Low dielectric resin composition

Abstract

The invention provides a low dielectric resin composition, which includes a benzocyclobutene hydrocarbon resin, a polyindene resin, a PPE resin, a polydivinylbenzene resin, a crosslinking agent, a halogen-free flame retardant, a spherical silicon dioxide, a peroxide accelerator and a siloxane coupling agent. A chemical structure of the benzocyclobutene hydrocarbon resin is shown in following Formula

Description

Technical Field

[0001] This invention relates to a resin composition, and more particularly to a low-dielectric resin composition. Prior Technology

[0002] With the development of 6G technology, the requirements for printed circuit boards (PCBs) are also increasing, mainly including lower dielectric loss tangent (Df), lower dielectric constant (Dk), higher reliability, stronger heat resistance, and lower coefficient of thermal expansion (CTE). Therefore, thermosetting resins with excellent dielectric properties, such as polyphenylene ether resin, bismaleimide resin, vinyl benzyl ether resin, and hydrocarbon resins, have become the focus of research. Currently, most mass-produced PCBs use composite thermosetting resins containing terminal vinyl polyphenylene ether and triallyl isocyanate (TAIC). Although these materials possess excellent mechanical properties and heat resistance, the polar groups in TAIC cause their dielectric constant (Dk) and dielectric loss tangent (Df) to fail to meet the requirements of next-generation communication technologies.

[0003] Low dielectric hydrocarbon resins (such as polypropylene and polystyrene) have attracted attention due to their lower Dk and Df; however, hydrocarbon resins have poor heat resistance and low glass transition temperature, and still do not meet the standards required for PCBs.

[0004] Benzocyclobutene is another special type of thermosetting resin with an all-carbon structure. Due to its excellent heat resistance, mechanical properties, extremely low dielectric loss, and extremely low dielectric constant, it has gradually become a new generation of high-performance electronic materials. The four-carbon ring double bond in benzocyclobutene can undergo the following reactions, which increase the cross-linking of the structure and the heat resistance: (1) Benzocyclobutene can react with vinyl groups at high temperatures to form a cyclohexane structure; (2) It dimers at a high temperature of about 260°C to form a cyclooctane structure. Summary of the Invention

[0005] This invention provides a low-dielectric resin composition, which uses polyindene resin as the main structure and is combined with a novel low-dielectric benzocyclobutene hydrocarbon resin, to prepare a substrate with an electrical conductivity (Df) of less than 0.00085 and a temperature (Tg) that can be maintained above 209°C.

[0006] This invention provides a low-dielectric resin composition comprising benzocyclobutene hydrocarbon resin, polyindene resin, PPE resin, polyvinylbenzene resin, crosslinking agent, halogen-free flame retardant, spherical silica, peroxide accelerator, and siloxane coupling agent. The chemical structure of the benzocyclobutene hydrocarbon resin is shown in the following formula (1): Equation (1) In equation (1), n ​​is an integer from 1 to 10, m is an integer from 1 to 10, and o is an integer from 1 to 15.

[0007] In one embodiment of the present invention, based on the total weight of the resin composition, the amount of benzocyclobutene hydrocarbon resin added is 1 wt% to 50 wt%, the amount of polyindene resin added is 1 wt% to 50 wt%, the amount of PPE resin added is 10 wt% to 40 wt%, the amount of polyvinylbenzene resin added is 10 wt% to 40 wt%, the amount of crosslinking agent added is 1 wt% to 10 wt%, the amount of spherical silica added is 20 wt% to 60 wt%, and the phosphorus content of the halogen-free flame retardant is 5 wt% to 20 wt%.

[0008] In one embodiment of the present invention, based on a resin composition content of 100 phr, the amount of peroxide accelerator added is 0.1 phr to 5 phr, and the amount of siloxane coupling agent added is 0.1 phr to 5 phr.

[0009] In one embodiment of the present invention, the molecular weight Mn of the benzocyclobutene hydrocarbon resin is 2100 to 3600.

[0010] In one embodiment of the present invention, the Dk of the benzocyclobutene hydrocarbon resin is 2.34 and the Df is 0.0012.

[0011] In one embodiment of the present invention, the polyindim resin has two or more reactive functional groups, said reactive functional groups including acrylic, styrene, or maleimide.

[0012] In one embodiment of the present invention, the molecular weight Mn of the polyindene resin is 300 to 1000.

[0013] In one embodiment of the present invention, the electrical properties of the resin composition are Dk of 3.0 to 3.1, Df of 0.00085 or less, and Tg of 209°C or more.

[0014] Based on the above, this invention provides a low-dielectric resin composition, using polyindene resin as the main structure and combined with a novel low-dielectric benzocyclobutene hydrocarbon resin, which can produce a substrate with an electrical conductivity (Df) of less than 0.00085 and a temperature (Tg) that can be maintained above 209°C. This achieves the standards required for PCBs and meets the needs of next-generation communication technologies. Simple Explanation of the Diagram

[0015] none Implementation

[0016] The embodiments of the present invention will now be described in detail. However, these embodiments are illustrative, and the present invention is not limited thereto.

[0017] In this document, the range expressed as "from one value to another" is a concise way of representing a range to avoid listing all the values ​​in that range in the specification. Therefore, the description of a particular range of values ​​covers any value within that range as well as the smaller range of values ​​defined by that value, just as the arbitrary value and the smaller range of values ​​are described in the explanatory text of the specification.

[0018] This invention provides a low-dielectric resin composition comprising benzocyclobutene hydrocarbon resin, polyindene resin, PPE resin, divinylbenzene resin, crosslinking agent, halogen-free flame retardant, spherical silica, peroxide accelerator, and siloxane coupling agent. The various components described above will be described in detail below. [Benzocyclobutene hydrocarbon resin]

[0019] In this embodiment, the benzocyclobutene hydrocarbon resin is polymerized from benzocyclobutene (BCB), styrene, divinylbenzene, and butadiene. The molecular weight Mn of the benzocyclobutene hydrocarbon resin is, for example, 2100 to 3600. The Dk of the benzocyclobutene hydrocarbon resin is, for example, 2.34, and the Df is, for example, 0.0012. The chemical structure of the benzocyclobutene hydrocarbon resin is shown in the following formula (1): Equation (1) In equation (1), n ​​is an integer from 1 to 10, m is an integer from 1 to 10, and o is an integer from 1 to 15. The amount of benzocyclobutene hydrocarbon resin added, based on the total weight of the resin composition, is, for example, 1 wt% to 50 wt%. If the amount of benzocyclobutene hydrocarbon resin added is too high and exceeds this range, it may cause the prepreg to become sticky. [Polyindium resin]

[0020] In this embodiment, the polyindim resin may have two or more reactive functional groups, which may include acrylic, styrene, or maleimide groups. The molecular weight Mn of the polyindim resin is, for example, 300 to 1000. The amount of polyindim resin added, based on the total weight of the resin composition, is, for example, 1 wt% to 50 wt%. [PPE] [Resin]

[0021] In this embodiment, the amount of PPE resin (polyphenylene ether) added, for example, is 10 wt% to 40 wt% based on the total weight of the resin composition. The polyphenylene ether resin is a thermosetting polyphenylene ether resin, and is a composition having styrene-type polyphenylene ether and acrylic-type polyphenylene ether at the end groups.

[0022] For example, the structure of styrene-type polyphenylene ether is shown in structural formula (A): R1 to R8 can be allyl, hydrogen, or C1 to C6 alkyl, or selected from one or more of the above groups. X can be O (oxygen atom) or the following structural formula: Where P1 is styrene-based. a = integers from 1 to 99. The structure of the acrylic polyphenylene ether at the end is shown in structural formula (B): R1 to R8 may be allyl, hydrogen, or C1 to C6 alkyl, or selected from one or more of the above groups. X can be O (oxygen atom) or the following structural formula: P2 is or b = integers from 1 to 99.

[0023] Specific examples of polyphenylene ether resins include, but are not limited to, dihydroxy polyphenylene ether resins (e.g., SA-90, available from Sabic), vinyl benzyl polyphenylene ether resins (e.g., OPE-2st-1200, available from Mitsubishi Gas Chemical), methacrylate polyphenylene ether resins (e.g., SA-9000, available from Sabic), vinyl benzyl-modified bisphenol A polyphenylene ether resins, or vinyl benzyl-modified bisphenol A polyphenylene ether resins. [Polyvinylbenzene resin]

[0024] In this embodiment, the amount of polyvinylbenzene resin added, based on the total weight of the resin composition, is, for example, 10 wt% to 40 wt%. The polyvinylbenzene resin is a low-dielectric resin (Poly-DVB), with a number-average molecular weight (Mn) of approximately 4,500 to 50,000, and a styrene content of 10% to 40%, a divinylbenzene content of 10% to 40%, and an ethylene content of 10% to 20%. By using a low-dielectric resin (Poly-DVB) to replace liquid rubber, the dielectric loss and / or dielectric constant of the resin composition can be effectively reduced, achieving low-dielectric electrical properties while simultaneously maintaining the flowability, filling properties, and absence of phase separation between resins. [Cross-linking agent]

[0025] In this embodiment, the crosslinking agent is used to improve the crosslinking degree of the thermosetting resin, adjust the rigidity and toughness of the substrate, and adjust the processability. The type used can be one or a combination of one or more of the following: triallyl cyanurate (TAC), triallyl isocyanurate (TAIC), trimethallyl isocyanurate (TMAIC), diallyl phthalate, divinylbenzene, 1,2,4-triallyl trimellitate, or divinyl-1,2-diphenylethane (BVPE). The amount of crosslinking agent added, for example, is 1 wt% to 10 wt% based on the total weight of the resin composition. [Halogen-free flame retardant]

[0026] In this embodiment, specific examples of halogen-free flame retardants can be phosphorus-based flame retardants selected from phosphate esters, such as: triphenyl phosphate (TPP), resorcinol bisphosphate (RDP), bisphenol A bis(diphenyl) phosphate (BPAPP), bisphenol A bis(dimethyl) phosphate (BBC), resorcinol diphosphate (CR-733S), resorcinol-bis(di-2,6-dimethylphenyl phosphate) (PX-200); phosphazenes can be selected from, such as: poly(phenoxy)phosphazene (SPB-100); ammonium polyphosphates, melamine phosphates (MPP, i.e., Melamine Polyphosphate), melamine cyanurate; combinations of one or more DOPO-based flame retardants, such as DOPO (e.g., structural formula C), DOPO-HQ (e.g., structural formula D), bisDOPO derivatives (e.g., structural formula E); and aluminum-containing hypophosphite (e.g., structural formula F). The phosphorus content of the halogen-free flame retardant, based on the total weight of the resin composition, is, for example, 5 wt% to 20 wt%. [Spherical silicon dioxide]

[0027] In this embodiment, the spherical silica is preferably prepared by synthesis to reduce electrical properties while maintaining flowability and filler properties. The spherical silica has an acrylic or vinyl surface modification, a purity of approximately 99.0% or higher, and an average particle size D50 of approximately 2.0 μm to 3.0 μm. The amount of spherical silica added, for example, is 20 wt% to 60 wt% based on the total weight of the resin composition. [Peroxide Accelerator]

[0028] In this embodiment, the peroxide accelerator may include tert-butylisopropylphenyl peroxide, dicumyl peroxide (DCP), benzoyl peroxide (BPO), 2,5-dimethyl-2,5-di(tert-butylperoxy)hexane, 2,5-dimethyl-2,5-di(tert-butylperoxy)hexyne, 1,1-di-(tert-butylperoxy)-3,3,5-trimethylcyclohexane, or di(tert-butylperoxyisopropyl)benzene, etc. Based on a resin composition content of 100 phr, the amount of peroxide accelerator added is, for example, 0.1 phr to 5 phr. [Siloxane Coupling Agent]

[0029] In this embodiment, the siloxane coupling agent may include, but is not limited to, siloxane compounds. Furthermore, based on the type of functional group, it can be classified into amino silane compounds, epoxide silane compounds, vinyl silane compounds, ester silane compounds, hydroxy silane compounds, isocyanate silane compounds, methacryloxy silane compounds, and acryloxy silane compounds. Based on a resin composition content of 100 phr, the amount of siloxane coupling agent added is, for example, 0.1 phr to 5 phr.

[0030] It should be noted that the resin composition of the present invention can be processed into a prepreg and a substrate according to the actual design requirements. The electrical properties of the resin composition are Dk of 3.0 to 3.1, Df of 0.00085 or less, and Tg of 209°C or more. [SBS] [Resin]

[0031] In this embodiment, the SBS resin has a styrene content of 10% to 40%, a 1,2-vinyl content of 60% to 90%, and a 1,4-vinyl content of 10% to 30%. The molecular weight (MW) of the SBS resin is approximately 3500 to 5500. The amount of SBS resin added, for example, is 1 wt% to 20 wt% based on the total weight of the resin composition. By using SBS resin to replace liquid rubber, the phase separation between resins is improved, and the flowability and filling properties are enhanced, thereby strengthening the overall processability while maintaining low dielectric properties.

[0032] The low-dielectric resin composition of the present invention will be described in detail below by way of examples. However, the following examples are not intended to limit the present invention. [Experimental Example] [Evaluation Methodology]

[0033] The substrates made from each example and comparative example were evaluated according to the following method.

[0034] Glass transition temperature Tg (°C) was measured using a dynamic mechanical analyzer (DMA).

[0035] Water absorption rate (%): The weight change of the sample before and after heating was calculated after heating in a pressure cooker at 120℃ and 2 atm for 120 minutes.

[0036] Heat resistance (seconds): The sample was heated in a pressure cooker at 120℃ and 2 atm for 120 minutes and then immersed in a soldering furnace at 288℃. The time required for the sample to delaminate was recorded.

[0037] Dielectric constant Dk: The dielectric constant Dk at a frequency of 10 GHz was measured using an HP Agilent E4991A dielectric analyzer.

[0038] Dielectric loss Df: Dielectric loss Df was measured at a frequency of 10 GHz using an HP Agilent E4991A dielectric analyzer. [Property Assessment]

[0039] Table 1 provides detailed information on each component as follows:

[0040] Polyindene: Japanese DIC, Model: NE-V-RD004

[0041] PPE: Mitsubishi Gas, Japan; Model: OPE-2ST-1200

[0042] Low dielectric resin (Poly-DVB): Denka, Japan, Model: LDM-03-07

[0043] SBS: Japan Soda, Model: 1, 2-SBS

[0044] Novel low-dielectric benzocyclobutene hydrocarbon resin: Sichuan Dongcai, Model: DFE-927

[0045] Flame retardant: Jin Yi Chemical, Model: PQ-60

[0046] Synthetic SiO2: Jiangsu Lianrui New Materials, Model: NQL6020V

[0047] Peroxide accelerator: ARKEMA, Model: Luperox F

[0048] Silicon oxyane coupling agent: Dow Toray, Model: Z6030

[0049] Fabric type: Quartz fabric 1078Q, Shin-Etsu; Model: SQX-Y1078C-imp Table 1 Example 1 Example 2 Example 3 Example 4 Comparative Example 1 Comparative Example 2 match square Compare example Polyindene 36% 36% 32% 28% 40% PPE 22.5% 15.5% 20% 17.5% 25% Low dielectric resin (Poly-DVB) 18% 25% 16% 14% 20% 20% SBS 9% 9% 8% 7% 10% 10% Benzocyclobutene hydrocarbon resin 10% 10% 20% 30% 65% Crosslinking agent (BVPE) 4.5% 4.5% 4% 3.5% 5% 5% Phosphorus-based flame retardants (P content) 3phr 3phr 3phr 3phr 3phr 3phr Synthetic method for SiO2 55% 55% 55% 55% 55% 55% Accelerator / Peroxide 0.7phr 0.7phr 0.7phr 0.7phr 0.7phr 0.7phr Siloxane coupling agent 0.5 phr 0.5 phr 0.5 phr 0.5 phr 0.5 phr 0.5 phr B-Stage 140℃ 140℃ 140℃ 140℃ 140℃ 140℃ Prepreg after impregnation Non-sticky Non-sticky Non-sticky Non-sticky Sticky Non-sticky Tg(DMA) 216℃ 209℃ 222℃ 225℃ 229℃ 195℃ PCT 1 / 2hr Water absorption rate 0.13% 0.12% 0.11% 0.13% 0.15% 0.15% Heat resistance OK OK OK OK OK OK PCT 2hr Water absorption rate 0.19% 0.16% 0.18% 0.19% 0.21% 0.21% Heat resistance OK OK OK OK OK OK Dk / Df (10GHz) 3.05 0.00085 3.05 0.00080 3.04 0.00081 3.06 0.00078 3.09 0.00096 3.09 0.00102 Glue flow at the edge of the board (cm) 1.0 0.8 1.0 1.5 >5 1.0

[0050] As can be seen from Table 1 above, Examples 1 to 4 use the low-dielectric resin composition of the present invention, with polyindene resin as the main structure and combined with a novel low-dielectric benzocyclobutene hydrocarbon resin, and the contents are all within a specific range. Therefore, a substrate with an electrical Dk of 3.0 to 3.1 and a Df of less than 0.00085 can be prepared, while the Tg can be maintained above 209°C, and the impregnated prepreg is not sticky.

[0051] In contrast, Comparative Example 1 did not use polyindene resin or PPE resin, and the content of benzocyclobutene hydrocarbon resin used exceeded the range claimed in this invention. Therefore, not only did the impregnated prepreg exhibit stickiness, but the electrical property Df was also higher (0.00096). Comparative Example 2 did not use benzocyclobutene hydrocarbon resin, therefore, the electrical property Df was higher (0.00102), and the Tg was lower (195°C).

[0052] In summary, this invention provides a low-dielectric resin composition, using polyindene resin as the main structure, and combined with a novel low-dielectric... [Benzocyclobutene hydrocarbon resin] can be used to prepare substrates with an electrical conductivity (Df) of less than 0.00085 and a temperature (Tg) that can be maintained above 209°C. The prepreg is also non-sticky after impregnation. This achieves the standards required for PCBs and meets the needs of next-generation communication technologies.

[0053] none

Claims

1. A resin composition comprising: Benzocyclobutene hydrocarbon resin; Polyindene resin; PPE resin; Polyvinylbenzene resin; crosslinking agent; halogen-free flame retardant; spherical silica; peroxide accelerator; SBS resin; and siloxane coupling agent, wherein the chemical structure of the benzocyclobutene hydrocarbon resin is as shown in the following formula (1): Formula (1) In formula (1), n ​​is an integer from 1 to 10, m is an integer from 1 to 10, and o is an integer from 1 to 15, wherein, based on the total weight of the resin composition, the amount of the benzocyclobutene hydrocarbon resin added is 1 wt% to 50 wt%, the amount of the polyindene resin added is 1 wt% to 50 wt%, the amount of the PPE resin added is 10 wt% to 40 wt%, the amount of the polyvinylbenzene resin added is 10 wt% to 40 wt%, the amount of the crosslinking agent added is 1 wt% to 10 wt%, and the amount of the spherical silica added is 20 wt% to 60 wt%. The phosphorus content of the halogen-free flame retardant is 5 wt% to 20 wt%, the amount of SBS resin added is 1 wt% to 20 wt%, wherein, based on the content of the resin composition being 100 phr, the amount of peroxide accelerator added is 0.1 phr to 5 phr, and the amount of silicate coupling agent added is 0.1 phr to 5 phr.

2. The resin composition as claimed in claim 1, wherein the molecular weight Mn of the benzocyclobutene hydrocarbon resin is from 2100 to 3600.

3. The resin composition as claimed in claim 1, wherein the benzocyclobutene hydrocarbon resin has a Dk of 2.34 and a Df of 0.0012.

4. The resin composition of claim 1, wherein the polyindene resin has two or more reactive functional groups, the reactive functional groups including acrylic, styrene, or maleimide.

5. The resin composition as claimed in claim 1, wherein the molecular weight Mn of the polyindene resin is 300 to 1000.

6. The resin composition as claimed in claim 1, wherein the electrical properties of the resin composition are Dk of 3.0 to 3.1, Df of 0.00085 or less, and Tg of 209°C or more.