Resin composition

Abstract

The invention provides a resin composition. The resin composition comprises epoxy resin, an active ester compound, acrylate resin, an inorganic filling material and an accelerant. The accelerator includes a first compound and a second compound. The curing temperature of the first compound is different from the curing temperature of the second compound, and the first compound and the second compound are selected from any one of pyridine compounds and imidazole compounds.

Description

Technical Field

[0001] This invention relates to a resin composition. Background Art

[0002] In recent years, with the rapid development of integrated circuit (IC) technology, the requirements for wiring density (L / S) and transmission rate of chips (such as high-speed computing chips) have increased. In order to reduce dielectric properties, most current products are resin compositions of epoxy resin combined with ester curing agents. However, these resin compositions are prone to embrittlement after curing and have a tendency to crack (break). Summary of the Invention

[0003] The present invention provides a resin composition that exhibits excellent performance in both electrical properties and crack resistance.

[0004] This invention discloses a resin composition comprising an epoxy resin, an active ester compound, an acrylate resin, an inorganic filler, and an accelerator. The accelerator comprises a first compound and a second compound. The curing temperature of the first compound differs from that of the second compound, and both the first compound and the second compound are selected from pyridine compounds and imidazole compounds.

[0005] In one embodiment of the present invention, when the first compound is a pyridine compound and the second compound is an imidazole compound, the weight percentage of the first compound in the resin composition is between 0.01 wt% and 0.3 wt%, and the weight percentage of the second compound in the resin composition is between 0.01 wt% and 0.3 wt%.

[0006] In one embodiment of the present invention, when both the first compound and the second compound are imidazole compounds, the weight percentage of the first compound in the resin composition is between 0.01 wt% and 0.3 wt%, and the weight percentage of the second compound in the resin composition is between 0.01 wt% and 0.3 wt%.

[0007] In one embodiment of the present invention, the epoxy resin accounts for a weight percentage of 5 wt% to 15 wt% in the resin composition, the active ester compound accounts for a weight percentage of 10 wt% to 20 wt% in the resin composition, the inorganic filler accounts for a weight percentage of more than 60 wt% in the resin composition, the acrylate resin accounts for a weight percentage of 1 wt% to 20 wt% in the resin composition, and the accelerator accounts for a weight percentage of 0.01 wt% to 0.3 wt% in the resin composition.

[0008] In one embodiment of the present invention, the epoxy resin includes biphenyl aryl epoxy resin, bisphenol A epoxy resin or a combination thereof, the active ester compound includes polyester resin, the acrylate resin includes methacrylate polyphenylene ether resin, and the inorganic filler material includes spherical silica.

[0009] In one embodiment of the present invention, the amount of the inorganic filler material used in the resin composition is greater than the amount of epoxy resin, reactive ester compound, acrylate resin and accelerator used in the resin composition.

[0010] In one embodiment of the present invention, the amount of the accelerator used in the resin composition is less than the amount of epoxy resin, reactive ester compound and acrylate resin used in the resin composition.

[0011] In one embodiment of the present invention, the curing temperature of the first compound is between 60°C and 100°C, while the curing temperature of the second compound is between 100°C and 160°C.

[0012] In one embodiment of the present invention, the above-mentioned pyridine compounds include 4-dimethylaminopyridine.

[0013] In one embodiment of the present invention, the imidazole compounds described above include 1-benzyl-2-phenylimidazolium, 1-cyanoethyl-2-phenylimidazolium, 2-heptadecylimidazolium, or combinations thereof.

[0014] Based on the above, the present invention uses at least two accelerators with different curing temperatures to reduce the film-forming speed (non-one-time film formation), so that the reaction occurs in different ranges during the continuous heating process of thermosetting, thereby effectively improving the crack (breakage) situation. Moreover, the resin composition including these accelerators still has low dielectric properties. In this way, the resin composition of the present invention can have good performance in both electrical properties and crack resistance.

[0015] To make the above features and advantages of the present invention more apparent and understandable, specific embodiments are described in detail below. DETAILED DESCRIPTION

[0016] In the following detailed description, exemplary embodiments disclosing specific details are set forth for illustrative purposes and not for limitation, to provide a thorough understanding of the various principles of the invention. However, it will be apparent to those skilled in the art that, thanks to this disclosure, the invention can be practiced in other embodiments that depart from the specific details disclosed herein.

[0017] Unless otherwise stated, the term "between" used in this specification to define numerical ranges is intended to cover the range equal to and between the endpoint values. For example, a size range between a first value and a second value means that the size range can cover the first value, the second value, and any value between the first value and the second value.

[0018] Unless otherwise defined, all terms used herein (including technical and scientific terms) have the same meaning as commonly understood by one of ordinary skill in the art to which this invention pertains.

[0019] In this embodiment, the resin composition includes epoxy resin, reactive ester compound, acrylate resin, inorganic filler, and accelerator. Further, the accelerator includes a first compound and a second compound, wherein the curing temperature of the first compound is different from that of the second compound, and both the first and second compounds are selected from pyridine compounds and imidazole compounds. Accordingly, this embodiment uses at least two accelerators with different curing temperatures (e.g., curing temperature ranges are not completely identical) to reduce the film-forming rate (non-one-time film formation), ensuring that the reaction occurs in different ranges during the continuous heating process of thermosetting, thereby effectively improving the crack (breakage) situation. Furthermore, the resin composition including these accelerators still possesses low dielectric properties. Thus, the resin composition of this embodiment exhibits good performance in both electrical properties and crack resistance.

[0020] In some embodiments, the curing temperature of the first compound is between 60°C and 100°C, and the curing temperature of the second compound is between 100°C and 160°C, but the present invention is not limited thereto.

[0021] In some embodiments, when the first compound is a pyridine compound (such as 4-dimethylaminopyridine, the like, or a combination thereof) and the second compound is an imidazole compound (such as 1-benzyl-2-phenylimidazolium, 1-cyanoethyl-2-phenylimidazolium, 2-heptadecylimidazolium, the like, or a combination thereof), the weight percentage of the first compound in the resin composition is between 0.01 wt% and 0.3 wt%, and the weight percentage of the second compound in the resin composition is between 0.01 wt% and 0.3 wt%. In this way, the high reactivity of pyridine compounds can be maintained and the problem of cracking caused by rapid film formation at lower temperatures can be improved. However, the present invention is not limited thereto.

[0022] In some embodiments, when both the first compound and the second compound are imidazole compounds (such as 1-benzyl-2-phenylimidazolium, 1-cyanoethyl-2-phenylimidazolium, 2-heptadecylimidazolium, similar compounds, or combinations thereof), the weight percentage of the first compound in the resin composition is between 0.01 wt% and 0.3 wt%, and the weight percentage of the second compound in the resin composition is between 0.01 wt% and 0.3 wt%, but the present invention is not limited thereto.

[0023] In some embodiments, the accelerator (such as the total weight of the first compound and the second compound) is present in the resin composition at a weight ratio between 0.01 wt% and 0.3 wt%, but the invention is not limited thereto.

[0024] In some embodiments, the epoxy resin includes biphenyl aralkyl type epoxy resin (such as naphthylene ether type epoxy resin), bisphenol A type epoxy resin, or combinations thereof, wherein the epoxy resin accounts for a weight percentage of 5 wt% to 15 wt% in the resin composition (e.g., 5 wt%, 7 wt%, 10 wt%, 12 wt%, 15 wt%, or any suitable value between 5 wt% and 15 wt%), but the invention is not limited thereto.

[0025] In some embodiments, the active ester compound comprises a polyester resin, wherein the active ester compound is present in the resin composition in a weight percentage between 10 wt% and 20 wt% (e.g., 10 wt%, 12 wt%, 15 wt%, 17 wt%, 20 wt%, or any suitable value between 10 wt% and 20 wt%), but the invention is not limited thereto.

[0026] In some embodiments, the acrylate resin includes methacrylate polyphenylene ether resin, wherein the acrylate resin accounts for a weight percentage of 1 wt% to 20 wt% in the resin composition (e.g., 1 wt%, 3 wt%, 5 wt%, 7 wt%, 15 wt%, 20 wt%, or any suitable value between 1 wt% and 20 wt%), but the invention is not limited thereto.

[0027] In some embodiments, the inorganic filler material comprises spherical silica, wherein the inorganic filler material accounts for more than 60 wt% of the resin composition by weight, but the invention is not limited thereto. Here, the median particle size (D) of the inorganic filler material is... 50 It can be less than 1 micrometer or any other suitable value.

[0028] In some embodiments, the inorganic filler material is prepared by synthesis, which modifies its surface to contain epoxy groups or acrylic groups to improve its performance. The synthesis method is, for example, a solid-state synthesis method, but the invention is not limited thereto.

[0029] In some embodiments, the purity of the inorganic filler material is greater than or equal to 99%, but the present invention is not limited thereto.

[0030] In some embodiments, the specific surface area of ​​the inorganic filler material is between 4m². 2 / g to 6m 2 The specific surface area of ​​the inorganic filler material is controlled within a certain range to maintain its low dielectric properties, such as Dk being between 3 and 3.3 and Df being less than or equal to 0.003. However, the present invention is not limited to this. The specific surface area of ​​the inorganic filler material can be determined according to the actual design requirements.

[0031] In some embodiments, the amount of inorganic filler used in the resin composition is greater than the amount of epoxy resin, reactive ester compound, acrylate resin and accelerator used in the resin composition, but the invention is not limited thereto.

[0032] In some embodiments, the amount of accelerator used in the resin composition is less than the amount of epoxy resin, reactive ester compound and acrylate resin used in the resin composition, but the invention is not limited thereto.

[0033] In some embodiments, the total weight ratio of epoxy resin, reactive ester compound, acrylate resin, inorganic filler and accelerator (such as the first compound and the second compound) in the resin composition is 100 wt%, but the present invention is not limited thereto.

[0034] It should be noted that the above-mentioned resin composition can be considered as a non-volatile component of a resin composition (varnish-like) dissolved in a solvent, but the present invention is not limited thereto. Furthermore, the resin composition of the present invention can be processed into prepreg and copper foil substrate (CCL) according to actual design requirements, and the specific embodiments listed above are not limitations of the present invention.

[0035] The following embodiments and comparative examples are provided to illustrate the effects of the present invention, but the scope of the present invention is not limited to the scope of the embodiments.

[0036] The products of each embodiment and comparative example were evaluated according to the following method.

[0037] Glass transition temperature (Tg) (°C): The glass transition temperature Tg (°C) of the material was determined using a thermomechanical analyzer (TMA) according to the standard test method of ASTM E1545.

[0038] Coefficient of thermal expansion (CTE) (xy plane): The coefficient of thermal expansion of the material in the XY plane, i.e., XY CTE (ppm / ℃), was determined using a thermomechanical analyzer (TMA) according to the standard test method of IPC-TM-650 2.4.24. The test temperature range was 25℃~150℃.

[0039] Dielectric constant Dk / Dielectric loss Df: A resin film made using the resin composition in Table 1 was heated to 200°C for 90 minutes to form a cured film. The cured film was cut into pieces with a length of 10 mm and a width of 7 mm. The dielectric constant (Dk, εr) and dielectric loss (Df, Tanδ) of the material under a 10 GHz signal were determined according to the standard test method of IPC-TM-650 (Method 2.5.5.3).

[0040] Resin sheet lamination and curing: A glass cloth epoxy resin substrate with copper foil was prepared as the inner layer substrate, and copper lamination was applied to both sides (Nanya Corporation's "NPG-180INBK"). The surface copper foil of this inner layer substrate was roughened. Using a vacuum laminator (Nikko-Material Corporation's "V-130"), the resin composition was bonded to the inner layer substrate under the following conditions: pressure reduction to below 1 hPa for 30 seconds, followed by pressing for 60 seconds at 100°C and 100 N. Subsequently, it was placed in an oven at 130°C for 30 minutes, and then transferred to an oven at 165°C for 30 minutes. Through the above heating, the resin composition was cured to obtain substrate A.

[0041] Resin residue removal treatment: To roughen the cured resin substrate, substrate A was immersed in DuPont's Sweller 7810 at 70°C for 10 minutes. Next, it was immersed in DuPont's Promoter 7820 at 85°C for 10 minutes. Finally, it was immersed in DuPont's Neutralizer 7831 at 40°C for 5 minutes to obtain the evaluation substrate B after resin residue removal treatment.

[0042] Crack resistance: Substrate B was obtained after substrate A underwent a desmearing process. Substrate B was then observed. ◎: No cracks were generated. X: Cracks larger than 0.2 cm appeared on the surface.

[0043] <Examples 1-5, Comparative Example 1>

[0044] The resin compositions shown in Table 1 were dissolved in solvents (toluene, methyl ethyl ketone, cyclohexanone) and coated onto a support (PET film) using a die coater. After drying to form a film layer, properties such as glass transition temperature, coefficient of thermal expansion, dielectric constant, and dielectric loss were evaluated. Crack resistance tests were also performed in the manner described above, and the results are detailed in Table 1. Comparing the results of Examples 1-5 and Comparative Example 1 in Table 1, the following conclusion can be drawn: Examples 1-5, which used at least two accelerators with different curing temperatures, exhibited better performance in both electrical properties and crack resistance compared to Comparative Example 1.

[0045] Table 1

[0046]

[0047] In summary, by using at least two accelerators with different curing temperatures, the present invention reduces the film-forming rate (non-one-time film formation), allowing the reaction to occur in different ranges during the continuous heating process of thermosetting, thereby effectively improving the crack (breakage) situation. Furthermore, the resin composition including these accelerators still has low dielectric properties. In this way, the resin composition of the present invention can have good performance in both electrical properties and crack resistance.

[0048] Finally, it should be noted that the above embodiments are only used to illustrate the technical solutions of the present invention, rather than to limit it. Although the present invention has been described in detail with reference to the above embodiments, those skilled in the art should understand that they can still modify the technical solutions described in the above embodiments, or replace some or all of the technical features therein with equivalents. However, these modifications or replacements do not cause the essence of the corresponding technical solutions to deviate from the scope of the technical solutions of the embodiments of the present invention.

Claims

1. A resin composition, characterized in that, include: Epoxy resin; Active ester compounds; Acrylic resin; Inorganic filler materials; as well as The accelerator includes a first compound and a second compound, wherein the curing temperature of the first compound is different from that of the second compound, and both the first compound and the second compound are selected from either pyridine compounds or imidazole compounds.

2. The resin composition according to claim 1, characterized in that, When the first compound is a pyridine compound and the second compound is an imidazole compound, the weight percentage of the first compound in the resin composition is between 0.01 wt% and 0.3 wt%, and the weight percentage of the second compound in the resin composition is between 0.01 wt% and 0.3 wt%.

3. The resin composition according to claim 1, characterized in that, When both the first compound and the second compound are imidazole compounds, the weight percentage of the first compound in the resin composition is between 0.01 wt% and 0.3 wt%, and the weight percentage of the second compound in the resin composition is between 0.01 wt% and 0.3 wt%.

4. The resin composition according to claim 1, characterized in that, The epoxy resin accounts for 5 wt% to 15 wt% of the resin composition by weight, the active ester compound accounts for 10 wt% to 20 wt% of the resin composition by weight, the inorganic filler accounts for more than 60 wt% of the resin composition by weight, the acrylate resin accounts for 1 wt% to 20 wt% of the resin composition by weight, and the accelerator accounts for 0.01 wt% to 0.3 wt% of the resin composition by weight.

5. The resin composition according to claim 1, characterized in that, The epoxy resin includes biphenyl aryl epoxy resin, bisphenol A epoxy resin or a combination thereof, the active ester compound includes polyester resin, the acrylate resin includes methacrylate polyphenylene ether resin, and the inorganic filler material includes spherical silica.

6. The resin composition according to claim 1, characterized in that, The amount of the inorganic filler in the resin composition is greater than the amount of the epoxy resin, the active ester compound, the acrylate resin, and the accelerator used in the resin composition.

7. The resin composition according to claim 1, characterized in that, The amount of the accelerator used in the resin composition is less than the amount of the epoxy resin, the active ester compound, and the acrylate resin used in the resin composition.

8. The resin composition according to claim 1, characterized in that, The curing temperature of the first compound is between 60°C and 100°C, while the curing temperature of the second compound is between 100°C and 160°C.

9. The resin composition according to claim 1, characterized in that, The pyridine compounds include 4-dimethylaminopyridine.

10. The resin composition according to claim 1, characterized in that, The imidazole compounds include 1-benzyl-2-phenylimidazolium, 1-cyanoethyl-2-phenylimidazolium, 2-heptadecylimidazolium, or combinations thereof.

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