Resin composition

Abstract

To provide a resin composition having good performance with respect to copper foil adhesion and roughness.SOLUTION: Provided is a resin composition including an epoxy resin, an active ester compound, an acrylate resin, an inorganic filler material, and an accelerator, the inorganic filler material including a first filler and a second filler, the first filler having a first particle size, the second filler having a second particle size, the first particle size being greater than the second particle size, the second particle size being less than 100 nanometers, and a weight proportion of the second filler in the resin composition being between 1 wt.% and 10 wt.%.SELECTED DRAWING: None

Description

[Technical Field]

[0001] The present invention relates to a resin composition. [Background technology]

[0002] In recent years, with the rapid development of integrated circuit (IC) technology, there has been an increasing demand for higher wiring density (L / S) and higher transmission speeds for chips (such as high-speed computing chips). However, current low-roughness resin compositions have many problems, such as poor copper clad adhesion, making them unsuitable for high-frequency, high-speed transmission applications. Summary of the Invention [Problem to be solved by the invention]

[0003] However, current low-roughness resin compositions have many problems such as poor copper clad adhesion, making them unsuitable for high-frequency, high-speed transmission applications.

[0004] The present invention provides a resin composition that has good performance in terms of copper clad adhesion and roughness. [Means for solving the problem]

[0005] The resin composition of the present invention includes an epoxy resin, an active ester compound, an acrylate resin, an inorganic filler, and an accelerator. The inorganic filler includes a first filler and a second filler. The first filler has a first particle size. The second filler has a second particle size. The first particle size is larger than the second particle size, and the second particle size is less than 100 nanometers. The weight percentage of the second filler in the resin composition is between 1 WT% and 10 WT%.

[0006] In one embodiment of the present invention, the second particle size is equal to or greater than 0.01 micrometers.

[0007] In one embodiment of the present invention, the first particle size is between 0.1 micrometers and 0.6 micrometers.

[0008] In one embodiment of the present invention, the weight percentage of the first filler in the above-mentioned resin composition is between 60 wt% and 75 wt%.

[0009] In one embodiment of the present invention, the weight percentage of epoxy resin in the resin composition is between 5 wt% and 15 wt%, the weight percentage of active ester compound in the resin composition is between 10 wt% and 20 wt%, the weight percentage of inorganic filler in the resin composition is more than 60 wt%, the weight percentage of acrylate resin in the resin composition is between 1 wt% and 15 wt%, and the weight percentage of accelerator in the resin composition is between 0.1 wt% and 0.5 wt%.

[0010] In one embodiment of the present invention, the epoxy resin includes a naphthalene ring epoxy resin, a bisphenol A type epoxy resin, or a combination thereof, the active ester compound includes a polyester resin, the acrylate resin includes a polyphenylene ether methacrylate resin, the inorganic filler includes spherical silica, and the accelerator includes 4-dimethylaminopyridine.

[0011] In one embodiment of the present invention, the amount of the first filler used in the resin composition is greater than the amount of the second filler used in the resin composition.

[0012] In one embodiment of the present invention, the amount of inorganic filler used in the resin composition is greater than the amounts of epoxy resin, active ester compound, acrylate resin and accelerator used in the resin composition.

[0013] In one embodiment of the present invention, the amount of the active ester compound used in the resin composition is greater than the amount of the epoxy resin used in the resin composition.

[0014] In one embodiment of the present invention, the amount of acrylate resin used in the resin composition is greater than the amount of accelerator used in the resin composition. [Effects of the Invention]

[0015] Based on the above, the present invention introduces a small particle size filler to effectively reduce roughness in subsequent processes. At the same time, by combining two fillers with different particle sizes, the addition ratio of the small particle size filler can be controlled within an appropriate range, thereby maintaining adhesion between the entire inorganic filler and copper. In this way, the resin composition of the present invention has good performance in terms of both copper clad adhesion and roughness.

[0016] In order to make the above-mentioned features and advantages of the present invention more apparent and understandable, the following specific examples are described in detail below. DETAILED DESCRIPTION OF THE INVENTION

[0017] In the following detailed description, for purposes of illustration and not limitation, exemplary embodiments disclosing specific details are set forth in order to provide a thorough understanding of various principles of the present invention. However, it will be apparent to one skilled in the art having the benefit of this disclosure that the present invention may be practiced in other embodiments that depart from the specific details disclosed herein.

[0018] Unless otherwise specified, the term "between" when used herein to define a numerical range is intended to include ranges equal to and between the endpoints. For example, a size range between a first number and a second number means that the size range can encompass the first value, the second value, and any value between the first and second values.

[0019] Unless otherwise defined, all terms (including technical and scientific terms) used herein have the same meaning as commonly understood by one of ordinary skill in the art to which this invention belongs.

[0020] In this embodiment, the resin composition includes an epoxy resin, an active ester compound, an acrylate resin, an inorganic filler, and an accelerator. The inorganic filler further includes a first filler and a second filler, wherein the first particle size of the first filler is larger than the second particle size of the second filler, and the second particle size is less than 100 nanometers (nm). Therefore, the first filler can be considered to have a large particle size, and the second filler can be considered to have a small particle size. The weight percentage of the second filler in the resin composition is between 1 wt% and 10 wt% (e.g., 1 wt%, 3 wt%, 5 wt%, 7 wt%, 10 wt%, or any suitable value between 1 wt% and 10 wt%). Therefore, in this embodiment, a small particle size filler is introduced to effectively reduce roughness in subsequent processes (e.g., after a desmearing process). At the same time, by combining two types of fillers with different particle sizes, the addition ratio of the small particle size filler can be controlled within an appropriate addition ratio range, thereby maintaining adhesion between the entire inorganic filler and copper. In this way, the resin composition of this embodiment has good performance in terms of both copper clad adhesion and roughness. Here, the first particle size and / or the second particle size are the median particle size (D 50 )

[0021] For example, if the particle size of the filler is small, the pores generated after the desmearing process will be small, thereby effectively improving roughness. At the same time, if the weight ratio of the second filler in the resin composition is greater than 10 wt%, the problem of poor adhesion to copper is likely to occur. Therefore, controlling the addition ratio of the small particle size filler to between 1 wt% and 10 wt% can reduce the possibility of this problem occurring. Furthermore, the design of the resin composition of this embodiment can also significantly improve the suspension stability of the filler.

[0022] In some embodiments, the second particle size is 0.01 micrometers or greater, although the invention is not limited in this respect.

[0023] In some embodiments, the first particle size is between 0.1 micrometers and 0.6 micrometers, although the invention is not limited in this respect.

[0024] In some embodiments, the first filler and / or the second filler are prepared by a synthetic method to include an epoxy or acrylic surface modification to enhance performance, including, but not limited to, solid-phase synthesis methods well known to those skilled in the art.

[0025] In some embodiments, the purity of the first filler and / or the second filler is 99% or greater, although the invention is not limited in this respect.

[0026] In some embodiments, the specific surface area of ​​the first filler and / or the second filler is set to 4 m or less in order to control the contact area with the functional group within a preferred range. 2 / g~10m 2 / g, and desirable low dielectric properties can be maintained, for example, Dk between 3 and 3.3 and Df equal to or less than 0.003. However, the present invention is not limited thereto, and the specific surface area of ​​the first filler and / or the second filler can be determined according to actual design requirements.

[0027] In some embodiments, the weight percentage of the first filler in the resin composition is between 60 wt % and 75 wt %, but the present invention is not limited thereto.

[0028] In some embodiments, the amount of the first filler used in the resin composition is greater than the amount of the second filler used in the resin composition, although the invention is not limited in this respect.

[0029] In some embodiments, the inorganic filler (first filler and / or second filler) comprises spherical silica, and the weight proportion of the inorganic filler (total weight of the first filler and second filler, etc.) in the resin composition is greater than 60 wt%, although the present invention is not limited thereto.

[0030] In some embodiments, the amount of inorganic filler used in the resin composition is greater than the amounts of epoxy resin, active ester compound, acrylate resin, and accelerator used in the resin composition, but the invention is not limited thereto.

[0031] In some embodiments, the epoxy resin includes a naphthalene ring epoxy resin (such as a naphthylene ether type epoxy resin), a bisphenol A type epoxy resin, or a combination thereof, and the weight ratio of the epoxy resin in the resin composition is between 5 wt % and 15 wt % (e.g., 5 wt %, 7 wt %, 10 wt %, 12 wt %, 15 wt %, or any suitable value between 5 wt % and 15 wt %), but the present invention is not limited thereto.

[0032] In some embodiments, the active ester compound comprises a polyester resin, and the weight percentage of the active ester compound in the resin composition is 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 present invention is not limited thereto.

[0033] In some embodiments, the acrylate resin comprises a polyphenylene ether methacrylate resin, and the weight percentage of the acrylate resin in the resin composition is between 1 wt% and 15 wt% (e.g., 1 wt%, 3 wt%, 5 wt%, 7 wt%, 15 wt%, or any suitable value between 1 wt% and 15 wt%), although the invention is not limited thereto.

[0034] In some embodiments, the accelerator comprises 4-dimethylaminopyridine (DMAP), and the weight percentage of the accelerator in the resin composition is between 0.1 wt % and 0.5 wt %, although the invention is not limited thereto.

[0035] In some embodiments, the total weight percentage of the epoxy resin, active ester compound, acrylate resin, inorganic filler (such as the first filler and the second filler), and accelerator in the resin composition is 100 wt %, but the present invention is not limited thereto.

[0036] In some embodiments, the amount of active ester compound used in the resin composition is greater than the amount of epoxy resin used in the resin composition, and / or the amount of acrylate resin used in the resin composition is greater than the amount of accelerator used in the resin composition, but the invention is not limited in this respect.

[0037] The resin composition described above can be considered 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 prepregs and copper foil substrates (CCL) according to actual design requirements. The specific embodiments listed above are not intended to limit the present invention.

[0038] The effects of the present invention will be explained below with reference to examples and comparative examples, but the scope of the present invention is not limited to these examples.

[0039] The products of the examples and comparative examples were evaluated according to the following methods.

[0040] Glass transition temperature (Tg) (°C): The glass transition temperature Tg (°C) of the material was measured using a thermomechanical analyzer (TMA) according to the standard test method of ASTM E1545.

[0041] Coefficient of thermal expansion (CTE) (xy plane direction): The coefficient of thermal expansion in the XY plane of the material, i.e., XY CTE (ppm / °C), was measured using a thermomechanical analyzer (TMA) in accordance with the standard test method IPC-TM-650 2.4.24. The test temperature range was 25°C to 150°C.

[0042] Dielectric constant Dk / dielectric loss Df: A resin film made from the resin composition shown in Table 1 was heated at 200°C for 90 minutes to form a cured film. The cured film was cut into a size of 10 mm in length and 7 mm in width. The dielectric constant (Dk) and dissipation factor (Df) of the material under a 10 GHz signal were measured according to the standard test method of IPC-TM-650 (Method 2.5.5.3).

[0043] Lamination and curing of resin sheet material: A copper-clad glass cloth epoxy resin substrate was prepared as an inner layer substrate, covered on both sides with a copper-clad laminate ("NPG-180INBK" manufactured by Nanya Plastics Co., Ltd.), and the copper foil on the surface of this inner layer substrate was roughened. The resin composition and the inner layer substrate were bonded together using a vacuum laminator ("V-130" manufactured by Nikko Materials Co., Ltd.). The pressure was reduced to below 1 hPa for 30 seconds, followed by pressing at 100°C and 100N for 60 seconds. The resulting substrate was then heated in an oven at 130°C for 30 minutes, and then transferred to an oven at 165°C for 30 minutes. The resin composition cured as a result of the heating process, yielding Substrate A.

[0044] Copper clad adhesion: Evaluation substrate A obtained after the above-mentioned vacuum laminator and heat curing, ⊚: Stable adhesion without peeling, ×: Peeling after baking.

[0045] Desmear treatment: To roughen the surface of the cured resin sheet 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 evaluation substrate B after desmear treatment.

[0046] Roughness Ra: Using a laser confocal microscope (Keyence VK-X3000), evaluation substrate B was measured under a 50x lens, and 10 points were randomly selected to measure the arithmetic mean roughness Ra. Areas without values ​​represent areas where the roughness could not be measured after desmearing due to poor adhesion to copper.

[0047] Suspension stabilization time: A solvent was added to the resin composition and mixed thoroughly, and the resulting coating was allowed to stand. The presence or absence of obvious stratification / settling time was observed with the naked eye and recorded.

[0048] <Examples 1 to 2, Comparative Examples 1 to 4>

[0049] The resin compositions shown in Table 1 were dissolved in solvents (toluene, methyl ethyl ketone, cyclohexanone), applied to a support (PET film) using a slit die coater, and dried to form a film layer. Properties such as glass transition temperature, thermal expansion coefficient, dielectric constant, dielectric loss, and roughness were evaluated, and copper clad adhesion and suspension stability time were tested using the methods described above. The results are shown in Table 1. Comparing the results of Examples 1 and 2 with those of Comparative Examples 1 to 4 in Table 1, the following conclusions can be drawn. Examples 1 and 2, which use filler particles with particle sizes less than 100 nanometers and additive ratios between 1 wt% and 10 wt%, exhibit better performance in terms of both copper clad adhesion and roughness than Comparative Examples 1 to 4. Comparative Examples 1 to 3 did not use fillers with particle sizes less than 100 nanometers, and Comparative Example 4 used filler particles with additive ratios exceeding 10 wt%.

[0050] [Table 1]

[0051] In summary, the present invention introduces a small particle size filler to effectively reduce roughness in subsequent processes. At the same time, by combining two fillers with different particle sizes, the addition ratio of the small particle size filler can be controlled within an appropriate range, thereby maintaining adhesion between the inorganic filler and copper. In this way, the resin composition of the present invention has good performance in terms of both copper clad adhesion and roughness.

[0052] Although the present invention has been disclosed through the above embodiments, they are not intended to limit the present invention, and a person having ordinary skill in the relevant technical field can make some changes and modifications without departing from the spirit and scope of the present invention. The protection scope of the present invention shall be determined by the appended claims. [Industrial Applicability]

[0053] The resin composition of the present invention can be applied to the field of resin compositions.

Claims

1. Epoxy resin, an active ester compound; an acrylate resin; an inorganic filler comprising a first filler having a first particle size and a second filler having a second particle size, wherein the first particle size is larger than the second particle size and the second particle size is less than 100 nanometers, and the weight percentage of the second filler in the resin composition is between 1 wt% and 10 wt%; A promoter; A resin composition comprising:

2. The second particle size is 0.01 micrometers or more. The resin composition according to claim 1.

3. the first particle size is between 0.1 micrometers and 0.6 micrometers; The resin composition according to claim 1.

4. The weight ratio of the first filler in the resin composition is between 60 wt % and 75 wt %. The resin composition according to claim 1.

5. the weight percentage of the epoxy resin in the resin composition is between 5 wt% and 15 wt%, the weight percentage of the active ester compound in the resin composition is between 10 wt% and 20 wt%, the weight percentage of the inorganic filler in the resin composition is more than 60 wt%, the weight percentage of the acrylate resin in the resin composition is between 1 wt% and 15 wt%, and the weight percentage of the accelerator in the resin composition is between 0.1 wt% and 0.5 wt%; The resin composition according to claim 1.

6. The epoxy resin includes a naphthalene ring epoxy resin, a bisphenol A type epoxy resin, or a combination thereof, the active ester compound includes a polyester resin, the acrylate resin includes a methacrylic acid polyphenylene ether resin, the inorganic filler includes spherical silica, and the accelerator includes 4-dimethylaminopyridine. The resin composition according to claim 1.

7. The amount of the first filler used in the resin composition is greater than the amount of the second filler used in the resin composition. The resin composition according to claim 1.

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

9. the amount of the active ester compound used in the resin composition is greater than the amount of the epoxy resin used in the resin composition; The resin composition according to claim 1.

10. The amount of the acrylate resin used in the resin composition is greater than the amount of the accelerator used in the resin composition. The resin composition according to claim 1.

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