Resin composition

Abstract

To provide a resin composition which has good dielectric characteristics, peeling resistance, and heating resistance.SOLUTION: A resin composition contains a resin mixture (A), a liquid rubber resin (B), an inorganic filler (C), a catalyst (D), and a siloxane coupling agent (E). The resin mixture (A) contains a bismaleimide resin.SELECTED DRAWING: None

Description

[Technical Field]

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

[0002] In recent years, with the development of 5th Generation Mobile Network (5G) technology, the demand for copper-clad laminate materials capable of high-capacity data transmission has also increased. To achieve high-speed transmission, reducing the surface roughness of the copper foil (e.g., Rz less than 0.5 micrometers) can achieve good signal transmission performance at high frequencies. However, reducing the surface roughness of the copper foil can reduce the physical adhesion strength to the circuit board in the laminate structure (e.g., peel strength less than 2 lb / in). Therefore, a solution that can solve the above problems is urgently needed. Summary of the Invention [Problem to be solved by the invention]

[0003] The present invention provides a resin composition having good dielectric properties, peel resistance, and heat resistance. [Means for solving the problem]

[0004] The resin composition of the present invention comprises a resin mixture (A), a liquid rubber resin (B), an inorganic filler (C), a catalyst (D), and a siloxane coupling agent (E). The resin mixture (A) comprises a bismaleimide resin.

[0005] In one embodiment of the present invention, the bismaleimide resin comprises a bismaleimide-modified olefin-based resin, a bismaleimide-modified polyphenylene ether resin, a bismaleimide-modified dicyclopentadiene-based resin, or a combination thereof.

[0006] In one embodiment of the present invention, the bismaleimide resin further comprises a biphenyl-based bismaleimide resin.

[0007] In one embodiment of the present invention, the weight average molecular weight of the bismaleimide resin is 500 grams / mole (g / mol) to 5000 g / mol.

[0008] In one embodiment of the present invention, the amount of resin mixture (A) used is 10 to 30 parts by weight relative to 100 parts by weight of the total amount of the resin composition used.

[0009] In one embodiment of the present invention, the liquid rubber resin (B) comprises LDM-02, LF-310T50, COD-103, a divinylbenzene-containing polymer, or a combination thereof.

[0010] In one embodiment of the present invention, the inorganic filler (C) comprises silica.

[0011] In one embodiment of the present invention, the inorganic filler (C) comprises a surface-modified silica having an acrylic group or a vinyl group.

[0012] In one embodiment of the present invention, the inorganic filler (C) has a median particle size of 0.3 micrometers to 3.0 micrometers.

[0013] In one embodiment of the present invention, the siloxane coupling agent (E) comprises a vinyl silane compound, an acryl silane, or a combination thereof.

[0014] In one embodiment of the present invention, the amount of liquid rubber resin (B) used is 30 to 50 parts by weight, the amount of inorganic filler (C) used is 25 to 50 parts by weight, the amount of catalyst (D) used is 0.1 to 2 parts by weight, and the amount of siloxane coupling agent (E) used is 0.1 to 5 parts by weight, relative to 100 parts by weight of the total amount of the resin composition used. [Effects of the Invention]

[0015] Based on the above, the resin composition of the present invention comprises a resin mixture (A), a liquid rubber resin (B), an inorganic filler (C), a catalyst (D), and a siloxane coupling agent (E). Here, the resin mixture (A) contains a bismaleimide resin. This provides the resin composition with excellent dielectric properties, peel resistance, and heat resistance.

[0016] In order to make the above features and advantages of the present invention more clear and understandable, the following examples are given, the details of which are set forth below. DETAILED DESCRIPTION OF THE INVENTION

[0017] The following examples are provided to more specifically describe the contents of the present invention. The implementation details provided in the embodiments are for illustrative purposes only and are not intended to limit the scope of protection of the present invention. Anyone skilled in the art can modify or change these implementation details according to the needs of actual implementation.

[0018] In this specification, ranges expressed as "from one value to another value" are summary expressions to avoid listing every single value within the range in the specification. Therefore, the description of a particular numerical range includes any value within that numerical range and any smaller numerical range bounded by any value within that numerical range, just as if any value and any smaller numerical range were described in the description of the specification.

[0019] <Resin composition>

[0020] The present invention provides a resin composition comprising a resin mixture (A), a liquid rubber resin (B), an inorganic filler (C), a catalyst (D), and a siloxane coupling agent (E). The resin composition of the present invention may further contain other additives, if necessary. The various components described above are described in detail below.

[0021] Resin mixture (A)

[0022] The resin mixture (A) contains a bismaleimide (BMI) resin. The bismaleimide resin is not particularly limited, and an appropriate bismaleimide resin can be selected as needed. In this embodiment, the bismaleimide resin may include a bismaleimide-modified olefin-based resin, a bismaleimide-modified polyphenylene ether resin (PPE-BMI), a bismaleimide-modified dicyclopentadiene-based resin (DCPD-BMI), a combination thereof, or another appropriate bismaleimide resin.

[0023] The bismaleimide-modified olefin-based resin may include BMI-3000 (trade name; manufactured by DMI (Designer Molecules Inc.)) or other suitable bismaleimide-modified olefin-based resins.

[0024] The bismaleimide-modified polyphenylene ether resin may be the bismaleimide-modified polyphenylene ether resin disclosed in Taiwan Patent Registration No. I774559 or other suitable bismaleimide-modified polyphenylene ether resins. The entire disclosure of Taiwan Patent Registration No. I774559 is incorporated herein by reference. For example, the chemical structure of the bismaleimide-modified polyphenylene ether resin can be represented by the following formula (1):

[0025] [ka]

[0026] In formula (1), R may be a direct bond, a methylene group, an ethylene group, an isopropylene group, a 1-methylpropyl group, a sulfonyl group, or a fluorenyl group; n may represent an integer of 3 to 25, and is preferably an integer of 10 to 18.

[0027] The bismaleimide-modified dicyclopentadiene resin may be the bismaleimide-modified dicyclopentadiene resin disclosed in Taiwan Patent Application No. 112131621 or other suitable bismaleimide-modified dicyclopentadiene resins. The entire disclosure of Taiwan Patent Application No. 112131621 is incorporated herein by reference. For example, the chemical structure of the bismaleimide-modified dicyclopentadiene resin can be represented by the following formula (2):

[0028] [ka]

[0029] In formula (2), m may represent an integer of 0 to 18, and is preferably an integer of 2 to 10.

[0030] The bismaleimide resin may further include a biphenyl-based bismaleimide resin or other suitable maleimide resin. The biphenyl-based bismaleimide resin may include a fluorinated biphenyl-based bismaleimide resin. The biphenyl-based bismaleimide resin may include MIR-3000 (trade name; manufactured by Nippon Kayaku Co., Ltd.), MIR-5000 (trade name; manufactured by Nippon Kayaku Co., Ltd.), DI-0928 (trade name; manufactured by Shifeng Technology Co., Ltd.), DI-0929 (trade name; manufactured by Shifeng Technology Co., Ltd.), or other suitable maleimide resin.

[0031] In this embodiment, the bismaleimide resin preferably contains at least one selected from the group consisting of a bismaleimide-modified olefin resin, a bismaleimide-modified polyphenylene ether resin, and a bismaleimide-modified dicyclopentadiene resin. The bismaleimide resin preferably contains a bismaleimide-modified olefin resin and a bismaleimide-modified polyphenylene ether resin, and may further contain a bismaleimide-modified dicyclopentadiene resin. When the bismaleimide resin contains a bismaleimide-modified polyphenylene ether resin, the resin composition has good peel resistance. When the bismaleimide resin contains a bismaleimide-modified dicyclopentadiene resin, the resin composition has good heat resistance.

[0032] In this embodiment, the weight average molecular weight of the bismaleimide resin may be 500 g / mol to 5000 g / mol, and preferably 600 g / mol to 4000 g / mol.

[0033] The amount of resin mixture (A) used is 10 to 30 parts by weight, and preferably 16.5 to 23.4 parts by weight, relative to 100 parts by weight of the total amount of the resin composition used.

[0034] Liquid rubber resin (B)

[0035] The liquid rubber resin (B) is not particularly limited, and an appropriate liquid rubber resin can be selected as needed. In this embodiment, the liquid rubber resin (B) may include LDM-02 (trade name; manufactured by Denka Company Limited), LF-310T50 (trade name; manufactured by Nippon Steel Corporation), COD-103 (trade name; manufactured by Nippon Soda Co., Ltd.), divinylbenzene-containing polymers (DVB resin series), combinations thereof, or other appropriate liquid rubber resins, and is preferably the LDM-02 series.

[0036] The amount of the liquid rubber resin (B) used is 30 to 50 parts by weight, and preferably 35 to 45 parts by weight, relative to 100 parts by weight of the total amount of the resin composition used.

[0037] Inorganic filler (C)

[0038] The inorganic filler (C) is not particularly limited, and an appropriate inorganic filler can be selected as needed. For example, the inorganic filler (C) may be spherical. In this embodiment, the inorganic filler (C) may include silica, preferably surface-modified silica, and more preferably surface-modified spherical silica. Specific examples of commercially available spherical silica include EQK0610-SMS (trade name; manufactured by Mitokiki Co., Ltd.) or other suitable spherical silica. The median particle size (particle size D50) of the inorganic filler (C) may be 0.3 micrometers to 3.0 micrometers, preferably 0.5 micrometers to 2 micrometers.

[0039] The inorganic filler (C) may comprise a surface-modified filler having an acrylic or vinyl group, and is preferably a surface-modified silica having an acrylic or vinyl group.Compared with unmodified silica, the surface-modified silica having an acrylic or vinyl group has better electrical properties, thereby enabling the resin composition to have good dielectric properties.

[0040] The amount of inorganic filler (C) used is 25 to 50 parts by weight, and preferably 30 to 40 parts by weight, relative to 100 parts by weight of the total amount of the resin composition used.

[0041] Catalyst (D)

[0042] The catalyst (D) is not particularly limited, and an appropriate catalyst can be selected as needed. For example, the catalyst (D) may include a peroxide or other suitable catalyst. Specific examples of commercially available peroxides include Luperox F (trade name, abbreviated as LuF; manufactured by Arkema), DCP (trade name; manufactured by Arkema), Percumyl P (trade name; manufactured by NOF Corporation), Trigonox A-W70 (trade name; manufactured by Akzo Nobel NV), combinations thereof, or other suitable peroxides.

[0043] The amount of catalyst (D) used is 0.1 to 2 parts by weight, and preferably 0.5 to 1 part by weight, relative to 100 parts by weight of the total amount of the resin composition used.

[0044] Siloxane coupling agent (E)

[0045] The siloxane coupling agent (E) is not particularly limited, and an appropriate siloxane coupling agent can be selected as needed. For example, the siloxane coupling agent (E) may include silane compounds (silanes) having different functional groups. In this embodiment, the siloxane coupling agent (E) may include a vinyl silane compound, an acrylic silane, a combination thereof, or other suitable siloxane coupling agents. Specific examples of commercially available siloxane coupling agents (E) include Z6030 (trade name; manufactured by Dow Corning Inc.), KBM503 (trade name; manufactured by Shin-Etsu Chemical Co., Ltd.), or other suitable siloxane coupling agents.

[0046] The amount of the siloxane coupling agent (E) used is 0.1 to 5 parts by weight, preferably 0.2 to 2 parts by weight, based on 100 parts by weight of the total amount of the resin composition used. When the resin composition contains the siloxane coupling agent (E), the compatibility and degree of crosslinking between the resin composition and the glass fiber cloth and powder can be improved.

[0047] <Method for preparing resin composition>

[0048] The method for preparing the resin composition is not particularly limited. For example, the components of the resin composition are placed in a stirrer and stirred to form a uniform solution, and a solvent may be added as needed. By mixing the components uniformly, a liquid resin composition can be obtained.

[0049] The solvent may include toluene, xylene, acetone, butanone, methyl isobutyl ketone (MIBK), cyclohexanone, dimethylacetamide, a combination thereof, or other suitable solvent. The amount of solvent used is not particularly limited, and an appropriate amount can be selected as needed. In the liquid resin composition, the solid content may be 10% to 40%. In this embodiment, the solid content can be fixed at 35%. This allows the amount of each component used in the resin composition to be calculated.

[0050] The resin composition of the present invention can be processed into resin-coated copper (RCC) substrates according to actual design requirements. Because the resin composition of the present invention has excellent dielectric properties, peel resistance, and heat resistance, a primer layer formed from the resin composition of the present invention has good compatibility with prepreg and copper foil. The copper foil substrate (RCC) formed therefrom also has a low dielectric constant, low dielectric dissipation factor, high peel strength, and good heat resistance, providing favorable reliability (maintaining desired electrical properties). More specifically, the resin-coated copper substrate including a primer layer formed from the resin composition may have a dielectric constant of about 3.0 to 3.35, a dielectric dissipation factor of less than about 0.002, a peel strength between the copper foil and the prepreg of greater than about 4 lb / in, and a laminate with a solder float value of greater than 10 minutes is considered to be of good quality. The pure primer layer formed from the resin composition may have a dielectric constant of about 2.71 and a dielectric dissipation factor of about 0.00088.

[0051] The present invention will be described in more detail below with reference to examples. The following examples are for the purpose of illustrating the present invention, and the scope of the present invention includes the scope described in the following patent applications and their alternatives and modifications, and is not limited to the scope of the examples.

[0052] Bismaleimide resin synthesis example

[0053] Synthesis Example 1: Bismaleimide-modified polyphenylene ether resin (PPE-BMI)

[0054] A low-molecular-weight polyphenylene ether resin material having a number-average molecular weight (Mn) of 12,000 or less or 10,000 or less (e.g., Mn = 500, 1400, 1600, or 1800) was dissolved in dimethylacetamide, followed by the addition of potassium carbonate and tetrafluoronitrobenzene. The reaction solution was heated to 140°C and reacted for 8 hours, then cooled to room temperature and filtered to remove solids. The filtrate was precipitated using methanol / water, and the precipitate was found to be a nitrated polyphenylene ether resin. The nitrated polyphenylene ether resin was then dissolved in dimethylacetamide and hydrogenated at 90°C for 8 hours to obtain an aminated polyphenylene ether resin. The aminated polyphenylene ether resin was then added to toluene, and maleic anhydride and p-toluenesulfonic acid were added thereto. The mixture was heated to 120°C under reflux and reacted for 8 hours to obtain a bismaleimide-modified polyphenylene ether resin (PPE-BMI).

[0055] Synthesis Example 2: Bismaleimide-modified dicyclopentadiene resin (DCPD-BMI)

[0056] A dicyclopentadiene phenol resin containing 1 mole of hydroxyl groups (e.g., weight-average molecular weight 1,300 (trade name ERM6140, manufactured by SONGWON), 1,100 (trade name ERM6115, manufactured by SONGWON), or 800 (trade name ERM6105, manufactured by SONGWON)) and 1.25 moles of 4-halonitrobenzene (wherein the halogen can be fluorine, chlorine, bromine, or iodine) were added to 6 moles of dimethylacetamide (DMAC) as a reaction solvent, and the mixture was reacted at 120°C for 300 minutes to carry out a nitration reaction. Hydrogen gas was then introduced, and the mixture was reacted at 90°C for 480 minutes to carry out a hydrogenation reaction, producing a modified dicyclopentadiene-type bisamine. Next, 3 moles of maleic anhydride and 9.7% by weight of toluenesulfonic acid were added and reacted at 120°C for 420 minutes to obtain a bismaleimide resin containing a dicyclopentadiene structure in the main chain (referred to as DCPD-BMI). This has the structure represented by the above formula (2) and may have an average molecular weight of 800 to 10,000, preferably 1,000 to 4,000.

[0057] Resin Composition Examples

[0058] Resin composition examples 1 to 5 and comparative examples 1 to 4 will be explained below.

[0059] Examples 1 to 5 and Comparative Examples 1 to 4

[0060] According to the contents of Tables 1 and 2, the resin composition of each experimental example was mixed with a mixed solvent of 50% toluene and 50% xylene to form a resin composition with a solids concentration of approximately 10 wt% to 40 wt%. The resulting resin composition was applied to a copper foil laminate surface (roughness Rz less than 1 μm, thickness approximately 35 μm). The dried film after application was approximately 1 to 2 μm, and was baked at 120°C for 3 to 5 minutes to form a resin-coated copper substrate. Two sheets of prepreg were laminated between 35 μm-thick copper foil (roughness Rz less than 1 μm). The prepreg model number was NPG188H (RC: 73%; 0.1 mm, manufactured by Nanya Plastics Industry Co., Ltd.), and a pressure of 25 kg / cm was applied using a hot press. 2 The copper foil substrate was pressed at 85°C and maintained at this temperature for 20 minutes. It was then heated to 220°C at a rate of 3°C / min, after which the temperature was maintained at this temperature for 90 minutes. It was then gradually cooled to 25°C, and the resulting copper foil substrate was evaluated according to the following evaluation methods. The results are shown in Table 2.

[0061] [Table 1]

[0062] [Table 2]

[0063] <Evaluation method>

[0064] Dielectric constant (Dk): The dielectric constant at a wave number of 10 GHz was measured using a dielectric analyzer (manufactured by Keysight Technologies, Inc.) A smaller dielectric constant indicates that the resin composition has better dielectric properties.

[0065] Dissipation factor (Df): The dielectric dissipation factor at a frequency of 10 GHz was measured using a dielectric analyzer (manufactured by Keysight Technologies, Inc.) A smaller dielectric dissipation factor indicates that the resin composition has better dielectric properties.

[0066] Peel strength: The peel strength of the metal substrate was tested according to the IPC-TM-650-2.4.8 test method, and the peel strength between the copper foil and the circuit carrier substrate was tested using a tensile tester. The higher the peel strength, the less likely the resin composition is to peel from the circuit substrate, i.e., the better the peel resistance.

[0067] Heat resistance: A copper foil substrate sample (referred to as a laminate) is placed in an oven at 288°C to induce swelling, and the time from the start time to the appearance of the first blister is measured. If the solder float value of the laminate is more than 10 minutes, it is considered to have good quality (abbreviated as "OK"), and if the solder float value of the laminate is less than 10 minutes, it is considered to have poor quality (abbreviated as "NG").

[0068] <Evaluation results>

[0069] As can be seen from Table 2, when the resin composition contains a resin mixture (A), a liquid rubber resin (B), an inorganic filler (C), a catalyst (D), and a siloxane coupling agent (E), and when the resin mixture (A) contains a bismaleimide resin (Examples 1 to 5), the resin composition simultaneously exhibits good dielectric properties, peel resistance, and heat resistance.

[0070] Furthermore, compared to resin compositions (Comparative Examples 1 to 4) in which the amount of resin mixture (A) used is outside the range of 10 parts by weight to 30 parts by weight per 100 parts by weight of the total amount of resin composition used, the resin compositions (Examples 1 to 5) in which the amount of resin mixture (A) used is within the above range have greater peel strength, i.e., more preferable peel resistance.

[0071] Furthermore, compared to resin compositions (Comparative Examples 1 to 4) in which the bismaleimide resin does not contain a bismaleimide-modified polyphenylene ether resin (PPE-BMI), the resin compositions (Examples 1 to 5) in which the bismaleimide resin contains a bismaleimide-modified polyphenylene ether resin have greater peel strength, i.e., more favorable peel resistance.

[0072] Furthermore, compared with resin compositions (Comparative Examples 2 to 4) that do not contain a bismaleimide-modified polyphenylene ether resin (PPE-BMI) or a bismaleimide-modified dicyclopentadiene resin (DCPD-BMI) as a bismaleimide resin, the resin compositions (Examples 1 to 3) that contain a bismaleimide-modified polyphenylene ether resin and a bismaleimide-modified dicyclopentadiene resin as a bismaleimide resin have greater peel strength and better heat resistance, i.e., more preferable peel resistance and heat resistance.

[0073] In summary, the resin composition of the present invention comprises a resin mixture (A), a liquid rubber resin (B), an inorganic filler (C), a catalyst (D), and a siloxane coupling agent (E), and since the resin mixture (A) contains a bismaleimide resin, the resin composition has good dielectric properties, peel resistance, and heat resistance, and has good applicability.

[0074] 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 scope of the attached patent application. [Industrial Applicability]

[0075] The resin composition of the present invention can be applied to electronic materials such as copper-clad laminates.

Claims

1. a resin mixture (A) containing a bismaleimide resin; A liquid rubber resin (B), an inorganic filler (C); a catalyst (D); a siloxane coupling agent (E); A resin composition comprising:

2. The bismaleimide resin includes a bismaleimide-modified olefin resin, a bismaleimide-modified polyphenylene ether resin, a bismaleimide-modified dicyclopentadiene resin, or a combination thereof. The resin composition according to claim 1.

3. The bismaleimide resin further includes a biphenyl-based bismaleimide resin. The resin composition according to claim 2.

4. The weight average molecular weight of the bismaleimide resin is 500 g / mol to 5000 g / mol. The resin composition according to claim 1.

5. The amount of the resin mixture (A) used is 10 parts by weight to 30 parts by weight relative to 100 parts by weight of the total amount of the resin composition used. The resin composition according to claim 1.

6. The liquid rubber resin (B) includes LDM-02, LF-310T50, COD-103, a divinylbenzene-containing polymer, or a combination thereof. The resin composition according to claim 1.

7. The inorganic filler (C) contains silica. The resin composition according to claim 1.

8. The inorganic filler (C) comprises a surface-modified silica having an acrylic group or a vinyl group; The resin composition according to claim 1.

9. The median particle size of the inorganic filler (C) is 0.3 micrometers to 3.0 micrometers. The resin composition according to claim 1.

10. The siloxane coupling agent (E) comprises a vinyl silane compound, an acryl silane, or a combination thereof; The resin composition according to claim 1.

11. the amount of the liquid rubber resin (B) used is 30 parts by weight to 50 parts by weight, the amount of the inorganic filler (C) used is 25 parts by weight to 50 parts by weight, the amount of the catalyst (D) used is 0.1 parts by weight to 2 parts by weight, and the amount of the siloxane coupling agent (E) used is 0.1 parts by weight to 5 parts by weight, relative to 100 parts by weight of the total amount of the resin composition used; The resin composition according to claim 1.

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