Resin composition

Abstract

To provide a resin composition having excellent performance in both electrical characteristic and crack resistance.SOLUTION: A resin composition includes an epoxy resin, an active ester compound, an acrylic ester resin, an inorganic filler, and an accelerator. The accelerator includes a first compound and a second compound. The first compound and the second compound are different in curing temperature. Both of the first compound and the second compound are any one selected from pyridine compounds and imidazole compounds.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). Furthermore, many current resin compositions combine epoxy resins with ester-based cured resin compositions to reduce dielectric properties. However, these resin compositions tend to become brittle after curing, making them prone to cracking. Summary of the Invention [Problem to be solved by the invention]

[0003] However, this resin composition is prone to becoming brittle after curing, and is prone to cracking.

[0004] The present invention provides a resin composition that has excellent performance in both electrical properties and crack resistance. [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 accelerator includes a first compound and a second compound. The first compound and the second compound have different curing temperatures, and both the first compound and the second compound are selected from pyridine compounds and imidazole compounds.

[0006] 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%.

[0007] In one embodiment of the present invention, when the first compound and the second compound are both 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%.

[0008] In one embodiment of the present invention, the weight percentage of the epoxy resin in the above-mentioned 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 acrylic ester resin in the resin composition is between 1 wt% and 20 wt%, and the weight percentage of the accelerator in the resin composition is between 0.01 wt% and 0.3 wt%.

[0009] In one embodiment of the present invention, the epoxy resin includes a biphenyl aralkyl epoxy resin, a bisphenol A type epoxy resin, or a combination thereof, the active ester compound includes a polyester resin, the acrylic ester resin includes a polyphenylene ether methacrylate resin, and the inorganic filler includes spherical silica.

[0010] 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, acrylic ester resin and accelerator used in the resin composition.

[0011] In one embodiment of the present invention, the amount of accelerator used in the resin composition is less than the amounts of epoxy resin, active ester compound and acrylic ester used in the resin composition.

[0012] In one embodiment of the present invention, 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.

[0013] In one embodiment of the present invention, the pyridine compound includes 4-dimethylaminopyridine.

[0014] In one embodiment of the present invention, the imidazole compound includes 1-benzyl-2-phenylimidazole, 1-cyanoethyl-2-phenylimidazole, 2-heptadecylimidazole, or a combination thereof. [Effects of the Invention]

[0015] Based on the above, the present invention uses at least two accelerators with different curing temperatures to reduce the film formation rate (non-single film formation), allowing reactions to occur in various sections during the continuous temperature rise process of thermal curing, effectively improving the cracking condition, while still maintaining low dielectric properties. Thus, the resin composition of the present invention has excellent performance in both electrical properties and crack resistance.

[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 activated ester compound, an acrylic ester resin, an inorganic filler, and an accelerator. The accelerator further includes a first compound and a second compound. The first compound and the second compound have different curing temperatures, and both compounds are selected from pyridine compounds and imidazole compounds. Therefore, in this embodiment, at least two accelerators with different curing temperatures (e.g., not completely identical curing temperature ranges) are used to reduce the film formation rate (non-single film formation). This allows reactions to occur in various sections during the continuous temperature rise process of thermal curing, thereby improving the cracking condition. Furthermore, resin compositions containing these accelerators still have low dielectric properties. Thus, the resin composition of this embodiment exhibits excellent performance in both electrical properties and crack resistance.

[0021] 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, although the present invention is not limited thereto.

[0022] In some embodiments, when the first compound is a pyridine compound (e.g., 4-dimethylaminopyridine (DMAP) or a combination thereof) and the second compound is an imidazole compound (e.g., 1-benzyl-2-phenylimidazole (1B2PZ), 1-cyanoethyl-2-phenylimidazole (2PZ-CN), 2-heptadecylimidazole (C17Z), 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 problem of cracking due to rapid film formation at low temperatures can be improved while maintaining the high reactivity of the pyridine compound, but the present invention is not limited thereto.

[0023] In some embodiments, when the first compound and the second compound are both imidazole compounds (such as 1-benzyl-2-phenylimidazole, 1-cyanoethyl-2-phenylimidazole, 2-heptadecylimidazole, 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%, although the present invention is not limited thereto.

[0024] In some embodiments, the weight percentage of the accelerator (e.g., the total weight of the first compound and the second compound) in the resin composition is between 0.01 wt% and 0.3 wt%, although the present invention is not limited thereto.

[0025] In some embodiments, the epoxy resin comprises a biphenyl aralkyl epoxy resin (naphthylene ether epoxy resin), a bisphenol A type epoxy resin, or a combination thereof, wherein the weight percentage 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.

[0026] In some embodiments, the active ester compound comprises a polyester resin, wherein 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 invention is not limited thereto.

[0027] In some embodiments, the acrylate resin comprises a polyphenylene ether methacrylate resin, wherein the weight percentage of the acrylate resin in the resin composition is between 1 wt % and 20 wt % (e.g., 1 wt %, 3 wt %, 5 wt %, 7 wt %, 15 wt %, 20 wt %, or any suitable value between 1 wt % and 20 wt %), although the invention is not limited thereto.

[0028] In some embodiments, the inorganic filler comprises spherical silica, and the weight ratio of the inorganic filler in the resin composition is greater than 60 wt%, although the present invention is not limited thereto. Here, the median particle size (D 50 ) may be less than 1 micrometer, or any other suitable value.

[0029] In some embodiments, inorganic fillers are prepared by synthetic methods, such as, but not limited to, solid phase synthesis, to include epoxy or acrylic surface modifications to enhance performance.

[0030] In some embodiments, the purity of the inorganic filler is 99% or greater, although the invention is not limited in this respect.

[0031] In some embodiments, the specific surface area of ​​the inorganic filler is set to 4 m or less in order to control the contact area with the functional group in a more preferable range. 2 / g~6m 2 / g, and can maintain desirable low dielectric properties, for example, Dk between 3 and 3.3, Df not more than 0.003, but the present invention is not limited thereto, and the specific surface area of ​​the inorganic filler can be determined according to actual design requirements.

[0032] In some embodiments, the amount of inorganic filler used in the resin composition is greater than the amounts of epoxy resin, active ester compound, acrylic ester resin, and accelerator used in the resin composition, but the present invention is not limited thereto.

[0033] In some embodiments, the amount of accelerator used in the resin composition is less than the amounts of epoxy resin, active ester compound, and acrylic ester resin used in the resin composition, but the present invention is not limited thereto.

[0034] In some embodiments, the total weight percentage of the epoxy resin, active ester compound, acrylic ester resin, inorganic filler, and accelerator (e.g., the first compound and the second compound) in the resin composition is 100 wt %, but the present invention is not limited thereto.

[0035] The resin composition described above 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 a prepreg and a copper foil substrate (CCL) according to actual design requirements, and the specific embodiments described above do not limit the present invention.

[0036] 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.

[0037] The products of the examples and comparative examples were evaluated according to the following methods.

[0038] 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.

[0039] 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.

[0040] 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).

[0041] 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.

[0042] 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.

[0043] Crack resistance: After desmearing the substrate A, the evaluation substrate B was obtained and observed. ⊚: No cracks occurred. ×: Cracks larger than 0.2 cm occurred on the surface.

[0044] <Examples 1 to 5, Comparative Example 1>

[0045] The resin compositions shown in Table 1 were dissolved in solvents (toluene, methyl ethyl ketone, cyclohexanone), applied to a support (PET film) using a die coater, and dried to form a film layer. Properties such as glass transition temperature, thermal expansion coefficient, relative dielectric constant, and dielectric loss were evaluated, and crack resistance was tested using the methods described above. The results are shown in Table 1. Comparing the results of Examples 1 to 5 in Table 1 with those of Comparative Example 1, the following conclusion can be drawn. Examples 1 to 5, which use accelerators using at least two different curing temperatures, have superior performance in both electrical properties and crack resistance compared to Comparative Example 1.

[0046] [Table 1]

[0047] In summary, the present invention uses at least two accelerators with different curing temperatures to reduce the film formation rate (non-single film formation), allowing reactions to occur in various sections during the continuous temperature rise process of thermal curing, thereby improving the cracking condition, and the resin composition containing these accelerators still has low dielectric properties. Thus, the resin composition of the present invention has excellent performance in both electrical properties and crack resistance.

[0048] 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]

[0049] 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 acrylic ester resin; an inorganic filler; an accelerator comprising a first compound and a second compound, wherein the curing temperature of the first compound is different from the curing temperature of the second compound, and both the first compound and the second compound are either selected from a pyridine compound or an imidazole compound; A resin composition comprising:

2. When the first compound is the pyridine compound and the second compound is the 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 %. The resin composition according to claim 1.

3. When the first compound and the second compound are both 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 %. The resin composition according to claim 1.

4. 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 greater than 60 wt %, the weight percentage of the acrylic ester resin in the resin composition is between 1 wt % and 20 wt %, and the weight percentage of the accelerator in the resin composition is between 0.01 wt % and 0.3 wt %; The resin composition according to claim 1.

5. the epoxy resin includes a biphenyl aralkyl epoxy resin, a bisphenol A type epoxy resin, or a combination thereof, the active ester compound includes a polyester resin, the acrylic acid ester resin includes a methacrylic acid polyphenylene ether resin, and the inorganic filler includes spherical silica; The resin composition according to claim 1.

6. 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 acrylic ester resin, and the accelerator used in the resin composition; The resin composition according to claim 1.

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

8. 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; The resin composition according to claim 1.

9. The pyridine compound includes 4-dimethylaminopyridine. The resin composition according to claim 1.

10. The imidazole compound includes 1-benzyl-2-phenylimidazole, 1-cyanoethyl-2-phenylimidazole, 2-heptadecylimidazole, or a combination thereof. The resin composition according to claim 1.

Images