Method for producing resin composition

Abstract

The invention relates to a manufacturing method of a resin composition. An inorganic filler, a first solvent and a dispersing agent are mixed, the dispersing agent is made of silane and / or polysiloxane containing an organic-philic end and an inorganic-philic end, the dispersing agent and the inorganic filler are subjected to a dealcoholization condensation reaction, and dispersion liquid containing the modified inorganic filler is formed; wherein the organophilic terminal comprises a carbonyl group, an epoxy group and / or an amino group. And dissolving epoxy resin into the dispersion liquid.

Description

Technical Field

[0001] The present invention relates to a method for producing a resin composition. Background Art

[0002] Copper clad laminate is an electronic component substrate, which is made of multiple insulating layers and copper foil layers stacked alternately. Usually, copper clad laminate uses special resin materials as insulating layers, and uses electroplating technology to form conductive holes through the insulating layers, thereby electrically connecting different layers of copper foil together.

[0003] With the development of 5G communication technology, the requirements for the properties of copper clad laminates (such as low dielectric properties and dielectric loss) continue to increase. In order to optimize copper clad laminates, many manufacturers add inorganic fillers to resin materials to improve the mechanical strength and thermal stability of resin materials. However, due to the small particle size of inorganic fillers and the high viscosity of resins, it is not easy to evenly disperse inorganic fillers in the resin. Summary of the invention

[0004] The invention provides a method for preparing a resin composition, which can improve the uniformity of an inorganic filler.

[0005] At least one embodiment of the present invention provides a method for manufacturing a resin composition, comprising the following steps: mixing an inorganic filler, a first solvent, and a dispersant, wherein the material of the dispersant is a silane and / or polysiloxane including an organophilic end and an inorganic end, and the dispersant and the inorganic filler undergo a dealcoholization condensation reaction to form a dispersion comprising a modified inorganic filler, wherein the organophilic end includes a carbonyl group, an epoxy group, and / or an amine group. Dissolving an epoxy resin in the dispersion. BRIEF DESCRIPTION OF THE DRAWINGS

[0006] Figure 1 is a schematic diagram of a method for manufacturing a resin composition according to an embodiment of the present invention.

[0007] Figure 2 is a schematic diagram of a method for manufacturing a resin composition according to an embodiment of the present invention.

[0008] Figure 3 is a schematic diagram of a method for manufacturing a resin composition according to an embodiment of the present invention.

[0009] Figure 4 is a schematic diagram of a method for manufacturing a resin composition according to an embodiment of the present invention.

[0010] Figure 5 is a schematic diagram of a method for manufacturing a resin composition according to an embodiment of the present invention. DETAILED DESCRIPTION

[0011] Figure 1 is a schematic diagram of a method for manufacturing a resin composition according to an embodiment of the present invention. Figure 1 In step S1, the inorganic filler, the first solvent and the dispersant are mixed. For example, the inorganic filler, the first solvent and the dispersant are mixed to form a dispersion by using a bead mill, a flow jet mixer, a high-speed impeller, a high-pressure wet micronizer, a ball mill, a pain shaker, a microfluidizer, an ultrasonic dispersion, a sand mill, a roller mill, a sand mill, a high-speed homogenizer, etc.

[0012] In some embodiments, the dispersion includes 53 wt % to 80 wt % of an inorganic filler, 19.9 wt % to 45 wt % of a first solvent, and 0.1 wt % to 2.0 wt % of a dispersant. In some embodiments, the content of the dispersant is 0.125 wt % to 3.773 wt % based on 100 wt % of the inorganic filler.

[0013] In some embodiments, the first solvent includes at least one of butanone, cyclohexanone, propylene glycol methyl ether, or a combination of the foregoing materials and other solvents.

[0014] In some embodiments, the inorganic filler includes silicon oxide (SiOx). For example, spherical silicon oxide, flaky silicon oxide or other types of silicon oxide. In some embodiments, the average particle size of the spherical silicon oxide is 0.1 micrometers to 1.2 micrometers.

[0015] The material of the dispersant is a silane and / or polysiloxane including an organophilic end and an inorganic end. The organophilic end includes a carbonyl group, an epoxy group and / or an amine group, and the inorganic end includes a group that can undergo dealcoholization condensation with an epoxy group. For example, the material of the dispersant is represented by any one of the following chemical structures (1) to (4):

[0016]

[0017] In the chemical structure (1), R1 and R2 are each independently a methyl group or an ethyl group, R3 is a long carbon chain having 2 to 6 carbon atoms, an ether group or a phenyl group, R4 is an alkyl group having 1 to 3 carbon atoms, R5 and R6 are each independently a methyl group or an ethyl group, a is a positive integer, and b is a positive integer;

[0018]

[0019] In the chemical structure (2), R1 and R2 are each independently a methyl group or an ethyl group, R3 is a long carbon chain having 2 to 6 carbon atoms, an ether group or a phenyl group, R4 is an alkyl group having 1 to 3 carbon atoms, R5 and R6 are each independently a methyl group or an ethyl group, a is a positive integer, and b is a positive integer;

[0020] as well as

[0021]

[0022] In step S1 , the dispersant and the inorganic filler undergo a dealcoholization condensation reaction to form a dispersion liquid including the modified inorganic filler.

[0023] Then, please refer to step S2, dissolving the epoxy resin into the dispersion. In some embodiments, the second solvent, epoxy resin, plasticizer and accelerator are optionally added to the dispersion. Then, the dispersion is mixed to form a slurry by a bead mill, a flowjet mixer, a high-speed impeller, a high-pressure wet micronizer, a ball mill, a pain shaker, a microfluidizer, an ultrasonic dispersion, a sand mill, a roller mill, a sand mill, a high-speed homogenizer, etc.

[0024] In some embodiments, the slurry includes 49.6wt% to 74.87wt% of the dispersion, 11.9wt% to 37.17wt% of the second solvent, 2.65wt% to 10.58wt% of the epoxy resin, 2.65wt% to 10.58wt% of the plasticizer, and 0.05phr to 0.8phr of the accelerator. In some embodiments, the content of the epoxy resin is 7 to 27 parts by weight based on 100 parts by weight of the inorganic filler. In some embodiments, the content of the plasticizer is 7 to 27 parts by weight based on 100 parts by weight of the inorganic filler.

[0025] In some embodiments, the second solvent includes at least one of toluene, butanone, cyclohexanone, or a combination of the foregoing materials and other solvents. The second solvent can be used to adjust the solid content and viscosity of the slurry.

[0026] In certain embodiments, epoxy resin comprises at least one of naphthalene epoxy resin, phenolic epoxy resin, ester epoxy resin, and bisphenol F epoxy resin. In certain embodiments, when the organophilic end of the material of the dispersant comprises an amine group, the epoxy group of the epoxy resin undergoes a ring-opening reaction and is cross-linked with the amine group of the organophilic end of the dispersant. In this case, the organophilic end of the dispersant is connected to the epoxy resin, and the inorganic end of the dispersant is connected to the inorganic filler, so that the modified inorganic filler (comprising the inorganic filler and the dispersant located on its surface) is evenly dispersed. In certain embodiments, when the organophilic end of the material of the dispersant comprises a carbonyl or epoxy group, since the epoxy group of the dispersant has a better compatibility with the epoxy resin, the modified inorganic filler is better dispersed and is not easy to agglomerate in the epoxy resin.

[0027] In the embodiments described herein, a dispersion containing modified inorganic fillers is first formed, and then the epoxy resin is dissolved in the dispersion. If the inorganic filler is directly mixed with the epoxy resin, the inorganic filler is easily difficult to fully disperse due to the high viscosity of the epoxy resin. In addition, the organic-philic end and the inorganic-philic end of the dispersant can reduce the probability of the inorganic filler agglomerating together, so the embodiments described herein can fully improve the uniformity of the inorganic filler. For example, the inorganic filler in the slurry can remain suspended even after standing for 48 hours.

[0028] In some embodiments, the plasticizer includes at least one of bismaleimide resin, amine polymer, epoxy polymer, etc. In some embodiments, the accelerator includes at least one of imidazole and phosphorus accelerator, etc.

[0029] In some embodiments, other silanes may be additionally added to the dispersion in step S2. The silane used here is used to enhance the adhesion between the coating of the resin composition formed subsequently and the substrate, and may include a different material from the silane used in the dispersant. For example, the silane added in step S2 optionally does not include an organophilic end and an inorganic philic end. For example, the silane added in step S2 includes at least one of materials containing epoxy functional groups and amine functional groups.

[0030] Referring to step S3, after adding the second solvent, epoxy resin and accelerator into the dispersion, a hardener and / or a cross-linking agent is added into the slurry. After mixing, the slurry is coated on the substrate to form a coating of the resin composition.

[0031] In some embodiments, the content of the hardener is 3 to 20 parts by weight based on 100 parts by weight of the epoxy resin. In some embodiments, the content of the cross-linking agent is 20 to 70 parts by weight based on 100 parts by weight of the epoxy resin.

[0032] In some embodiments, the hardener includes at least one of an ester hardener, an amine hardener, and a phenolic hardener. In some embodiments, the crosslinking agent includes at least one of a tertiary amine, a benzoxazine resin, and an aromatic amine.

[0033] In some embodiments, because the inorganic filler is uniformly dispersed in the coating of the resin composition, the coating of the resin composition has a higher glass transition temperature (e.g., greater than 320°C), a lower thermal expansion coefficient (e.g., less than 4 ppm / °C), and a low water absorption rate (e.g., less than or equal to 0.45%).

[0034] Table 1 provides a comparison of the properties of the slurry and the coating of the resin composition obtained in Examples 1 to 4 of the present invention and Comparative Example 1. In Examples 1 to 4, a dispersion comprising a dispersant, a first solvent and an inorganic filler is first formed, and then the resin material is mixed with the dispersion to form a slurry. However, in Comparative Example 1, the inorganic filler is directly mixed with the resin material. In Table 1, the sample after the PCT (Pressure Cooker Test) saturated steam test is immersed in a 288°C tin furnace. If there is no delamination in 10 minutes, it means that the heat resistance passes the standard.

[0035] Table 1

[0036]

[0037] From Table 1, it can be seen that the coatings of the resin compositions obtained in Examples 1 to 4 have lower water absorption, and the solid components in the slurry have better suspension. In addition, in Examples 1 to 4, the resin compositions obtained in Examples 1 and 3 have lower water absorption, and the resin compositions obtained in Examples 1 and 2 have higher Tg. By comparing Examples 1 to 4, it can be seen that the material of the dispersant is better when adding chemical structure 1, and the obtained resin has the advantages of low water absorption and high Tg at the same time, because the dispersant of chemical structure 1 has better crosslinking with the inorganic filler and the resin.

[0038] Figure 2 is a schematic diagram of a method for manufacturing a resin composition according to an embodiment of the present invention. It must be noted that: Figure 2 The implementation examples are used Figure 1 Please refer to the examples of Figure 2 In this embodiment, the dispersant 10 is represented by the chemical structure (1). The dispersant 10 has an inorganic-philic end 11 and an organic-philic end 12.

[0039] First, the dispersant 10 is mixed with the inorganic filler 20 (eg Figure 1In step S1), the inorganic end 11 of the dispersant 10 undergoes a dealcoholization condensation reaction with the inorganic filler 20 to form a modified inorganic filler 20'.

[0040] Next, the epoxy resin 30 is mixed with the modified inorganic filler 20' (eg Figure 1 Step S2). The epoxy group of the epoxy resin 30 undergoes a ring-opening reaction and cross-links with the amine group of the organic end 12.

[0041] In this embodiment, the epoxy group of the epoxy resin 30 includes a three-membered ring, but the present invention is not limited thereto. In other embodiments, the epoxy group of the epoxy resin 30 includes a three-membered ring, a four-membered ring, or a five-membered ring.

[0042] Figure 3 is a schematic diagram of a method for manufacturing a resin composition according to an embodiment of the present invention. It must be noted that: Figure 3 The implementation examples are used Figure 1 Please refer to the examples of Figure 3 In this embodiment, the dispersant 10a is represented by the chemical structure (2). The dispersant 10a has an inorganic-philic end 11a and an organic-philic end 12a.

[0043] First, the dispersant 10a is mixed with the inorganic filler 20 (eg Figure 1 In step S1), the inorganic end 11a of the dispersant 10a undergoes a dealcoholization condensation reaction with the inorganic filler 20 to form a modified inorganic filler 20a'.

[0044] Next, the epoxy resin 30 is mixed with the modified inorganic filler 20a' (eg Figure 1 Step S2). The epoxy resin 30 and the organophilic end 12a of the dispersant 10a both include epoxy groups, so the modified inorganic filler 20a' has good compatibility with the epoxy resin 30, so that the modified inorganic filler 20a' can be evenly dispersed in the epoxy resin 30. In this embodiment, the epoxy groups of the organophilic end 12a of the epoxy resin 30 and the dispersant 10a both include three-membered rings, but the present invention is not limited to this. In other embodiments, the epoxy groups of the organophilic end 12a of the epoxy resin 30 and the dispersant 10a include three-membered rings, four-membered rings or five-membered rings. In some embodiments, the epoxy resin 30 and the organophilic end 12a of the dispersant 10a include different epoxy groups.

[0045] Figure 4 is a schematic diagram of a method for manufacturing a resin composition according to an embodiment of the present invention. It must be noted that: Figure 4 The implementation examples are used Figure 1 Please refer to the examples of Figure 4In this embodiment, the dispersant 10b is represented by the chemical structure (3). The dispersant 10b has an inorganic-philic end 11b and an organic-philic end 12b.

[0046] First, the dispersant 10b is mixed with the inorganic filler 20 (eg Figure 1 In step S1), the inorganic end 11b of the dispersant 10b undergoes a dealcoholization condensation reaction with the inorganic filler 20 to form a modified inorganic filler 20b'.

[0047] In this embodiment, the inorganic-philic ends 11 b of the dispersants 10 b also undergo a dealcoholization condensation reaction with each other, so that the dispersants 10 b are connected with each other.

[0048] Next, the epoxy resin 30 is mixed with the modified inorganic filler 20b' (eg Figure 1 Step S2). The epoxy resin 30 and the organophilic end 12b of the dispersant 10b both include epoxy groups, so the modified inorganic filler 20b' has good compatibility with the epoxy resin 30, so that the modified inorganic filler 20b' can be evenly dispersed in the epoxy resin 30. In this embodiment, the epoxy groups of the organophilic end 12b of the epoxy resin 30 and the dispersant 10b both include three-membered rings, but the present invention is not limited to this. In other embodiments, the epoxy groups of the organophilic end 12b of the epoxy resin 30 and the dispersant 10b include three-membered rings, four-membered rings or five-membered rings. In some embodiments, the epoxy resin 30 and the organophilic end 12b of the dispersant 10b include different epoxy groups.

[0049] Figure 5 is a schematic diagram of a method for manufacturing a resin composition according to an embodiment of the present invention. It must be noted that: Figure 5 The implementation examples are used Figure 1 Please refer to the examples of Figure 5 In this embodiment, the dispersant 10c is represented by the chemical structure (4). The dispersant 10c has an inorganic-philic end 11c and an organic-philic end 12c.

[0050] First, the dispersant 10c is mixed with the inorganic filler 20 (eg Figure 1 In step S1), the inorganic end 11c of the dispersant 10c undergoes a dealcoholization condensation reaction with the inorganic filler 20 to form a modified inorganic filler 20c'.

[0051] Next, the epoxy resin 30 is mixed with the modified inorganic filler 20c' (eg Figure 1Step S2). The epoxy resin 30 includes epoxy groups and the organophilic end 12b of the dispersant 10c includes carbonyl groups, so the modified inorganic filler 20c′ has good compatibility with the epoxy resin 30, so that the modified inorganic filler 20c′ can be uniformly dispersed in the epoxy resin 30.

Claims

1. A method for producing a resin composition, comprising: Mixing an inorganic filler, a first solvent and a dispersant, wherein the material of the dispersant is silane and / or polysiloxane including an organophilic end and an inorganic end, and the dispersant and the inorganic filler undergo a dealcoholization condensation reaction to form a dispersion liquid including the modified inorganic filler, wherein the organophilic end includes a carbonyl group, an epoxy group and / or an amine group: and Epoxy resin is dissolved in the dispersion.

2. The method for producing a resin composition according to claim 1, wherein the organophilic end of the material of the dispersant comprises an amine group, and the epoxy group of the epoxy resin undergoes a ring-opening reaction and cross-links with the amine group of the organophilic end.

3. The method for producing a resin composition according to claim 1, further comprising: The second solvent, the epoxy resin, the plasticizer and the accelerator are added into the dispersion. 4 . The method for producing a resin composition according to claim 3 , wherein after the second solvent, the epoxy resin and the accelerator are added to the dispersion, a hardener and / or a cross-linking agent is added. 5 . The method for producing a resin composition according to claim 4 , wherein the first solvent comprises at least one of butanone, cyclohexanone, and propylene glycol methyl ether, and the second solvent comprises at least one of toluene, butanone, and cyclohexanone.

6. The method for producing a resin composition according to claim 1, wherein the material of the dispersant is represented by any one of the following chemical structures (1) to (4): In the chemical structure (1), R1 and R2 are each independently a methyl group or an ethyl group, R3 is a long carbon chain having 2 to 6 carbon atoms, an ether group, or a phenyl group, R4 is an alkyl group having 1 to 3 carbon atoms, R5 and R6 are each independently a methyl group or an ethyl group, a is a positive integer, and b is a positive integer; In the chemical structure (2), R1 and R2 are each independently a methyl group or an ethyl group, R3 is a long carbon chain having 2 to 6 carbon atoms, an ether, or a phenyl group, R4 is an alkyl group having 1 to 3 carbon atoms, R5 and R6 are each independently a methyl group or an ethyl group, a is a positive integer, and b is a positive integer; as well as 7 . The method for producing a resin composition according to claim 1 , wherein the epoxy resin comprises at least one of a naphthalene epoxy resin, a phenolic epoxy resin, an ester epoxy resin, and a bisphenol F epoxy resin. 8 . The method for producing a resin composition according to claim 1 , wherein the content of the dispersant is 0.1 to 1.5 parts by weight based on 100 parts by weight of the inorganic filler. 9 . The method for producing a resin composition according to claim 1 , wherein the content of the epoxy resin is 8 to 55 parts by weight based on 100 parts by weight of the inorganic filler. 10 . The method for producing a resin composition according to claim 1 , wherein the inorganic filler comprises silicon oxide.

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