Epoxy resin molding material and preparation method and application thereof

Abstract

The present invention relates to the field of epoxy resin compositions, and in particular to a method for preparing and applying a molding material of epoxy resin compositions. The epoxy resin molding material is made of a composition containing epoxy resin, phenolic resin, inorganic filler, curing accelerator and flame retardant, wherein the flame retardant is a mixture of hexaphenoxy cyclotriphosphazene, magnesium hydroxide and zinc borate, wherein, based on the total weight of the flame retardant as 100% by weight, the content of the hexaphenoxy cyclotriphosphazene is 30-50% by weight, and the total content of the magnesium hydroxide and zinc borate is 50-70% by weight. The molding material of the epoxy resin composition prepared by the present invention has V-0 grade flame retardant effect, good fluidity, and the composition has lower cost and is environmentally friendly.

Description

Technical Field

[0001] The present invention relates to the field of epoxy resin compositions, and in particular to a preparation method and application of an epoxy resin molding material. Background Art

[0002] In recent years, the domestic application of semiconductor devices has rapidly increased. Semiconductor devices are often used in electronic and electrical equipment. However, the temperature of electronic and electrical equipment increases during prolonged use, posing safety risks. These risks range from component failure to fire. Epoxy resin, due to its excellent airtightness and adhesive properties, is currently widely used as an encapsulation material for electronic and electrical equipment. Adding an appropriate amount of flame retardant to epoxy resin compositions can effectively reduce safety risks associated with the use of electronic and electrical equipment, as well as the likelihood of defects in the encapsulation process and poor appearance and operability. Summary of the Invention

[0003] The present invention aims to overcome the problems currently encountered in semiconductor encapsulation, such as poor flame retardancy, high cost, and leaks caused by poor fluidity, resulting from the use of certain flame retardant compositions. The present invention provides a method for preparing and applying an epoxy resin molding material. The epoxy resin molding material contains a specific type and ratio of flame retardants, resulting in a molding material with V-0 flame retardancy and good fluidity. Furthermore, the composition is low in cost and environmentally friendly.

[0004] To achieve the above objectives, the present invention provides, in a first aspect, an epoxy resin molding material, which is made of a composition containing an epoxy resin, a phenolic resin, an inorganic filler, a curing accelerator and a flame retardant, wherein the flame retardant contains hexaphenoxycyclotriphosphazene, magnesium hydroxide and zinc borate. Based on the total weight of the flame retardant as 100 weight%, the content of hexaphenoxycyclotriphosphazene is 30-50 weight%, and the total content of the magnesium hydroxide and zinc borate is 50-70 weight%.

[0005] Preferably, based on the total weight of the flame retardant being 100 weight %, the content of the hexaphenoxycyclotriphosphazene is 30-40 weight %, and the total content of the magnesium hydroxide and the zinc borate is 60-70 weight %;

[0006] Preferably, the weight ratio of the magnesium hydroxide to the zinc borate is 1:3-5.

[0007] Preferably, in the composition, the weight ratio of the flame retardant, epoxy resin, phenolic resin, inorganic filler and curing accelerator is 1:2.4-7:0.8-3.5:15-38.5:0.02-0.075.

[0008] Preferably, the epoxy resin is selected from bisphenol A epoxy resin and / or o-cresol novolac epoxy resin. More preferably, the epoxy resin is o-cresol novolac epoxy resin. Further preferably, the epoxy equivalent weight of the o-cresol novolac epoxy resin is 195-205 g / eq.

[0009] Preferably, the phenolic resin is selected from one or more of linear bisphenol A formaldehyde resin, XYLOK phenolic resin, biphenyl phenolic resin, nitrogen-containing phenolic resin, and phosphorus-containing phenolic resin; more preferably, the phenolic resin is linear bisphenol A formaldehyde resin; further preferably, the hydroxyl equivalent of the linear bisphenol A formaldehyde resin is 103-109 g / eq.

[0010] Preferably, the inorganic filler is silica powder. More preferably, the inorganic filler is one or more of fused angular silica powder, fused spherical silica powder, and crystalline angular silica powder. Further preferably, the inorganic filler is fused angular silica powder and / or crystalline angular silica powder. Even more preferably, the maximum particle size of the inorganic filler is 100-150 μm.

[0011] Preferably, the curing accelerator is selected from 2-phenyl-4-methylimidazole and / or 2-methylimidazole. More preferably, the curing accelerator is 2-phenyl-4-methylimidazole.

[0012] A second aspect of the present invention provides a method for preparing the aforementioned epoxy resin molding material, characterized in that the preparation method comprises the following steps:

[0013] S1, mixing a composition containing an epoxy resin, a phenolic resin, an inorganic filler, a curing accelerator and a flame retardant to obtain a mixture;

[0014] S2, processing and molding the mixed material to prepare epoxy resin molding material.

[0015] Preferably, in step S1, the speed of the twin-screw extruder is 170-190 r / min. More preferably, the material temperature during the mixing process is measured to be 125-135°C.

[0016] A third aspect of the present invention provides an application of the above-mentioned epoxy resin molding material as a semiconductor packaging material.

[0017] Through the above technical solution, the epoxy resin molding material provided by the present invention and its application achieve the following beneficial effects:

[0018] The epoxy resin molding material provided by the present invention contains organic flame retardants and inorganic flame retardants of specific types and proportions, so that the molding material of the composition has significantly improved flow properties while achieving V-0 level flame retardancy, thereby improving the stability of the packaging process, reducing the probability of packaging leakage, and thus improving packaging efficiency, while having low cost and being environmentally friendly. DETAILED DESCRIPTION

[0019] 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 intended to limit the present invention.

[0020] The endpoints of the ranges and any values ​​disclosed herein 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 endpoints of each range, the endpoints of each range and 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 considered to be specifically disclosed herein.

[0021] A first aspect of the present invention provides an epoxy resin molding material, which is made of a composition containing an epoxy resin, a phenolic resin, an inorganic filler, a curing accelerator and a flame retardant, wherein the flame retardant contains hexaphenoxycyclotriphosphazene, magnesium hydroxide and zinc borate. Based on the total weight of the flame retardant as 100 weight%, the content of hexaphenoxycyclotriphosphazene is 30-50 weight%, and the total content of the magnesium hydroxide and zinc borate is 50-70 weight%.

[0022] In a specific embodiment, based on the total weight of the flame retardant as 100 weight%, the content of the hexaphenoxycyclotriphosphazene may be 30 weight%, 32 weight%, 34 weight%, 36 weight%, 38 weight%, 40 weight%, 42 weight%, 44 weight%, 46 weight%, 48 weight% or 50 weight%; the total content of the magnesium hydroxide and zinc borate may be 50 weight%, 52 weight%, 54 weight%, 56 weight%, 58 weight%, 60 weight%, 62 weight%, 64 weight%, 66 weight%, 68 weight% or 70 weight%.

[0023] In the epoxy resin molding material of the present invention, in a preferred embodiment, based on 100 weight % of the total weight of the flame retardant, the content of the hexaphenoxycyclotriphosphazene is 30-40 weight %, and the total content of the magnesium hydroxide and the zinc borate is 60-70 weight %.

[0024] In the epoxy resin molding material of the present invention, in a specific embodiment, the weight ratio of the magnesium hydroxide to the zinc borate can be 1:3-5, for example, 1:3, 1:3.5, 1:4, 1:4.5, or 1:5.

[0025] In the epoxy resin molding material of the present invention, in a preferred embodiment, the weight ratio of the magnesium hydroxide to the zinc borate is 1:4

[0026] In the epoxy resin molding material of the present invention, in a specific embodiment, in the composition, the weight ratio of the flame retardant, epoxy resin, phenolic resin, inorganic filler, and curing accelerator can be 1:2.4-7:0.8-3.5:15-38.5:0.02-0.075, for example, it can be 1:2.4-3:0.8-1.5:15:18:0.02-0.04, 1:3-5:1.5-3:18-25:0.04-0.05, 1:5-6:3-3.5:25-30:0.05-0.06, 1:6-7:3-3.5:30-38.5:0.06-0.075.

[0027] In the epoxy resin molding material of the present invention, in a preferred embodiment, in the composition, the weight ratio of the flame retardant, epoxy resin, phenolic resin, inorganic filler, and curing accelerator is 1:2.85-3:1.0-1.4:15-18:0.02-0.04.

[0028] In the epoxy resin molding material of the present invention, in a specific embodiment, the epoxy resin can be a bisphenol A type epoxy resin and / or an o-cresol novolac epoxy resin. In a preferred embodiment, the epoxy resin is an o-cresol novolac epoxy resin. In a more preferred embodiment, the epoxy equivalent weight of the o-cresol novolac epoxy resin is 195-205 g / eq, for example, 195 g / eq, 197 g / eq, 199 g / eq, 201 g / eq, 203 g / eq or 205 g / eq.

[0029] In the epoxy resin molding material of the present invention, in a specific embodiment, the phenolic resin can be one or more of linear bisphenol A formaldehyde resin, XYLOK phenolic resin, biphenyl phenolic resin, nitrogen-containing phenolic resin, and phosphorus-containing phenolic resin. In a preferred embodiment, the phenolic resin is linear bisphenol A formaldehyde resin. In a more preferred embodiment, the hydroxyl equivalent weight of the linear bisphenol A formaldehyde resin is 103-109 g / eq, for example, 103 g / eq, 104 g / eq, 105 g / eq, 106 g / eq, 107 g / eq, 108 g / eq, or 109 g / eq.

[0030] In the epoxy resin molding material of the present invention, in a specific embodiment, the inorganic filler may be silica powder. In a preferred embodiment, the inorganic filler is one or more of fused angular silica powder, fused spherical silica powder, and crystalline angular silica powder. In a more preferred embodiment, the inorganic filler is fused angular silica powder and / or crystalline angular silica powder. In a further preferred embodiment, the maximum particle size of the inorganic filler is 100-150 μm.

[0031] In the epoxy resin molding material of the present invention, in a specific embodiment, the curing accelerator can be 2-phenyl-4-methylimidazole and / or 2-methylimidazole. In a preferred embodiment, the curing accelerator is 2-phenyl-4-methylimidazole.

[0032] A second aspect of the present invention provides a method for preparing an epoxy resin molding material, characterized in that the preparation method comprises the following steps:

[0033] S1, the composition containing epoxy resin, phenolic resin, inorganic filler, curing accelerator and fire retardant is mixed according to a certain proportion, in a specific embodiment, the gross weight based on the described fire retardant is 100 % by weight, the content of hexaphenoxy cyclotriphosphazene can be 30-50 % by weight, and the total content of magnesium hydroxide and zinc borate can be 50-70 % by weight, and by mixing and extruding through a twin-screw extruder, obtain the compound of composition epoxy resin. In a preferred embodiment, the gross weight based on the described fire retardant is 100 % by weight, the content of hexaphenoxy cyclotriphosphazene is 30-40 % by weight, and the total content of magnesium hydroxide and zinc borate is 60-70 % by weight.

[0034] S2, processing and molding the mixed material to obtain an epoxy resin molding material.

[0035] In the method of the present invention, in step S1, the twin-screw extruder has a rotational speed of 170-190 r / min. In a specific embodiment, the rotational speed may be, for example, 170 r / min, 180 r / min, or 190 r / min. In a preferred embodiment, the twin-screw extruder has a rotational speed of 180 r / min.

[0036] In the method of the present invention, in step S1, the mixing temperature during the mixing process is 125-135° C. In a specific embodiment, for example, it can be 125° C., 130° C., or 135° C. In a preferred embodiment, the mixing temperature during the mixing process is 130° C.

[0037] In the method of the present invention, in step S2, there is no particular limitation on the molding conditions, as long as a molding material of the epoxy resin composition that meets the requirements such as shape can be produced.

[0038] A third aspect of the present invention provides an application of the above-mentioned epoxy resin molding material as a semiconductor packaging material.

[0039] The present invention will be described in detail below through examples, but the protection scope of the present invention is not limited thereto.

[0040] In the following examples and comparative examples:

[0041] Epoxy resin: o-cresol epoxy resin: ICI viscosity (P, 150°C / 400 Hz): 2.3-2.7, epoxy equivalent (g / eq): 195-205, purchased from Jinan Shengquan Group Co., Ltd., brand SQCN700-3;

[0042] Phenolic resin a: linear phenol formaldehyde resin: ICI viscosity (P, 150°C / 400 Hz): 1.4-2.0, hydroxyl equivalent (g / eq): 103-109, purchased from Jinan Shengquan Group Co., Ltd., brand name Resicare 3010;

[0043] Phenolic resin b: linear phenol formaldehyde resin: ICI viscosity (P, 150°C / 400 Hz): 4.8-5.8, hydroxyl equivalent (g / eq): 103-109, purchased from Jinan Shengquan Group Co., Ltd., brand name Resicare 3015;

[0044] Inorganic filler a: angular crystalline silica powder, with a maximum particle size of 100-150 μm, purchased from Jixi Huangshan Quartz Co., Ltd., brand JG-A7;

[0045] Inorganic filler b: angular fused silica powder, with a maximum particle size of 100-150 μm, purchased from Jiangsu Lianrui New Materials Co., Ltd., brand DF-19;

[0046] Curing accelerator: 2-phenyl-4-methylimidazole, purchased from Shikoku Chemical;

[0047] Organic flame retardant a1: hexaphenoxycyclotriphosphazene, purchased from Wuhan Haishan Technology Co., Ltd.;

[0048] Organic flame retardant a2: triphenylphosphine oxide, purchased from Wuhan Haishan Technology Co., Ltd.;

[0049] Organic flame retardant a3: brominated epoxy resin, purchased from Wuhan Haishan Technology Co., Ltd.;

[0050] Inorganic flame retardant b1: a mixture of magnesium hydroxide and zinc borate in a weight ratio of 1:4. Magnesium hydroxide was purchased from Wuxi Zehui Chemical Co., Ltd., and zinc borate was purchased from Wuxi Zehui Chemical Co., Ltd.;

[0051] Inorganic flame retardant b2: antimony trioxide, purchased from Wuxi Zehui Chemical Co., Ltd.

[0052] Inorganic flame retardant b3: aluminum hydroxide, purchased from Wuxi Zehui Chemical Co., Ltd.

[0053] Examples 1-4 and Comparative Examples 1-13 were carried out in the following manner:

[0054] S1. Epoxy resin, phenolic resin, inorganic filler, curing accelerator and flame retardant were mixed according to the proportions shown in Table 1, and mixed and extruded through a twin-screw extruder, wherein the speed of the twin-screw extruder was 180 r / min, and the material temperature during the mixing process was measured to be 130° C.;

[0055] S2. The mixed material is processed and formed to obtain a product which is a molding material of the epoxy resin composition.

[0056] Table 1: Raw material ratios for Examples 1-4 and Comparative Examples 1-13

[0057]

[0058]

[0059] Proportion (1)*: The proportion of organic flame retardant a1 in the total amount of flame retardants used, wt%.

[0060] Proportion (2)*: the proportion of inorganic flame retardant b1 in the total amount of flame retardants used, wt%.

[0061] Test Case

[0062] (1) Spiral flow length: Take 20±5g of the powdered molding material sample for testing; put the obtained powdered resin product into the injection molding machine, and inject the material into a special spiral test mold at 175℃ under the conditions of injection pressure of 60bar and injection time of 15s. After 120s of curing, the resin product is hardened and taken out, and the spiral flow length is measured;

[0063] (2) Flame retardancy: The molding material samples were made into 1 / 16 inch thick specimens at 175°C / 25 MPa, and then cured at 175°C / 6 h. The flame retardancy test was then conducted using the vertical burning method according to GB4609-84.

[0064] The results of testing the fluidity, flame retardancy and environmental friendliness of the epoxy resin molding materials prepared in Examples 1 to 4 and Comparative Examples 1 to 13 are shown in Table 2.

[0065]

[0066] Comparison of the test results of Examples 1-4 and Comparative Examples 1-13 shows that the molding material of the epoxy resin composition of the present invention has good flame retardancy and fluidity, is environmentally friendly, can meet the safety of semiconductor devices during use, and complies with domestic policies promoting environmental protection. Good fluidity can also reduce the probability of defects in the packaging process.

[0067] The above are merely 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 any direct or indirect application in other related technical fields, are also included in the patent protection scope of the present invention.

Claims

1. An epoxy resin molding material, characterized in that: The epoxy resin molding material is made of a composition containing epoxy resin, phenolic resin, inorganic filler, curing accelerator and flame retardant, wherein the flame retardant contains hexaphenoxy cyclotriphosphazene, magnesium hydroxide and zinc borate, and based on the total weight of the flame retardant as 100 weight%, the content of hexaphenoxy cyclotriphosphazene is 30-40 weight%, the total content of magnesium hydroxide and zinc borate is 60-70 weight%, and the weight ratio of magnesium hydroxide to zinc borate is 1:3-5; In the composition, the weight ratio of the flame retardant, epoxy resin, phenolic resin, inorganic filler and curing accelerator is 1:2.4-7:0.8-3.5:15-38.5:0.02-0.

075.

2. The epoxy resin molding material according to claim 1, characterized in that: The epoxy resin is selected from bisphenol A epoxy resin and / or o-cresol epoxy resin. 3 . The epoxy resin molding material according to claim 2 , wherein the epoxy resin is o-cresol epoxy resin.

4. The epoxy resin molding material according to claim 3, characterized in that: The epoxy equivalent of the o-cresol-formaldehyde epoxy resin is 195-205 g / eq.

5. The epoxy resin molding material according to claim 1, characterized in that: The phenolic resin is selected from one or more of linear bisphenol A formaldehyde resin, XYLOK phenolic resin, biphenyl phenolic resin, nitrogen-containing phenolic resin and phosphorus-containing phenolic resin.

6. The epoxy resin molding material according to claim 5, characterized in that: The phenolic resin is linear bisphenol A formaldehyde resin.

7. The epoxy resin molding material according to claim 6, characterized in that: The hydroxyl equivalent of the linear bisphenol A formaldehyde resin is 103-109 g / eq.

8. The epoxy resin molding material according to claim 1, characterized in that: The inorganic filler is silicon dioxide powder.

9. The epoxy resin molding material according to claim 8, characterized in that: The inorganic filler is one or more of fused angular silica powder, fused spherical silica powder and crystalline angular silica powder.

10. The epoxy resin molding material according to claim 9, characterized in that: The inorganic filler is fused angular silica powder and / or crystalline angular silica powder.

11. The epoxy resin molding material according to claim 1, characterized in that: The maximum particle size of the inorganic filler is 100-150 μm.

12. The epoxy resin molding material according to claim 1, characterized in that: The curing accelerator is selected from 2-phenyl-4-methylimidazole and / or 2-methylimidazole.

13. The epoxy resin molding material according to claim 12, characterized in that: The curing accelerator is 2-phenyl-4-methylimidazole.

14. A method for preparing the epoxy resin molding material according to any one of claims 1 to 13, characterized in that: The method comprises the following steps: S1, mixing a composition containing an epoxy resin, a phenolic resin, an inorganic filler, a curing accelerator and a flame retardant to obtain a mixture; S2, processing and molding the mixed material to prepare epoxy resin molding material.

15. The method according to claim 14, characterized in that In step S1, the mixing conditions include: the mixing temperature is 125-135°C; and the mixing device is a twin-screw extruder.

16. The method according to claim 15, characterized in that The rotation speed of the twin-screw extruder is 170-190r / min.

17. Use of the epoxy resin molding material according to any one of claims 1 to 13 or the epoxy resin molding material prepared by the method according to any one of claims 14 to 16 as a semiconductor packaging material.

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