Resin composition

Abstract

The invention provides a resin composition. The resin composition comprises epoxy resin, an active ester compound, free radical polymerization resin, an inorganic filling material and an accelerant. The radically polymerizable resin includes an olefin compound. The olefin compound comprises a methacrylic acid compound, a styrene compound, an allyl compound or a combination thereof.

Description

Technical Field

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

[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 be more suitable for application in high-frequency and high-speed transmission fields, the electrical requirements for resin composition have also been increasing. Summary of the Invention

[0003] The present invention provides a resin composition that can optimize the electrical properties of an epoxy resin system while simultaneously meeting the requirements for copper plating adhesion and film formation.

[0004] This invention discloses a resin composition comprising an epoxy resin, an active ester compound, a free radical polymerizable resin, an inorganic filler, and an accelerator. The free radical polymerizable resin includes olefin compounds. Olefin compounds include methacrylic acid compounds, styrene compounds, allyl compounds, or combinations thereof.

[0005] In one embodiment of the present invention, the free radical polymerizable resin is selected from at least two of methacrylic acid compounds, styrene compounds, and allyl compounds.

[0006] In one embodiment of the present invention, at least one of the above-mentioned free radical polymerizable resins is a methacrylic acid compound.

[0007] In one embodiment of the present invention, the weight percentage of the above-mentioned methacrylic acid compound in the resin composition is between 1 wt% and 10 wt%.

[0008] 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 free radical polymerizable 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 0.1 wt% to 0.5 wt% in the resin composition.

[0009] 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 inorganic filler material includes spherical silica, and the accelerator includes 4-dimethylaminopyridine.

[0010] 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, free radical polymerizable resin and accelerator used in the resin composition.

[0011] In one embodiment of the present invention, the amount of the free radical polymerizable resin used in the resin composition is greater than the amount of the accelerator used in the resin composition.

[0012] In one embodiment of the present invention, the amount of the free radical polymerizable resin used in the resin composition is less than the amount of epoxy resin used in the resin composition.

[0013] In one embodiment of the present invention, the olefinic compounds mentioned above include methacrylate polyphenylene ether resin, hydrogenated styrene elastomer, vinyl benzyl polyphenylene ether resin, hydrocarbon resin, polybutadiene resin, or combinations thereof.

[0014] Based on the above, the present invention reduces the number of polar functional groups in the epoxy resin system by introducing a free radical polymerizable resin into the resin composition. In this way, the dielectric properties can be effectively reduced, thus optimizing the electrical performance of the epoxy resin system and simultaneously meeting the requirements of copper plating adhesion and film formation.

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

[0016] In the following detailed description, exemplary embodiments disclosing specific details are set forth for illustrative purposes and not for limitation, in order 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, free radical polymerizable resin, inorganic filler, and accelerator. Further, the free radical polymerizable resin includes olefin compounds (with unsaturated bonds), wherein the olefin compounds include methacrylic acid compounds, styrene compounds, allyl compounds, or combinations thereof. Accordingly, this embodiment, by incorporating a free radical polymerizable resin into the resin composition, reduces the number of polar functional groups in the epoxy resin system. This effectively reduces dielectric properties, thus optimizing the electrical performance of the epoxy resin system while simultaneously meeting the requirements for copper plating adhesion and film formation.

[0020] In some embodiments, the olefinic compound includes methacrylate polyphenylene ether resin, hydrogenated styrene elastomer, vinyl benzyl polyphenylene ether resin, hydrocarbon resin, polybutadiene resin, or combinations thereof, but the invention is not limited thereto.

[0021] In some embodiments, the free radical polymerizable resin is selected from at least two of methacrylic compounds, styrene compounds, and allyl compounds to have superior dielectric properties, but the present invention is not limited thereto.

[0022] In some embodiments, at least one of the free radical polymerizable resins is a methacrylic acid compound, such as polyphenylene methacrylate resin, and the weight percentage of the methacrylic acid compound in the resin composition is between 1 wt% and 10 wt% (e.g., 1 wt%, 3 wt%, 5 wt%, 10 wt%, or any suitable value between 1 wt% and 10 wt%), but the invention is not limited thereto.

[0023] In some embodiments, the free radical polymerizable resin accounts for a weight percentage of between 1 wt% and 20 wt% in the resin composition (e.g., 1 wt%, 5 wt%, 10 wt%, 15 wt%, 20 wt%, or any suitable value between 1 wt% and 20 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 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.

[0027] 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.

[0028] 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.

[0029] 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 0.0025. 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.

[0030] In some embodiments, the accelerator includes 4-dimethylaminopyridine, wherein the accelerator is present in a weight percentage between 0.1 wt% and 0.5 wt% of the resin composition, but the invention is not limited thereto.

[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, free radical polymerizable resin and accelerator used in the resin composition, but the present invention is not limited thereto.

[0032] In some embodiments, the amount of free radical polymerizable resin used in the resin composition is greater than the amount of accelerator used in the resin composition and / or the amount of free radical polymerizable resin used in the resin composition is less than the amount of epoxy resin used in the resin composition, but the present invention is not limited thereto.

[0033] In some embodiments, the total weight ratio of epoxy resin, reactive ester compound, free radical polymerizable resin, inorganic filler and accelerator 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] Copper cladding adhesion: Evaluation substrate A obtained after vacuum lamination and heat curing as described above, ◎: can be stably bonded without falling off, X: falls off after baking.

[0042] Film-forming properties: The resin composition is mixed in a solvent (65 wt% solid weight), and coated onto a support (PET film) using a die coater. After drying to form a film, it is placed at 200℃ for 90 minutes. ◎: A complete film surface can be obtained after curing. X: A complete film surface cannot be obtained after curing.

[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 transfer temperature, coefficient of thermal expansion, dielectric constant, and dielectric loss were evaluated. Copper adhesion and film-forming properties were also tested in the manner described above. The results are detailed in Table 1. Comparing the results of Examples 1-5 and Comparative Example 1 in Table 1, the following conclusions can be drawn: Examples 1-5, which use free radical polymerizable resins, can optimize the electrical properties of the epoxy resin system and simultaneously meet the requirements for copper adhesion and film-forming properties compared to Comparative Example 1.

[0045] Table 1

[0046]

[0047] In summary, this invention reduces the number of polar functional groups in the epoxy resin system by introducing a free radical polymerizable resin into the resin composition. This effectively reduces the dielectric properties, thereby optimizing the electrical performance of the epoxy resin system while simultaneously meeting the requirements for copper plating adhesion and film formation.

[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; Free radical polymerizable resins, including olefin compounds, wherein the olefin compounds include methacrylic acid compounds, styrene compounds, allyl compounds, or combinations thereof; Inorganic filler materials; and Accelerator.

2. The resin composition according to claim 1, characterized in that, The free radical polymerizable resin is selected from at least two of the methacrylic acid compounds, the styrene compounds, and the allyl compounds.

3. The resin composition according to claim 1, characterized in that, At least one of the free radical polymerizable resins is a methacrylic acid compound.

4. The resin composition according to claim 3, characterized in that, The methacrylic acid compound is present in the resin composition at a weight ratio between 1 wt% and 10 wt%.

5. 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 free radical polymerizable resin accounts for 1 wt% to 20 wt% of the resin composition by weight, and the accelerator accounts for 0.1 wt% to 0.5 wt% of the resin composition by weight.

6. 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 inorganic filler material includes spherical silica, and the accelerator includes 4-dimethylaminopyridine.

7. 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 free radical polymerizable resin, and the accelerator used in the resin composition.

8. The resin composition according to claim 1, characterized in that, The amount of the free radical polymerizable resin used in the resin composition is greater than the amount of the accelerator used in the resin composition.

9. The resin composition according to claim 1, characterized in that, The amount of the free radical polymerizable resin used in the resin composition is less than the amount of the epoxy resin used in the resin composition.

10. The resin composition according to claim 1, characterized in that, The olefin compounds include methacrylate polyphenylene ether resin, hydrogenated styrene elastomer, vinyl benzyl polyphenylene ether resin, hydrocarbon resin, polybutadiene resin, or combinations thereof.

Images