TWI778506B - A thermosetting resin composition, prepreg and copper-clad laminate using the same - Google Patents

Abstract

The present invention provides a thermosetting resin composition, a prepreg and a copper-clad laminate using the same, and the thermosetting resin composition includes the following components: (A) styrene-butadiene- Styrene triblock copolymer, (B) thermosetting polyphenylene ether resin, (C) silane coupling agent; wherein the number-average molecular weight of the component (A) is less than 20,000, and the molecule contains 10-60% by weight styrene structure, and the content of butadiene added at the 1 and 2 positions in the molecule is greater than or equal to 90% by weight. Low dielectric constant D _k and low dielectric loss D _f , excellent heat resistance, interlayer adhesion and peel strength, and excellent CAF resistance.

Description

A thermosetting resin composition, a prepreg and a copper-clad laminate using the same

The invention belongs to the technical field of laminates, and provides a thermosetting resin composition, a prepreg using the same, and a copper-clad laminate.

In recent years, with the development of high-performance, high-function and networking of computers and information communication equipment, in order to transmit and process large-capacity information at high speed, the operation signal tends to be high-frequency, so the material of the circuit substrate is required. , especially in those electronic devices that use broadband, such as mobile communication devices, there is a rapid development.

Among existing materials for printed circuit boards, epoxy resins having excellent adhesive properties are widely used. However, epoxy circuit substrates generally have high dielectric constant and dielectric loss tangent (dielectric constant D _k is greater than 4, dielectric loss tangent D _f is about 0.02), and the high-frequency characteristics are not sufficient, which cannot adapt to the high frequency of the signal. requirements. Therefore, it is necessary to develop resins with excellent dielectric properties, that is, resins with low dielectric constant and dielectric loss tangent. For a long time, those with ordinary knowledge in the technical field have conducted research on thermosetting polyphenylene ether resin, bismaleimide resin, vinylbenzyl ether resin, hydrocarbon resin, etc. with good dielectric properties; Curable and cross-linked hydrocarbon resins (polyolefin resins) have low dielectric loss tangent D _f (comparable to PTFE resins) and good fluidity, which attracts the majority of the general technical field. Knowledgeable people have conducted a lot of in-depth research on it, but due to its insufficient peel strength and interlayer adhesion, it cannot meet the process requirements of high-level multi-layer printed circuit boards, and it needs to be used in conjunction with the selection of specific resins.

The application of the modified polyphenylene ether resin with active groups at the end of the molecular chain or side chain in the high-speed circuit substrate is generally to form a resin composition in combination with a cross-linking agent. The crosslinking agent has reactive groups that can react with the modified polyphenylene ether. According to literature research, for the modified polyphenylene ether with C=C double bond, the commonly used crosslinking agents are polybutadiene, butadiene styrene copolymer, etc. For example, the patents of CN 101370866A, CN 102161823 and CN 102304264 use polybutadiene or butadiene styrene copolymer as the crosslinking agent of modified polyphenylene ether to prepare high-speed circuit substrates. Although the comprehensive properties of the sheet are excellent, but polybutadiene or butadiene styrene copolymer reduces the peel strength and interlayer adhesion of the sheet.

In addition, according to literature research, TW201710363A uses a modified polyphenylene ether containing C=C double bonds, and the crosslinking agent is a macromolecular styrene-butadiene-styrene triblock copolymer, and the 1 and 2 positions in the molecule are The added butadiene has a low weight ratio content, and a high-speed circuit substrate is prepared. Although the sheet has excellent dielectric properties, due to the large molecular weight of styrene-butadiene-styrene triblock copolymer (SBS), SBS is difficult to dissolve, and it is difficult to wet glass fiber cloth, and the resistance to CAF is poor; molecular The content of butadiene added in the 1 and 2 positions is relatively low, so that the reaction degree and Tg of the system are low, and the system is still a thermoplastic substrate, which is difficult to meet the lead-free reflow soldering requirements of high-speed transmission and high-layer PCBs. Requirements.

【Prior technical literature】

【Patent Literature】

[Patent Document 1] CN 101370866A

[Patent Document 2] CN 102161823

[Patent Document 3] CN 102304264

[Patent Document 4] TW201710363A

In view of the deficiencies of the prior art, the object of the present invention is to provide a thermosetting resin composition, a prepreg using the same, and a copper-clad laminate. The thermosetting resin composition has low dielectric constant D _k and low dielectric loss D _f , excellent heat resistance, interlayer adhesion and peel strength, and excellent CAF resistance, and meets the requirements of high-speed circuit substrates for dielectric constant, dielectric loss, The requirements of heat resistance, peel strength, interlayer adhesion and CAF can be used to prepare high-speed circuit substrates.

For this purpose, the present invention adopts the following technical means:

In one aspect, the present invention provides a thermosetting resin composition comprising the following components: (A) a styrene-butadiene-styrene triblock copolymer containing 1,2-vinyl units, (B) thermosetting polyphenylene ether resin, (C) silane coupling agent; wherein the number-average molecular weight of the component (A) is less than 20,000, the molecule contains 10-60% by weight of styrene structure, and the molecule The content of butadiene added at the 1 and 2 positions is greater than or equal to 90% by weight.

In the present invention, the component (A) styrene-butadiene-styrene triblock copolymer (SBS) containing 1,2-vinyl units can significantly improve the crosslinking density of the resin composition after curing, And effectively improve the interlayer adhesion of the substrate and the peel strength of the copper foil and the substrate, and meet the lead-free reflow soldering requirements of high-speed transmission and high-layer PCBs. It has better compatibility with thermosetting polyphenylene ether, and its low molecular weight is conducive to infiltration of glass fiber cloth, improving CAF resistance and improving the reliability of multi-layer printed circuit boards. And its molecules do not contain polar groups, which can ensure low water absorption and excellent dielectric properties of circuit substrates. In addition, the synergistic effect of component (A) and component (C) in the present invention can improve the peel strength and interlayer adhesion of the system.

In the present invention, the number-average molecular weight of component (A) is less than 20,000, such as 18,000, 15,000, 13,000, 10,000, 8,000, 6,000, 4,000, 2,000, 1,000, etc.; ideally, the number-average number of component (A) The molecular weight is 1,000 to 20,000, more preferably 1,000 to 10,000, and still more preferably 1,000 to 6,000.

Unless otherwise specified, the number-average molecular weight described in the present invention refers to the number-average molecular weight measured by gel permeation chromatography.

In the present invention, if the number average molecular weight of the SBS resin is too large, it is difficult to dissolve, and the compatibility with polyphenylene ether is poor, so it is easy to precipitate. In addition, if the number-average molecular weight of the SBS resin is too large, it is difficult to infiltrate the glass fiber cloth during sizing, and the CAF resistance of the board is poor.

In the present invention, the molecule of component (A) contains 10-60% by weight of styrene structure, for example, the weight ratio of styrene can be 10%, 15%, 20%, 25%, 30%, 35% %, 40%, 45%, 50%, 55% or 60%; too high styrene content will lead to insufficient butadiene content, resulting in too low crosslinking density of the system, and poor interlayer adhesion and peel strength. Meet the requirements for use; if the styrene content is too low, it will lead to poor compatibility with polyphenylene ether and insufficient rigidity.

In the present invention, the content of butadiene added at the 1,2 position in the molecule of component (A) is greater than or equal to 90% by weight, which means that the content of butadiene added at the 1,2 position accounts for the proportion of the butadiene in the (A) molecule. The weight ratio of the total diene weight is greater than or equal to 90%, such as 90%, 91%, 92%, 93%, 95%, 96%, 97%, 98% or 99%, etc. If the weight ratio of butadiene added at the 1,2 position is less than 90%, its reactivity is poor (it is in an unreacted free state in the system, forming a thermoplastic phase), so that the crosslinking density of the system is too low, and the interlayer Adhesion and peel strength are also poor and cannot meet the requirements of use.

Ideally, the component (B) thermosetting polyphenylene ether resin is a polyphenylene ether resin having a structure represented by the following formula (1):

式(1)

Formula 1)

In formula (1), a and b are independently an integer from 1 to 30 (for example, 1, 3, 5, 8, 10, 15, 20, 25, or 30, etc.), and Z is represented by formula (2) or formula (3) The defined structure:

In formula (3), A is an arylene group, a carbonyl group or an alkylene group having 1 to 10 carbon atoms (for example, 1, 2, 3, 4, 5, 6, 7, 8, 9 or 10), and m is An integer from 0 to 10 (such as 0, 1, 2, 3, 4, 5, 6, 7, 8, 9 or 10), R ₁ to R ₃ are the same or different, and are hydrogen or have 10 or less carbon atoms (such as 1 , 2, 3, 4, 5, 6, 7, 8, 9 or 10) alkyl;

-(-O-Y-)- in formula (1) is the structure defined by formula (4):

In formula (4), R ₄ and R ₆ are the same or different, and are a hydrogen atom, a halogen atom, an alkyl group having 8 or less carbon atoms (for example, 1, 2, 3, 4, 5, 6, 7, 8) or benzene group, R ₅ and R ₇ are the same or different, and are halogen atoms, alkyl groups with less than 8 carbon atoms, or phenyl groups;

In formula (1) -(-O-X-O-)- is the structure defined by formula (5):

、

、

、

或

，n為0或1；R₁₆為氫原子或碳原 子數為1~10(例如1、2、3、4、5、6、7、8、9或10)的烴基。 In formula (5), R ₈ , R ₉ , R ₁₀ , R ₁₁ , R ₁₂ , R ₁₃ , R ₁₄ and R ₁₅ are the same or different, and are a hydrogen atom, a halogen atom, or an alkyl group having 8 or less carbon atoms or phenyl, and B is a hydrocarbylene group with 20 or less carbon atoms (for example, 20, 18, 16, 14, 10, 8, 5, 3, etc.), -O-,

,

,

,

or

, n is 0 or 1; R ₁₆ is a hydrogen atom or a hydrocarbon group with 1 to 10 carbon atoms (for example, 1, 2, 3, 4, 5, 6, 7, 8, 9 or 10).

Ideally, the number average molecular weight of the thermosetting polyphenylene ether resin is 500-10000 g/mol, such as 500 g/mol, 800 g/mol, 1000 g/mol, 3000 g/mol, 5000 g/mol, 8000 g/mol or 10000 g/mol, Ideally, it is 800 to 8000 g/mol, and more preferably 1000 to 4000 g/mol.

The resin component of the thermosetting resin composition of the present invention does not contain polar hydroxyl groups, and does not generate polar groups such as secondary hydroxyl groups during the curing process, which can ensure low water absorption and excellent dielectric properties of the circuit substrate. .

Ideally, based on the total of components (A)+(B) being 100 parts by weight, the amount of the component (B) thermosetting polyphenylene ether resin is 10 to 90 parts by weight, such as 15 parts by weight, 25 parts by weight, 35 parts by weight parts, 45 parts by weight, 55 parts by weight, 65 parts by weight, 75 parts by weight, 85 parts by weight, etc. Based on the total of components (A)+(B) as 100 parts by weight, the amount of the styrene-butadiene-styrene triblock copolymer containing 1,2-vinyl unit of component (A) is 10~90 Parts by weight, for example, 15 parts by weight, 25 parts by weight, 35 parts by weight, 45 parts by weight, 55 parts by weight, 65 parts by weight, 75 parts by weight, 85 parts by weight, and the like.

Ideally, the component (C) silane coupling agent is selected from methacrylate-based silane coupling agent, epoxy silane coupling agent, vinyl silane coupling agent, amino silane coupling agent, phenyl One or a combination of at least two of a silane coupling agent, an anilino silane coupling agent, or an oligomer-based silane coupling agent.

Ideally, based on the total of components (A) + (B) as 100 parts by weight, component (C) The total amount of the silane coupling agent is 0.1 to 5 parts by weight, such as 0.1 parts by weight, 0.3 parts by weight, 0.5 parts by weight, 0.8 parts by weight, 1 part by weight, 1.5 parts by weight, 2 parts by weight, 2.5 parts by weight , 3 parts by weight, 3.5 parts by weight, 4 parts by weight, 4.5 parts by weight or 5 parts by weight, etc.

In the present invention, by adding a silane coupling agent, it has a synergistic effect with styrene-butadiene-styrene triblock copolymer (SBS) and polyphenylene ether, which helps to further improve the interlayer adhesion and Improve the peel strength of copper foil and substrate to prevent the risk of dropped wires and pads during the use of printed circuit boards.

Desirably, the thermosetting resin composition further includes component (D) a free radical initiator.

Ideally, based on the total of components (A) + (B) being 100 parts by weight, the amount of the free radical initiator of component (D) is 0.1 to 5 parts by weight, for example, it can be 0.1 parts by weight, 0.3 parts by weight, 0.5 parts by weight, 0.8 parts by weight, 1 part by weight, 1.5 parts by weight, 2 parts by weight, 2.5 parts by weight, 3 parts by weight, 3.5 parts by weight, 4 parts by weight, 4.5 parts by weight or 5 parts by weight, etc.

Ideally, the free radical initiator is a first initiator, a second initiator, or a combination of a first initiator and a second initiator; the first initiator has a 1-minute half-life temperature of 50-160°C (eg can be 50°C, 60°C, 70°C, 80°C, 90°C, 100°C, 110°C, 120°C, 130°C, 140°C, 150°C or 160°C, etc.), the 1 minute half-life of the second initiator The temperature is 161-300°C (for example, it can be 162°C, 170°C, 180°C, 190°C, 200°C, 210°C, 220°C, 230°C, 240°C, 250°C, 260°C, 270°C, 280°C, 290°C ℃ or 300℃, etc.).

Ideally, the first initiator is selected from the group consisting of tert-butyl peroxyacetate, 2,2-bis(tert-butylperoxy)octane, tert-butylperoxyisopropyl carbonate, 1,1- Bis(tert-butylperoxy)cyclohexanone, 1,1-bis(tert-butylperoxy)-3,3,5-trimethylcyclohexanone, tert-butylperoxyoctanoate, tert-butylperoxycaprylate Butyl Peroxyisobutyrate, Disuccinic Acid Peroxide, Di-m-Toluene Peroxide, Xylyl Peroxide, Diacetyl Peroxide, Cumyl Peroxyoctanoate, Diklein Acetyl peroxide, dioctyl peroxide, didodecyl peroxide, bis(3,5,5-trimethylacetate peroxide), tert-butylperoxypivalate, tert-butylperoxypivalate Hexyl peroxytrimethyl acetate, tert-butyl peroxy neocaproate, tert-hexyl peroxy neocaproate, bis(3-methyl-3-methoxybutyl peroxybicarbonate), tert-hexyl peroxynecaproate, tert-butyl peroxynecaproate, cumyl peroxynecaproate, bismethoxyisopropylperoxybicarbonate, ditetradecylperoxide Bicarbonate, bisallyl peroxybicarbonate, cumyl peroxynecaprate, di-n-propyl peroxybicarbonate, bis(2-hydroxyethylhexyl peroxybicarbonate), Bis(2-ethylhexyl peroxybicarbonate), di-n-butyl peroxybicarbonate, diisobutyl peroxybicarbonate, diisobutylene peroxide, diisopropyl peroxybicarbonate and One or a combination of at least two of the acetylcyclohexylsulfonyl peroxides.

Ideally, the second initiator is selected from the group consisting of tert-butyl hydroperoxide, tetramethylbutane peroxide, 2,5-dimethyl-2,5-bis(tert-butylperoxy)hexyne, Di-tert-butylperoxide, a,a-bis(tert-butylperoxy-m-cumyl), 2,5-dimethyl-2,5-bis(tert-butylperoxy)hexane , tert-butyl cumyl peroxide, tert-butyl peroxyallyl bicarbonate, dicumyl peroxide (DCP), tert-butyl peroxybenzoate, di-tert-butyl peroxide Oxidized isophthalate, n-butyl-4,4-bis(tert-butylperoxy)valerate, tert-butylperoxy(3,5,5-trimethyl acetate), tert-butylperoxy Oxylaurate, one or at least two of 2,5-dimethyl-2,5-bis(dibenzylperoxy)hexane and 2,2-bis(tert-butylperoxy)butane combination.

Desirably, the thermosetting resin composition further includes component (E) a co-crosslinking agent.

Ideally, the co-crosslinking agent is triallyl cyanurate, triallyl cyanurate, multifunctional acrylate compound, bismaleimide resin, divinylbenzene, styrene - One or a mixture of at least two of butadiene copolymers, polybutadiene and styrene-butadiene-divinylbenzene copolymers, polyfunctional vinylaromatic copolymers. Ideally triallyl cyanurate, triallyl cyanurate, polyfunctional acrylate compound, polyfunctional One or a mixture of at least two of the vinyl aromatic copolymers.

Ideally, the co-crosslinking agent (E) is added in an amount of 3 to 60 parts by weight, for example, 3 parts by weight, 6 parts by weight, 10 parts by weight, based on the total of components (A)+(B) being 100 parts by weight , 15 parts by weight, 20 parts by weight, 25 parts by weight, 30 parts by weight, 40 parts by weight, 50 parts by weight or 60 parts by weight.

Desirably, the thermosetting resin composition further includes a filler.

Ideally, the filler is used in an amount of 10 to 300 parts by weight, for example, 10 parts by weight, 30 parts by weight, 50 parts by weight, 80 parts by weight, 100 parts by weight parts by weight, 150 parts by weight, 200 parts by weight, 250 parts by weight or 300 parts by weight.

Ideally, the filler is an organic filler or an inorganic filler.

Ideally, the inorganic filler is selected from crystalline silica, fused silica, spherical silica, hollow silica, glass powder, aluminum nitride, boron nitride, silicon carbide, aluminum hydroxide, titanium dioxide, One or a combination of at least two of strontium titanate, barium titanate, alumina, barium sulfate, talc, calcium silicate, calcium carbonate or mica.

Desirably, the organic filler is selected from one or a combination of at least two of polytetrafluoroethylene powder, polyphenylene sulfide, polyetherimide, polyphenylene oxide or polyether titanate powder.

Desirably, the thermosetting resin composition further includes a flame retardant.

Ideally, the flame retardant is a bromine-containing flame retardant or a halogen-free flame retardant.

The inclusion of a flame retardant in the thermosetting resin composition of the present invention is determined by the requirement of flame retardancy, so that the resin cured product has flame retardant properties and meets the requirements of UL 94 V-0. The flame retardant added as needed is not particularly limited, and it is preferable that it does not affect the dielectric properties.

Ideally, the bromine-containing flame retardant is one or at least two of decabromodiphenyl ether, decabromodiphenylethane, ethylene bistetrabromophthalimide or brominated polycarbonate. combination. The optional commercial brominated flame retardants are BT-93, BT-93W, HP-8010 or HP-3010, but not limited to the above categories.

Ideally, the halogen-free flame retardant is one or a combination of at least two of a phosphorus-containing halogen-free flame retardant, a nitrogen-containing halogen-free flame retardant and a silicon-containing halogen-free flame retardant.

Ideally, the halogen-free flame retardant is tris(2,6-dimethylphenyl)phosphine, 10-(2,5-dihydroxyphenyl)-9,10-dihydro-9-oxa- 10-Phosphinophenanthrene-10-oxide, 2,6-bis(2,6-dimethylphenyl)phosphinobenzene or 10-phenyl-9,10-dihydro-9-oxa-10-phosphine One or a combination of at least two of phenanthrene-10-oxide, phenoxyphosphine cyanide, phosphate or polyphosphate.

The optional commercial halogen-free flame retardants are SPB-100, PX-200, PX-202, LR-202, LR-700, OP-930, OP-935, LP-2200, XP-7866, but not Not limited to the above categories.

In the present invention, the amount of the flame retardant is determined according to the requirement that the cured product reaches the UL 94 V-0 level, and is not particularly limited. Considering that the heat resistance, dielectric properties and hygroscopicity of the cured product are not sacrificed, the amount of the flame retardant is 5 to 80 parts by weight based on the total of components (A)+(B) being 100 parts by weight, For example, 5 parts by weight, 8 parts by weight, 10 parts by weight, 20 parts by weight, 30 parts by weight, 40 parts by weight, 50 parts by weight, 60 parts by weight, 70 parts by weight or 80 parts by weight, ideally 10 to 60 parts by weight, more Ideally, it is 15 to 40 parts by weight. When the amount of flame retardant added is insufficient, a good flame retardant effect cannot be achieved; when the amount of flame retardant added is more than 80 parts, it will bring the risk of a decrease in the heat resistance of the system, an increase in water absorption, and the dielectric properties of the system. will also be deteriorated.

Ideally, the thermosetting resin composition also contains additives introduced to solve certain problems, the additives are antioxidants, heat stabilizers, light stabilizers, plasticizers, lubricants, flow modifiers, anti-drip One or a combination of at least two of the additives, antiblocking agents, antistatic agents, flow enhancers, processing aids, substrate adhesives, mold release agents, toughening agents, low shrinkage additives, or stress relief additives.

In the thermosetting resin composition of the present invention, the amount of the additive is not Specifically limited, based on the total of components (A)+(B) being 100 parts by weight, the dosage of the additive is ideally 0.1 to 10 parts by weight, such as 0.1 part by weight, 0.5 part by weight, 0.8 part by weight, 1 part by weight, 2 parts by weight, 3 parts by weight, 4 parts by weight, 5 parts by weight, 6 parts by weight, 7 parts by weight, 8 parts by weight, 9 parts by weight, or 10 parts by weight, more preferably 0.5 to 8 parts by weight, more preferably 1 to 10 parts by weight 5 parts by weight.

On the other hand, the present invention provides the above-mentioned preparation method of the thermosetting resin composition, and the preparation method can use conventional methods to compound, stir and mix the styrene-butadiene-styrene triblock Segmented copolymer (SBS), thermosetting polyphenylene ether, silane coupling agent and optional co-crosslinking agent, free radical initiator, powder filler, as well as various flame retardants, various additives, to prepare.

On the other hand, the present invention provides a resin glue solution obtained by dissolving or dispersing the above-mentioned thermosetting resin composition in a solvent.

The solvent in the present invention is not particularly limited, and specific examples include alcohols such as methanol, ethanol, and butanol, ethyl cellosolve, butyl cellosolve, ethylene glycol-methyl ether, carbitol, and butyl alcohol. Ethers such as base carbitol, ketones such as acetone, methyl ethyl ketone, methyl ethyl ketone, methyl isobutyl ketone, cyclohexanone, etc., aromatic hydrocarbons such as toluene, xylene, mesitylene, ethoxy Ethyl acetate, ethyl acetate and other esters, N,N-dimethylformamide, N,N-dimethylacetamide, N-methyl-2-pyrrolidone and other nitrogen-containing solvents. The above-mentioned solvents can be used alone or in combination of two or more, ideally aromatic hydrocarbon solvents such as toluene, xylene, mesitylene, and acetone, methyl ethyl ketone, methyl ethyl ketone, methyl isophthalate, etc. Ketone fluxes such as butyl ketone and cyclohexanone are used in combination. The amount of the solvent used can be selected by those with ordinary knowledge in the technical field according to their own experience, so that the obtained resin glue can reach a viscosity suitable for use.

During the process of dissolving or dispersing the resin composition in the solvent as described above, an emulsifier may be added. By dispersing with an emulsifier, powder fillers and the like can be uniformly dispersed in the glue solution.

In another aspect, the present invention provides a prepreg comprising a base material and the above thermosetting resin composition adhered to the base material after impregnation and drying.

The prepreg of the present invention can also be called a prepreg, which can also be made by impregnating the substrate with the above-mentioned resin glue, and then heating and drying it to remove the organic solvent and partially cure the resin composition in the substrate. material to obtain a prepreg. The substrate can also be referred to as a reinforcing material in the present invention.

Ideally, the substrate is a woven or non-woven fabric made of organic fibers, carbon fibers or inorganic fibers.

Ideally, the organic fibers include aramid fibers, such as Kevlar fibers from DuPont.

There is no particular limitation on the woven or non-woven fabrics made from inorganic fibers, ideally, the components of the woven or non-woven fabrics made from the inorganic fibers contain a weight ratio of 50 to 99.9% (for example, 50%, 55%, 58%, 60%, 65%, 70%, 75%, 80%, 85%, 88%, 90%, 95% or 99%) of SiO ₂ , weight ratio 0~30% (eg 0%, 5% , 10%, 15%, 20%, 25% or 30%) of CaO, 0 to 20% by weight (eg 0%, 5%, 10%, 15% or 20%) of Al ₂ O ₃ , by weight 0~25% (such as 0%, 5%, 10%, 15%, 20% or 25%) of B ₂ O ₃ and 0~5% by weight (such as 0%, 0.5%, 1%, 2%, 3%, 4% or 5%) of MgO, not limited to the above components. Ideally, the base material (reinforcing material) is ideally woven fiber cloth, which can be selected from E-Glass, T-Glass, NE-Glass, L-Glass, L2-Glass, Q-Glass, D-Glass, especially ideal NE-Glass and/or L-Glass. The thickness of the base material to be used is also not particularly limited.

The resin content for impregnating the above-mentioned base material is desirably such that 30 mass % or more of the resin content in semi-curing, for example, 30 mass %, 35 mass %, 40 mass %, 50 mass %, 60 mass %, 70 mass % % or higher. Since the dielectric constant of the base material is often higher than that of the resin composition, in order to lower the dielectric constant of the laminates obtained from these prepregs, the content of the resin composition components in the prepreg is desirably the above-mentioned content.

Ideally, the drying temperature of the above-mentioned prepreg is 80-200°C, such as 80°C, 90°C, 110°C, 120°C, 130°C, 140°C, 150°C, 170°C, 190°C or 200°C, etc.; The drying time is 1 to 30 minutes, such as 1 minute, 5 minutes, 8 minutes, 13 minutes, 17 minutes, 21 minutes, 24 minutes, 28 minutes or 30 minutes, etc.

In another aspect, the present invention provides a laminate comprising at least one prepreg as described above.

In another aspect, the present invention provides a metal foil clad laminate, the metal foil clad laminate comprising one or at least two superimposed prepregs as described above, and one or both sides of the superimposed prepregs metal foil.

Ideally, the metal foil is copper foil. Ideally, the copper foil is electrolytic copper foil or rolled copper foil, and its surface roughness is less than 5 microns, such as less than 4 microns, less than 3 microns, less than 2 microns, less than 1 microns, less than 0.8 microns, less than 0.5 microns, etc. It can improve and increase the signal loss of laminate materials used in high frequency and high speed printed circuit boards.

At the same time, in order to improve the adhesion of one side of the copper foil prepreg, further ideally, the copper foil is chemically treated with a silane coupling agent, and the silane coupling agent used is a methacrylate-based silane coupling agent, an epoxy silane One or at least two of coupling agents, vinyl silane coupling agents, amino silane coupling agents, phenyl silane coupling agents, anilino silane coupling agents or oligomeric silane coupling agents combination.

In another aspect, the present invention provides a high-frequency and high-speed circuit substrate, wherein the high-frequency and high-speed circuit substrate includes one or at least two superimposed prepregs as described above.

Specifically, the high-speed circuit substrate of the present invention is prepared by the following method: stacking at least one of the above-mentioned prepregs, placing copper foils on the upper and lower sides of the overlapping prepregs, and performing lamination molding. The overlap is ideal to use an automated stacking operation, thereby making the process easier to operate.

The lamination molding is ideally vacuum lamination molding, and vacuum lamination molding can be realized by a vacuum laminator. The lamination time is 70 to 130 minutes, such as 70 minutes, 75 minutes, 80 minutes, 85 minutes, 90 minutes, 95 minutes, 100 minutes, 105 minutes, 110 minutes, 115 minutes, 120 minutes, 125 minutes or 130 minutes. minutes, etc.; the lamination temperature is 180~220°C, such as 180°C, 185°C, 190°C, 195°C, 200°C, 205°C, 210°C, 215°C or 220°C; the lamination pressure is 20~60kg/cm ² , such as 20kg/cm ² , 25kg/cm ² , 30kg/cm ² , 35kg/cm ² , 40kg/cm ² , 45kg/cm ² , 50kg/cm ² , 55kg/cm ² , 58kg/ cm ² or 60kg/cm ² etc.

The electronic circuit substrate prepared by the method of the present invention has low dielectric constant D _k and low dielectric loss D _f , excellent heat resistance, interlayer adhesion and peel strength, and excellent CAF resistance, which meets the requirements of high speed. The requirements of circuit substrates for dielectric constant, dielectric loss, heat resistance, peel strength, interlayer adhesion and CAF are very suitable for high-level multi-layer printed circuit board processing.

In addition, in order to further improve the application of the material in the field of high frequency and high speed, in the production of the copper clad laminate of the present invention, the copper foil used can be selected from electrolytic copper foil or rolled copper foil, and its surface roughness is less than 5 microns. Improve and increase the signal loss of laminate materials used in high-frequency and high-speed printed circuit boards; at the same time, in order to improve the adhesion of one side of the copper foil prepreg, the copper foil can also be chemically treated with a silane coupling agent. The silane coupling agent used The agent is methacrylate silane coupling agent, epoxy silane coupling agent, vinyl silane coupling agent, amino silane coupling agent, phenyl silane coupling agent, anilino silane coupling agent or low One or a combination of at least two of the polymer-based silane coupling agents is used to provide the bonding force between the copper foil and the substrate, and to prevent the risk of dropped wires and pads during the use of the printed circuit board.

Compared with the prior art, the present invention has the following effects:

By adopting the present invention, the styrene-butadiene-styrene triblock copolymer (SBS) containing a large amount of 1,2-vinyl units can be used, which can obviously improve the crosslinking density of the resin composition after curing, and effectively improve the base material. The interlayer adhesion and the peel strength of copper foil and substrate meet the requirements of lead-free reflow soldering of high-speed transmission and high multi-layer PCB; the number-average molecular weight of the styrene-butadiene-styrene triblock copolymer (SBS) It is less than 20000, which can be beneficial to solvent dissolution and improve processability. In addition, low molecular weight styrene-butadiene-styrene triblock copolymer (SBS) is beneficial to have a better phase with thermosetting polyphenylene ether in the resin system. Capacitance and low molecular weight are conducive to infiltrating glass fiber cloth, improving CAF resistance, and improving the reliability of multi-layer printed circuit boards. In addition, the molecules of the styrene-butadiene-styrene triblock copolymer (SBS) do not contain polar groups, which can ensure low water absorption and excellent dielectric properties of the circuit substrate. Circuit substrates prepared from resin compositions prepared from styrene-butadiene-styrene triblock copolymer (SBS), polyphenylene ether and co-crosslinking agent have low dielectric constant D _k and low dielectric loss D _f , excellent heat resistance, interlayer adhesion and peel strength, and excellent CAF resistance, which meets the requirements of high-speed circuit substrates for dielectric constant, dielectric loss, heat resistance, peel strength, interlayer adhesion and CAF performance requirements, suitable for high-frequency It is used in the field of high-speed printed circuit boards and is suitable for multi-layer printed circuit board processing.

The technical means of the present invention will be further described below through specific embodiments. It should be understood by those with ordinary knowledge in the technical field that the embodiments are only for helping the understanding of the present invention, and should not be regarded as a specific limitation of the present invention.

The raw materials selected in the embodiment of the present invention and the comparative example are as follows:

(A) Component:

SBS-Atype: Styrene-butadiene-styrene triblock copolymer of Japan Caoda, the number average molecular weight (Mn) is 20000, the molecule contains 50% by weight of styrene structure, the 1,2-position addition The content of butadiene by weight is 94%;

SBS-Ctype: Styrene-butadiene-styrene triblock copolymer of Japan Caoda, the number average molecular weight (Mn) is 5000, the molecule contains 20% by weight of styrene structure, the 1,2-position addition The content of butadiene by weight is 94%;

D-1101: Styrene-butadiene-styrene triblock copolymer from Kraton, USA, the number average molecular weight (Mn) is greater than 100000, the molecule contains 31% by weight of styrene structure, 1 and 2-position addition The butadiene weight ratio content is less than 60%;

(B) Polyphenylene ether: SA9000: Sabic's methyl methacrylate-terminated polyphenylene ether resin, the number average molecular weight (Mn) is 2800;

OPE-2ST 2200: styrene-terminated polyphenylene ether resin of Mitsubishi Gas, the number average molecular weight (Mn) is 2200;

(C) Silane coupling agent:

KBM-403: Shin-Etsu Chemical's epoxy silane coupling agent;

KBM-503: methacrylate-based silane coupling agent of Shin-Etsu Chemical;

(D) Radical Initiator:

DCP: dicumyl peroxide (free radical initiator) from Shanghai Gaoqiao;

(E) Co-crosslinking agent

TAIC: triallyl isocyanate from Hunan Fangruida;

ODV-XET: Nippon Steel's multifunctional vinyl aromatic copolymer;

Ricon 100: Sartomer's styrene-butadiene copolymer (Mn: 4500, 1,2-vinyl content 70%);

Filler: S0-C2: Spherical silicon powder from Admatechs, median particle size D50: 0.5μm;

Flame retardant: Saytex 8010: Albemarle's brominated flame retardant decabromodiphenylethane;

Glass cloth: L-Glass: 2116 L-Glass from Asahi;

Copper foil: HVLP Copper foil: HS2-M2-VSP H Oz from Taiwan Mitsui Company.

Example 1

70.0 parts by weight of methyl methacrylate-terminated polyphenylene ether resin SA9000, 30.0 parts by weight of styrene-butadiene-styrene triblock copolymer (SBS-Atype), and 2.0 parts by weight of free radical initiator DCP, 1.0 parts by weight of methacrylate-based silane coupling agent KBM-503, 25 parts by weight of bromine flame retardant Saytex 8010, 80 parts by weight of silicon micropowder S0-C2, dissolved in toluene solvent, and adjusted to suitable viscosity. The resin glue solution was infiltrated with Low _Dk -glass fiber cloth (Asahi, type 2116L), controlled by the clamping shaft to fit the unit weight, and dried in an oven to remove the toluene solvent to obtain a prepreg of 2116. 6 sheets of 2116 prepreg and 12 sheets of 2116 prepreg were overlapped respectively, and the upper and lower sides were matched with HOZ-thick copper foil, which was vacuum laminated and cured in a press for 120 minutes, the curing pressure was 50kg/cm ² , and the curing temperature was 210 ℃. High-speed circuit board with two thickness specifications (12*2116-1.52mm thick plate is used for external processing CAF pattern test). The physical properties of the prepared copper foil substrate were tested, and the results are shown in Table 2.

Example 2

70.0 parts by weight of methyl methacrylate-terminated polyphenylene ether resin SA9000, 30.0 parts by weight of styrene-butadiene-styrene triblock copolymer (SBS-Ctype), and 2.0 parts by weight of free radical initiator DCP, 1.0 parts by weight of methacrylate-based silane coupling agent KBM-503, 25 parts by weight of bromine flame retardant Saytex 8010, 80 parts by weight of silicon micropowder S0-C2, dissolved in toluene solvent, and adjusted to suitable viscosity. The resin glue solution was infiltrated with Low _Dk -glass fiber cloth (Asahi, type 2116L), controlled by the clamping shaft to fit the unit weight, and dried in an oven to remove the toluene solvent to obtain a prepreg of 2116. 6 sheets of 2116 prepreg and 12 sheets of 2116 prepreg are overlapped respectively, and the upper and lower sides are matched with copper foil of HOZ thickness, and vacuum lamination is cured in a press for 120 minutes, the curing pressure is 50kg/cm ² , and the curing temperature is 210 ℃. High-speed circuit board with two thickness specifications (12*2116-1.52mm thick plate is used for external processing CAF pattern test). The physical properties of the prepared copper foil substrate were tested, and the results are shown in Table 2.

Example 3

70.0 parts by weight of Mitsubishi Gas' styrene-terminated polyphenylene ether resin OPE-2ST 2200, 30.0 parts by weight of styrene-butadiene-styrene triblock copolymer (SBS-Ctype), 2.0 parts by weight of free base initiator DCP, 1.0 parts by weight of methacrylate-based silane coupling agent KBM-503, 25 parts by weight of brominated flame retardant Saytex 8010, 80 parts by weight of silicon powder S0-C2, dissolved in toluene solvent, and Adjust to suitable viscosity. The resin glue solution was infiltrated with Low _Dk -glass fiber cloth (Asahi, type 2116L), controlled by the clamping shaft to fit the unit weight, and dried in an oven to remove the toluene solvent to obtain a prepreg of 2116. 6 sheets of 2116 prepreg and 12 sheets of 2116 prepreg were overlapped respectively, and the upper and lower sides were matched with HOZ-thick copper foil, which was vacuum laminated and cured in a press for 120 minutes, the curing pressure was 50kg/cm ² , and the curing temperature was 210 ℃. High-speed circuit board with two thickness specifications (12*2116-1.52mm thick plate is used for external processing CAF pattern test). The physical properties of the prepared copper foil substrate were tested, and the results are shown in Table 2.

Example 4

85.0 parts by weight of methyl methacrylate-terminated polyphenylene ether resin SA9000, 15.0 parts by weight of styrene-butadiene-styrene triblock copolymer (SBS-Ctype), 15.0 parts by weight of triallyl Trimeric isocyanate TAIC, 2.0 parts by weight of free radical initiator DCP, 1.0 parts by weight of methacrylate-based silane coupling agent KBM-503, 25 parts by weight of bromine flame retardant Saytex 8010, 80 parts by weight of silicon micropowder S0 -C2, dissolved in toluene solvent and adjusted to suitable viscosity. The resin glue solution was infiltrated with Low _Dk -glass fiber cloth (Asahi, type 2116L), controlled by the clamping shaft to fit the unit weight, and dried in an oven to remove the toluene solvent to obtain a prepreg of 2116. 6 sheets of 2116 prepreg and 12 sheets of 2116 prepreg were overlapped respectively, and the upper and lower sides were matched with HOZ-thick copper foil, which was vacuum laminated and cured in a press for 120 minutes, the curing pressure was 50kg/cm ² , and the curing temperature was 210 ℃. High-speed circuit board with two thickness specifications (12*2116-1.52mm thick plate is used for external processing CAF pattern test). The physical properties of the prepared copper foil substrate were tested, and the results are shown in Table 2.

Example 5

85.0 parts by weight of methyl methacrylate-terminated polyphenylene ether resin SA9000, 15.0 parts by weight of styrene-butadiene-styrene triblock copolymer (SBS-Ctype), and 15.0 parts by weight of styrene-butyl Diene copolymer Ricon 100, 2.0 parts by weight of free radical initiator DCP, 1.0 parts by weight of methacrylate-based silane coupling agent KBM-503, 25 parts by weight of bromine flame retardant Saytex 8010, 80 parts by weight of silicon Micropowder S0-C2, dissolved in toluene solvent, and adjusted to suitable viscosity. The resin glue solution was infiltrated with Low _Dk -glass fiber cloth (Asahi, type 2116L), controlled by the clamping shaft to fit the unit weight, and dried in an oven to remove the toluene solvent to obtain a prepreg of 2116. 6 sheets of 2116 prepreg and 12 sheets of 2116 prepreg were overlapped respectively, and the upper and lower sides were matched with HOZ-thick copper foil, which was vacuum laminated and cured in a press for 120 minutes, the curing pressure was 50kg/cm ² , and the curing temperature was 210 ℃. High-speed circuit board with two thickness specifications (12*2116-1.52mm thick plate is used for external processing CAF pattern test). The physical properties of the prepared copper foil substrate were tested, and the results are shown in Table 2.

Example 6

85.0 parts by weight of methyl methacrylate-terminated polyphenylene ether resin SA9000, 15.0 parts by weight of styrene-butadiene-styrene triblock copolymer (SBS-Ctype), and 15.0 parts by weight of Nippon Steel's Multifunctional vinyl aromatic copolymer ODV-XET, 2.0 parts by weight of free radical initiator DCP, 1.0 parts by weight of methacrylate-based silane coupling agent KBM-503, 25 parts by weight of bromine flame retardant Saytex 8010, 80 parts by weight of silicon micropowder S0-C2, dissolved in toluene solvent, and adjusted to suitable viscosity. The resin glue solution was infiltrated with Low _Dk -glass fiber cloth (Asahi, type 2116L), controlled by the clamping shaft to fit the unit weight, and dried in an oven to remove the toluene solvent to obtain a prepreg of 2116. 6 sheets of 2116 prepreg and 12 sheets of 2116 prepreg were overlapped respectively, and the upper and lower sides were matched with HOZ-thick copper foil, which was vacuum laminated and cured in a press for 120 minutes, the curing pressure was 50kg/cm ² , and the curing temperature was 210 ℃. High-speed circuit board with two thickness specifications (12*2116-1.52mm thick plate is used for external processing CAF pattern test). The physical properties of the prepared copper foil substrate were tested, and the results are shown in Table 2.

Example 7

40.0 parts by weight of methyl methacrylate-terminated polyphenylene ether resin SA9000, 60.0 parts by weight of styrene-butadiene-styrene triblock copolymer (SBS-Ctype), and 30.0 parts by weight of Nippon Steel's Multifunctional vinyl aromatic copolymer ODV-XET, 4.0 parts by weight of free radical initiator DCP, 3.0 parts by weight of Shin-Etsu Chemical's epoxy silane coupling agent KBM-403, 40.0 parts by weight of bromine flame retardant Saytex 8010 , 110 parts by weight of silicon powder S0-C2, dissolved in toluene solvent, and adjusted to suitable viscosity. The resin glue solution was infiltrated with Low _Dk -glass fiber cloth (Asahi, type 2116L), controlled by the clamping shaft to fit the unit weight, and dried in an oven to remove the toluene solvent to obtain a prepreg of 2116. 6 sheets of 2116 prepreg and 12 sheets of 2116 prepreg were overlapped respectively, and the upper and lower sides were matched with HOZ-thick copper foil, which was vacuum laminated and cured in a press for 120 minutes, the curing pressure was 50kg/cm ² , and the curing temperature was 210 ℃. High-speed circuit board with two thickness specifications (12*2116-1.52mm thick plate is used for external processing CAF pattern test). The physical properties of the prepared copper foil substrate were tested, and the results are shown in Table 2.

Comparative Example 1

70.0 parts by weight of methyl methacrylate-terminated polyphenylene ether resin SA9000, 30.0 parts by weight of triallyl isocyanate TAIC, 2.0 parts by weight of free radical initiator DCP, and 1.0 parts by weight of methacrylate group Silane coupling agent KBM-503, 25 parts by weight of brominated flame retardant Saytex 8010, and 80 parts by weight of silicon micropowder S0-C2 were dissolved in toluene solvent and adjusted to a suitable viscosity. The resin glue solution was infiltrated with Low _Dk -glass fiber cloth (Asahi, type 2116L), controlled by the clamping shaft to fit the unit weight, and dried in an oven to remove the toluene solvent to obtain a prepreg of 2116. 6 sheets of 2116 prepreg and 12 sheets of 2116 prepreg were overlapped respectively, and the upper and lower sides were matched with HOZ-thick copper foil, which was vacuum laminated and cured in a press for 120 minutes, the curing pressure was 50kg/cm ² , and the curing temperature was 210 ℃. High-speed circuit board with two thickness specifications (12*2116-1.52mm thick plate is used for external processing CAF pattern test). The physical properties of the prepared copper foil substrate were tested, and the results are shown in Table 3.

Comparative Example 2

70.0 parts by weight of methyl methacrylate-terminated polyphenylene ether resin SA9000, 30.0 parts by weight of styrene-butadiene copolymer Ricon 100, 2.0 parts by weight of free radical initiator DCP, and 1.0 parts by weight of methacrylic acid Ester-based silane coupling agent KBM-503, 25 parts by weight of bromine flame retardant Saytex 8010, 80 parts by weight of silicon micropowder S0-C2, dissolved in toluene solvent and adjusted to suitable viscosity. The resin glue solution was infiltrated with Low _Dk -glass fiber cloth (Asahi, type 2116L), controlled by the clamping shaft to fit the unit weight, and dried in an oven to remove the toluene solvent to obtain a prepreg of 2116. 6 sheets of 2116 prepreg and 12 sheets of 2116 prepreg were overlapped respectively, and the upper and lower sides were matched with HOZ-thick copper foil, which was vacuum laminated and cured in a press for 120 minutes, the curing pressure was 50kg/cm ² , and the curing temperature was 210 ℃. High-speed circuit board with two thickness specifications (12*2116-1.52mm thick plate is used for external processing CAF pattern test). The physical properties of the prepared copper foil substrate were tested, and the results are shown in Table 3.

Comparative Example 3

70.0 parts by weight of methyl methacrylate-terminated polyphenylene ether resin SA9000, 30.0 parts by weight of Nippon Steel's multifunctional vinyl aromatic copolymer ODV-XET, 2.0 parts by weight of free radical initiator DCP, 1.0 part by weight methacrylate-based silane coupling agent KBM-503, 25 parts by weight of bromine flame retardant Saytex 8010, 80 parts by weight of silicon micropowder S0-C2, dissolved in toluene solvent, and adjusted to suitable viscosity. The resin glue solution was infiltrated with Low _Dk -glass fiber cloth (Asahi, type 2116L), controlled by the clamping shaft to fit the unit weight, and dried in an oven to remove the toluene solvent to obtain a prepreg of 2116. 6 sheets of 2116 prepreg and 12 sheets of 2116 prepreg were overlapped respectively, and the upper and lower sides were matched with HOZ-thick copper foil, which was vacuum laminated and cured in a press for 120 minutes, the curing pressure was 50kg/cm ² , and the curing temperature was 210 ℃. High-speed circuit board with two thickness specifications (12*2116-1.52mm thick plate is used for external processing CAF pattern test). The physical properties of the prepared copper foil substrate were tested, and the results are shown in Table 3.

Comparative Example 4

70.0 parts by weight of methyl methacrylate-terminated polyphenylene ether resin SA9000, 30.0 parts by weight of macromolecular styrene-butadiene-styrene triblock copolymer (D-1101), 2.0 parts by weight of free base initiator DCP, 1.0 parts by weight of methacrylate-based silane coupling agent KBM-503, 25 parts by weight of brominated flame retardant Saytex 8010, 80 parts by weight of silicon powder S0-C2, dissolved in toluene solvent, and Adjust to suitable viscosity. The resin glue solution was infiltrated with Low _Dk -glass fiber cloth (Asahi, type 2116L), controlled by the clamping shaft to fit the unit weight, and dried in an oven to remove the toluene solvent to obtain a prepreg of 2116. 6 sheets of 2116 prepreg and 12 sheets of 2116 prepreg were overlapped respectively, and the upper and lower sides were matched with HOZ-thick copper foil, which was vacuum laminated and cured in a press for 120 minutes, the curing pressure was 50kg/cm ² , and the curing temperature was 210 ℃. High-speed circuit board with two thickness specifications (12*2116-1.52mm thick plate is used for external processing CAF pattern test). The physical properties of the prepared copper foil substrate were tested, and the results are shown in Table 3.

Comparative Example 5

70.0 parts by weight of Mitsubishi Gas' styrene-terminated polyphenylene ether resin OPE-2ST 2200, 30.0 parts by weight of macromolecular styrene-butadiene-styrene triblock copolymer (D-1101), 15.0 parts by weight parts by weight of styrene-butadiene copolymer Ricon 100, 2.0 parts by weight of free radical initiator DCP, 1.0 parts by weight of methacrylate-based silane coupling agent KBM-503, 25 parts by weight of bromine flame retardant Saytex 8010 , 80 parts by weight of silicon powder S0-C2, dissolved in toluene solvent, and adjusted to suitable viscosity. The resin glue solution was infiltrated with Low _Dk -glass fiber cloth (Asahi, type 2116L), controlled by the clamping shaft to fit the unit weight, and dried in an oven to remove the toluene solvent to obtain a prepreg of 2116. 6 sheets of 2116 prepreg and 12 sheets of 2116 prepreg were overlapped respectively, and the upper and lower sides were matched with HOZ-thick copper foil, which was vacuum laminated and cured in a press for 120 minutes, the curing pressure was 50kg/cm ² , and the curing temperature was 210 ℃. High-speed circuit board with two thickness specifications (12*2116-1.52mm thick plate is used for external processing CAF pattern test). The physical properties of the prepared copper foil substrate were tested, and the results are shown in Table 1 and Table 2.

〔Table 1〕

〔Table 2〕

The test methods for the above characteristics are as follows:

1) Glass transition temperature (Tg): According to dynamic thermomechanical analysis (DMA), the Tg of the laminate was measured according to the DMA method specified in IPC-TM-650 2.4.24.4.

2) Glass transition temperature (Tg): According to dynamic thermomechanical analysis (DSC), the Tg of the laminate was measured according to the DSC method specified in IPC-TM-650 2.4.25D.

3) Dielectric constant D _k and dielectric loss factor D _f : Tested according to the method of Split Post Dielectric Resonator (Split Post Dielectric Resonator), and the test frequency is 10 GHz.

4) Test method for peel strength (state A): refers to the tensile force required to peel off each millimeter of copper foil from the copper clad laminate at room temperature.

5) Peel strength (thermal stress) test method: refers to the tensile force required to peel off the copper clad laminate per millimeter of copper foil after immersion in tin at 288°C for 10 minutes.

6) Interlayer adhesion test method: refers to the tension required to peel each millimeter of copper foil between the adhesive sheets of the substrate at room temperature. As the test progresses, the tension value fluctuates continuously, and the range of the lowest and highest tension is recorded. .

7) CAF performance test: double-sided copper clad laminates are processed out of PCB to form a CAF test model, pre-processed for 5 times of reflow soldering, 85RH%/85℃ high temperature and high humidity treatment for 96 hours (no bias), and then placed at 85RH %/85℃ constant temperature and humidity box, pass 50V bias test, test for 240 hours.

Physical analysis:

From the physical property data in Table 2 and Table 3, it can be seen that in Examples 1-7, styrene-butadiene-styrene triblock copolymers (SBS) with small molecules and high content of 1,2-vinyl units and After the thermosetting polyphenylene ether is cured, the substrate has low dielectric constant D _k and low dielectric loss D _f , excellent heat resistance, interlayer adhesion and peel strength, and excellent CAF resistance; while Comparative Examples 4 and 5 , the crosslinking density of the substrate is significantly lower and the Tg is significantly higher after using the styrene-butadiene-styrene triblock copolymer (D-1101) with macromolecules and low 1,2-vinyl unit content The amplitude decreases (mainly thermoplastic), the heat resistance is obviously deteriorated, and the CAF resistance is obviously insufficient due to the poor wettability of the macromolecular styrene-butadiene-styrene triblock copolymer to the glass fiber.

Compared with Comparative Examples 1-3, Example 2 used a styrene-butadiene-styrene triblock copolymer (SBS) with small molecules and high 1,2-vinyl unit content, and the peel strength of the substrate and The interlayer adhesion is significantly improved.

As described above, the circuit substrate of the present invention has a low dielectric constant D _k and a low dielectric loss D _f , and is excellent in heat resistance, interlayer adhesion, peel strength, and CAF resistance, compared with general laminates. It meets the requirements of high-speed circuit substrates for dielectric constant, dielectric loss, heat resistance, peel strength, interlayer adhesion and CAF, and can be used to prepare high-speed circuit substrates.

The applicant declares that the present invention describes the thermosetting resin composition, the prepreg and the copper-clad laminate using the above-mentioned embodiments of the present invention, but the present invention is not limited to the above-mentioned embodiments, which does not mean that the present invention must rely on Only the above-mentioned embodiment can be implemented. Those with ordinary knowledge in the technical field should understand that any improvement of the present invention, the equal replacement of each raw material of the product of the present invention, the addition of auxiliary components, the selection of specific methods, etc., all fall within the protection scope and disclosure scope of the present invention. .

Claims (10)

A high-frequency and high-speed circuit substrate is characterized in that the high-frequency and high-speed circuit substrate includes one or at least two superimposed prepregs, the prepreg includes a base material and a thermosetting resin composition attached to the base material after impregnation and drying. The resin composition is composed of the following components: (A) styrene-butadiene-styrene triblock copolymer containing 1,2-vinyl units, (B) thermosetting polyphenylene ether resin, (C) silane coupling Linking agent, (D) free radical initiator, filler and flame retardant; wherein the number-average molecular weight of the component (A) is less than or equal to 20000, the molecule contains 10-60% by weight of styrene structure, and 1 , 2-position addition of butadiene weight ratio content is greater than or equal to 90%. The high-frequency and high-speed circuit substrate according to claim 1, wherein the component (B) thermosetting polyphenylene ether resin is a polyphenylene ether resin having a structure represented by the following formula (1):

In formula (1), a and b are independently integers from 1 to 30, and Z is a structure defined by formula (2) or formula (3):

In formula (3), A is an arylene group, a carbonyl group or an alkylene group having 1 to 10 carbon atoms, m is an integer of 0 to 10, and R ₁ to R ₃ are the same or different, and are hydrogen or carbon atoms of 10 The following alkyl groups; -(-OY-)- in formula (1) is the structure defined by formula (4):

In formula (4), R ₄ and R ₆ are the same or different, and are a hydrogen atom, a halogen atom, an alkyl group having 8 or less carbon atoms, or a phenyl group, and R ₅ and R ₇ are the same or different, and are a halogen atom or a carbon atom. 8 or less alkyl or phenyl; in formula (1) -(-OXO-)- is the structure defined by formula (5):

In formula (5), R ₈ , R ₉ , R ₁₀ , R ₁₁ , R ₁₂ , R ₁₃ , R ₁₄ and R ₁₅ are the same or different, and are a hydrogen atom, a halogen atom, or an alkyl group having 8 or less carbon atoms or phenyl, and B is a hydrocarbylene group with 20 or less carbon atoms, -O-,

,

,

,

or

, n is 0 or 1; R ₁₆ is a hydrogen atom or a hydrocarbon group with 1-10 carbon atoms. The high-frequency and high-speed circuit substrate according to claim 1 or 2, wherein the number-average molecular weight of the thermosetting polyphenylene ether resin is 500-10000 g/mol. The high-frequency high-speed circuit substrate according to claim 1 or 2, wherein the component (B) thermosetting polyphenylene ether resin is 10 to 90 parts by weight based on the total of components (A) + (B) being 100 parts by weight parts; component (A) the styrene-butadiene-styrene triblock copolymer containing 1,2-vinyl units is 10 to 90 parts by weight. The high-frequency high-speed circuit substrate according to claim 1, wherein the component (C) silane coupling agent is selected from the group consisting of methacrylate-based silane coupling agent, epoxy silane coupling agent, vinyl silane coupling agent One or a combination of at least two of the silane coupling agent, amino silane coupling agent, phenyl silane coupling agent, anilino silane coupling agent or oligomeric silane coupling agent; with component (A)+ The total amount of (B) is 100 parts by weight, and the total amount of the component (C) silane coupling agent is 0.1 to 5 parts by weight. The high-frequency and high-speed circuit substrate according to claim 1, wherein the (D) radical initiator Hair preparation, based on the total of components (A) + (B) as 100 parts by weight, the amount of the free radical initiator of component (D) is 0.1 to 5 parts by weight. The high-frequency high-speed circuit substrate according to claim 6, wherein the radical initiator is a first initiator, a second initiator, or a combination of the first initiator and the second initiator; 1 of the first initiator The minute half-life temperature was 50-160°C, and the 1-minute half-life temperature of the second initiator was 161-300°C. The high-frequency high-speed circuit substrate according to claim 7, wherein the first initiator is selected from the group consisting of tert-butyl peroxyacetate, 2,2-bis(tert-butylperoxy)octane, tert-butyl peroxyacetate, Isopropyl carbonate oxide, 1,1-bis(tert-butylperoxy)cyclohexanone, 1,1-bis(tert-butylperoxy)-3,3,5-trimethylcyclohexanone , tert-butyl peroxycaprylate, tert-butyl peroxyisobutyrate, disuccinic acid peroxide, di-m-toluene peroxide, xylene peroxide, diacetyl peroxide, iso Propylphenyl peroxyoctanoate, dicaprylyl peroxide, dioctyl peroxide, didodecanoyl peroxide, bis(3,5,5-trimethylacetate peroxide), tert-butyl peroxypivalate, tert-hexyl peroxytrimethyl acetate, tert-butyl peroxynecaproate, tert-hexyl peroxynecaproate, bis(3-methyl-3-methyl) oxybutyl peroxybicarbonate), tert-hexyl peroxynecaproate, tert-butyl peroxynecaproate, cumyl peroxynecaproate, bismethoxyisopropylperoxide Bicarbonate, ditetradecyl peroxybicarbonate, bisallyl peroxybicarbonate, cumyl peroxynecaprate, di-n-propyl peroxybicarbonate, bis(2- hydroxyethylhexyl peroxybicarbonate), bis(2-ethylhexyl peroxybicarbonate), di-n-butyl peroxybicarbonate, diisobutyl peroxybicarbonate, diisobutylene peroxide , one or a combination of at least two in diisopropyl peroxyhydrocarbonate and acetylcyclohexyl sulfonyl peroxide; the second initiator is selected from tert-butyl hydroperoxide, tetramethyl butyl Alkyl peroxide, 2,5-dimethyl-2,5-bis(tert-butylperoxy)hexyne, di-tert-butylperoxide, a,a-bis(tert-butylperoxy-m- cumyl), 2,5-dimethyl-2,5-bis(tert-butylperoxy)hexane, tert-butylcumyl peroxide, tert-butyl Allyl peroxide peroxycarbonate, dicumyl peroxide (DCP), tert-butyl peroxybenzoate, di-tert-butyl peroxyisophthalate, n-butyl-4,4-bis (tert-butylperoxy)valerate, tert-butylperoxy(3,5,5-trimethylacetate), tert-butylperoxylaurate, 2,5-dimethyl-2,5 - one or a combination of at least two of bis(dibenzylperoxy)hexane and 2,2-bis(tert-butylperoxy)butane. The high-frequency and high-speed circuit substrate according to claim 1, wherein the filler is used in an amount of 10 to 300 parts by weight, based on the total of components (A)+(B) being 100 parts by weight. The high-frequency high-speed circuit substrate according to claim 1, wherein the flame retardant is a bromine-containing flame retardant or a halogen-free flame retardant; the bromine-containing flame retardant is decabromodiphenyl ether, decabromodiphenyl ethyl One or a combination of at least two of alkane, ethylenebistetrabromophthalimide or brominated polycarbonate; the halogen-free flame retardant is tris(2,6-dimethylphenyl)phosphine , 10-(2,5-dihydroxyphenyl)-9,10-dihydro-9-oxa-10-phosphine-10-oxide, 2,6-bis(2,6-dimethylbenzene) base) phosphinobenzene or one of 10-phenyl-9,10-dihydro-9-oxa-10-phosphinophenanthrene-10-oxide, phenoxyphosphine cyanide compound, phosphate ester or polyphosphate ester or A combination of at least two kinds; based on 100 parts by weight of components (A)+(B), the amount of the flame retardant is 5-80 parts by weight.