CN115521576A - 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 and its preparation method and application. In this method, epoxy resin, curing agent, filler, release agent, coupling agent and coloring agent are mixed under high-speed stirring at first, and then melted and extruded, cooled and pulverized to obtain an intermediate, and the prepared intermediate is mixed with Accelerators of a certain weight are mixed under high-speed stirring, melted and extruded, then cooled and pulverized to obtain epoxy resin materials. Adopt the epoxy resin material prepared by the present invention to carry out HTRB (high temperature reverse bias) test after encapsulating semiconductor device TO-263 and semiconductor device TO-247, have the characteristic of zero failure ratio, significantly improve the reliability of HTRB after semiconductor encapsulation sex.

Description

A kind of epoxy resin material and its preparation method and application

technical field

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

Background technique

In recent years, with the rapid development of the semiconductor industry, the packaging industry of integrated circuits and semiconductor devices has also begun to develop rapidly. At present, due to the development of the semiconductor and integrated circuit industries towards thinner and lighter terminals, the products produced by epoxy molding compound packaging technology have also begun to develop in the direction of miniaturization, thinning and ultra-large-scale. At the same time, the reliability and The appearance also puts forward higher requirements. HTRB (High Temperature Reverse Bias) is a method of reliability testing of semiconductor devices, and its requirements are increasing day by day, which also drives packaging and testing manufacturers to put forward higher requirements on the performance of plastic packaging compounds.

Contents of the invention

The purpose of the present invention is to address the deficiencies in the prior art, thereby providing a kind of epoxy resin material and its preparation method and application, this epoxy resin material is carried out HTRB (high temperature after semiconductor device TO-263 and semiconductor device TO-247) Reverse bias) test, with the characteristic of zero failure ratio, significantly improves the HTRB reliability of packaged semiconductor devices.

In order to achieve the above object, the present invention provides a kind of method for preparing epoxy resin material on the one hand, this method comprises the following steps:

(1) Stir and mix epoxy resin, curing agent, inorganic filler, release agent, coupling agent and colorant, melt and extrude, then cool and pulverize to obtain an intermediate;

(2) Stir and mix the intermediate prepared in step (1) with the accelerator, melt and extrude, then cool and pulverize to obtain an epoxy resin material;

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

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

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

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

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 180-230rpm, and the stirring time is 20-60min;

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

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

Preferably, the epoxy resin is selected from novolac epoxy resin, bisphenol A epoxy resin, biphenyl epoxy resin, naphthalene epoxy resin, o-cresol epoxy, DCPD epoxy resin, One or more of polyfunctional epoxy resins and alicyclic epoxy resins.

Preferably, the curing agent is selected from one or both of novolac resins, XY-lock phenolic resins, bisphenol A phenolic resins, DCPD phenolic resins, biphenyl phenolic resins and multifunctional phenolic resins above.

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

Preferably, the inorganic filler is selected from one or more of silica powder, titanium dioxide powder, alumina powder and magnesia powder; more preferably, the silica powder is selected from crystalline silica One or more of 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 of epoxy silane coupling agents, amino silane coupling agents, mercapto silane coupling agents, isocyanate silane coupling agents and vinyl silane coupling agents or two or more groups.

The method for preparing the epoxy resin material provided by the present invention adopts the raw material formula with a specific ratio content, and at the same time, 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 carried out Mixing for the second time, melt extrusion makes epoxy resin material, makes to carry out HTRB (high temperature reverse bias) test after the epoxy resin material package semiconductor device TO-263 and semiconductor device TO-247 that make with this method, It has the characteristic of zero failure ratio, which significantly improves the HTRB reliability of semiconductor devices after packaging. Compared with the conventional production method, this method adds a high-speed mixing and a melting 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 description

The following will be described in detail in combination with specific embodiments of the present invention. It should be understood that the specific embodiments described here are only used to illustrate and explain the present invention, and are not intended to limit the present invention.

Neither the endpoints nor any values of the ranges disclosed herein are limited to such precise ranges or values, and these ranges or values are understood to include values approaching these ranges or values. For numerical ranges, between the endpoints of each range, between the endpoints of each range and individual point values, and between individual point values can be combined with each other to obtain one or more new numerical ranges, these values Ranges should be considered as specifically disclosed herein.

The first aspect of the present invention provides a kind of method for preparing epoxy resin material, and this method comprises the following steps:

(1) Stir and mix epoxy resin, curing agent, inorganic filler, release agent, coupling agent and colorant, melt and extrude, then cool and pulverize to obtain an intermediate;

(2) Stir and mix the intermediate prepared in step (1) with the accelerator, melt and extrude, then cool and pulverize to obtain an epoxy resin material;

Among them, the weight ratio of the amount of epoxy resin, curing agent, accelerator, inorganic filler, release agent, coupling agent and coloring agent 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 the amount of epoxy resin, curing agent, accelerator, inorganic filler, release agent, coupling agent and coloring agent 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 may be 180-230rpm, such as 180rpm, 190rpm, 200rpm, 205rpm, 210rpm, 215rpm, 220rpm or 230rpm; The stirring time may be 20-60 min, for example, 20 min, 25 min, 30 min, 35 min, 40 min, 45 min, 50 min, 55 min or 60 min. In a preferred embodiment, the stirring speed is 205-215 rpm, and the stirring time is 45-55 min.

In the method of the present invention, in a specific embodiment, in step (1), the melt extrusion temperature may be 100-125°C, such as 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 may be 180-230rpm, such as 180rpm, 190rpm, 200rpm, 205rpm, 210rpm, 215rpm, 220rpm or 230rpm; The stirring time may be 20-60 min, for example, 20 min, 25 min, 30 min, 35 min, 40 min, 45 min, 50 min, 55 min or 60 min. In a preferred embodiment, the stirring speed is 205-215 rpm, and the stirring time is 30-50 min.

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

In the method of 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, two-roll mill, Single-screw extruder, twin-screw extruder, kneader, mixer and other processing equipment.

In the method of the present invention, in a specific embodiment, the epoxy resin is selected from novolac epoxy resin, bisphenol A epoxy resin, biphenyl epoxy resin, naphthalene epoxy resin, ortho One or more of cresol-type epoxy, DCPD-type 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 novolac resin, XY-lock type phenolic resin, bisphenol A type phenolic resin, DCPD type phenolic resin, biphenyl type phenolic resin and One or two or more types of multifunctional phenolic resins.

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

In the method of the present invention, in a specific embodiment, the inorganic filler is selected from one or more of silica powder, titanium dioxide powder, alumina 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 epoxy silane coupling agent, amino silane coupling agent, mercapto silane coupling agent, isocyanate silane coupling agent agent and vinyl silane coupling agent or two or more.

The second aspect of the present invention provides an epoxy resin material prepared by the aforementioned method.

A third aspect of the present invention provides an application of the above-mentioned epoxy resin material in semiconductor packaging.

The present invention will be described in detail through examples below, 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: the number average molecular weight is 3000, the epoxy equivalent is 205g/mol, purchased from Shandong Shengquan resin, the product brand is SQCN700-1.3;

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

Curing agent: novolak resin: the number average molecular weight is 1200, purchased from Shandong Shengquan resin, the product brand is PF8010;

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

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

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

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

Inorganic filler: alumina, purchased from Tianjin Zexi;

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

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

Coloring agent: carbon black, purchased from Sichuan.

Example 1

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

The method that present embodiment prepares epoxy resin material is as follows:

(1) Epoxy resin, curing agent, filler, mold release agent, coupling agent and coloring agent are 210rpm with stirring speed, stirring time is 50min stirring and mixing, then in twin-screw extruder with melting extrusion temperature Extrude at 110°C, and finally cool and pulverize to obtain the intermediate;

(2) The intermediate and accelerator prepared in step (1) are stirred and mixed according to a certain ratio at a stirring speed of 210rpm and a stirring time of 40min, and then extruded in a twin-screw extruder with a melt extrusion temperature of 115°C out, and finally cooled and pulverized to obtain epoxy resin materials.

Example 2

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

The method that present embodiment prepares epoxy resin material is as follows:

(1) Epoxy resin, curing agent, filler, demoulding agent, coupling agent and coloring agent are 205rpm with stirring speed, and the stirring time is 55min stirring and mixing, then in twin-screw extruder with melting extrusion temperature Extrude at 115°C, and finally cool and pulverize to obtain the intermediate;

(2) Stir and mix the intermediate and accelerator prepared in step (1) according to a certain ratio at a stirring speed of 210rpm and a stirring time of 50min, and then extrude it in a twin-screw extruder with a melt extrusion temperature of 110°C. out, and finally cooled and pulverized to obtain epoxy resin materials.

Example 3

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

The method that present embodiment prepares epoxy resin material is as follows:

(1) Epoxy resin, curing agent, filler, demoulding agent, coupling agent and coloring agent are 215rpm with stirring speed, and stirring time is 50min stirring and mixing, then in twin-screw extruder with melting extrusion temperature Extrude at 120°C, and finally cool and pulverize to obtain the intermediate;

(2) The intermediate and accelerator prepared in step (1) are mixed according to a certain ratio at a stirring speed of 215rpm and a stirring time of 45min, and then extruded in a twin-screw extruder with a melt extrusion temperature of 120°C. out, and finally cooled and pulverized to obtain epoxy resin materials.

Example 4

Example 4 See Table 1 for the raw material components for preparing epoxy resin materials.

The method that present embodiment prepares epoxy resin material is as follows:

(1) Epoxy resin, curing agent, filler, demoulding agent, coupling agent and coloring agent are 220rpm with stirring speed, and stirring time is 50min stirring and mixing, then in twin-screw extruder with melting extrusion temperature Extrude at 125°C, and finally cool and pulverize to obtain the intermediate;

(2) The intermediate and accelerator prepared in step (1) are mixed according to a certain ratio at a stirring speed of 220rpm and a stirring time of 50min, and then extruded in a twin-screw extruder with a melt extrusion temperature of 115°C. out, and finally cooled and pulverized to obtain epoxy resin materials.

Comparative example 1

See Table 1 for the raw material components of the epoxy resin material prepared in Comparative Example 1.

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

(1) Epoxy resin, curing agent, filler, mold release agent, coupling agent and coloring agent are 210rpm with stirring speed, stirring time is 50min stirring and mixing, then in twin-screw extruder with melting extrusion temperature Extrude at 110°C, and finally cool and pulverize to obtain the intermediate;

(2) The intermediate and accelerator prepared in step (1) are stirred and mixed according to a certain ratio at a stirring speed of 210rpm and a stirring time of 40min, and then extruded in a twin-screw extruder with a melt extrusion temperature of 115°C out, and finally cooled and pulverized to obtain epoxy resin materials.

Comparative example 2

See Table 1 for the raw material components of the epoxy resin material prepared in Comparative Example 2.

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

(1) Epoxy resin, curing agent, filler, mold release agent, coupling agent and coloring agent are 210rpm with stirring speed, stirring time is 50min stirring and mixing, then in twin-screw extruder with melting extrusion temperature Extrude at 110°C, and finally cool and pulverize to obtain the intermediate;

(2) The intermediate and accelerator prepared in step (1) are stirred and mixed according to a certain ratio at a stirring speed of 210rpm and a stirring time of 40min, and then extruded in a twin-screw extruder with a melt extrusion temperature of 115°C out, and finally cooled and pulverized to obtain epoxy resin materials.

Comparative example 3

See Table 1 for the raw material components of the epoxy resin material prepared in Comparative Example 3.

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

Epoxy resin, curing agent, accelerator, filler, release agent, coupling agent and colorant are pulverized with a pulverizer at room temperature, and the pulverized material is stirred and mixed at a stirring speed of 210rpm and a stirring time of 40min, and then mixed in a double Extrude in a screw extruder with a melt extrusion temperature of 115° C., and finally cool and pulverize to obtain an epoxy resin material.

Comparative example 4

See Table 1 for the raw material components of the epoxy resin material prepared in Comparative Example 4.

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

Epoxy resin, curing agent, accelerator, filler, release agent, coupling agent and colorant are pulverized with a pulverizer at room temperature, and the pulverized material is stirred and mixed with a stirring speed of 210rpm and a stirring time of 50min, and then mixed in a double Extrude in a screw extruder with a melt extrusion temperature of 110° C., and finally cool and pulverize to obtain an epoxy resin material.

Comparative example 5

See Table 1 for the raw material components of the epoxy resin material prepared in Comparative Example 5.

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

Epoxy resin, curing agent, accelerator, filler, release agent, coupling agent and colorant are pulverized with a pulverizer at room temperature, and the pulverized material is stirred and mixed with a stirring speed of 210rpm and a stirring time of 50min, and then mixed in a double Extrude in a screw extruder with a melt extrusion temperature of 110° C., and finally cool and pulverize to obtain an epoxy resin material.

Comparative example 6

See Table 1 for the raw material components of the epoxy resin material prepared in Comparative Example 6.

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

Epoxy resin, curing agent, accelerator, filler, release agent, coupling agent and colorant are pulverized with a pulverizer at room temperature, and the pulverized material is stirred and mixed with a stirring speed of 210rpm and a stirring time of 50min, and then mixed in a double Extrude in a screw extruder with a melt extrusion temperature of 110° C., and finally cool and pulverize to obtain an epoxy resin material.

The raw material components of the epoxy resin material of table 1 embodiment 1-4 and comparative example 1-6

test case

HTRB (High Temperature Reverse Bias): According to JESD22-A108, the test conditions are as follows: 150°C, 80% BVdssRating, 500hrs, 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) test after encapsulating TO-263 and TO-247 respectively, and the test results are shown in Table 2 and Table 3 .

The HTRB test result of the epoxy resin material encapsulation semiconductor device TO-263 that table 2 embodiment 1-4 and comparative example 1-6 prepare

The HTRB test result of the epoxy resin material encapsulation semiconductor device TO-247 that table 3 embodiment 1-4 and comparative example 1-6 prepare

As can be seen from the test results of Examples 1-4 and Comparative Examples 1-6, by using a specific ratio of raw material components, combined with the improved preparation method of the epoxy resin material, that is, other raw materials except accelerators are processed Mix and melt extrude for the first time to make an intermediate, and then mix a certain weight ratio of the accelerator with the intermediate for the second time, and melt and extrude to make an epoxy resin material. Because this method increases a high-speed mixing and a The melt extrusion process is beneficial to the uniformity of material mixing and the combination of the organic resin part and the inorganic filler part, so that the epoxy resin material prepared by this method is HTRB after packaging the semiconductor device TO-263 and the semiconductor device TO-247. (High Temperature Reverse Bias) test, which has the characteristics of zero failure ratio, which significantly improves the HTRB reliability of semiconductor devices after packaging.

The above are only examples of the present invention, and are not intended to limit the patent scope of the present invention. All equivalent transformations made using the content of the description of the present invention, or directly or indirectly used in other related technical fields, are equally included in the scope of the present invention. within the scope of patent protection.

Claims (10)

1. a method for preparing epoxy resin material, is characterized in that, the method may further comprise the steps: (1) Stir and mix epoxy resin, curing agent, inorganic filler, release agent, coupling agent and colorant, melt and extrude, then cool and pulverize to obtain an intermediate; (2) Stir and mix the intermediate prepared in step (1) with the accelerator, melt and extrude, then cool and pulverize to obtain an epoxy resin material; Among them, the weight ratio of the amount of epoxy resin, curing agent, accelerator, inorganic filler, release agent, coupling agent and coloring agent is 12.5-35:12.5-35:0.75-3:212-297:0.5-10 :1.25-10:1. 2. method according to claim 1 is characterized in that, the weight ratio of the consumption of epoxy resin, curing agent, accelerator, inorganic filler, release agent, coupling agent and coloring agent is 15-27:15- 27:1.8-2.5:215-294:3-7:3-6:1. 3. The method according to claim 1, characterized in that, in step (1), the stirring speed is 180-230rpm, and the stirring time is 20-60min; Preferably, in step (1), the stirring speed is 205-215rpm, and the stirring time is 45-55min; 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 180-230rpm, and the stirring time is 20-60min; Preferably, in step (2), the stirring speed is 205-215rpm, and the stirring time is 30-50min; Preferably, in step (2), the melt extrusion temperature is 110-120°C. 4. according to the described method of claim 1 or 3, it is characterized in that, described epoxy resin is selected from novolak type epoxy resin, bisphenol A type epoxy resin, biphenyl type epoxy resin, naphthalene type epoxy resin , one or more of o-cresol epoxy resins, DCPD epoxy resins, multifunctional epoxy resins and cycloaliphatic epoxy resins; Preferably, the curing agent is selected from one or both of novolac resins, XY-lock phenolic resins, bisphenol A phenolic resins, DCPD phenolic resins, biphenyl phenolic resins and multifunctional phenolic resins above. 5. The method according to claim 1 or 3, characterized in that, the accelerator is selected from one or more of organophosphorus compounds, imidazole compounds and tertiary amine compounds. 6. The method according to claim 1 or 3, wherein the inorganic filler is selected from one or more of silica powder, titanium dioxide powder, alumina powder and magnesium oxide powder; Preferably, the silica powder is selected from one or more of crystalline silica powder, fused angular silica powder and fused spherical silica powder. 7. The method according to claim 1 or 3, wherein the release agent is selected from one or more of mineral wax, vegetable wax, polyethylene and polyamide wax; Preferably, the colorant is carbon black. 8. The method according to claim 1 or 3, wherein the coupling agent is selected from epoxy silane coupling agent, aminosilane coupling agent, mercaptosilane coupling agent, isocyanate base silane One or more of coupling agent and vinyl silane coupling agent. 9. An epoxy resin material, characterized in that the epoxy resin material is prepared by the method according to any one of claims 1-8. 10. The epoxy resin material prepared by the method according to any one of claims 1-8 or the application of the epoxy resin material described in claim 9 in semiconductor packaging.