CN115521576B - Epoxy resin material and preparation method and application thereof - Google Patents

Abstract

The invention relates to the field of epoxy resin compositions, in particular to an epoxy resin material, a preparation method and application thereof. The method comprises the steps of firstly mixing epoxy resin, a curing agent, a filler, a release agent, a coupling agent and a colorant under high-speed stirring, then carrying out melt extrusion, cooling and crushing to obtain an intermediate, mixing the obtained intermediate with a certain weight part of accelerator under high-speed stirring, carrying out melt extrusion, and then carrying out cooling and crushing to obtain the epoxy resin material. The epoxy resin material prepared by the invention is subjected TO HTRB (high temperature reverse bias) test after packaging the semiconductor device TO-263 and the semiconductor device TO-247, has the characteristic of zero failure proportion, and remarkably improves the HTRB reliability after packaging the semiconductor.

Description

Epoxy resin material and preparation method and application thereof

Technical Field

The invention relates to the technical field of epoxy molding compounds, in particular to the technical field of thermosetting plastics, and specifically to an epoxy resin material and a preparation method and application thereof.

Background technique

In recent years, with the rapid development of the semiconductor industry, the integrated circuit and semiconductor device packaging industry has also begun to develop rapidly. At present, as the semiconductor and integrated circuit industries are developing towards lightweight terminals, the products produced by epoxy molding compound packaging technology are also beginning to develop in the direction of miniaturization, thinness and ultra-large scale, and at the same time, higher requirements are put forward for the reliability and appearance of the packaged products. As a method of semiconductor device reliability testing, HTRB (High Temperature Reverse Bias) is also increasingly required, which has also led to higher requirements for the performance of plastic packaging materials by packaging and testing manufacturers.

Summary of the invention

The purpose of the present invention is to address the deficiencies in the prior art and thereby provide an epoxy resin material and a preparation method and application thereof. The epoxy resin material is subjected to HTRB (high temperature reverse bias) testing after packaging semiconductor devices TO-263 and TO-247, and has the characteristic of zero failure rate, thereby significantly improving the HTRB reliability of the semiconductor devices after packaging.

In order to achieve the above object, the present invention provides a method for preparing an epoxy resin material, which comprises the following steps:

(1) mixing epoxy resin, curing agent, inorganic filler, release agent, coupling agent and colorant, melt-extruding, cooling and pulverizing to obtain an intermediate;

(2) mixing the intermediate obtained in step (1) with a promoter, melt-extruding, cooling, and crushing to obtain an epoxy resin material;

The weight ratio of epoxy resin, curing agent, accelerator, inorganic filler, release agent, coupling agent and colorant is 12.5-35:12.5-35:0.75-3:212-297:0.5-10:1.25-10:1.

Preferably, the weight ratio of epoxy resin, curing agent, accelerator, inorganic filler, release agent, coupling agent and colorant is 15-27:15-27:1.8-2.5:215-294:3-7:3-6:1.

Preferably, in step (1), the stirring speed is 180-230 rpm, and the stirring time is 20-60 min.

Preferably, in step (1), the stirring speed is 205-215 rpm, and the stirring time is 45-55 min;

Preferably, in step (1), the melt extrusion temperature is 100-125°C, more preferably 110-120°C;

Preferably, in step (2), the stirring speed is 180-230 rpm, and the stirring time is 20-60 min;

Preferably, in step (2), the stirring speed is 205-215 rpm, and the stirring time is 30-50 min;

Preferably, in step (2), the melt extrusion temperature is 110-120°C.

Preferably, the epoxy resin is selected from one or more of phenolic epoxy resin, bisphenol A epoxy resin, biphenyl epoxy resin, naphthalene epoxy resin, o-cresol epoxy, DCPD epoxy resin, multifunctional epoxy resin and alicyclic epoxy resin.

Preferably, the curing agent is selected from one or more of linear phenolic resin, XY-lock phenolic resin, bisphenol A phenolic resin, DCPD phenolic resin, biphenyl phenolic resin and multifunctional phenolic resin.

Preferably, the accelerator is selected from one or more of an organic phosphorus compound, an imidazole compound and a tertiary amine compound.

Preferably, the inorganic filler is selected from one or more of silica powder, titanium dioxide powder, aluminum oxide powder and magnesium oxide powder; more preferably, the silica powder is selected from one or more of crystalline silica powder, fused angular silica powder and fused spherical silica powder.

Preferably, the release agent is selected from one or more of mineral wax, vegetable wax, polyethylene and polyamide wax.

Preferably, the colorant is carbon black.

Preferably, the coupling agent is selected from one or more groups of epoxy silane coupling agents, amino silane coupling agents, mercapto silane coupling agents, isocyanate silane coupling agents and vinyl silane coupling agents.

The method for preparing epoxy resin material provided by the present invention adopts a raw material formula with a specific proportion of content, and at the same time, the other raw materials except the accelerator are mixed for the first time and melt-extruded to obtain an intermediate, and then the accelerator and the intermediate are mixed for the second time, and melt-extruded to obtain the epoxy resin material, so that the epoxy resin material prepared by the method is packaged with semiconductor devices TO-263 and semiconductor devices TO-247 and then subjected to HTRB (high temperature reverse bias) test, and has the characteristic of zero failure ratio, which significantly improves the HTRB reliability of the semiconductor devices after packaging. Compared with the conventional production method, the method adds one high-speed mixing and one melt extrusion process, which is beneficial to the uniformity of material mixing and the combination of the organic resin part and the inorganic filler part.

Detailed ways

The following is a detailed description of the specific embodiments of the present invention. It should be understood that the specific embodiments described herein are only used to illustrate and explain the present invention, and are not used to limit the present invention.

The endpoints and any values of the ranges disclosed in this article are not limited to the precise ranges or values, and these ranges or values should be understood to include values close to these ranges or values. For numerical ranges, the endpoint values of each range, the endpoint values of each range and the individual point values, and the individual point values can be combined with each other to obtain one or more new numerical ranges, which should be regarded as specifically disclosed in this article.

A first aspect of the present invention provides a method for preparing an epoxy resin material, the method comprising the following steps:

(1) mixing epoxy resin, curing agent, inorganic filler, release agent, coupling agent and colorant, melt-extruding, cooling and pulverizing to obtain an intermediate;

(2) mixing the intermediate obtained in step (1) with a promoter, melt-extruding, cooling, and crushing to obtain an epoxy resin material;

The weight ratio of epoxy resin, curing agent, accelerator, inorganic filler, release agent, coupling agent and colorant is 12.5-35:12.5-35:0.75-3:212-297:0.5-10:1.25-10:1.

In the method of the present invention, in a preferred embodiment, the weight ratio of epoxy resin, curing agent, accelerator, inorganic filler, release agent, coupling agent and colorant is 15-27:15-27:1.8-2.5:215-294:3-7:3-6:1.

In the method of the present invention, in a specific embodiment, in step (1), the stirring speed can be 180-230rpm, for example, 180rpm, 190rpm, 200rpm, 205rpm, 210rpm, 215rpm, 220rpm or 230rpm; the stirring time can be 20-60min, for example, 20min, 25min, 30min, 35min, 40min, 45min, 50min, 55min or 60min. In a preferred embodiment, the stirring speed is 205-215rpm, and the stirring time is 45-55min.

In the method of the present invention, in a specific embodiment, in step (1), the melt extrusion temperature can be 100-125° C., for example, 100° C., 110° C., 120° C. or 125° C. In a preferred embodiment, the melt extrusion temperature is 110-120° C.

In the method of the present invention, in a specific embodiment, in step (2), the stirring speed can be 180-230rpm, for example, 180rpm, 190rpm, 200rpm, 205rpm, 210rpm, 215rpm, 220rpm or 230rpm; the stirring time can be 20-60min, for example, 20min, 25min, 30min, 35min, 40min, 45min, 50min, 55min or 60min. In a preferred embodiment, the stirring speed is 205-215rpm, and the stirring time is 30-50min.

In the method of the present invention, in a specific embodiment, in step (2), the melt extrusion temperature can be 110-120°C, for example, 110°C, 115°C or 120°C.

In the method described in the present invention, in a specific embodiment, the melt extrusion described in step (1) and step (2) can use conventional processing equipment in the art, for example, a twin-roll mill, a single-screw extruder, a twin-screw extruder, a kneader, a stirrer and other processing equipment.

In the method described in the present invention, in a specific embodiment, the epoxy resin is selected from one or more of phenolic epoxy resin, bisphenol A epoxy resin, biphenyl epoxy resin, naphthalene epoxy resin, o-cresol epoxy, DCPD epoxy resin, multifunctional epoxy resin and alicyclic epoxy resin.

In the method of the present invention, in a specific embodiment, the curing agent is selected from one or more of linear phenolic resin, XY-lock phenolic resin, bisphenol A phenolic resin, DCPD phenolic resin, biphenyl phenolic resin and multifunctional phenolic resin.

In the method of the present invention, in a specific embodiment, the accelerator is selected from one or more of an organic phosphorus compound, an imidazole compound and a tertiary amine compound.

In the method described in the present invention, in a specific embodiment, the inorganic filler is selected from one or more of silica powder, titanium dioxide powder, aluminum oxide powder and magnesium oxide powder; in a preferred embodiment, the silica powder is selected from one or more of crystalline silica powder, fused angular silica powder and fused spherical silica powder.

In the method of the present invention, in a specific embodiment, the release agent is selected from one or more of mineral wax, vegetable wax, polyethylene and polyamide wax.

In the method of the present invention, in a specific embodiment, the colorant is carbon black.

In the method of the present invention, in a specific embodiment, the coupling agent is selected from one or more of epoxy silane coupling agents, amino silane coupling agents, mercapto silane coupling agents, isocyanate silane coupling agents and vinyl silane coupling agents.

A second aspect of the present invention provides an epoxy resin material prepared by the above method.

A third aspect of the present invention provides a use of the above epoxy resin material in semiconductor packaging.

The present invention will be described in detail below through examples, but the protection scope of the present invention is not limited thereto.

In the following examples and comparative examples:

Epoxy resin: o-cresol type epoxy resin: number average molecular weight is 3000, epoxy equivalent is 205g/mol, purchased from Shandong Shengquan Resin, product brand is SQCN700-1.3;

Epoxy resin: biphenyl type epoxy resin: number average molecular weight is 2500, epoxy equivalent is 195g/mol, purchased from DIC Corporation of Japan, product brand is YX-4000;

Curing agent: linear phenolic resin: number average molecular weight is 1200, purchased from Shandong Shengquan Resin, product brand is PF8010;

Curing agent: biphenyl phenolic resin: number average molecular weight is 2000, purchased from Shanghai Hengfeng New Materials, product brand is Resicare3900;

Accelerator: 2-methylimidazole, purchased from Shikoku Chemical Industry Co., Ltd., Japan;

Inorganic filler: crystalline silica, purchased from Jiangsu Lianrui, product brand DF-1220M;

Inorganic filler: fused spherical silica, purchased from Jiangsu Lianrui, product brand NQ-101;

Inorganic filler: Alumina, purchased from Tianjin Zexi;

Release agent: carnauba wax, purchased from Bangluk Trading Co., Ltd.

Coupling agent: propyl ether trimethoxysilane (purchased from Jiangsu Chenguang);

Colorant: Carbon black, purchased from Sichuan Zhenghao.

Example 1

Example 1 The raw material components for preparing epoxy resin material are shown in Table 1.

The method for preparing the epoxy resin material in this embodiment is as follows:

(1) mixing epoxy resin, curing agent, filler, release agent, coupling agent and colorant at a stirring speed of 210 rpm for 50 min, and then extruding in a twin-screw extruder at a melt extrusion temperature of 110° C., and finally cooling and pulverizing to obtain an intermediate;

(2) The intermediate obtained in step (1) and the accelerator are stirred and mixed in a certain proportion at a stirring speed of 210 rpm for a stirring time of 40 min, and then extruded in a twin-screw extruder at a melt extrusion temperature of 115° C., and finally cooled and crushed to obtain an epoxy resin material.

Example 2

Example 2 The raw material components for preparing epoxy resin material are shown in Table 1.

The method for preparing the epoxy resin material in this embodiment is as follows:

(1) mixing epoxy resin, curing agent, filler, release agent, coupling agent and colorant at a stirring speed of 205 rpm for 55 min, and then extruding in a twin-screw extruder at a melt extrusion temperature of 115° C., and finally cooling and pulverizing to obtain an intermediate;

(2) The intermediate obtained in step (1) and the accelerator are stirred and mixed in a certain ratio at a stirring speed of 210 rpm for a stirring time of 50 min, and then extruded in a twin-screw extruder at a melt extrusion temperature of 110° C., and finally cooled and crushed to obtain an epoxy resin material.

Example 3

Example 3 The raw material components for preparing epoxy resin material are shown in Table 1.

The method for preparing the epoxy resin material in this embodiment is as follows:

(1) mixing epoxy resin, curing agent, filler, release agent, coupling agent and colorant at a stirring speed of 215 rpm for 50 min, and then extruding in a twin-screw extruder at a melt extrusion temperature of 120° C., and finally cooling and pulverizing to obtain an intermediate;

(2) The intermediate obtained in step (1) and the accelerator are stirred and mixed in a certain ratio at a stirring speed of 215 rpm for a stirring time of 45 min, and then extruded in a twin-screw extruder at a melt extrusion temperature of 120° C., and finally cooled and crushed to obtain an epoxy resin material.

Example 4

Example 4 The raw material components for preparing epoxy resin material are shown in Table 1.

The method for preparing the epoxy resin material in this embodiment is as follows:

(1) mixing epoxy resin, curing agent, filler, release agent, coupling agent and colorant at a stirring speed of 220 rpm for 50 min, and then extruding in a twin-screw extruder at a melt extrusion temperature of 125° C., and finally cooling and pulverizing to obtain an intermediate;

(2) The intermediate obtained in step (1) and the accelerator are stirred and mixed in a certain proportion at a stirring speed of 220 rpm for a stirring time of 50 min, and then extruded in a twin-screw extruder at a melt extrusion temperature of 115° C., and finally cooled and crushed to obtain an epoxy resin material.

Comparative Example 1

Comparative Example 1 The raw material components for preparing epoxy resin material are shown in Table 1.

The method for preparing the epoxy resin material in this comparative example is as follows:

(1) mixing epoxy resin, curing agent, filler, release agent, coupling agent and colorant at a stirring speed of 210 rpm for 50 min, and then extruding in a twin-screw extruder at a melt extrusion temperature of 110° C., and finally cooling and pulverizing to obtain an intermediate;

(2) The intermediate obtained in step (1) and the accelerator are stirred and mixed in a certain proportion at a stirring speed of 210 rpm for a stirring time of 40 min, and then extruded in a twin-screw extruder at a melt extrusion temperature of 115° C., and finally cooled and crushed to obtain an epoxy resin material.

Comparative Example 2

Comparative Example 2 The raw material components for preparing epoxy resin material are shown in Table 1.

The method for preparing the epoxy resin material in this comparative example is as follows:

(1) mixing epoxy resin, curing agent, filler, release agent, coupling agent and colorant at a stirring speed of 210 rpm for 50 min, and then extruding in a twin-screw extruder at a melt extrusion temperature of 110° C., and finally cooling and pulverizing to obtain an intermediate;

(2) The intermediate obtained in step (1) and the accelerator are stirred and mixed in a certain proportion at a stirring speed of 210 rpm for a stirring time of 40 min, and then extruded in a twin-screw extruder at a melt extrusion temperature of 115° C., and finally cooled and crushed to obtain an epoxy resin material.

Comparative Example 3

The raw material components for preparing epoxy resin material in Comparative Example 3 are shown in Table 1.

The method for preparing the epoxy resin material in this comparative example is as follows:

The epoxy resin, curing agent, accelerator, filler, release agent, coupling agent and colorant were crushed in a crusher at room temperature, the crushed materials were stirred and mixed at a stirring speed of 210 rpm and a stirring time of 40 min, and then extruded in a twin-screw extruder at a melt extrusion temperature of 115° C., and finally cooled and crushed to obtain an epoxy resin material.

Comparative Example 4

The raw material components for preparing epoxy resin material in Comparative Example 4 are shown in Table 1.

The method for preparing the epoxy resin material in this comparative example is as follows:

The epoxy resin, curing agent, accelerator, filler, release agent, coupling agent and colorant were crushed in a crusher at room temperature, the crushed materials were stirred and mixed at a stirring speed of 210 rpm and a stirring time of 50 min, and then extruded in a twin-screw extruder at a melt extrusion temperature of 110° C., and finally cooled and crushed to obtain an epoxy resin material.

Comparative Example 5

The raw material components for preparing epoxy resin material in Comparative Example 5 are shown in Table 1.

The method for preparing the epoxy resin material in this comparative example is as follows:

The epoxy resin, curing agent, accelerator, filler, release agent, coupling agent and colorant were crushed in a crusher at room temperature, the crushed materials were stirred and mixed at a stirring speed of 210 rpm and a stirring time of 50 min, and then extruded in a twin-screw extruder at a melt extrusion temperature of 110° C., and finally cooled and crushed to obtain an epoxy resin material.

Comparative Example 6

The raw material components for preparing epoxy resin material in Comparative Example 6 are shown in Table 1.

The method for preparing the epoxy resin material in this comparative example is as follows:

The epoxy resin, curing agent, accelerator, filler, release agent, coupling agent and colorant were crushed in a crusher at room temperature, the crushed materials were stirred and mixed at a stirring speed of 210 rpm and a stirring time of 50 min, and then extruded in a twin-screw extruder at a melt extrusion temperature of 110° C., and finally cooled and crushed to obtain an epoxy resin material.

Table 1 Raw material components of epoxy resin materials of Examples 1-4 and Comparative Examples 1-6

Test Case

HTRB (High Temperature Reverse Bias): According to JESD22-A108, the test conditions are as follows: 150°C, 80% BVdssRating, 500 hrs, where the failure criterion is leakage current I _DSS ≥ 1mA.

The epoxy resin materials prepared in Examples 1-4 and Comparative Examples 1-6 were subjected to HTRB (high temperature reverse bias) tests after packaging TO-263 and TO-247, respectively. The test results are shown in Tables 2 and 3.

Table 2 HTRB test results of semiconductor devices TO-263 encapsulated with epoxy resin materials prepared in Examples 1-4 and Comparative Examples 1-6

Table 3 HTRB test results of semiconductor devices TO-247 encapsulated with epoxy resin materials prepared in Examples 1-4 and Comparative Examples 1-6

It can be seen from the test results of Examples 1-4 and Comparative Examples 1-6 that by using a specific proportion of raw material components and combining with the improved preparation method of the epoxy resin material, that is, the other raw materials except the accelerator are mixed for the first time and melt-extruded to obtain an intermediate, and then the accelerator in a certain weight ratio is mixed with the intermediate for a second time, and melt-extruded to obtain the epoxy resin material. Since this method adds one high-speed mixing and one melt extrusion process, it is beneficial to the uniformity of material mixing and the combination of the organic resin part and the inorganic filler part. The epoxy resin material prepared by this method has the characteristic of zero failure rate when the HTRB (high temperature reverse bias) test is performed after packaging the semiconductor device TO-263 and the semiconductor device TO-247, which significantly improves the HTRB reliability of the semiconductor device after packaging.

The above are only embodiments of the present invention, and are not intended to limit the patent scope of the present invention. Any equivalent transformations made using the contents of the present invention specification, or directly or indirectly applied in other related technical fields, are also included in the patent protection scope of the present invention.

Claims (14)

1. A method for preparing an epoxy resin material, characterized in that the method comprises the following steps: (1) mixing epoxy resin, curing agent, inorganic filler, release agent, coupling agent and colorant, melt-extruding, cooling and pulverizing to obtain an intermediate; (2) mixing the intermediate obtained in step (1) with a promoter, melt-extruding, cooling, and crushing to obtain an epoxy resin material; The weight ratio of epoxy resin, curing agent, accelerator, inorganic filler, release agent, coupling agent and colorant is 15-27:15-27:1.8-2.5:215-294:3-7:3-6:1; In step (1), the stirring speed is 180-230 rpm, and the stirring time is 20-60 min; In step (1), the melt extrusion temperature is 100-125°C; In step (2), the stirring speed is 180-230 rpm, and the stirring time is 20-60 min; In step (2), the melt extrusion temperature is 110-120°C. 2. The method according to claim 1, characterized in that in step (1), the stirring speed is 205-215 rpm and the stirring time is 45-55 min. 3. The method according to claim 1, characterized in that in step (1), the melt extrusion temperature is 110-120°C. 4. The method according to claim 1 or 2, characterized in that in step (2), the stirring speed is 205-215 rpm, and the stirring time is 30-50 min. 5. The method according to any one of claims 1 to 4, characterized in that the epoxy resin is selected from one or more of phenolic epoxy resin, bisphenol A epoxy resin, biphenyl epoxy resin, naphthalene epoxy resin, o-cresol epoxy, DCPD epoxy resin, multifunctional epoxy resin and alicyclic epoxy resin. 6. The method according to any one of claims 1 to 4, characterized in that the curing agent is selected from one or more of linear phenolic resin, XY-lock phenolic resin, bisphenol A phenolic resin, DCPD phenolic resin, biphenyl phenolic resin and multifunctional phenolic resin. 7. The method according to any one of claims 1 to 4, characterized in that the accelerator is selected from one or more of an organic phosphorus compound, an imidazole compound and a tertiary amine compound. 8. The method according to any one of claims 1 to 4, characterized in that the inorganic filler is selected from one or more of silicon dioxide powder, titanium dioxide powder, aluminum oxide powder and magnesium oxide powder. 9. The method according to claim 8, characterized in that the silica powder is selected from one or more of crystalline silica powder, fused angular silica powder and fused spherical silica powder. 10. The method according to any one of claims 1 to 4, characterized in that the release agent is selected from one or more of mineral wax, vegetable wax, polyethylene and polyamide wax. 11. The method according to any one of claims 1 to 4, characterized in that the colorant is carbon black. 12. The method according to any one of claims 1 to 4, characterized in that the coupling agent is selected from one or more of epoxy silane coupling agents, amino silane coupling agents, mercapto silane coupling agents, isocyanate silane coupling agents and vinyl silane coupling agents. 13. An epoxy resin material, characterized in that the epoxy resin material is prepared by the method according to any one of claims 1 to 12. 14. Use of the epoxy resin material prepared by the method of any one of claims 1 to 12 or the epoxy resin material according to claim 13 in semiconductor packaging.