TWI858851B - Thermosetting resin composition - Google Patents

Abstract

The present disclosure provides a thermosetting resin composition. The thermosetting resin composition is 100 parts by weight, and includes (A) 30 to 50 parts by weight of unsaturated polyphenylene ether resin, (B ) 10 to 30 parts by weight of styrene-butylene block copolymer, (C) 5 to 25 parts by weight of cycloolefin compound, (D) 1 to 10 parts by weight of vinyl phenyl compound and (E) 5 to 25 parts by weight of crosslinking agent. In detail, the unsaturated polyphenylene ether resin includes at least one carbon-carbon double bond or carbon-carbon triple bond, and at least one carboxyl group. The thermosetting resin composition of the present disclosure has specific components and proportions, and is applied to electronic circuit substrates to provide the characteristics of low dielectric constant, low dielectric loss and high peel strength of electronic circuit substrates.

Description

Thermosetting resin composition

The present invention relates to a thermosetting resin composition, in particular to a thermosetting resin composition used for making copper-clad laminates and prepregs for PCB circuit boards.

The advancement of modern information processing technology has prompted digital circuits to enter a stage of high-speed information processing and high-frequency signal transmission. In high-frequency circuits, electrical signal transmission loss is represented by the sum of dielectric loss, conductor loss, and radiation loss. The higher the frequency of the electrical signal, the greater the electrical signal transmission loss.

Since transmission loss will cause electrical signals to attenuate and destroy the reliability of electrical signals, dielectric loss, conductor loss and radiation loss must be reduced. The dielectric loss of electrical signals is proportional to the product of the dielectric loss angle of the insulator forming the circuit and the frequency of the electrical signal used. Therefore, by selecting insulating materials with a small dielectric loss angle, the transmission loss of electrical signals can be reduced.

US Patent US9428646B2 discloses the use of unsaturated polyphenylene ether and polybutadiene resin mixed to control the dielectric properties of the insulating plate, but the compatibility of unsaturated polyphenylene ether and butadiene is poor, and the mixed product is prone to precipitation. Furthermore, bismaleimide is added to provide better copper bonding, however, the laminate prepared from these materials has a relatively high dissipation factor.

US Patent US5223568A discloses a laminate made of polybutadiene, polyisoprene and thermoplastic elastomer, and the obtained laminate has the characteristic of low loss. However, the polybutadiene sheet has poor peel strength when bonded to copper foil, and other properties such as mechanical strength, flammability and heat resistance are even worse.

Therefore, it is necessary to provide a thermosetting resin composition for use in electronic circuits to meet the requirements of electronic circuit substrates for comprehensive properties such as low dielectric constant, low dielectric loss, and high peel strength.

The main purpose of the present invention is to provide a thermosetting resin composition, wherein the total weight of the thermosetting resin composition is 100 parts by weight, the thermosetting resin composition comprises: (A) 30 to 50 parts by weight of an unsaturated polyphenylene ether resin; (B) 10 to 30 parts by weight of a styrene-butylene block copolymer; (C) 5 to 25 parts by weight of a cycloolefin compound; (D) 1 to 10 parts by weight of a vinylphenyl compound; and (E) 5 to 25 parts by weight of a crosslinking agent; wherein the unsaturated polyphenylene ether resin comprises at least one carbon-carbon double bond or carbon-carbon triple bond and at least one carboxyl group.

In one embodiment of the present invention, the unsaturated polyphenylene ether resin comprises at least one carboxyl group selected from the group consisting of carboxylic acid, anhydride, amide and ester.

In one embodiment of the present invention, the styrene-butylene block copolymer is a block copolymer derived from an alkenyl aromatic compound block and a conjugated diene block.

In one embodiment of the present invention, the styrene-butylene block copolymer is a styrene-butylene block copolymer grafted with maleic anhydride.

In one embodiment of the present invention, the styrene-butylene block copolymer is at least one selected from the group consisting of styrene-butadiene diblock copolymer (SB), styrene-butadiene-styrene triblock copolymer (SBS), styrene-isoprene diblock copolymer (SI), styrene-isoprene-styrene triblock copolymer (SIS), styrene-(ethylene-butylene)-styrene triblock copolymer (SEBS), styrene-(ethylene-propylene)-styrene triblock copolymer (SEPS) and styrene-(ethylene-butylene) diblock copolymer (SEB).

In one embodiment of the present invention, the cycloolefin compound is at least one selected from the group consisting of dicyclopentadiene (DCPD) monomer, dicyclopentadiene polymer, norbornene monomer and 5-norbornene polymer.

In one embodiment of the present invention, the vinylphenyl compound is selected from stilbene and/or bromostyrene.

In one embodiment of the present invention, the crosslinking agent is at least one selected from the group consisting of triallyl isocyanurate, triallyl cyanurate, bismaleimide resin and divinylbenzene.

In one embodiment of the present invention, the thermosetting resin composition further comprises: an accelerator, and the accelerator is selected from di-tert-butyl peroxide, dilauryl peroxide, dibenzoyl peroxide, tert-butyl peroxyacetate, tert-butyl peroxybenzoate, 1,1-di-tert-butyl peroxy-3,5,5-trimethylcyclohexane, 1,1-di-tert-butyl peroxycyclohexane, 2,2-di(tert-butyl peroxy)butyl At least one of the group consisting of 2,5-dimethyl-2,5-di-tert-butylperoxyhexane, 2,5-dimethyl-2,5-di-tert-butylperoxyhexyne and diisopropylbenzene hydroperoxide.

In one embodiment of the present invention, the thermosetting resin composition further includes: an inorganic filler, and the inorganic filler is at least one selected from the group consisting of silicon dioxide, aluminum oxide, aluminum hydroxide, magnesium oxide, magnesium hydroxide, calcium carbonate, aluminum nitride, boron nitride, aluminum silicon carbide, silicon carbide, titanium dioxide, zinc oxide, zirconium oxide, barium sulfate, magnesium carbonate, barium carbonate, mica, talc and graphene.

One of the beneficial effects of the present invention is that the thermosetting resin composition provided by the present invention can provide and meet the requirements of electronic circuit substrates for comprehensive properties such as low dielectric constant, low dielectric loss, and high peel strength through the technical solution of "the unsaturated polyphenylene ether resin includes at least one carbon-carbon double bond or carbon-carbon triple bond, and at least one carboxyl group" and a specific formula ratio.

The technical solution adopted by the present invention is to provide a thermosetting resin composition, wherein the total weight of the thermosetting resin composition is 100 parts by weight, and the thermosetting resin composition includes: (A) 30 to 50 parts by weight of unsaturated polyphenylene ether resin; (B) 10 to 30 parts by weight of styrene-butylene block copolymer; (C) 5 to 25 parts by weight of cycloolefin compound; (D) 1 to 10 parts by weight of vinylphenyl compound; and (E) 5 to 25 parts by weight of crosslinking agent; wherein the unsaturated polyphenylene ether resin includes multifunctional groups: at least one carbon-carbon double bond or carbon-carbon triple bond, and at least one carboxyl group.

Specifically, polyphenylene ether (PPE) resin has good mechanical properties and excellent dielectric properties, with a Dk/Df of about 2.45/0.0007 at a frequency of 1 MHz, and is the preferred resin material for substrates of high-frequency printed circuit boards. Preferably, the unsaturated polyphenylene ether resin used in the present invention is modified and includes the following multifunctional compounds: at least one carbon-carbon double bond or carbon-carbon triple bond, and at least one carboxyl group, for example, carboxylic acid, anhydride, amide, ester. More specifically, the unsaturated polyphenylene ether resin used in the present invention can be selected from terminal vinyl benzyl modified polyphenylene ether resin or difunctional methacrylate modified polyphenylene ether resin.

The styrene-butylene block copolymer comprises a block copolymer of (A) a block derived from an alkenyl aromatic compound and (B) a block derived from a conjugated diene. More specifically, the styrene-butylene block copolymer can be selected from at least one of the group consisting of styrene-butadiene diblock copolymer (SB), styrene-butadiene-styrene triblock copolymer (SBS), styrene-isoprene diblock copolymer (SI), styrene-isoprene-styrene triblock copolymer (SIS), styrene-(ethylene-butylene)-styrene triblock copolymer (SEBS), styrene-(ethylene-propylene)-styrene triblock copolymer (SEPS) and styrene-(ethylene-butylene) diblock copolymer (SEB). In a specific embodiment of the present invention, the styrene-butylene block copolymer is a styrene-butylene block copolymer grafted with maleic anhydride.

The vinyl phenyl compound is selected from stilbene and/or bromostyrene compounds, for example, Saytex 3010 bromostyrene commercially available from Albemarle. More specifically, the bromostyrene compound provides high flame retardancy, thermal stability, good compatibility, and no precipitation.

The cycloolefin is at least one selected from the group consisting of dicyclopentadiene (DCPD) monomers having a bridging cycloolefin, dicyclopentadiene polymers, norbornene monomers and norbornene polymers, or a combination thereof.

Preferably, the crosslinking agent can be at least one selected from the group consisting of triallyl isocyanurate (TAIC), triallyl cyanurate (TAC), dimaleimide resin and divinylbenzene. If the crosslinking agent ratio is too high, the thermal conductivity of the crosslinked resin composition will be reduced (for example, the thermal conductivity coefficient K value will be reduced). If the crosslinking agent ratio is too low, the thermal properties of the crosslinked resin composition will be poor (for example, the glass transition temperature Tg will be reduced).

Furthermore, different promoters can be used depending on the physical property requirements of the product. Preferably, the promoter is a peroxide crosslinking promoter, more specifically, an organic peroxide free radical initiator. For example, the accelerator is at least one selected from the group consisting of di-tert-butyl peroxide, dilauryl peroxide, dibenzoyl peroxide, tert-butyl peroxyacetate, tert-butyl peroxybenzoate, 1,1-di-tert-butylperoxy-3,5,5-trimethylcyclohexane, 1,1-di-tert-butylperoxycyclohexane, 2,2-di(tert-butylperoxy)butane, bis(4-tert-butylcyclohexyl)peroxydicarbonate, hexadecyl peroxydicarbonate, tetradecyl peroxydicarbonate, dipentyl peroxide, diisopropylbenzene peroxide, di(tert-butylperoxyisopropyl)benzene, 2,5-dimethyl-2,5-di-tert-butylperoxyhexane, 2,5-dimethyl-2,5-di-tert-butylperoxyhexyne, and diisopropylbenzene hydroperoxide. In one embodiment, the accelerator is dicumyl peroxide (DCP) commercially available from Arkema.

Silane coupling agents can improve the metal adhesion of polyolefin materials. Silane coupling agents commonly used in the art can be selected. For example, the inorganic functional group of the silane coupling agent is a trifunctional group, i.e., Si-(OR2). In one embodiment of the present invention, the silane coupling agent can be vinyl silane, amino silane, methacryloxy silane, etc.

Preferably, the flame retardant is a phosphorus-containing flame retardant and a brominated flame retardant. Examples of brominated flame retardants include ethylene-bis(tetrabromophenylene dicarboxamide), decabromodiphenylethane, and 2,4,6-tris(2,4,6-tribromophenoxy)-1,3,5-triazine. Examples of phosphorus-containing flame retardants include bisphenol diphenyl phosphate, ammonium polyphosphate, hydroquinone bis(diphenyl phosphate), bisphenol A bis(diphenyl phosphate), tri(2-carboxyethyl)phosphine (TCEP), tri(chloroisopropyl) phosphate, trimethyl phosphate (TMP), dimethyl methylphosphonate (DMMP), resorcinol bis(xylyl phosphate), phosphazene, melamine polyphosphate, 9,10-dihydro-9-oxo-10-phosphaphenanthrene-10-oxide (DOPO) and its derivatives or resins, melamine cyanurate, and trihydroxyethyl isocyanurate.

In one embodiment of the present invention, the flame retardant may be a DOPO compound, such as a DOPO resin (DOPO-HQ, DOPO-NQ, DOPO-PN or DOPO-BPN) and an epoxy resin containing DOPO. More specifically, DOPO-BPN may be selected from bisphenol-formaldehyde novolac compounds, such as DOPO-BPAN, DOPO-BPFN or DOPO-BPSN.

The inorganic filler is selected from the group consisting of silica, alumina, barium sulfate, talc, clay, mica powder, and boron nitride. More preferably, the inorganic filler is selected from the group consisting of fused silica, amorphous silica, and hollow silica, such as Lianrui D1028L spherical silica, which can adjust the dielectric constant, dielectric loss, and thermal expansion coefficient of the dielectric substrate layer. Specifically, the inorganic filler can increase the thermal conductivity of the resin composition, improve its thermal expansion and mechanical strength.

[Example]

Tables 1 and 2 of the present invention provide the composition ratios of the thermosetting resin composition of Examples 1 to 7 and Comparative Examples 1 to 5, respectively. The thermosetting resin composition is prepared according to each composition ratio, and the reinforcing material is immersed in or wetted by roller coating. The solvent is evaporated by baking and the resin is semi-cured, cooled and rolled to form a semi-cured film. The semi-cured film is further subjected to heat pressing to form a dielectric substrate layer. Specifically, the heat pressing is performed on four and two 18 semi-cured films of the same batch. μm copper foil is stacked in the order of copper foil, four semi-cured adhesive sheets, and copper foil, and then pressed at 220℃ for 2 hours under vacuum conditions to form a copper foil substrate, in which the four semi-cured adhesive sheets are cured to form an insulating layer between the two copper foils.

The physical properties of the obtained copper foil substrate were further tested and recorded in Table 1 and Table 2.

[Physical property test]

Peel strength: Peel tensile test is performed according to industry standards.

Heat resistance of copper foil laminate (T288): Also known as "soldering result", the heat resistance experiment is based on the industry standard IPC-TM-650 2.4.24.1, which is to immerse the copper foil laminate in a 288℃ tin furnace until the time required for the board to explode.

Dielectric constant (Dk): Measured according to IPC-TM-650 2.5.5 test specification. The dielectric constant represents the electronic insulation properties of the produced film. The lower the value, the better the electronic insulation properties.

Dielectric loss (Df): Measured according to IPC-TM-650 2.5.5 test specification. Dielectric loss indicates the ability of a substance to absorb microwaves of a certain frequency at a certain temperature. Usually in the specifications of communication products, the lower the dielectric loss value, the better.

Coefficient of thermal expansion (CTE): measured according to IPC-TM-650-2.4.24 test standard.

Table 1. Examples 1 to 4 and Comparative Examples 1 to 2 Product Name Embodiment 1 Embodiment 2 Embodiment 3 Embodiment 4 Comparison Example 1 Comparison Example 2 Polyphenylene oxide SA9000 43 43 43 OPE-2st 43 SA90 43 PPO640 43 Styrene-butylene block copolymer D1118 twenty two twenty two twenty two twenty two twenty two twenty two G1648 KIC19-023 Vinylphenyl compounds Saytex3010 15 15 15 15 15 15 Cycloolefins DCPD monomer 5 5 5 5 5 5 Topas 5013 Crosslinking agent TAIC 15 15 15 15 15 15 MIR3000 Enhancer DCP 1.5 1.5 1.5 1.5 1.5 1.5 Silane coupling agent KBM503 1.8 1.8 1.8 1.8 1.8 1.8 Flame retardant Saytex8010 5 5 5 5 5 5 Inorganic filler D1028L 200 200 200 200 200 200 Reinforcement Materials E-Glass NE-Glass PS-Glass E-Glass E-Glass E-Glass Peel strength Lb/inch 4.2 4.08 4.16 4.01 5.5 6.7 Heat resistant tinning 288℃ ＞10min ＞10min ＞10min ＞10min 2min ＜1min DK 10G 3.7 3.3 3.1 3.6 4,3 3.7 DF 10G 0.005 0.0021 0.0011 0.0042 0.0073 0.0061 CTE % 1.83% 1.68% 2.20% 1.81% 2.28% 2.20%

Table 2. Examples 5 to 7 and Comparative Examples 3 to 5 Product Name Embodiment 5 Embodiment 6 Embodiment 7 Comparison Example 3 Comparison Example 4 Comparison Example 5 Polyphenylene oxide SA9000 43 43 43 20 43 43 OPE-2st SA90 PPO640 Styrene-butylene block copolymer D1118 G1648 twenty two KIC19-023 twenty two twenty two 45 twenty two twenty two Vinylphenyl compounds Saytex3010 15 15 15 15 15 Cycloolefins DCPD monomer 5 5 20 Topas 5013 5 5 5 Crosslinking agent TAIC 15 15 15 15 30 MIR3000 Enhancer DCP 1.5 1.5 1.5 1.5 1.5 1.5 Silane coupling agent KBM503 1.8 1.8 1.8 1.8 1.8 1.8 Flame retardant Saytex8010 5 5 5 5 5 5 Inorganic filler D1028L 200 200 200 200 200 200 Reinforcement Materials E-Glass E-Glass E-Glass E-Glass E-Glass E-Glass Peel strength Lb/inch 4.02 4.46 4.4 5.12 3.63 3.82 Heat resistant tinning 288℃ ＞10min ＞10min ＞10min 4min 6min 1min DK 10G 3.58 3.57 3.48 3.63 3.68 3.67 DF 10G 0.004 0.0042 0.0039 0.0048 0.0043 0.0048 CTE % 1.93% 1.95% 2.05% 2.45% 2.20% 2.10%

OPE-2St 2200: Terminal vinyl benzyl-modified polyphenylene ether (Mw: about 3600, purchased from Mitsubishi Gas Chemical Co., Ltd.)

SA-9000: Bifunctional methacrylate modified polyphenylene ether (Mw: 1700, purchased from SABIC)

SA90: Unmodified polyphenylene ether (Mw: 1700, commercially available from Saudi Basic Industries Company Innovative Plastics Co., Ltd.)

PPO640: unmodified polyphenylene ether, (molecular weight: 18000, commercially available from Saudi Basic Industries Company Innovative Plastics Co., Ltd.)

D-1118: Solid SB-SBS copolymer (commercially available from Keten Polymers)

G1648: SEBS compound (commercially available from Kalten Polymers)

KIC19-023: Maleic anhydride grafted SEBS copolymer (commercially available from Keten Polymers)

Saytex3010: Brominated styrene

DCPD monomer: dicyclopentadiene (purchased from Zibo Luhua Hongjin New Materials Co., Ltd.)

Topas COC 5013: Cyclic olefin copolymer with non-reactive functional groups

TAIC: Triallyl isocyanurate

MIR3000: Biphenyl BMI

DCP: dicumyl peroxide (commercially available from Arkema)

KBM503: Vinyl silane (purchased from Shin-Etsu Corporation, Japan)

saytex 8010:Decabromodiphenylethane

D1028L: Spherical silica purchased from Lianrui Commercial

Referring to Table 1, Examples 1 to 4 and Comparative Examples 1 and 2 show that the dielectric properties of the unmodified polyphenylene ether deteriorate due to the presence of hydroxyl groups. In addition, the unmodified polyphenylene ether has better bleaching heat resistance.

As shown in Table 2, maleic anhydride-modified styrene-butylene block copolymers can effectively improve peel strength, and their effect on dielectric properties is relatively small. Comparative Example 3 shows that a decrease in the proportion of polyphenylene ether in the thermosetting resin composition will lead to poor heat resistance, while the addition of vinyl phenyl compounds and crosslinking agents (triallyl isocyanurate, TAIC) helps to improve heat resistance.

The beneficial effect of the present invention is that the thermosetting resin composition provided by the present invention can provide and meet the requirements of electronic circuit substrates for comprehensive properties such as low dielectric constant, low dielectric loss, and high peel strength through the technical solution of "the unsaturated polyphenylene ether resin includes multiple functional groups: at least one carbon-carbon double bond or carbon-carbon triple bond, and at least one carboxyl group" and a specific formula ratio.

More specifically, the unsaturated polyphenylene ether resin modified with specific groups improves the low dielectric properties caused by the hydroxyl group in polyphenylene ether and increases heat resistance. The styrene-butylene block copolymer modified with maleic anhydride further improves the peel strength while maintaining its dielectric properties.

The above description is only a preferred specific example of the present invention, and does not limit the patent scope of the present invention. Therefore, all equivalent changes made by applying the contents of the present invention are also included in the scope of the present invention and are appropriately stated.

without

without

Claims (9)

A thermosetting resin composition, with the total weight of the thermosetting resin composition being 100 parts by weight, comprises: (A) 30 to 50 parts by weight of an unsaturated polyphenylene ether resin; (B) 10 to 30 parts by weight of a styrene-butylene block copolymer grafted with maleic anhydride; (C) 5 to 25 parts by weight of a cycloolefin compound; (D) 1 to 10 parts by weight of a vinylphenyl compound; and (E) 5 to 25 parts by weight of a crosslinking agent; wherein the unsaturated polyphenylene ether resin comprises at least one carbon-carbon double bond or carbon-carbon triple bond, and at least one carboxyl group, and the thermosetting resin composition is not prepolymerized using a ruthenium catalyst. The thermosetting resin composition as described in claim 1, wherein the unsaturated polyphenylene ether resin comprises at least one carboxyl group selected from the group consisting of carboxylic acids, anhydrides, amides and esters. The thermosetting resin composition as described in claim 1, wherein the styrene-butylene block copolymer is a block copolymer derived from an alkenyl aromatic compound block and a conjugated diene block. The thermosetting resin composition as described in claim 1, wherein the styrene-butylene block copolymer is at least one selected from the group consisting of styrene-butadiene diblock copolymer (SB), styrene-butadiene-styrene triblock copolymer (SBS), styrene-isoprene diblock copolymer (SI), styrene-isoprene-styrene triblock copolymer (SIS), styrene-(ethylene-butylene)-styrene triblock copolymer (SEBS), styrene-(ethylene-propylene)-styrene triblock copolymer (SEPS) and styrene-(ethylene-butylene) diblock copolymer (SEB). The thermosetting resin composition as described in claim 1, wherein the cycloolefin compound is at least one selected from the group consisting of dicyclopentadiene (DCPD) monomers, dicyclopentadiene polymers, norbornene monomers and 5-norbornene polymers. The thermosetting resin composition as described in claim 1, wherein the vinylphenyl compound is diphenylethylene and/or bromostyrene. The thermosetting resin composition as described in claim 1, wherein the crosslinking agent is at least one selected from the group consisting of triallyl isocyanurate, triallyl cyanurate, dimaleimide resin and divinylbenzene. The thermosetting resin composition as claimed in claim 1 further comprises: an accelerator, wherein the accelerator is selected from di-tert-butyl peroxide, dilauryl peroxide, dibenzoyl peroxide, tert-butyl peroxyacetate, tert-butyl peroxybenzoate, 1,1-di-tert-butylperoxy-3,5,5-trimethylcyclohexane, 1,1-di-tert-butylperoxycyclohexane, 2,2-di(tert-butylperoxy)butane, di-tert-butylperoxy-1,1-di-tert-butylperoxy-2,2-di-tert-butylperoxy-1 ... At least one of the group consisting of (4-tert-butylcyclohexyl) peroxydicarbonate, hexadecyl peroxydicarbonate, tetradecyl peroxydicarbonate, dipentylhexyl peroxide, diisopropylbenzene peroxide, di(tert-butylperoxyisopropyl)benzene, 2,5-dimethyl-2,5-di-tert-butylperoxyhexane, 2,5-dimethyl-2,5-di-tert-butylperoxyhexyne and diisopropylbenzene hydroperoxide. The thermosetting resin composition as described in claim 1 further comprises: an inorganic filler, and the inorganic filler is at least one selected from the group consisting of silicon dioxide, aluminum oxide, aluminum hydroxide, magnesium oxide, magnesium hydroxide, calcium carbonate, aluminum nitride, boron nitride, aluminum silicon carbide, silicon carbide, titanium dioxide, zinc oxide, zirconium oxide, barium sulfate, magnesium carbonate, barium carbonate, mica, talc and graphene.