding 10% hydrochloric acid/ethanol solution with volume ratio of the reaction product of 3-5:1, heating and stirring until the solution is completely dissolved, reacting at constant temperature for 4-6h, and distilling ethanol under reduced pressure to obtain the amino diphenyl ether resin.

Further, the amino-terminated butadiene-acrylonitrile rubber comprises an amino-terminated butadiene-acrylonitrile copolymer.

Further, the modified filler is formed by mixing an inorganic filler and a surface modifier according to the mass ratio of 100: 15-18; the inorganic filler is prepared from the following components in a mass ratio of 1: 1-3 of sepiolite velvet powder and mica powder; the surface modifier is amino functional group silane, ethanol, acetone and barium hydroxide in a mass ratio of 1-3:40-50:1-2: 1.

Further, the imidazole curing accelerator is at least one of 2-methylimidazole, 2-ethyl-4-methylimidazole, 2-phenylimidazole, 2-undecylimidazole, 1-benzyl-2-methylimidazole, 2-heptadecylimidazole, 2-isopropylimidazole, 2-phenyl-4-methylimidazole, 2-dodecylimidazole and 1-cyanoethyl-2-methylimidazole.

The preparation method of the prepreg prepared from the epoxy resin composition comprises the following steps: dissolving the epoxy resin composition with a solvent to prepare a glue solution, soaking a reinforcing material in the glue solution, and heating and drying.

Further, the reinforcing material comprises glass fiber cloth, non-woven fabric or carbon fiber.

A laminated board prepared from the prepreg comprises the following steps: and covering at least one surface of the prepreg with a metal foil, or covering at least one surface of the prepreg with a metal foil after laminating at least two prepregs, and performing hot press molding.

Further, the metal foil is a copper foil.

The invention has the following beneficial effects:

the amino diphenyl ether resin selected by the invention is prepared by reacting methoxy diphenyl ether with acetanilide, has good dielectric property and heat resistance, low dielectric constant and dielectric loss, can be copolymerized with epoxy resin, and the prepared laminated board has high mechanical strength and good high temperature resistance. The imidazole curing accelerator can improve the film forming performance of the composition, improve the bonding strength between the laminated board and the metal layer and improve the peeling strength of the laminated board. The inorganic filler is modified by the surface modifier, so that the wettability and the dispersibility of the inorganic filler in a solvent can be improved, the mechanical property, the heat resistance, the scratch resistance, the wear resistance and the weather resistance of the material are improved, and the thickness flatness of the laminated plate is improved. The amino-terminated butadiene-acrylonitrile rubber is used as a toughening agent, so that the flexibility of the laminated board can be improved, and the problems of increased brittleness and easy breakage of the laminated board caused by the filler are effectively avoided.

Detailed Description

The present invention will be described in detail with reference to examples, which are only preferred embodiments of the present invention and are not intended to limit the present invention.

The following table shows the formulation of 3 examples and 3 comparative examples of epoxy resin compositions according to the invention (unit: parts):

components	Example 1	Example 2	Example 3	Comparative example 1	Comparative example 2	Comparative example 3
							Bisphenol A epoxy resin	40	50	60	40	50	60
Amino diphenyl ether resin	30	35	50	/	35	50
							Polyphenylene ether	/	/	/	30	/	/
Amino-terminated butadiene-acrylonitrile copolymers	30	35	40	30	35	40
							Modified filler	30	60	80	30	/	80
Filler material	/	/	/	/	60 sepiolite velvet powder and mica powder	/
							2-ethyl-4-methylimidazole	2	2	2	2	2	/

The preparation method of the amino diphenyl ether resin comprises the following steps: diphenyl ether resin and ethanilide are mixed according to a molar ratio of 1: 1-2, adding 1-5wt% of p-toluenesulfonic acid, reacting at constant temperature of 120 ℃ for 1-2h, adding 10% hydrochloric acid/ethanol solution with volume ratio of the reaction product of 3-5:1, heating and stirring until the solution is completely dissolved, reacting at constant temperature for 4-6h, and distilling ethanol under reduced pressure to obtain the amino diphenyl ether resin.

The modified filler is formed by mixing an inorganic filler and a surface modifier according to the mass ratio of 100: 15; the inorganic filler is prepared from the following components in a mass ratio of 1: 3, sepiolite velvet powder and mica powder; the surface modifier is amino functional group silane, ethanol, acetone and barium hydroxide in a mass ratio of 3:50:2: 1.

The preparation method of the prepreg prepared from the epoxy resin compositions of examples 1-3 and comparative examples 1-3 comprises the following steps: dissolving the epoxy resin composition by using a solvent to prepare a glue solution, soaking glass fiber cloth in the glue solution, and heating to 200-230 ℃ for baking for 5 min.

A laminated board prepared from the prepreg comprises the following steps: covering at least one side of the prepreg with copper foil, or covering at least one side of the prepreg with metal foil after laminating at least two prepregs, and covering at least one side of the prepreg with metal foil at 220 ℃ and 30kgf/cm²Hot pressing for 2h under the condition of (1) and forming.

The performance of each set of laminates was tested:

1. measuring the dip weldability at 300 ℃, and observing the layered foaming condition for 5min according to IPC-TM-6502.4.13.1;

2 dielectric Properties were tested according to IPC-TM-6502.5.5.9;

3. peel Strength (PS) the peel strength of the metal cap was tested and observed for delamination blistering according to the "post thermal stress" experimental conditions in the IPC-TM-6502.4.8 procedure.

The test results are given in the following table:

test items

Example 1

Example 2

Example 3

Comparative example 1

Comparative example 2

Comparative example 3

Dip weldability

No delamination and no bubbles

No delamination and no bubbles

No delamination and no bubbles

Slightly layered with a few bubbles

No delamination and no bubbles

No delamination and no bubbles

Dk(1GHZ)

3.83

3.78

3.81

3.85

3.80

3.81

Df(1GHZ)

0.0090

0.0087

0.0089

0.0091

0.0088

0.0089

Peel strength

No delamination and no bubbles

No delamination and no bubbles

No delamination and no bubbles

Slightly layered with a few bubbles

No delamination and no bubbles

Slight demixing, small amount of bubbles

Therefore, the laminated board prepared by the epoxy resin composition has good heat resistance, dielectric property and mechanical property.