Method for producing resin composition
The use of a silane and polysiloxane dispersant with affinity ends addresses the dispersion challenge, achieving uniform inorganic filler distribution and improved resin properties for copper-clad laminates.
Patent Information
- Application Number
- JP2023207315
- Authority / Receiving Office
- JP · JP
- Patent Type
- Applications
- Current Assignee / Owner
- Priority Date
- 2023-07-07
- Filing Date
- 2023-12-07
- Publication Date
- 2025-01-21
- Estimated Expiration
- Not applicable · inactive patent
AI Technical Summary
Existing methods face challenges in uniformly dispersing inorganic fillers in resin materials due to their small particle size and the high viscosity of the resin, which affects the uniformity and performance of copper-clad laminates.
A method involving the use of a silane and/or polysiloxane dispersant with organic and inorganic affinity ends to form a dispersion through a dealcoholization condensation reaction, followed by mixing with an epoxy resin to achieve uniform dispersion of inorganic fillers.
The method ensures uniform dispersion of inorganic fillers, enhancing mechanical strength and thermal stability of resin compositions, resulting in improved copper-clad laminates with low water absorption and high glass transition temperature.
Smart Images
Figure 2025010463000001_ABST
Abstract
Description
[Technical field]
[0001] The present invention relates to a method for producing a resin composition. [Background technology]
[0002] A copper-clad laminate is an electronic component board that is made up of multiple insulating layers and copper foil layers stacked alternately. Typically, copper-clad laminates use a special resin material as the insulating layer, and use electroforming technology to form conductive holes that pass through the insulating layer to electrically connect the copper foil of different layers.
[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 the resin material to improve the mechanical strength, thermal stability and other properties of the resin material. However, due to the small particle size of the inorganic filler and the high viscosity of the resin, it is difficult to uniformly disperse the inorganic filler in the resin. Summary of the Invention [Problem to be solved by the invention]
[0004] The present invention provides a method for producing a resin composition capable of improving the uniformity of an inorganic filler. [Means for solving the problem]
[0005] At least one embodiment of the present invention provides a method for producing a resin composition, comprising the steps of: mixing an inorganic filler, a first solvent, and a dispersant; the material of the dispersant is a silane and / or polysiloxane having an organophilic end and an inorganic affinity end, and the dispersant and the inorganic filler undergo an alcoholysis condensation reaction to form a dispersion containing a modified inorganic filler; the organophilic end includes a carbonyl group, an epoxy group, and / or an amino group; and dissolving an epoxy resin in the dispersion. Effect of the Invention
[0006] The method for producing a resin composition of the present invention can uniformly disperse the inorganic filler in the resin. [Brief description of the drawings]
[0007] [Figure 1] FIG. 1 is a schematic diagram of a method for producing a resin composition according to one embodiment of the present invention. [Diagram 2] FIG. 1 is a schematic diagram of a method for producing a resin composition according to one embodiment of the present invention. [Diagram 3] FIG. 1 is a schematic diagram of a method for producing a resin composition according to one embodiment of the present invention. [Figure 4] FIG. 1 is a schematic diagram of a method for producing a resin composition according to one embodiment of the present invention. [Diagram 5] FIG. 1 is a schematic diagram of a method for producing a resin composition according to one embodiment of the present invention. DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENTS
[0008] Fig. 1 is a schematic diagram of a method for producing a resin composition according to one embodiment of the present invention. Referring to Fig. 1, in step S1, an inorganic filler, a first solvent, and a dispersant are mixed. For example, the inorganic filler, the first solvent, and the dispersant are mixed using a bead mill, a flowjet mixer, a high-speed impeller, a high-pressure wet atomizer, a ball mill, a paint shaker, a microfluidizer, ultrasonic dispersion, a sand mill, a roller mill, a sander, a high-speed homogenizing mixer, etc. to form a dispersion.
[0009] In some embodiments, the dispersion contains 53% to 80% by weight of inorganic filler, 19.9% to 45% by weight of a first solvent, and 0.1% to 2.0% by weight of a dispersant. In some embodiments, the content of the dispersant is 0.125 parts by weight to 3.773 parts by weight per 100 parts by weight of the inorganic filler.
[0010] In some embodiments, the first solvent comprises at least one of butanone, cyclohexanone, and propylene glycol methyl ether, or combinations thereof, and other solvents.
[0011] In some embodiments, the inorganic filler includes silicon oxide (SiOx), such as spherical silicon oxide, silicon flakes, or other types of silicon oxide. In some embodiments, the average particle size of the spherical silicon oxide is 0.1 μm to 1.2 μm.
[0012] The dispersant material includes a silane and / or polysiloxane having an organophilic end and an inorganic affinity end. The organophilic end includes a carbonyl group, an epoxy group, and / or an amine group, and the inorganic affinity end includes a group capable of dealcoholizing and condensing with the epoxy group. For example, the dispersant material is represented by any of the following chemical structures (1) to (4).
[0013] [ka]
[0014] In chemical structure (1), R1 and R2 are each independently a methyl or ethyl group, R3 is a long carbon chain having 2 to 6 carbons, an ether group, or a phenyl group, R4 is an alkyl group having 1 to 3 carbons, R5 and R6 are each independently a methyl or ethyl group, a is a positive integer, and b is a positive integer.
[0015] [ka]
[0016] In 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 carbons, an ether group, or a phenyl group, R4 is an alkyl group having 1 to 3 carbons, R5 and R6 are each independently a methyl group or an ethyl group, a is a positive integer, and b is a positive integer.
[0017] [ka]
[0018] In step S1, the dispersant and the inorganic filler undergo a dealcoholization condensation reaction to form a dispersion containing a modified inorganic filler.
[0019] Next, referring to step S2, the epoxy resin is dissolved in the dispersion. In some embodiments, the second solvent, the epoxy resin, the plasticizer, and the accelerator are selectively added together to the dispersion, and then mixed using a bead mill, a flow jet mixer, a high-speed impeller, a high-pressure wet atomizer, a ball mill, a paint shaker, a microfluidizer, an ultrasonic disperser, a sand mill, a roller mill, a sander, a high-speed homogenizing mixer, etc. to form a slurry.
[0020] In some embodiments, the slurry includes 49.6 wt% to 74.87 wt% of the dispersion liquid, 11.9 wt% to 37.17 wt% of the second solvent, 2.65 wt% to 10.58 wt% of the epoxy resin, 2.65 wt% to 10.58 wt% of the plasticizer, and 0.05 phr to 0.8 phr of the accelerator. In some embodiments, the content of the epoxy resin is 7 parts by weight to 27 parts by weight per 100 parts by weight of the inorganic filler. In some embodiments, the content of the plasticizer is 7 parts by weight to 27 parts by weight per 100 parts by weight of the inorganic filler.
[0021] In some embodiments, the second solvent comprises at least one of toluene, butanone, cyclohexanone, or a combination thereof, and other solvents. The second solvent is used to adjust the solids content and viscosity of the slurry.
[0022] In some embodiments, the epoxy resin comprises at least one of naphthalene ring epoxy resin, novolac epoxy resin, ester epoxy resin, and bisphenol F epoxy resin. In some embodiments, when the organophilic end of the dispersant material comprises an amine group, the epoxy group of the epoxy resin undergoes a ring-opening reaction to crosslink 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 affinity end of the dispersant is connected to the inorganic filler, so that the modified inorganic filler (including the inorganic filler and the dispersant located on its surface) is uniformly dispersed. In some embodiments, when the organophilic end of the dispersant material comprises a carbonyl group or an epoxy group, the epoxy group of the dispersant has favorable compatibility with the epoxy resin, so that the modified inorganic filler is favorably dispersed and does not easily aggregate in the epoxy resin.
[0023] In the embodiment described herein, the epoxy resin is dissolved in the dispersion after the dispersion containing the modified inorganic filler is formed. If the inorganic filler is directly mixed with the epoxy resin, it is difficult for the inorganic filler to be completely dispersed due to the high viscosity of the epoxy resin. In addition, the organophilic and inorganic affinity ends of the dispersant can reduce the probability of the inorganic filler agglomerating. Therefore, the embodiment described herein can sufficiently improve the uniformity of the inorganic filler. For example, the inorganic filler in the slurry can be kept in suspension even after being left for 48 hours.
[0024] In some embodiments, the plasticizer comprises at least one of the following materials: bismaleimide resins, amine polymers, epoxy-based polymers, etc. In some embodiments, the accelerator comprises at least one of the following materials: imidazole accelerators, phosphorus-based accelerators, etc.
[0025] In some embodiments, other types of silanes may be additionally added to the dispersion in step S2. The silanes used here are used to improve adhesion between the subsequently formed coating of the resin composition and the substrate, and may include materials different from the silanes used in the dispersion. For example, the silanes added in step S2 may not include an organophilic end and an inorganic affinity end. For example, the silanes added in step S2 may include at least one of materials such as epoxy functional groups and amine functional groups.
[0026] Referring to step S3, after the second solvent, epoxy resin, and accelerator are added to the dispersion, a curing agent and / or crosslinking agent is added to the slurry. After mixing, the slurry is applied onto a substrate to form a coating of the resin composition.
[0027] In some embodiments, the amount of the curing agent is 3 parts by weight to 20 parts by weight per 100 parts by weight of the epoxy resin. In some embodiments, the amount of the crosslinking agent is 20 parts by weight to 70 parts by weight per 100 parts by weight of the epoxy resin.
[0028] In some embodiments, the curing agent comprises at least one of the following materials: ester curing agents, amine curing agents, phenolic curing agents, etc. In some embodiments, the crosslinking agent comprises at least one of the following materials: tertiary amines, benzoxazine resins, aromatic amines, etc.
[0029] In some embodiments, the inorganic filler is uniformly dispersed within the resin composition coating, such that the resin composition coating has a high glass transition temperature (e.g., higher than 320° C.), a low coefficient of thermal expansion (e.g., lower than 4 ppm / ° C.), and a low water absorption rate (e.g., 0.45% or less).
[0030] Table 1 provides a comparison of the properties of the coating of the slurry and resin composition obtained in Examples 1 to 4 of the present invention and Comparative Example 1. In Examples 1 to 4, a dispersion containing a dispersant, a first solvent, and an inorganic filler was first formed, and then the resin material and the dispersion were mixed to form a slurry. However, in Comparative Example 1, the inorganic filler was directly mixed with the resin material. In Table 1, the sample after the pressure cooker test (PCT) saturated steam test was immersed in a tin furnace at 288°C. No delamination for 10 minutes means that the heat resistance passed the standard.
[0031] [Table 1]
[0032] As can be seen from Table 1, the coatings of the resin compositions obtained in Examples 1 to 4 have low water absorption rates, and the suspension of the solid composition in the slurry is preferable. In addition, in Examples 1 to 4, the resin compositions obtained in Examples 1 and 3 have low water absorption rates, and the resin compositions obtained in Examples 1 and 2 have high Tg. In Comparative Example 1 to Example 4, it can be seen that the dispersant material to which the chemical structure (1) is added is preferable, and the obtained resin has the advantages of low water absorption rate and high Tg at the same time. This is because the dispersant of chemical structure 1 has a preferable crosslinking with the inorganic filler and the resin.
[0033] Fig. 2 is a schematic diagram of a method for producing a resin composition according to one embodiment of the present invention. It should be noted that the embodiment of Fig. 2 inherits part of the content of the embodiment of Fig. 1. Referring to Fig. 2, in this embodiment, a dispersant 10 is represented by a chemical structure (1). The dispersant 10 has an inorganic affinity end 11 and an organic affinity end 12.
[0034] First, the dispersant 10 and the inorganic filler 20 are mixed (see step S1 in FIG. 1). The inorganic affinity end 11 of the dispersant 10 and the inorganic filler 20 undergo a dealcoholization condensation reaction to form a modified inorganic filler 20'.
[0035] Next, the epoxy resin 30 and the modified inorganic filler 20' are mixed (see step S2 in FIG. 1). The epoxy groups of the epoxy resin 30 undergo a ring-opening reaction to crosslink with the amine groups of the organophilic ends 12.
[0036] 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.
[0037] Fig. 3 is a schematic diagram of a method for producing a resin composition according to one embodiment of the present invention. It should be noted that the embodiment of Fig. 3 inherits part of the content of the embodiment of Fig. 1. Referring to Fig. 3, in this embodiment, a dispersant 10a is represented by chemical structure (2). The dispersant 10a has an inorganic affinity end 11a and an organic affinity end 12a.
[0038] First, the dispersant 10a and the inorganic filler 20 are mixed (see step S1 in FIG. 1). The inorganic affinity end 11a of the dispersant 10a and the inorganic filler 20 undergo a dealcoholization condensation reaction to form a modified inorganic filler 20a'.
[0039] Next, the epoxy resin 30 and the modified inorganic filler 20a' are mixed (see step S2 in FIG. 1). Since both the epoxy resin 30 and the organophilic end 12a of the dispersant 10a contain epoxy groups, the modified inorganic filler 20a' has favorable compatibility with the epoxy resin 30, so that the modified inorganic filler 20a' can be uniformly dispersed in the epoxy resin 30. In this embodiment, the epoxy groups of the epoxy resin 30 and the organophilic end 12a of the dispersant 10a both contain three-membered rings, but the present invention is not limited thereto. In other embodiments, the epoxy groups of the epoxy resin 30 and the organophilic end 12a of the dispersant 10a contain 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 contain different epoxy groups.
[0040] Fig. 4 is a schematic diagram of a method for producing a resin composition according to one embodiment of the present invention. It should be noted that the embodiment of Fig. 4 inherits part of the content of the embodiment of Fig. 1. Referring to Fig. 4, in this embodiment, a dispersant 10b is represented by chemical structure (3). The dispersant 10b has an inorganic affinity end 11b and an organic affinity end 12b.
[0041] First, the dispersant 10b and the inorganic filler 20 are mixed (see step S1 in FIG. 1). The inorganic affinity end 11b of the dispersant 10b and the inorganic filler 20 undergo a dealcoholization condensation reaction to form a modified inorganic filler 20b'.
[0042] In this embodiment, the inorganic affinity ends 11b of the dispersants 10b also undergo a dealcoholization condensation reaction with each other, so that the dispersants 10b are connected to each other.
[0043] Next, the epoxy resin 30 and the modified inorganic filler 20b' are mixed (see step S2 in FIG. 1). The epoxy resin 30 and the organophilic end 12b of the dispersant 10b both contain epoxy groups. Therefore, the modified inorganic filler 20b' has favorable compatibility with the epoxy resin 30, so that the modified inorganic filler 20b' can be uniformly dispersed in the epoxy resin 30. In this embodiment, the epoxy groups of the epoxy resin 30 and the organophilic end 12b of the dispersant 10b both contain three-membered rings, but the present invention is not limited thereto. In other embodiments, the epoxy groups of the epoxy resin 30 and the organophilic end 12b of 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.
[0044] Fig. 5 is a schematic diagram of a method for producing a resin composition according to one embodiment of the present invention. It should be noted that the embodiment of Fig. 5 inherits part of the content of the embodiment of Fig. 1. Referring to Fig. 5, in this embodiment, a dispersant 10c is represented by a chemical structure (4). The dispersant 10c has an inorganic affinity end 11c and an organic affinity end 12c.
[0045] First, the dispersant 10c and the inorganic filler 20 are mixed (see step S1 in FIG. 1). The inorganic affinity end 11c of the dispersant 10c and the inorganic filler 20 undergo a dealcoholization condensation reaction to form a modified inorganic filler 20c'.
[0046] Next, the epoxy resin 30 and the modified inorganic filler 20c' are mixed (see step S2 in FIG. 1). Since the epoxy resin 30 contains an epoxy group and the organophilic end 12b of the dispersant 10c contains a carbonyl group, the modified inorganic filler 20c' has favorable compatibility with the epoxy resin 30, so that the modified inorganic filler 20c' can be uniformly dispersed in the epoxy resin 30. [Industrial Applicability]
[0047] The method for producing a resin composition of the present invention can be applied to improve the uniformity of inorganic fillers, thereby enhancing properties such as mechanical strength and thermal stability of the resin material, and achieving the purpose of optimizing the copper-clad laminate. [Explanation of symbols]
[0048] S1, S2, S3 steps
Claims
1. Mixing an inorganic filler, a first solvent, and a dispersant, the material of the dispersant being a silane and / or polysiloxane containing an organophilic end and / or an inorganic affinity end, the dispersant and the inorganic filler undergo a dealcoholization condensation reaction to form a dispersion containing a modified inorganic filler, the organophilic end containing a carbonyl group, an epoxy group, and / or an amine group; dissolving an epoxy resin in the dispersion; A method for producing a resin composition comprising the steps of:
2. 2. The method of claim 1, wherein the organophilic end of the dispersant material comprises an amine group, and an epoxy group of the epoxy resin undergoes a ring-opening reaction to crosslink with the amine group of the organophilic end.
3. 10. The method of claim 1 further comprising adding a second solvent, the epoxy resin, a plasticizer, and an accelerator together to the dispersion.
4. The method for producing a resin composition according to claim 3, further comprising adding a curing agent and / or a crosslinking agent after adding the second solvent, the epoxy resin, and the accelerator to the dispersion.
5. The method for producing a resin composition according to claim 4, wherein the first solvent includes at least one of butanone, cyclohexanone, and propylene glycol methyl ether, and the second solvent includes 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). 【Chemistry 1】 (In chemical structure (1), R １ and R ２ are each independently a methyl group or an ethyl group, R ３ is a long carbon chain having 2 to 6 carbons, an ether group, and a phenyl group; R ４ is an alkyl group having 1 to 3 carbon atoms; R ５ and R ６ are each independently a methyl group or an ethyl group, a is a positive integer, and b is a positive integer. 【Chemistry 2】 (In chemical structure (2), R １ and R ２ are each independently a methyl group or an ethyl group, R ３ is a long carbon chain having 2 to 6 carbons, an ether group, and a phenyl group; R ４ is an alkyl group having 1 to 3 carbon atoms; R ５ and R ６ are each independently a methyl group or an ethyl group, a is a positive integer, and b is a positive integer. 【Chemistry 3】
7. The method for producing a resin composition according to claim 1 , wherein the epoxy resin comprises at least one of a naphthalene ring epoxy resin, a novolac epoxy resin, an ester epoxy resin, and a bisphenol F epoxy resin.
8. 2. 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. 2. The method for producing a resin composition according to claim 1, wherein the content of the epoxy resin is 8 parts by weight to 55 parts by weight per 100 parts by weight of the inorganic filler.
10. The method for producing a resin composition according to claim 1 , wherein the inorganic filler contains silicon oxide.
Citation Information
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