Epoxy resin curing agent masterbatch with latent catalysis and preparation method thereof

Abstract

The invention relates to the technical field of electronic packaging materials, in particular to an epoxy resin curing agent masterbatch with latent catalysis and a preparation method of the epoxy resin curing agent masterbatch. The raw materials of the catalyst comprise triphenylphosphine and benzoquinone. By adopting the specific raw materials and the specific preparation process and strictly controlling the raw material adding sequence and the heating temperature, the epoxy resin composition prepared from the masterbatch has a larger processing window and excellent flowability and storage performance.

Description

Technical Field

[0001] The present invention relates to the technical field of electronic packaging materials, and particularly relates to a latent-catalytic epoxy resin curing agent masterbatch and a preparation method thereof. Background Art

[0002] With the booming development of the information technology industry, it has promoted the rapid development of electronic packaging testing and materials. The development trend of miniaturization and high density of electronic components and the continuous increase in market demand have, on the one hand, promoted the development of packaging forms towards high integration, fine wiring, large chip size, and thinness, and on the other hand, increased the lead frame density to improve production efficiency while keeping the packaging form unchanged.

[0003] For packaging devices with complex structures and fine wiring, higher requirements are put forward for epoxy molding compounds, especially for operability. Conventional epoxy molding compounds with a small process window will have problems such as incomplete filling and wire flushing during use and cannot meet normal use; in addition, conventional epoxy molding compounds with poor storage performance will also have similar problems during use.

[0004] In order to produce epoxy molding compounds with a large process window and excellent storage performance, latent catalysts can be selected for use. Currently, commonly used latent catalysts include triphenylphosphine (TPPK) and triphenylphosphine-1,4-benzoquinone adduct (TPP-BQ), etc. Chinese Patent CN106280254A discloses a low dielectric constant molding epoxy underfill and its preparation method and uses, using TPP-BQ as a promoter, which has characteristics such as low dielectric constant and dielectric loss, good heat resistance, high filling rate, and excellent mechanical properties, but its manufacturing cost is relatively high and it is not conducive to industrial production. Summary of the Invention

[0005] In order to solve the problems in the prior art, the first aspect of the present invention provides a latent-catalytic epoxy resin curing agent masterbatch, and its preparation raw materials include catalyst raw materials and phenolic resin; the catalyst raw materials include triphenylphosphine and benzoquinone.

[0006] In one embodiment, the viscosity requirement of the phenolic resin is: at 150 °C, the viscosity is lower than 5 Pa·s.

[0007] In one embodiment, the phenolic resin includes any one of linear phenolic resin, MFN type phenolic resin, xylok type phenolic resin, and MAR type phenolic resin.

[0008] In one embodiment, the viscosity of the linear phenolic resin at 150 °C is 0.04 Pa·s.

[0009] In one embodiment, the linear phenolic resin is purchased from Meiko Kasei of Japan, and the brand is P-200.

[0010] In one embodiment, the viscosity of the MFN type phenolic resin at 150 °C is 0.13 Pa·s.

[0011] In one embodiment, the MFN type phenolic resin is purchased from Meiwafosis Co., Ltd. of Japan, and the grade is MEH-7500-3S.

[0012] In one embodiment, the viscosity of the xylok type phenolic resin at 150 °C is 0.2 Pa·s.

[0013] In one embodiment, the xylok type phenolic resin is purchased from Mitsui Chemicals, Inc. of Japan, and the grade is XLC-3L.

[0014] In one embodiment, the viscosity of the MAR type phenolic resin at 150 °C is 0.15 Pa·s.

[0015] In one embodiment, the MAR type phenolic resin is purchased from Meiwafosis Co., Ltd. of Japan, and the grade is MEH-7851S.

[0016] In one embodiment, the mass ratio of triphenylphosphine to benzoquinone in the catalyst raw material is 1.19:0.45.

[0017] In one embodiment, the mass ratio of the catalyst raw material to the phenolic resin is (0.01 - 0.3):1.

[0018] In one embodiment, the mass ratio of the catalyst raw material to the phenolic resin is (0.05 - 0.15):1.

[0019] In one embodiment, the mass ratio of the catalyst raw material to the phenolic resin is 1.64:16.3.

[0020] The second aspect of the present invention provides a preparation method of an epoxy resin curing agent masterbatch with latent catalytic activity, including the following steps: heating and stirring the catalyst raw material and the phenolic resin to obtain the epoxy resin curing agent masterbatch with latent catalytic activity.

[0021] In one embodiment, the specific steps of the preparation method are as follows: first, heat and stir the phenolic resin and benzoquinone until completely melted, then add triphenylphosphine, and continue heating and stirring until it becomes transparent to obtain the epoxy resin curing agent masterbatch with latent catalytic activity.

[0022] In one embodiment, the temperature of the heating and stirring is controlled at 130 - 170 °C.

[0023] In one embodiment, the temperature of the heating and stirring is 150 °C.

[0024] Beneficial effects

[0025] 1. The present invention directly synthesizes a latent catalyst during the preparation of the masterbatch, which not only simplifies the preparation process but also has the price advantage of low cost.

[0026] 2. The epoxy resin curing agent masterbatch prepared by the present invention is applicable to various resin systems such as o-cresol type epoxy resin and linear phenolic resin, MFN type epoxy resin and MFN type phenolic resin, BP type epoxy resin and xylok type phenolic resin, and BP type epoxy resin and MAR type phenolic resin, and the preparation process is simple.

[0027] 3. Based on the system of the present invention, by using a phenolic resin with a viscosity lower than 5 Pa·s and strictly controlling the dosage ratio of the catalyst raw materials triphenylphosphine and benzoquinone, the catalytic performance of the masterbatch can be synergistically improved while shortening the gel time.

[0028] 4. In the present invention, by adopting specific raw materials and a specific preparation process and strictly controlling the raw material addition sequence and heating temperature, the epoxy resin composition prepared using this masterbatch has a large processing window, excellent fluidity and storage performance.

[0029] 5. The preparation method provided by the present invention can be applied to industrial production and has higher practical value. Specific Embodiments

[0030] In order to make the objectives, technical solutions and advantages of the present invention clearer, the present invention will be further described in detail below with reference to the embodiments. It should be understood that the specific embodiments described herein are only used to explain the present invention and are not used to limit the present invention. The experimental methods without specific conditions noted in the embodiments are carried out according to conventional conditions or conditions recommended by the manufacturer. The reagents or instruments without the manufacturer noted are all conventional products that can be obtained through commercial purchase.

[0031] Among them, the o-cresol type epoxy resin is purchased from Nippon Kayaku Co., Ltd., with the brand number EOCN-1020; the MFN type epoxy resin is purchased from Shandong Aimont Co., Ltd., with the brand number EMTE350; the BP type epoxy resin is purchased from Mitsubishi Corporation of Japan, with the brand number YX4000H.

[0032] Example 1

[0033] In the first aspect of this embodiment, a kind of epoxy resin curing agent masterbatch with latent catalytic properties is provided, and its preparation raw materials include catalyst raw materials and phenolic resin; the catalyst raw materials are triphenylphosphine and benzoquinone.

[0034] The viscosity requirement of the phenolic resin is: at 150 °C, the viscosity is lower than 5 Pa·s.

[0035] The phenolic resin is a linear phenolic resin with a viscosity of 0.04 Pa·s at 150°C, purchased from Meiwafosis Co., Ltd., Japan, with the product number DL-65.

[0036] In the catalyst raw material, the mass ratio of triphenylphosphine to benzoquinone is 1.19:0.45.

[0037] The mass ratio of the catalyst raw material to the phenolic resin is 1.64:16.3.

[0038] In the second aspect of this example, a preparation method of an epoxy resin curing agent masterbatch with latent catalytic activity is provided. The specific steps are as follows: First, heat and stir the phenolic resin and benzoquinone at 150°C until completely melted, then add triphenylphosphine, and continue to heat and stir until it becomes transparent, thus obtaining the epoxy resin curing agent masterbatch with latent catalytic activity.

[0039] Example 2

[0040] In the first aspect of this example, an epoxy resin curing agent masterbatch with latent catalytic activity is provided. Its preparation raw materials include a catalyst raw material and a phenolic resin; the catalyst raw material is triphenylphosphine and benzoquinone.

[0041] The viscosity requirement of the phenolic resin is: at 150°C, the viscosity is lower than 5 Pa·s.

[0042] The phenolic resin is an MFN type phenolic resin with a viscosity of 0.13 Pa·s at 150°C, purchased from Meiwafosis Co., Ltd., Japan, with the product number MEH-7500-3S.

[0043] In the catalyst raw material, the mass ratio of triphenylphosphine to benzoquinone is 1.19:0.45.

[0044] The mass ratio of the catalyst raw material to the phenolic resin is 1.64:16.3.

[0045] In the second aspect of this example, a preparation method of an epoxy resin curing agent masterbatch with latent catalytic activity is provided. The specific steps are as follows: First, heat and stir the phenolic resin and benzoquinone at 150°C until completely melted, then add triphenylphosphine, and continue to heat and stir until it becomes transparent, thus obtaining the epoxy resin curing agent masterbatch with latent catalytic activity.

[0046] Example 3

[0047] In the first aspect of this example, an epoxy resin curing agent masterbatch with latent catalytic activity is provided. Its preparation raw materials include a catalyst raw material and a phenolic resin; the catalyst raw material is triphenylphosphine and benzoquinone.

[0048] The viscosity requirement of the phenolic resin is: at 150°C, the viscosity is lower than 5 Pa·s.

[0049] The phenolic resin is xylok type phenolic resin, with a viscosity of 0.2 Pa·s at 150 °C, purchased from Mitsui Chemicals, Japan, and the grade is XLC-3L.

[0050] In the catalyst raw material, the mass ratio of triphenylphosphine to benzoquinone is 1.19:0.45.

[0051] The mass ratio of the catalyst raw material to the phenolic resin is 1.64:16.3.

[0052] In the second aspect of this example, a preparation method of an epoxy resin curing agent masterbatch with latent catalytic activity is provided. The specific steps are as follows: First, heat and stir the phenolic resin and benzoquinone at 150 °C until completely melted, then add triphenylphosphine, and continue to heat and stir until it becomes transparent, thus obtaining the epoxy resin curing agent masterbatch with latent catalytic activity.

[0053] Example 4

[0054] In the first aspect of this example, an epoxy resin curing agent masterbatch with latent catalytic activity is provided. Its preparation raw materials include a catalyst raw material and a phenolic resin; the catalyst raw material is triphenylphosphine and benzoquinone.

[0055] The viscosity requirement of the phenolic resin is: at 150 °C, the viscosity is lower than 5 Pa·s.

[0056] The phenolic resin is MAR type phenolic resin, with a viscosity of 0.15 Pa·s at 150 °C, purchased from Meiwafosis Co., Ltd., Japan, and the grade is MEH-7851S.

[0057] In the catalyst raw material, the mass ratio of triphenylphosphine to benzoquinone is 1.19:0.45.

[0058] The mass ratio of the catalyst raw material to the phenolic resin is 1.64:16.3.

[0059] In the second aspect of this example, a preparation method of an epoxy resin curing agent masterbatch with latent catalytic activity is provided. The specific steps are as follows: First, heat and stir the phenolic resin and benzoquinone at 150 °C until completely melted, then add triphenylphosphine, and continue to heat and stir until it becomes transparent, thus obtaining the epoxy resin curing agent masterbatch with latent catalytic activity.

[0060] Comparative Example 1

[0061] The specific implementation mode of this example is basically the same as that of Example 1, and the difference lies in:

[0062] The catalyst raw material is triphenylphosphine.

[0063] The mass ratio of the catalyst raw material to the phenolic resin is 0.1:1.

[0064] Comparative Example 2

[0065] The specific implementation manner of this comparative example is basically the same as that of Example 2, and the difference lies in:

[0066] The catalyst raw material is triphenylphosphine.

[0067] The mass ratio of the catalyst raw material to the phenolic resin is 0.1:1.

[0068] Comparative Example 3

[0069] The specific implementation manner of this comparative example is basically the same as that of Example 3, and the difference lies in:

[0070] The catalyst raw material is triphenylphosphine.

[0071] The mass ratio of the catalyst raw material to the phenolic resin is 0.1:1.

[0072] Comparative Example 4

[0073] The specific implementation manner of this comparative example is basically the same as that of Example 4, and the difference lies in:

[0074] The catalyst raw material is triphenylphosphine.

[0075] The mass ratio of the catalyst raw material to the phenolic resin is 0.1:1.

[0076] Comparative Example 5

[0077] The specific implementation manner of this comparative example is basically the same as that of Example 1, and the difference lies in:

[0078] The catalyst raw material uses the TPP-BQ catalyst.

[0079] The TPP-BQ catalyst is purchased from TPP-BQ of Nippon Seiko Chemical Co., Ltd.

[0080] Comparative Example 6

[0081] The specific implementation manner of this comparative example is basically the same as that of Example 1, and the difference lies in:

[0082] The preparation raw material is the 2E4MZ curing agent and the phenolic resin.

[0083] The mass ratio of the 2E4MZ curing agent to the phenolic resin is 0.1:1.

[0084] The 2E4MZ curing agent is purchased from Shikoku Chemicals Corporation.

[0085] Comparative Example 7

[0086] The specific implementation manner of this comparative example is basically the same as that of Example 4, and the difference lies in:

[0087] The phenolic resin is MAR type phenolic resin, with a viscosity of 5 Pa·s at 150 °C, purchased from Meiwafosis Co., Ltd., Japan, and the grade is MEH-7851-3H.

[0088] Comparative Example 8

[0089] The specific implementation manner of this comparative example is basically the same as that of Example 1, and the difference lies in:

[0090] The mass ratio of the catalyst raw material to the phenolic resin is 1.64:5.43.

[0091] Performance Test

[0092] 1. The samples prepared in Examples 1-4 and Comparative Examples 1-8 were respectively prepared into resin compositions, denoted as Compositions 1-12. By weight, the formulations of each composition are shown in Table 1 below. The preparation method of the resin composition is as follows: Weigh various materials according to the formulation, put them into a pulverizer and mix them to obtain. The gel time, viscosity, and DSC inflection point temperature of the prepared Compositions 1-12 were tested, and the test results are shown in Table 3. In Tables 1 and 2, " / " represents that the substance is not contained, and in Table 3, " / " represents that this test item is not carried out.

[0093] Table 1

[0094]

[0095]

[0096] 2. The samples prepared in Example 1, Comparative Example 1, and Comparative Example 5 were respectively prepared into epoxy molding compounds 1, epoxy molding compounds 2, and epoxy molding compounds 3. By weight, the formulations of each epoxy molding compound are shown in Table 2 below; the preparation method of the epoxy molding compound is as follows: Put various materials (the particle size of the materials is below 30 mesh) into a high-speed mixer and mix them, then put the materials after high-speed mixing into an extruder. The materials are heated and kneaded into a melt by the extruder, and then extruded into sheets by a calender to obtain. The polyethylene wax in Table 2 was purchased from Clariant GmbH, Germany, and the model is Licowax PED522. The D50 of the spherical silica powder is 21 μm, and 3-mercaptopropyltrimethoxysilane was purchased from Evonik Industries AG, and the model is Dynasylan MTMO.

[0097] 3. The prepared epoxy molding compounds 1-3 were tested for spiral flow length, gel time, thermal hardness, and viscosity, and a storage experiment was carried out. The storage experiment method: The sheet-shaped epoxy molding compound samples were placed in an oven at 40 °C for 48 hours, and then the spiral flow length and gel time were tested, and compared with the data before the storage experiment. The test results are shown in Table 3.

[0098] It can be seen from Table 3 that the epoxy resin curing agent masterbatch prepared in Examples 1-4 of the present application is suitable for various resin systems such as o-cresol type epoxy resin and linear phenolic resin, MFN type epoxy resin and MFN type phenolic resin, BP type epoxy resin and xylok type phenolic resin, and BP type epoxy resin and MAR type phenolic resin, and the preparation process is simple.

[0099] It can be seen from the experimental data of composition 1 and compositions 4, 9, and 10 that the epoxy resin catalyst masterbatch prepared in the present application performs the same as the purchased TPP-BQ catalyst, and the viscosity and DSC data are basically consistent. The latency of both is better than that of triphenylphosphine and 2E4MZ.

[0100] It can be seen from the experimental data of composition 4 and composition 11 that the masterbatch made by using the phenolic resin with too high viscosity is not transparent, and the gel time of the resin formula is long and the catalytic effect is poor.

[0101] It can be seen from the experimental data of composition 1 and composition 12 that the ratio of the catalyst raw materials - triphenylphosphine and benzoquinone to the phenolic resin in the masterbatch should not be too high. If the ratio is too high, the masterbatch will not be dispersed well, the phenolic resin will not be able to completely dissolve triphenylphosphine and benzoquinone, and the masterbatch will be opaque and the gel time will be too long.

[0102] The spiral flow length and gel time of the epoxy molding compound 1 prepared by the masterbatch of the present application and the epoxy molding compound 3 prepared by the purchased TPP-BQ catalyst changed little before and after the storage experiment, indicating that the homemade epoxy resin curing agent masterbatch of the present application has the same excellent latency and storage performance as the purchased TPP-BQ.

[0103] Table 2

[0104] Raw material name Epoxy molding compound 1 Epoxy molding compound 2 Epoxy molding compound 3 o-Cresol type epoxy resin 65.57 65.57 65.57 Low-viscosity linear phenolic resin 18.13 5.43 18.13 Sample of Example 1 17.94 / / Sample of Comparative Example 1 / 31.9 / Sample of Comparative Example 5 / / 17.94 Spherical silica powder 580 580 580 3-Mercaptopropyltrimethoxysilane 0.7 0.7 0.7 Pigment carbon black 0.01 0.01 0.01 Polyethylene wax 2.5 2.5 2.5

[0105] Table 3

[0106]

[0107]

Claims

1. A latent catalytic epoxy resin curing agent masterbatch, characterized in that: The preparation raw materials include catalyst raw materials and phenolic resin; the catalyst raw materials include triphenylphosphine and benzoquinone.

2. The epoxy resin curing agent masterbatch with latent catalysis according to claim 1, characterized in that: The viscosity requirement of the phenolic resin is: at 150° C., the viscosity is lower than 5 Pa·s.

3. The epoxy resin curing agent masterbatch with latent catalysis according to claim 2, characterized in that: The phenolic resin includes any one of linear phenolic resin, MFN phenolic resin, xylok phenolic resin and MAR phenolic resin.

4. The epoxy resin curing agent masterbatch with latent catalysis according to claim 1, characterized in that: The mass ratio of triphenylphosphine to benzoquinone in the catalyst raw material is 1.19:0.

45.

5. The epoxy resin curing agent masterbatch with latent catalysis according to claim 4, characterized in that: The mass ratio of the catalyst raw material to the phenolic resin is (0.01-0.3):

1.

6. The epoxy resin curing agent masterbatch with latent catalysis according to claim 5, characterized in that: The mass ratio of the catalyst raw material to the phenolic resin is (0.05-0.15):

1.

7. The epoxy resin curing agent masterbatch with latent catalysis according to claim 6, characterized in that: The mass ratio of the catalyst raw material to the phenolic resin is 1.64:16.

3.

8. A method for preparing the epoxy resin curing agent masterbatch with latent catalysis according to any one of claims 1 to 7, characterized in that: The method comprises the following steps: heating and stirring the catalyst raw material and the phenolic resin to obtain the epoxy resin curing agent masterbatch with latent catalysis.

9. The method for preparing the epoxy resin curing agent masterbatch with latent catalysis according to claim 8, characterized in that: The specific steps of the preparation method are as follows: firstly, phenolic resin and benzoquinone are heated and stirred until they are completely melted, then triphenylphosphine is added, and heating and stirring are continued until they are transparent, so as to obtain a masterbatch of epoxy resin curing agent with latent catalysis.

10. The method for preparing the epoxy resin curing agent masterbatch with latent catalysis according to claim 8, characterized in that: The temperature of the heating and stirring is controlled at 130-170°C.

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