TWI822113B - Low dielectric resin composition - Google Patents

Abstract

The invention provides a low dielectric resin composition, which includes a SBS resin, a cross-linking agent, a PPE resin, a halogen-free flame retardant, a spherical silica and a siloxane coupling agent. The low dielectric resin composition of the invention improves the state of phase separation, enhances the fluidity and filling properties, and further increases the overall processability.

Description

Low dielectric resin composition

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

In recent years, with the development of 5G communications, copper-clad laminate materials have been developed towards the goal of lower dielectric properties. The dielectric constant of current substrates is about 3.2 to 5.0, which is not conducive to future high-frequency fast transmission applications. A certain proportion of liquid rubber is added to current low dielectric formulas. Liquid rubber has the characteristics of low molecular weight (Mn 1000 to 5000), high solubility, and multiple reactive groups (1, 2 vinyl: 10% to 90%). , suitable for high-frequency and high-speed substrate formulations. However, adding a large amount of liquid rubber can easily cause phase separation between resins, and the fluidity and rubber filling properties will become worse, resulting in a decrease in overall processability.

Based on the above, developing a low-dielectric resin composition can effectively change the phase separation situation, improve fluidity and gel-filling properties, and thereby enhance overall processability. This is an urgent goal for those skilled in the art.

The present invention provides a low dielectric resin composition that can effectively change the phase separation situation, improve fluidity and gel-filling properties, and thereby enhance overall processability.

The resin composition of the present invention includes SBS resin, cross-linking agent, polyphenylene ether resin, halogen-free flame retardant, spherical silica and siloxane coupling agent.

In one embodiment of the present invention, based on the total weight of the resin composition, the added amount of SBS resin is 20 wt% to 50 wt%, the added amount of cross-linking agent is 5 wt% to 30 wt%, and the polyphenylene ether is added in an amount of 20 wt% to 50 wt%. The added amount of resin is 10 wt% to 60 wt%, and the added amount of spherical silica is 20 wt% to 50 wt%.

In an embodiment of the present invention, the added amount of halogen-free flame retardant is 10 wt% to 25 wt%.

In an embodiment of the present invention, the added amount of the siloxane coupling agent is 0.1 phr to 5 phr.

In one embodiment of the present invention, the SBS resin has a styrene ratio of 10% to 40%, a 1,2 vinyl ratio of 60% to 90%, and a 1,2 vinyl ratio of 10% to 30%. 4 vinyl ratio.

In an embodiment of the present invention, the molecular weight MW of the SBS resin is 3500 to 5500.

In one embodiment of the present invention, the spherical silica has acrylic or vinyl surface modification.

In one embodiment of the present invention, the purity of spherical silica is above 99.0%.

In an embodiment of the present invention, the average particle size D50 of the spherical silica is 2.0 μm to 3.0 μm.

In an embodiment of the present invention, the dielectric constant of the substrate made of the resin composition is 3.0 to 3.1, and the dielectric loss is less than 0.002.

Based on the above, the resin composition of the present invention uses SBS resin instead of liquid rubber to improve the phase separation between resins, improve fluidity and rubber filling properties, thereby enhancing overall processability while maintaining low dielectric properties.

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

In this article, the range expressed by "one value to another value" is a summary expression that avoids enumerating all the values in 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 are written in the description. The numerical range is the same.

The resin composition of the present invention includes SBS resin, cross-linking agent, polyphenylene ether resin, halogen-free flame retardant, spherical silica and siloxane coupling agent. Below, the various components mentioned above will be described in detail. SBS resin

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%. Proportion. The molecular weight MW of SBS resin is about 3500 to 5500. Based on the total weight of the resin composition, the added amount of SBS resin is, for example, 20 wt% to 50 wt%. By using SBS resin instead of liquid rubber, the phase separation between resins is improved, and the fluidity and filling properties are improved, thereby enhancing the overall processability while maintaining low dielectric properties. Cross-linking agent

In this embodiment, the cross-linking agent is used to increase the cross-linking degree of the thermosetting resin, adjust the rigidity and toughness of the base material, and adjust the processability; the type used can be 1,3,5-triallyl cyanurate. Triallyl cyanurate (TAC), triallyl isocyanurate (TAIC), trimethallyl isocyanurate (TMAIC), diallyl phthalate One or more combinations of (diallyl phthalate), divinylbenzene or 1,2,4-Triallyl trimellitate. Based on the total weight of the resin composition, the added amount of the cross-linking agent is, for example, 5 wt% to 30 wt%. Polyphenylene ether resin

In this embodiment, the polyphenylene ether resin is a thermosetting polyphenylene ether resin, and is a composition having a terminal group of styrene-type polyphenylene ether and a terminal acrylic-type polyphenylene ether. Based on the total weight of the resin composition, the added amount of the polyphenylene ether resin is, for example, 10 wt% to 60 wt%. For example, the structure of styrenic polyphenylene ether is shown in structural formula (A):

Wherein R1~R8 can be allyl, hydrogen or C1~C6 alkyl, or selected from one or more of the above groups, X can be: O (oxygen atom), ;where P1 is styrene group, , a=an integer from 1 to 99.

The structure of an acrylic polyphenylene ether terminal is shown in structural formula (B):

Wherein R1~R8 can be allyl, hydrogen or C1~C6 alkyl, or be selected from one or more of the above groups. X can be: O (oxygen atom), ; P2 is or , b=an integer from 1 to 99.

Specific examples of polyphenylene ether resins include, but are not limited to, bishydroxy polyphenylene ether resin (such as SA-90, available from Sabic Corporation), vinyl benzyl polyphenylene ether resin (such as OPE-2st, available from Mitsubishi Gas Chemical Co., Ltd. ), methacrylate polyphenylene ether resin (such as SA-9000, available from Sabic Company), vinyl benzyl modified bisphenol A polyphenylene ether resin or vinyl extended chain sawn ether resin. The aforementioned polyphenylene ether is preferably vinyl polyphenylene ether. Halogen-free flame retardant

In this embodiment, a specific example of a halogen-free flame retardant may be a phosphorus flame retardant selected from phosphate esters, such as: triphenyl phosphate (TPP), resorcinol bisphosphate (RDP), bisphosphonate Phenol A bis(diphenyl)phosphate (BPAPP), bisphenol A bis(dimethyl)phosphate (BBC), resorcinol diphosphate (CR-733S), resorcin-bis(di -2,6-Dimethylphenylphosphate) (PX-200); can be selected from phosphazenes, such as: polybis(phenoxy)phosphazene (SPB-100); ammonium polyphosphates , Melamine Polyphosphate (MPP, Melamine Polyphosphate), Melamine cyanurate; one or more combinations of DOPO flame retardants can be selected, such as DOPO (such as structural formula C), DOPO-HQ (such as structural formula D), double DOPO derived structures (such as structural formula E), etc.; aluminum-containing hypophosphorous lipids (such as structural formula F). The added amount of the halogen-free flame retardant is, for example, 10 wt% to 25 wt%. Spherical silica

In this embodiment, spherical silica can preferably be prepared using a synthetic method to reduce electrical properties and maintain fluidity and gel-filling properties. Spherical silica has acrylic or vinyl surface modification, the purity is about 99.0% or more, and the average particle size D50 is about 2.0 μm to 3.0 μm. Based on the total weight of the resin composition, the added amount of spherical silica is, for example, 20 wt% to 50 wt%. Siloxane coupling agent

In this embodiment, the siloxane coupling agent may include but is not limited to siloxane compounds. In addition, according to the type of functional group, it can be divided into amino silane compound (amino silane), epoxy silane compound (epoxide silane), vinyl silane compound, ester silane compound, hydroxy silane compound, isocyanate silane compound, methyl silane compound Acryloxysilane compound and acryloxysilane compound. The added amount of the siloxane coupling agent is, for example, 0.1 phr to 5 phr.

It should be noted that the resin composition of the present invention can be processed into prepregs and copper foil substrates (CCL) according to actual design requirements. Therefore, prepregs made from the resin composition of the present invention are used. And the copper foil substrate also has better reliability (can maintain the required electrical characteristics). In more detail, the dielectric constant of the substrate made of the resin composition is about 3.0 to 3.1, and the dielectric loss is less than about 0.002.

Hereinafter, the impact-resistant and flame-retardant polyester material of the present invention will be described in detail through experimental examples. However, the following experimental examples are not intended to limit the present invention. Experimental example

In order to prove that the resin composition proposed by the present invention can effectively improve the phase separation between resins while maintaining low dielectric properties, this experimental example is specially conducted below. Assessment method

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

The glass transition temperature (°C) is measured with a dynamic mechanical analyzer (DMA).

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

288℃ soldering heat resistance (seconds): The sample is heated in a 120℃ and 2atm pressure cooker for 120 minutes and then immersed in a 288℃ soldering furnace, and the time required for the sample to explode and delaminate is recorded.

Dielectric constant Dk: Use dielectric analyzer (Dielectric Analyzer) HP Agilent E4991A to measure the dielectric constant Dk at a frequency of 10GHz.

Dielectric loss Df: Use dielectric analyzer (Dielectric Analyzer) HP Agilent E4991A to test the dielectric loss Df at a frequency of 10GHz.

Resin flow rate: Use a press at 170°C plus or minus 2.8°C to press at 200 plus or minus 25 PSI for 10 minutes. After fusion and cooling, punch out the disc. Accurately weigh the disc and calculate the resin outflow.

Resin phase separation (slice analysis): Step 1: Cut the copper foil substrate into a size of 1cm*1cm and place it into the mold for resin grouting. Step 2: After the resin is completely dry and hardened, grind and polish the sample. Step 3: Use high-resolution microscopes such as OM/SEM to analyze the sample to confirm whether there is resin phase separation inside the sample. Property assessment

The resin compositions shown in Table 1 and Table 2 were mixed with toluene to form a varnish of a thermosetting resin composition. The above varnish was impregnated with Nanya fiberglass cloth (Nanya Plastics Company, cloth type 1078LD) at room temperature. Then dry it at 170°C (impregnation machine) for a few minutes to obtain a prepreg with a resin content of 79wt%. Finally, 4 pieces of prepreg are stacked layer by layer between two pieces of 35μm thick copper foil, and the pressure and temperature are 25kg/cm2. Keep the constant temperature at 85°C for 20 minutes, then heat to 210°C at a heating rate of 3°C/min, maintain the constant temperature for 120 minutes, and then slowly cool to 130°C to obtain a 0.59mm thick copper foil substrate.

In Table 1 and Table 2, the details of each component are as follows: Polyphenylene ether resin (purchased from Sabic Company, model: SA-9000) Liquid rubber resin (Japan Soda, model: B-2000) SBS resin (Japan Soda) Cross-linking agent (triallyl isocyanurate, TAIC) Synthetic silica (Sanshiji, model: EQ2410-SMC) Table 1 Comparative example Example 1 2 3 1 Recipe ratio Polyphenylene ether resin (%) 50 50 50 50 Liquid rubber resin (%) 35 20 15 - SBS resin (%) - 15 20 35 Cross-linking agent (%) 15 15 15 15 Halogen-free flame retardant (phr) 30 30 30 30 Synthetic silica (%) 40 40 40 40 Peroxide (phr) 0.5 0.5 0.5 0.5 Siloxane coupling agent (phr) 0.5 0.5 0.5 0.5 B-stage curing temperature (℃) 130 130 130 130 Glass transition temperature (℃) 198 202 204 205 Water absorption (PCT 1/2 hour) (%) 0.15 0.16 0.17 0.18 Heat resistance (PCT 1/2 hour) OK OK OK OK Water absorption (PCT 2 hours) (%) 0.21 0.22 0.22 0.24 Heat resistance (PCT 2 hours) OK OK OK OK Dielectric constant (Dk) (measurement frequency 10GHz) 3.05 3.05 3.06 3.06 Loss factor (Df) (measurement frequency 10GHz) 0.0018 0.0018 0.0018 0.0018 Resin fluidity(%) twenty three 25 30 36 Resin phase separation (section analysis) There is phase separation There is phase separation No phase separation No phase separation

As can be seen from Table 1 above, Comparative Examples 1 and 2 mainly use liquid rubber, so there is a disadvantage of phase separation between resins. In Comparative Example 3, more SBS resin was added. Although no phase separation occurred, the fluidity was lower than that in Example 1. In comparison, Example 1 uses the resin composition formula of the present invention, in which SBS resin is used instead of liquid rubber. Therefore, the phase separation between resins can be effectively improved, and the fluidity and rubber filling properties can be improved while maintaining low Dielectric properties. Table 2 Comparative example Example 4 5 2 Recipe ratio Polyphenylene ether resin (%) 50 50 50 SBS resin (%) 35 35 35 Cross-linking agent (%) 15 15 15 Halogen-free flame retardant (phr) 30 30 30 Synthetic silica (%) - - 40 Combustion method silica (%) 40 - - Explosive silicon dioxide (%) - 40 - Peroxide (phr) 0.5 0.5 0.5 Siloxane coupling agent (phr) 0.5 0.5 0.5 B-stage curing temperature (℃) 130 130 130 Glass transition temperature (℃) 206 203 205 Water absorption (PCT 1/2 hour) (%) 0.23 0.21 0.18 Heat resistance (PCT 1/2 hour) OK OK OK Water absorption (PCT 2 hours) (%) 0.29 0.26 0.24 Heat resistance (PCT 2 hours) OK OK OK Dielectric constant (Dk) (measurement frequency 10GHz) 3.10 3.08 3.06 Loss factor (Df) (measurement frequency 10GHz) 0.0021 0.0020 0.0018 Resin fluidity(%) 35 36 36 Resin phase separation (section analysis) No phase separation No phase separation No phase separation

As can be seen from Table 2 above, Comparative Examples 4 and 5 used combustion silica and explosive silica respectively instead of the synthetic silica of the present invention. Therefore, the dielectric constant (Dk) and loss The performance of factors (Df) are all poor. In comparison, Example 2 uses the resin composition formula of the present invention, which uses synthetic silica. Therefore, the electrical properties can be effectively reduced while maintaining fluidity and gel-filling properties.

In summary, the resin composition of the present invention uses SBS resin instead of liquid rubber to effectively improve the phase separation between resins, improve fluidity and rubber filling properties, thereby enhancing overall processability while maintaining low dielectric characteristic. In addition, the resin composition of the present invention uses spherical silica prepared by a synthetic method to reduce electrical properties and maintain fluidity and gel-filling properties. On the other hand, the resin composition of the present invention contains a siloxane coupling agent to enhance the compatibility and cross-linking degree with glass fiber cloth and powder.

without

without

Claims (7)

A resin composition, including: SBS resin; cross-linking agent, including 1,3,5-triallyl cyanurate (TAC), triallyl isocyanurate (triallyl isocyanurate, TAIC), trimethallyl isocyanurate (TMAIC), diallyl phthalate, divinylbenzene, 1,2,4-trimethallyl isocyanurate Allyl ester (1,2,4-Triallyl trimellitate) or a combination thereof; polyphenylene ether resin; halogen-free flame retardant; spherical silica, the spherical silica is prepared using a synthetic method; and siloxane A mixture, wherein based on the total weight of the resin composition, the added amount of the SBS resin is 20wt% to 50wt%, the added amount of the cross-linking agent is 5wt% to 30wt%, and the polyphenylene ether resin is added The added amount is 10wt% to 60wt%, the added amount of the spherical silica is 20wt% to 50wt%, the added amount of the halogen-free flame retardant is 10wt% to 25wt%, the siloxane coupling agent is added The added amount is 0.1phr to 5phr. The resin composition according to claim 1, wherein the SBS resin has a styrene ratio of 10% to 40%, a 1,2 vinyl ratio of 60% to 90%, and a styrene ratio of 10% to 90%. 30% 1,4 vinyl ratio. The resin composition according to claim 1, wherein the SBS resin has a molecular weight MW of 3500 to 5500. The resin composition according to claim 1, wherein the spherical silica has acrylic or vinyl surface modification. The resin composition according to claim 1, wherein the purity of the spherical silica is 99.0% or more. The resin composition according to claim 1, wherein the average particle diameter D50 of the spherical silica is 2.0 μm to 3.0 μm. The resin composition according to claim 1, wherein the substrate made of the resin composition has a dielectric constant of 3.0 to 3.1 and a dielectric loss of less than 0.002.