TWI897751B - Low dielectric resin composition - Google Patents

Abstract

The invention provides a low dielectric resin composition, including a nitrogen-containing aromatic cyclone polymer resin, a PPE resin, a polyethylene resin, a SBS resin, a cross-linked agent, a phosphorus flame retardant, a spherical silica, a silicon dioxide hollow microsphere or silicon dioxide hollow microsphere suspension, a peroxide promoter, and a siloxane coupling agent. As for the low dielectric resin composition of the invention, the appearance after processing is excellent and the dielectric constant and dielectric loss have been further reduced.

Description

Low dielectric resin composition

The present invention relates to a resin composition, and in particular to a low dielectric resin composition.

The dielectric constant of current substrates is approximately 3.2 to 5.0, making it unsuitable for future high-frequency, fast transmission applications. In existing technologies, hollow silicon dioxide microspheres are added to the material forming the dielectric substrate layer to reduce the dielectric constant, increase the mechanical strength, and make the dielectric substrate layer lightweight.

Factors such as the type and surface modification of hollow silica microspheres can affect processability. It is known that using hollow microspheres with unmodified or improperly modified surfaces results in low density and a pronounced tendency to float in the adhesive used to prepare the substrate. This leads to uneven distribution of the adhesive, resulting in poor appearance in the processed resin sheets and prepregs. Furthermore, the dielectric constant fluctuates between batches of prepared substrates, failing to meet customer requirements for consistent dielectric constant performance between batches. The shell thickness, hollowness, and hardness of the hollow microspheres also affect the integrity of the hollow microspheres within the substrate after high-temperature, high-pressure hot pressing, ensuring that the material's low dielectric properties remain intact. Therefore, the dielectric substrates currently available on the market still need to be improved. The present invention aims to solve the above-mentioned problem and has the following objectives: to provide a resin composition with excellent appearance after processing and further reduced dielectric constant and dielectric loss.

The present invention provides a resin composition having an excellent appearance after processing and further reduced dielectric constant and dielectric loss.

The resin composition of the present invention includes a nitrogen-containing heteroaromatic cyclostyrene polymer resin, a PPE resin, a polydivinylbenzene resin, an SBS resin, a crosslinking agent, a phosphorus-based flame retardant, spherical silica, hollow silica microspheres or a suspension of hollow silica microspheres, a peroxide accelerator, and a silicone coupling agent.

In one embodiment of the present invention, based on the total weight of the resin composition, the nitrogen-containing heteroaromatic cyclostyrene polymer resin is added in an amount of 10 wt% to 60 wt%, the PPE resin is added in an amount of 10 wt% to 40 wt%, the polydivinylbenzene resin is added in an amount of 10 wt% to 40 wt%, the SBS resin is added in an amount of 1 wt% to 30 wt%, the crosslinking agent is added in an amount of 1 wt% to 20 wt%, the phosphorus content of the phosphorus-based flame retardant is 2 phr to 5 phr, the spherical silica is added in an amount of 20 wt% to 60 wt%, and the hollow silica microspheres or the hollow silica microsphere suspension is added in an amount of 1 wt% to 20 wt%.

In one embodiment of the present invention, based on 100 phr of the resin composition, the amount of the peroxide accelerator added is 0.1 phr to 5 phr, and the amount of the silicone coupling agent added is 0.1 phr to 5 phr.

In one embodiment of the present invention, the nitrogen-containing heteroaromatic ring of the nitrogen-containing heteroaromatic ring styrene polymer resin includes a pyrimidine ring, a pyrazine ring, a oxazine ring, a pyridine ring, a pyrrole ring, or a pyrazole ring.

In one embodiment of the present invention, the molecular weight Mn of the nitrogen-containing heteroaromatic cyclostyrene polymer resin is 1500 to 3100.

In one embodiment of the present invention, the hollow silica microspheres or the hollow silica microspheres in the suspension have a median particle size (D50) of 0.1 µm to 10 µm, a hollow ratio of 50% to 80%, and the outer shell surface is modified to an acrylic or vinyl group.

In one embodiment of the present invention, the solvent of the silica hollow microsphere suspension includes toluene or butanone.

In one embodiment of the present invention, the electrical properties of the resin composition are Dk of 3.0 to 3.2 and Df less than 0.00130.

Based on the above, the present invention provides a resin composition that utilizes a nitrogen-containing heteroaromatic cyclostyrene polymer resin as its main framework and partially replaces the spherical solid synthetic silica filler with hollow silica microspheres or a suspension of hollow silica microspheres. This allows for the preparation of a substrate with a uniformly dispersed formulation, excellent post-processing appearance, and electrical properties of Dk below 3.10 and Df < 0.00130.

Hereinafter, embodiments of the present invention will be described in detail. However, these embodiments are illustrative only, and the present invention is not limited thereto.

In this document, a range expressed as "from a value to another value" is a summary expression method that avoids listing all the values within the range one by one in the specification. Therefore, the description of a specific numerical range covers any numerical value within the numerical range and the smaller numerical range defined by any numerical value within the numerical range, just as if the arbitrary numerical value and the smaller numerical range were written in the specification text.

The resin composition of the present invention includes a nitrogen-containing heteroaromatic cyclostyrene polymer resin, a PPE resin, a polydivinylbenzene resin, an SBS resin, a crosslinking agent, a phosphorus-based flame retardant, spherical silica, hollow silica microspheres or a suspension of hollow silica microspheres , a peroxide accelerator, and a siloxane coupling agent. The various components described above are described in detail below.

In this embodiment, the nitrogen-containing heteroaromatic ring of the nitrogen-containing heteroaromatic styrene polymer resin may include a pyrimidine ring, a pyrazine ring, a oxazine ring, a pyridine ring, a pyrrole ring, or a pyrazole ring. The molecular weight Mn of the nitrogen-containing heteroaromatic styrene polymer resin is, for example, 1500 to 3100. The amount of the nitrogen-containing heteroaromatic styrene polymer resin added is, for example, 10 wt% to 60 wt% based on the total weight of the resin composition. By using the nitrogen-containing heteroaromatic styrene polymer resin as the main structure, a substrate with uniformly dispersed formulation, excellent appearance after processing, and electrical properties Dk of less than 3.10 and Df < 0.00130 can be prepared. PPE resin

In this embodiment, the amount of PPE resin (polyphenylene ether) added is, for example, 10 wt% to 40 wt% based on the total weight of the resin composition. The polyphenylene ether resin is a thermosetting polyphenylene ether resin comprising a styrene-terminated polyphenylene ether and an acrylic-terminated polyphenylene ether.

For example, the structure of polyphenylene ether (PSE) is shown in formula (A): Wherein R1-R8 may be allyl, hydrogen, or C1-C6 alkyl, or one or more selected from the above groups, and X may be O (oxygen atom) or the following structural formula: Where P1 is a styryl group , a = an integer from 1 to 99. The structure of the acrylic polyphenylene ether at the end is shown in structural formula (B): Wherein R1-R8 can be allyl, hydrogen, or C1-C6 alkyl, or one or more selected from the above groups. X can be O (oxygen atom) or the following structure: P2 is or , b = an integer between 1 and 99.

Specific examples of polyphenylene ether resins include, but are not limited to, dihydroxy polyphenylene ether resins (e.g., SA-90, available from Sabic), vinylbenzyl polyphenylene ether resins (e.g., OPE-2st, available from Mitsubishi Gas Chemical Co., Ltd.), methacrylate polyphenylene ether resins (e.g., SA-9000, available from Sabic), vinylbenzyl-modified bisphenol A polyphenylene ether resins, or vinyl-expanded sawdust polyphenylene ether resins.

In this embodiment, the amount of polydivinylbenzene resin added is, for example, 10 wt% to 40 wt% based on the total weight of the resin composition. Polydivinylbenzene resin (Poly-DVB) is a low-dielectric resin with a number average molecular weight (Mn) of approximately 4,500 to 50,000. It contains 10% to 40% styrene, 10% to 40% divinylbenzene, and 10% to 20% ethylene. By using 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 specifications while maintaining the fluidity and filling properties of the resin composition and the absence of phase separation between resins .

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

In this embodiment, the crosslinking agent is used to increase 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 more combinations of 1,3,5-triallyl cyanurate (TAC), triallyl isocyanurate (TAIC), trimethallyl isocyanurate (TMAIC), diallyl phthalate, divinylbenzene or 1,2,4-Triallyl trimellitate. The amount of the crosslinking agent added is, for example, 1 wt% to 20 wt% based on the total weight of the resin composition. Phosphorus-based flame retardant

In this embodiment, the phosphorus flame retardant can be selected from phosphates, such as triphenyl phosphate (TPP), resorcinol bisphosphate (RDP), bisphenol A di(diphenyl) phosphate (BPAPP), bisphenol A di(dimethyl) phosphate (BBC), resorcinol diphosphate (CR-733S), resorcinol-bis(di-2,6-dimethylphenyl phosphate) (PX-200); can be selected from phosphazenes, such as polybis(phenoxy)phosphazene (SPB-100); ammonium polyphosphates, melamine phosphates (MPP, i.e., Melamine Polyphosphate), melamine cyanurate (Melamine cyanurate); one or more DOPO-based flame retardants, such as DOPO (e.g., structure (C)), DOPO-HQ (e.g., structure (D)), and bis-DOPO derivatives (e.g., structure (E)); and aluminum-containing hypophosphites. The phosphorus-based flame retardant is added in an amount, for example, of 2 to 5 parts by weight (phr) of phosphorus. Spherical silica

In this embodiment, spherical silica is preferably prepared using a synthetic method to reduce electrical properties while maintaining fluidity and filling properties. The spherical silica has an acrylic or vinyl surface modification, a purity of approximately 99.0% or greater, and an average particle size D50 of approximately 2.0 μm to 3.0 μm. The amount of spherical silica added is, for example, 20 wt% to 60 wt% based on the total weight of the resin composition. Silica hollow microspheres or silica hollow microsphere suspensions

In this embodiment, the hollow silica microspheres or the suspension of hollow silica microspheres have a median particle size (D50) of, for example, 0.1 µm to 10 µm, a hollow fraction of, for example, 50% to 80%, and a shell surface modified with, for example, acrylic or vinyl. The solvent for the suspension of hollow silica microspheres may include toluene or butanone. The amount of the hollow silica microspheres or the suspension of hollow silica microspheres added is, for example, 1 wt% to 20 wt% based on the total weight of the resin composition. By using hollow silica microspheres or a suspension of hollow silica microspheres to partially replace spherical solid synthetic silica fillers, a substrate with uniform dispersion of the formulated colloid can be prepared, with excellent appearance after processing, and electrical properties of Dk below 3.10 and Df < 0.00130.

In this embodiment, the peroxide accelerator may include tert-butyl isopropyl 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. Based on 100 phr of the resin composition, the amount of the peroxide accelerator added is, for example, 0.1 phr to 5 phr.

In this embodiment, the siloxane coupling agent may include, but is not limited to, a siloxane compound. Furthermore, depending on the type of functional group, siloxanes may be further classified into aminosilane compounds, epoxidesilane compounds, vinylsilane compounds, estersilane compounds, hydroxysilane compounds, isocyanatesilane compounds, methacryloxysilane compounds, and acryloxysilane compounds. Based on 100 phr of the resin composition, the amount of the siloxane coupling agent added is, for example, 0.1 to 5 phr.

It should be noted that the resin composition of the present invention can be processed into prepregs and substrates based on actual design requirements. The electrical specifications of the resin composition are Dk of 3.0 to 3.2 and Df less than 0.00130.

The following examples are used to illustrate the low dielectric resin composition of the present invention in detail. However, the following examples are not intended to limit the present invention .

In order to demonstrate that the resin composition proposed in the present invention can be used to prepare a substrate with uniform dispersion of the formulated colloid, excellent appearance after processing, and electrical properties Dk below 3.10 and Df < 0.00130, the following example is specifically used. Evaluation Method

The substrates produced in each example and comparative example were evaluated according to the following method.

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

Water absorption (%): The sample was heated in a pressure cooker at 120°C and 2 atm for 120 minutes, and the weight change before and after heating was calculated.

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

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

Dielectric loss Df: The dielectric loss Df at a frequency of 10 GHz was measured using a dielectric analyzer (HP Agilent E4991A).

The resin compositions listed in Table 1 were mixed with toluene to form a thermosetting resin varnish. This varnish was then impregnated with Nan Ya fiberglass cloth (Nan Ya Plastics, fabric model 1078LD) at room temperature. The varnish was then dried in an impregnation machine at 130°C for several minutes to produce a prepreg with a resin content of 70wt%. Finally, four prepregs were stacked between two 35μm-thick copper foils. The prepregs were maintained at 85°C under a pressure of 25kg/ ^cm² for 20 minutes. The prepregs were then heated to 210°C at a rate of 3°C/min, then maintained at that temperature for 120 minutes. The prepregs were then slowly cooled to 130°C to produce a 0.59mm thick substrate.

In Table 1, the detailed information of each component is as follows: Nitrogen-containing heteroaromatic cyclostyrene polymer resin: Japan JSR, model: HC-G0024 PPE resin: Japan Mitsubishi Gas, model: OPE-2ST-1200 Polydivinylbenzene resin: Japan Denka, model: LDM-03-07 SBS resin: Japan Soda, model: 1,2-SBS Flame retardant: Jinyi Chemical, model: PQ-60 Peroxide accelerator: ARKEMA, model: Luperox F Siloxane coupling agent: Dow Toray, model: Z6030 Spherical silica: Jiangsu Lianrui New Materials, model: NQL6020V Silica hollow microsphere suspension A: Korea Advanced Nano Products, Model: LS Series Dispersion Silica Hollow Microspheres B: Japan AGC, Model: HS Series Table 1 Comparative example 1 Comparative example 2 Example 1 Example 2 Example 3 Example 4 Recipe ratio Nitrogen-containing heteroaromatic cyclostyrene polymer 40wt% 40wt% 40wt% 40wt% 40wt% 40wt% PPE 25wt% 25wt% 25wt% 25wt% 25wt% 25wt% Low dielectric resin (Poly-DVB) 20wt% 20wt% 20wt% 20wt% 20wt% 20wt% SBS 10wt% 10wt% 10wt% 10wt% 10wt% 10wt% Crosslinking agent (TAIC) 5wt% 5wt% 5wt% 5wt% 5wt% 5wt% Phosphorus flame retardant (P content) 3phr 3phr 3phr 3phr 3phr 3phr Siloxane coupling agent 0.5phr 0.5phr 0.5phr 0.5phr 0.5phr 0.5phr Accelerator/Peroxide 0.7phr 0.7phr 0.7phr 0.7phr 0.7phr 0.7phr Solid filler Synthetic SiO ₂ (D50=2.4µm) 55wt% 52wt% 52wt% 50wt% 52wt% 52wt% Hollow filler _SiO2 hollow microsphere suspension A (D50=0.5µm) 3wt% 5wt% 5wt% _SiO2 hollow microspheres B (D50=2.0µm) 3wt% B-Stage 130℃ 130℃ 130℃ 130℃ 130℃ 130℃ Tg(DMA) 195℃ 194℃ 195℃ 193℃ 196℃ 192℃ PCT 1/2hr Water absorption 0.10wt% 0.15wt% 0.16wt% 0.15wt% 0.14wt% 0.13wt% Heat resistance OK OK OK OK OK OK PCT 2hr Water absorption 0.16wt% 0.18wt% 0.19wt% 0.20wt% 0.20wt% 0.18wt% Heat resistance OK OK OK OK OK OK Dk / Df (10GHz) 3.21 0.00130 3.20 0.00132 3.08 0.00130 3.06 0.00130 3.07 0.00132 3.10 0.00138 Hollow sphere state in the formula substrate -- -- Hollow balls are evenly dispersed Hollow balls are evenly dispersed Hollow balls are evenly dispersed Hollow balls are evenly dispersed

As can be seen in Table 1 above, Comparative Examples 1 and 2 primarily utilize spherical, solid, synthetic silica fillers, without using hollow silica microspheres or a suspension of hollow silica microspheres. In contrast, Examples 1 through 4 utilize the resin composition formulation of the present invention, partially replacing the spherical, solid, synthetic silica fillers with hollow silica microspheres or a suspension of hollow silica microspheres. This allows the production of substrates with uniformly dispersed colloids, excellent post-processing appearance, and electrical properties (Dk) below 3.10.

In summary, the present invention provides a resin composition that utilizes a nitrogen-containing heteroaromatic cyclostyrene polymer resin as its main framework and partially replaces the spherical solid synthetic silica filler with hollow silica microspheres or a suspension of hollow silica microspheres. This allows for the preparation of a substrate with a uniformly dispersed formulation, excellent post-processing appearance, and electrical properties (Dk) below 3.10 and Df < 0.00130, further reducing both the dielectric constant and dielectric loss.

without

without

Claims (6)

A resin composition comprising: a nitrogen-containing heteroaromatic cyclostyrene polymer resin; a PPE resin; a polydivinylbenzene resin; an SBS resin; a crosslinking agent; a phosphorus-based flame retardant; spherical silica; hollow silica microspheres or a suspension of hollow silica microspheres; a peroxide accelerator; and a siloxane coupling agent, wherein, based on the total weight of the resin composition, the nitrogen-containing heteroaromatic cyclostyrene polymer resin is added in an amount of 10 wt% to 60 wt%, the PPE resin is added in an amount of 10 wt% to 40 wt%, the polydivinylbenzene resin is added in an amount of 10 wt% to 40 wt%, the SBS resin is added in an amount of 1 wt% to 30 wt%, and the crosslinking agent is added in an amount of 1 The phosphorus content of the phosphorus-based flame retardant is 2 phr to 5 phr, the spherical silica is added in an amount of 20 wt% to 60 wt%, the hollow silica microspheres or the hollow silica microsphere suspension is added in an amount of 1 wt% to 20 wt%, wherein, based on 100 phr of the resin composition, the peroxide accelerator is added in an amount of 0.1 phr to 5 phr, and the siloxane coupling agent is added in an amount of 0.1 phr to 5 phr. The resin composition of claim 1, wherein the nitrogen-containing heteroaromatic ring of the nitrogen-containing heteroaromatic ring styrene polymer resin includes a pyrimidine ring, a pyrazine ring, a oxazine ring, a pyridine ring, a pyrrole ring or a pyrazole ring. The resin composition of claim 1, wherein the molecular weight Mn of the nitrogen-containing heteroaromatic cyclostyrene polymer resin is 1500 to 3100. The resin composition as described in claim 1, wherein the median particle size (D50) of the hollow silica microspheres or the hollow microspheres in the suspension of hollow silica microspheres is 0.1 µm to 10 µm, the hollow ratio is 50% to 80%, and the outer shell surface is modified to an acrylic or vinyl group. The resin composition of claim 1, wherein the solvent of the silica hollow microsphere suspension comprises toluene or butanone. The resin composition of claim 1, wherein the electrical properties of the resin composition are Dk of 3.0 to 3.2 and Df of less than 0.00130.