Resin composition

Abstract

The invention relates to a resin composition. Wherein the component (1) is thermosetting resin, and the thermosetting resin is composed of any one or more of thermosetting polyphenyl ether (PPE), thermosetting hydrocarbon resin (PCH), epoxy resin (EP), polycyanate resin (CE), polyimide resin (PI) and modified resin of the thermosetting polyphenyl ether PPE, the thermosetting hydrocarbon resin PCH, the epoxy resin EP, the polycyanate resin CE and the polyimide resin PI; and the component (2) comprises a silicon-containing crosslinking component and the like. The composition can be used in the field of metal-clad laminates, especially high-frequency copper-clad plates.

Description

TECHNICAL FIELD

[0001] The present application relates to the technical field of metal-clad laminated boards, in particular to a resin composition and application thereof to metal-clad laminated boards and printed circuits. BACKGROUND

[0002] It is known that polyphenylene ether (PPE) is excellent in dielectric properties such as dielectric constant and dielectric loss tangent, and is also excellent in dielectric properties in a high frequency range from MHz to GHz. Therefore, polyphenylene ether is studied for use as a molding material for high frequencies. More specifically, it is studied for use as a substrate material or the like for a base material for a printed wiring board provided in electronic devices utilizing a high frequency range. When the resin is utilized as a molding material for a substrate material or the like, not only excellent dielectric properties are required, but also low heat absorption moisture, low water absorption, and the like are required.

[0003] CN105358595B discloses a polyphenylene ether resin composition containing (A) a modified polyphenylene ether having a terminal modified with a substituent having a carbon-carbon unsaturated double bond; and (B) a crosslinking agent having a carbon-carbon unsaturated double bond, wherein the crosslinking agent of component (B) contains (B-1) divinylbenzene and (B-2) polybutadiene in a proportion of 50-100 mass%.

[0004] CN113527818B discloses a resin composition comprising the following components: (A) a thermosetting resin comprising a combination of at least two of a thermosetting polyphenylene ether, a multifunctional vinyl aromatic polymer, a thermosetting hydrocarbon resin, or a co-crosslinking agent containing at least two unsaturated functional groups; (B) silica prepared by an organosilicon hydrolysis method; the resin composition not only has a low dielectric constant and a low dielectric loss tangent, but also has a small change rate of dielectric loss tangent after heat absorption moisture, a low water absorption, and a high thermal stability.

[0005] CN103764697A discloses a free radical polymerization curable composition, in order to reduce the softening point, other free radical reactive compounds of component C can be added, such as divinylbenzene, trivinylbenzene, 2, 3-divinyl naphthalene, 1, 4-bis (dimethyl vinyl silyl) benzene, etc., preferably triallyl isocyanurate, and the influence of which on heat absorption moisture is not mentioned. SUMMARY

[0006] The metal-clad laminate manufactured by the resin composition for a metal-clad laminate known for a long time has a problem of insufficient heat resistance and water resistance. The applicant found that the silicon-containing crosslinking component represented by Formula a can significantly reduce the hygrothermal properties of the thermosetting resin as a substrate for a metal-clad laminate, especially for a printed wiring board in an electronic device in a high frequency band. And the silicon-containing crosslinking component of the present application exhibits different synergies when combined with different thermosetting resins, such as reducing water absorption when combined with thermosetting polyphenyl ether, optimizing relative dielectric constant when combined with thermosetting hydrocarbon resin, and exhibiting overall optimization of peel strength, water absorption, relative dielectric constant, and dielectric loss tangent when combined with thermosetting polyphenyl ether composition and thermosetting hydrocarbon resin.

[0007] a In a first aspect, the present application provides a resin composition, which comprises the following components: component (1) a thermosetting resin, which is composed of any one or more of thermosetting polyphenyl ether PPE, thermosetting hydrocarbon resin PCH, epoxy resin EP, polycyanate resin CE, polyimide resin PI and modified resins thereof; component (2) a silicon-containing crosslinking component represented by Formula a. The resin composition can manufacture a metal-clad laminate with excellent hygrothermal properties.

[0008] a The thermosetting resin refers to a thermosetting resin with excellent dielectric properties on the market for metal-clad laminates, which is composed of any one or more of thermosetting polyphenyl ether PPE, thermosetting hydrocarbon resin PCH, epoxy resin EP, polycyanate resin CE, polyimide resin PI and modified resins thereof.

[0009] The thermosetting polyphenyl ether includes epoxy-modified polyphenyl ether resin, vinyl-modified polyphenyl ether resin or acyl-modified polyphenyl ether resin, etc., preferably polyphenyl ether containing unsaturated groups, more preferably polyphenyl ether with unsaturated hydrocarbon groups at the end.

[0010] Specifically, functional groups with vinyl benzyl groups can be mentioned, such as vinyl benzyl ether polyphenyl ether resin or vinyl phenyl ether polyphenyl ether resin. Specifically, functional groups with acrylate can be mentioned, such as (meth) acrylate-terminated polyphenyl ether resin or acrylate-terminated polyphenyl ether resin.

[0011] Preferably, polyphenyl ether with acrylate, more preferably (meth) acrylate-terminated polyphenyl ether resin.

[0012] The number-average molecular weight of thermosetting polyphenylene ether is not particularly limited, and is selected from 1000-7000 g / mol, preferably 1000-5000 g / mol, and more preferably 1000-3000 g / mol. Furthermore, the number-average molecular weight can be measured using any common molecular weight measurement method; specifically, values ​​measured using gel permeation chromatography (GPC) can be cited as examples.

[0013] In this invention, the thermosetting polyphenylene ether can be purchased through commercial channels, such as OPE-2ST from Mitsubishi Gas Industries of Japan and / or NORYL SA9000 from SABIC of Saudi Arabia.

[0014] The thermosetting polyphenylene ether in the thermosetting resin composition has a mass percentage content of 10-90%, preferably 20-80%, more preferably 25-70%, and for example, it can be 30%, 35%, 40%, 45%, 50%, 55%, 60%, 65%, 70%, etc.

[0015] The intrinsic viscosity of thermosetting polyphenylene ether is preferably 0.03-0.12 dl / g, more preferably 0.04-0.11 dl / g, and even more preferably 0.06-0.10 dl / g. If the intrinsic viscosity is too low, there is a tendency for low molecular weight, making it difficult to obtain low dielectric constant and low dielectric loss tangent. Furthermore, if the intrinsic viscosity is too high, the viscosity is too high, insufficient flowability cannot be obtained, and the formability of the cured product tends to decrease. Therefore, if the intrinsic viscosity of the modified polyphenylene ether is within the above range, the cured product can exhibit excellent heat resistance and adhesion. The above intrinsic viscosity was tested according to the test method of SABIC, Saudi Arabia.

[0016] The thermosetting hydrocarbon resins include polybutadiene, copolymers of butadiene and styrene, styrene-butadiene-divinylbenzene copolymers, styrene-butadiene-styrene copolymers, styrene-isoprene-styrene copolymers, maleimide-modified polybutadiene resins, epoxy-modified polybutadiene resins, styrene resins, methylstyrene resins, ethylstyrene resins, divinylbenzene resins, isoprene resins, benzocyclobutene resins, etc. Preferably composed of polybutadiene and / or styrene-butadiene-styrene copolymer (styrene-butadiene resin), more preferably polybutadiene.

[0017] Examples include 1,4-polybutadiene, 1,2-polybutadiene, terminal acrylate-modified polybutadiene, and terminal urethanemethacrylate-modified polybutadiene.

[0018] The number-average molecular weight of the thermosetting hydrocarbon resin is not particularly limited, but is selected from resins with a number-average molecular weight of 100-5000 g / mol, preferably 500-4000 g / mol, and more preferably 1000-3500 g / mol.

[0019] In this invention, the thermosetting hydrocarbon resin can be purchased through commercial channels, such as B-3000 from Nippon Soda, R154 from Clayville, RB810 from JSR, or R100 from Clayville.

[0020] The thermosetting hydrocarbon resin in the thermosetting resin composition has a mass percentage content of 10-90%, preferably 20-80%, more preferably 25-70%, and for example, it can be 30%, 35%, 40%, 45%, 50%, 55%, 60%, 65%, 70%, etc.

[0021] The epoxy resin includes bisphenol A type brominated epoxy resin, non-brominated bisphenol A type epoxy resin, phenolic resin, cresol phenolic resin, bisphenol A type phenolic epoxy resin, DCPC type epoxy resin, biphenyl type epoxy resin, naphthol type epoxy resin, alkylphenol type epoxy resin, aliphatic epoxy resin, trifunctional epoxy resin, or nitrogen-containing epoxy resin, etc., preferably epoxy resin containing unsaturated groups. For example, dicyclopentadiene epoxy resin (XD-1000L, Nippon Chemicals).

[0022] In this invention, the epoxy resin can be purchased from the market, for example, Nippon's XD-1000L.

[0023] The epoxy resin in the thermosetting resin composition has a mass percentage content of 10-90%, preferably 20-80%, more preferably 25-70%, and for example, it can be 30%, 35%, 40%, 45%, 50%, 55%, 60%, 65%, 70%, etc.

[0024] The cyanate ester resins include bisphenol A type cyanate ester resins, DCPD type cyanate ester resins, bisphenol M type cyanate ester resins, bisphenol F type cyanate ester resins, phenolic type cyanate ester resins, alkylphenol type cyanate ester resins, or naphthol type cyanate ester resins, etc.

[0025] In this invention, the cyanate ester resin can be purchased commercially, such as Primset HTL-300 from LONZA.

[0026] The mass percentage of cyanate ester resin in the thermosetting resin composition is 10-90%, preferably 20-80%, more preferably 25-70%, and for example, it can be 30%, 35%, 40%, 45%, 50%, 55%, 60%, 65%, 70%, etc.

[0027] The polyimide resin is preferably a bismaleimide type polyimide resin, such as 4,4'-diphenylmethane bismaleimide, 4,4'-diphenylisopropyl bismaleimide, or 4,4'-diphenyl ether bismaleimide. The bismaleimide resin preferably includes one or more of diamine-modified bismaleimide resin and allyl-modified bismaleimide resin.

[0028] In this invention, the bismaleimide resin can be purchased commercially, such as Ciby-Geigy's XU292.

[0029] The mass percentage of polyimide resin in the thermosetting resin composition is 10-90%, preferably 20-80%, more preferably 25-70%, and for example, it can be 30%, 35%, 40%, 45%, 50%, 55%, 60%, 65%, 70%, etc.

[0030] Preferably, the thermosetting resin is composed of one or more of thermosetting polyphenylene ether, thermosetting hydrocarbon resin and modified resin thereof.

[0031] Preferably, the mass ratio of thermosetting polyphenylene ether to thermosetting hydrocarbon resin is between 0.01 and 100, more preferably between 0.02 and 50, and even more preferably between 0.1 and 10, for example, 0.2, 0.3, 0.4, 0.5, 0.6, 0.7, 0.8, 0.9, 1, 2, 3, 4, 5, 6, 7, 8, and 9.

[0032] With the total mass of the resin components as 100%, the mass percentage of the thermosetting resin in component (1) is 20-80 wt%, preferably 30-70 wt%, more preferably 45-65 wt%, for example, it can be 46 wt%, 47 wt%, 48 wt%, 49 wt%, 50 wt%, 51 wt%, 52 wt%, 53 wt%, 54 wt%, 55 wt%, 56 wt%, 57 wt%, 58 wt%, 59 wt%, 60 wt%, 61 wt%, 62 wt%, 63 wt%, 64 wt%, etc.

[0033] The term "resin component" refers to a mixture or monomer of organic polymers containing hydrocarbon structures, mainly including thermosetting resins, silicon-containing crosslinking components, co-crosslinking agents and other organic components, excluding fillers, initiators, flame retardants, solvents and reinforcing materials.

[0034] The component (2) is a silicon-containing crosslinked component as shown in formula a. a Wherein, R is independently selected from hydrocarbon groups with 1 to 8 carbon atoms, preferably hydrocarbon groups with 1 to 6 carbon atoms, and more preferably phenyl, methyl or ethyl; R Independently selected from SiC-bonded substituted and / or unsubstituted unsaturated hydrocarbon groups having 1 to 16 carbon atoms, which may be interrupted by heteroatoms and / or carbonyl groups; Preferably, the unsaturated hydrocarbon group has 2-10 carbon atoms, such as vinyl, phenyl vinyl, allyl, isopropenyl, acrylate or methacrylic acid, 4-vinylcyclohexyl and 3-norbornenyl; More preferably, it is selected from alkenyl groups with 2 to 10 carbon atoms.

[0035] Specifically, the silicon-containing crosslinking component is selected from one or more of bis(dimethylvinylsilyl)benzene, bis(dimethylallylsilyl)benzene, bis(dimethylphenylvinylsilyl)benzene, bis(dimethylisopropenylsilyl)benzene, bis(dimethacrylatesilyl)benzene, and bis(dimethylmethacrylatesilyl)benzene.

[0036] Preferably selected from 1,2-bis(dimethylvinylsilyl)benzene, 1,3-bis(dimethylvinylsilyl)benzene, 1,4-bis(dimethylvinylsilyl)benzene, more preferably 1,4-bis(dimethylvinylsilyl)benzene (formula b) or one or more.

[0037] b With the total mass of the resin component as 100%, the mass percentage of the silicon-containing crosslinked component (2) as shown in Formula a is 2-80 wt%, preferably 2-60 wt%, more preferably 2-40 wt%, for example, it can be 5 wt%, 8 wt%, 10 wt%, 15 wt%, 18 wt%, 20 wt%, 21 wt%, 22 wt%, 23 wt%, 24 wt%, 25 wt%, 26 wt%, 27 wt%, 28 wt%, 29 wt%, 30 wt%, 31 wt%, 32 wt%, 33 wt%, 34 wt%, 35 wt%, 36 wt%, 37 wt%, 38 wt%, 39 wt%, etc.

[0038] Preferably, the resin composition further includes component (3) a crosslinking agent, which includes any one or more of triallyl isocyanurate (TAIC), triallyl cyanurate (TAC), trimethylallyl isocyanate (TMAIC), divinylbenzene (DVB), 1,2-bis(p-vinylphenyl)ethane (BVPE) or 1,2,4-trivinylcyclohexane (TVCH).

[0039] With the total mass of the resin component being 100%, the mass of the crosslinking agent is 1-40%, preferably 1-35%, more preferably 1-30%, for example, it can be 5%, 6%, 7%, 8%, 9%, 10%, 11%, 12%, 13%, 14%, 15%, 16%, 17%, 18%, 19%, 20%, 21%, 22%, 23%, 24%, 25%, 26%, 27%, 28%, 29%, etc.

[0040] Preferably, the resin composition further includes component (4) an initiator, which includes any one or more combinations of organic peroxide initiators, azo initiators, or carbon-based free radical initiators.

[0041] Preferably, the organic peroxide initiator includes any one or more combinations of tert-butylisopropylphenyl peroxide, dicumyl peroxide, benzoyl peroxide, 2,5-dimethyl-2,5-bis(tert-butylperoxy)hexane, 2,5-dimethyl-2,5-bis(tert-butylperoxy)hexyne, or 1,1-bis(tert-butylperoxy)-3,3,5-dimethylcyclohexane, and more preferably 2,5-dimethyl-2,5-bis(tert-butylperoxy)hexane or dicumyl peroxide.

[0042] Preferably, the carbon-based free radical initiator includes cyclohexane and / or polycyclohexane.

[0043] With the total mass of the resin component being 100%, the mass of the initiator is 0.001-5%, preferably 0.002-3%, for example, it can be 0.003%, 0.005%, 0.008%, 0.01%, 0.03%, 0.05%, 0.08%, 0.1%, 0.3%, 0.5%, 0.8%, 1%, 1.2%, 1.5%, 1.8%, 2%, 2.2%, 2.5%, or 2.8%, etc.

[0044] Solvents may also be added to the above-mentioned resin composition. The amount of solvent added is selected by those skilled in the art based on experience and process requirements, so that the resin composition reaches a suitable viscosity for use, facilitating impregnation, coating, etc. During subsequent drying, semi-curing, or complete curing stages, the solvent in the resin composition will partially or completely evaporate.

[0045] There are no particular restrictions on the choice of solvent. Generally, ketones such as acetone, butanone, and cyclohexanone, aromatic hydrocarbons such as toluene and xylene, and esters such as ethyl acetate and butyl acetate can be used. They can be used alone or in mixtures of two or more. Ketones such as acetone, butanone, and cyclohexanone, as well as aromatic hydrocarbons such as toluene and xylene, are preferred.

[0046] Preferably, the resin composition further includes component (5) a flame retardant, which is not particularly limited. Specifically, examples include halogenated flame retardants such as bromine-based flame retardants and phosphorus-based flame retardants.

[0047] As halogen-based flame retardants, they can be selected from bromine-based flame retardants such as pentabromodiphenyl ether, octabromodiphenyl ether, decabromodiphenyl ether, tetrabromobisphenol A, and hexabromocyclododecane, and chlorine-based flame retardants such as chlorinated paraffin. They can be used alone or in combination of two or more.

[0048] Examples of phosphorus-based flame retardants include condensed phosphate esters, cyclic phosphate esters, phosphazene compounds such as cyclic phosphazene compounds, phosphazene salts such as aluminum dialkylphosphines, melamine phosphate, and melamine polyphosphate. They can be used individually or in combination of two or more.

[0049] With the total mass of resin components being 100%, the mass percentage of flame retardant in the resin composition is 1-50%, preferably 10-25%, such as 11%, 13%, 15%, 17%, 19%, 20%, 21%, 22%, 23%, or 24%.

[0050] Preferably, the resin composition further includes component (6) an inorganic filler material, which includes one or more of silicon dioxide, alumina, talc, aluminum hydroxide, magnesium hydroxide, titanium dioxide, mica, aluminum borate, barium sulfate, and calcium carbonate.

[0051] When inorganic fillers are added, there is no particular limitation on the amount added. Specifically, the mass percentage is 10-300wt%, preferably 50-150wt%, such as 60wt%, 70wt%, 80wt%, 90wt%, 100wt%, 110wt%, 120wt%, 130wt%, 140wt%, etc., with the total mass of the resin component being 100%.

[0052] The resin composition comprises 20-98 wt% of component (1) a thermosetting resin and 2-80 wt% of component (2) a silicone crosslinking component as shown in formula a, with the total mass of the resin components being 100%. Preferably, 30-98 wt% of component (1) is a thermosetting resin, 2-70 wt% of component (2) is a silicon-containing crosslinking component as shown in formula a, and 0-40 wt% is a co-crosslinking agent, with the total mass of the resin component being 100%.

[0053] More preferably, the total mass of the resin components is 100%, containing 45-98 wt% of component (1) thermosetting resin, such as 46 wt%, 47 wt%, 48 wt%, 49 wt%, 50 wt%, 51 wt%, 52 wt%, 53 wt%, 54 wt%, 55 wt%, 56 wt%, 57 wt%, 58 wt%, 59 wt%, 60 wt%, 61 wt%, 62 wt%, 63 wt%, 64 wt%, 70 wt%, 75 wt%, 80 wt%, 85 wt%, 90 wt%, 95 wt%; 2-60wt% Component (2) Silicon-containing crosslinked components as shown in Formula a, for example 5 wt%, 8 wt%, 10 wt%, 15 wt%, 18 wt%, 20 wt%, 21 wt%, 22 wt%, 23 wt%, 24 wt%, 25 wt%, 26 wt%, 27 wt%, 28 wt%, 29 wt%, 30 wt%, 31 wt%, 32 wt%, 33 wt%, 34 wt%, 35 wt%, 36 wt%, 37 wt%, 38 wt%, 39 wt%, 40 wt%, 45 wt%, 50 wt%, 55 wt%, 58 wt%; and 5-25wt% co-crosslinking agent, such as 6 wt%, 7 wt%, 8 wt%, 9 wt%, 10 wt%, 11 wt%, 12 wt%, 13 wt%, 14 wt%, 15 wt%, 16 wt%, 17 wt%, 18 wt%, 19 wt%, 20 wt%, 21 wt%, 22 wt%, 23 wt%, 24wt%.

[0054] In the total mass of the resin components, the mass percentage of component (1) thermosetting resin, component (2) silicon-containing crosslinking component as shown in formula a and component (3) co-crosslinking agent is more than 70 wt%, preferably 80 wt%, more preferably 90 wt%, and even more preferably 95 wt%.

[0055] The ratio of the weight of the thermosetting resin to that of the silicon-containing crosslinking component (2) as shown in Formula a is between 0.01 and 100, preferably 0.02 to 50, for example 0.04 to 40, 0.05 to 30, 0.06 to 20, 0.07 to 15, more preferably 0.1 to 10, for example 0.2, 0.3, 0.4, 0.5, 0.6, 0.7, 0.8, 0.9, 1, 2, 3, 4, 5, 6, 7, 8, 9.

[0056] In the total mass of the resin components, the mass percentage of component (1) thermosetting resin and component (2) silicon-containing crosslinked component as shown in formula a is 50 wt% or more, preferably 60 wt% or more, more preferably 70 wt% or more, for example 75 wt%, 80 wt%, 85 wt%, 90 wt%, 95 wt%.

[0057] In a second aspect, the present invention provides a prepreg comprising a reinforcing material and a resin composition that is partially cured by drying after impregnation and coating.

[0058] Preferably, the reinforcing material includes any one or more combinations of natural fibers, organic synthetic fibers, organic fabrics, and inorganic fibers; for example, glass cloth, aramid cloth, polyester cloth, glass nonwoven cloth, aramid nonwoven cloth, polyester nonwoven cloth, pulp paper, and cotton linter paper, etc. Low dielectric reinforcing materials, such as NE glass fiber cloth, can also be selected as needed.

[0059] Thirdly, the present invention provides a metal-clad laminate.

[0060] The metal-clad laminate is prepared by the following method, which includes: stacking metal foil on one or both sides of a prepreg and curing it to obtain the metal-clad laminate; or, stacking at least two prepregs into a laminate, then stacking metal foil on one or both sides of the laminate and curing it to obtain the metal-clad laminate, or metal-clad laminate.

[0061] Preferably, the metal foil is a copper foil.

[0062] Preferably, the curing temperature is 150-300℃, such as 155℃, 160℃, 165℃, 170℃, 175℃, 180℃, 185℃, 190℃, 195℃, 200℃, 205℃, 210℃, 212℃, 215℃, 218℃, 220℃, 223℃, 225℃, 228℃, 230℃, 235℃, 240℃, 245℃, 250℃, 255℃, 260℃, 265℃, 270℃, 275℃, 280℃, 285℃, or 290℃.

[0063] Preferably, the curing pressure is 1.2-5 MPa, more preferably 1.2-4 MPa, such as 1.3 MPa, 1.4 MPa, 1.5 MPa, 1.6 MPa, 1.7 MPa, 1.8 MPa, 1.9 MPa, 2.0 MPa, 2.1 MPa, 2.2 MPa, 2.3 MPa, 2.4 MPa, 2.5 MPa, 2.6 MPa, 2.7 MPa, 2.8 MPa, 2.9 MPa, 3.0 MPa, 3.1 MPa, 3.2 MPa, 3.3 MPa, 3.4 MPa, 3.5 MPa, 3.6 MPa, 3.7 MPa, 3.8 MPa, 3.9 MPa, etc.

[0064] Preferably, the curing time is 60-360 min, such as 80 min, 90 min, 100 min, 120 min, 140 min, 150 min, 160 min, 180 min, 200 min, 220 min, 240 min, 260 min, 280 min, 300 min, 320 min, or 340 min.

[0065] Fourthly, the present invention provides a printed circuit board, the printed circuit board comprising one or more of the prepreg or the metal-clad laminate.

[0066] Compared with the prior art, the present invention has the following beneficial effects: The silicon-containing crosslinking component of this application can significantly reduce the thermal hygroscopicity of thermosetting resins as substrates for metal-clad laminates, especially for printed wiring boards in high-frequency electronic devices. The resin composition and metal-clad laminate of this application exhibit excellent thermal hygroscopicity, solving the problem of dielectric property deterioration caused by water absorption due to high-frequency heating. Furthermore, the silicon-containing crosslinking component of this application exhibits different synergistic effects when combined with different thermosetting resins. For example, it reduces water absorption when polymerized with thermosetting polyphenylene ether, optimizes relative permittivity when polymerized with thermosetting hydrocarbon resin, and comprehensively optimizes metal foil peel strength, water absorption, and dielectric properties when combined with both thermosetting polyphenylene ether compositions and thermosetting hydrocarbon resins. Detailed Implementation

[0067] Thermosetting polyphenylene ether: NORYL SA9000 (meth)acrylate-terminated polyphenylene ether resin (supplied by SABIC); Thermosetting hydrocarbon resin: Polybutadiene B-3000 (supplied by NIPPON SODA); Silicon-containing crosslinking component: 1,4-bis(dimethylvinylsilyl)benzene (supplied by Wacker Chemie). Crosslinking agent: Triallyl isocyanurate (TAIC) (commercially available); Initiator: Dicumyl peroxide (DCP) (commercially available); Solvent: Xylene (XYL) (commercially purchased); Filler: Spherical silica (supplied by Suzhou Jinyi New Materials); Reinforcing material: NE fiberglass cloth 1080 (commercial purchase) Metal foil: 35 micrometers thick copper foil (provided by Jiangxi Copper Corporation) Copper-clad laminate preparation method: The resin composition was formulated in the proportions shown in Table 1-2 and dissolved in xylene XYL to obtain a varnish. The varnish was cut into 25cm pieces. A 25cm square glass cloth was fully impregnated with varnish and heated in an oven at 150°C for 5 minutes to prepare a prepreg. Six prepregs were overlapped and copper foil with a thickness of 35 micrometers was placed on both sides to form a laminate. The laminate was heated and pressurized at 280°C and 1.5 MPa for 180 minutes to obtain a copper-clad laminate with copper foil bonded to both sides.

[0068] The copper foil peel strength of the copper-clad laminate was tested. The water absorption rate (%), PCT thermal moisture absorption rate (%), dielectric constant Dk (10GHz), and dielectric loss tangent Df (10GHz) of the copper-clad laminate after etching were also tested and recorded in Table 1-2.

[0069] Copper foil peel strength (PS, lb / in): The peel strength of the copper foil was tested according to IPC-TM-650 2.4.8. Water absorption rate (%): The water absorption rate was tested according to IPC-TM-650 2.6.2.1; PCT heat absorption rate (%): The weight change before and after heating is calculated after the sample is treated at 121℃, 105KPa and 100% relative humidity for 180 minutes.

[0070] Dielectric constant Dk (10GHz): The dielectric constant Dk at a frequency of 10GHz was tested according to IPC-TM-650 2.5.5.13. Dielectric loss tangent Df (10GHz): Dielectric loss tangent Df at 10GHz was tested according to IPC-TM-650 2.5.5.13. Table 1

[0071] As shown in Table 1, compared to the copper-clad laminate prepared with resin without 1,4-bis(dimethylvinylsilyl)benzene in C.Ex.1, Ex.2-3 all exhibited excellent PCT (polycarbonate) thermal moisture absorption rates. Furthermore, Ex.2 showed a decrease in water absorption rate, while Ex.3 showed an optimization of the Df (dimethylvinylsilyl) value.

[0072] Table 2

[0073] As shown in Table 2, compared with the copper-clad laminate prepared by the resin without 1,4-bis(dimethylvinylsilyl)benzene in C.Ex.4, the resin in Ex.5, which contains thermosetting hydrocarbon resin B3000, thermosetting polyphenylene ether resin SA9000 and silicon-containing crosslinking component 1,4-bis(dimethylvinylsilyl)benzene, not only exhibits excellent PCT heat absorption rate, but also achieves comprehensive optimization of its peel strength, water absorption rate, Dk, and Df.

Claims

1. A resin composition comprising: Component (1) thermosetting resin, which is composed of any one or more of thermosetting polyphenylene ether, thermosetting hydrocarbon resin, epoxy resin, polycyanate resin, polyimide resin and modified resin thereof; component (2) a silicon-containing crosslinking component as shown in formula a. a Wherein, R is independently selected from hydrocarbon groups with 1-8 carbon atoms, preferably hydrocarbon groups with 1-6 carbon atoms, and more preferably phenyl, methyl, or ethyl; R Independently selected from SiC-bonded substituted and / or unsubstituted unsaturated hydrocarbon groups having 1 to 16 carbon atoms, which may be interrupted by heteroatoms and / or carbonyl groups, preferably the unsaturated hydrocarbon groups having 2 to 10 carbon atoms, such as vinyl, phenyl vinyl, allyl, isopropenyl, acrylate or methacrylic acid, more preferably alkenyl groups having 2 to 10 carbon atoms.

2. The resin composition according to claim 1, characterized in that, The thermosetting resin is composed of one or more thermosetting polyphenylene ethers and thermosetting hydrocarbon resins. Preferably, the mass ratio of thermosetting polyphenylene ether to thermosetting hydrocarbon resin is between 0.01 and 100, more preferably between 0.02 and 50, and even more preferably between 0.1 and 10, for example, 0.2, 0.3, 0.4, 0.5, 0.6, 0.7, 0.8, 0.9, 1, 2, 3, 4, 5, 6, 7, 8, and 9.

3. The resin composition according to claim 1 or 2, characterized in that, It also includes component (3) a crosslinking agent, which includes any one or more combinations of triallyl isocyanurate (TAIC), triallyl cyanurate (TAC), trimethylallyl isocyanate (TMAIC), divinylbenzene (DVB), 1,2-bis(p-vinylphenyl)ethane (BVPE) or 1,2,4-trivinylcyclohexane (TVCH).

4. The resin composition according to any one of claims 1-3, characterized in that, The number average molecular weight of the thermosetting polyphenylene ether is selected from 1000-7000 g / mol, preferably 1000-5000 g / mol, and more preferably 1000-3000 g / mol.

5. The resin composition according to any one of claims 1-4, characterized in that, The thermosetting hydrocarbon resin includes polybutadiene and / or styrene-butadiene-styrene copolymer, preferably polybutadiene.

6. The resin composition according to any one of claims 1-5, characterized in that, The number average molecular weight of the thermosetting hydrocarbon resin is 100-5000 g / mol, preferably 500-4000 g / mol, and more preferably 1000-3500 g / mol.

7. The resin composition according to any one of claims 1-6, characterized in that, The component (2) is bis(dimethylvinylsilyl)benzene, preferably 1,4-bis(dimethylvinylsilyl)benzene.

8. The resin composition according to any one of claims 1-7, characterized in that, The resin composition comprises 20-98 wt% of component (1) a thermosetting resin and 2-80 wt% of component (2) a silicone crosslinking component as shown in formula a, with the total mass of the resin components being 100%. Preferably, 30-98 wt% of component (1) is a thermosetting resin, 2-70 wt% of component (2) is a silicon-containing crosslinking component as shown in formula a, and 0-40 wt% is a co-crosslinking agent, with the total mass of the resin component being 100%; More preferably, 45-98 wt% of component (1) thermosetting resin, 2-60 wt% of component (2) a silicon-containing crosslinking component as shown in formula a, and 5-25 wt% of component (3) a co-crosslinking agent, with the total mass of the resin components being 100%.

9. The resin composition according to any one of claims 1-8, characterized in that, In the total mass of the resin components, the mass percentage of component (1) thermosetting resin, component (2) silicon-containing crosslinking component as shown in formula a and component (3) co-crosslinking agent is more than 70 wt%, preferably 80 wt%, more preferably 90 wt%, and even more preferably 95 wt%.

10. The resin composition according to any one of claims 1-9, characterized in that, The ratio of the weight of the thermosetting resin to that of the silicon-containing crosslinking component (2) as shown in Formula a is between 0.01 and 100, preferably between 0.02 and 50, more preferably between 0.1 and 10, for example 0.2, 0.3, 0.4, 0.5, 0.6, 0.7, 0.8, 0.9, 1, 2, 3, 4, 5, 6, 7, 8, 9. In the total mass of the resin components, the mass percentage of component (1) thermosetting resin and component (2) silicon-containing crosslinked component as shown in formula a is 70 wt% or more, preferably 75 wt% or more, more preferably 80 wt% or more, for example 85 wt%, 90 wt%, 95 wt%.

11. The use of the resin composition according to any one of claims 1-10 in a metal-clad laminate substrate.

12. A prepreg, characterized in that, It comprises a reinforcing material and a resin composition according to any one of claims 1-10.

13. A metal-clad laminate, characterized in that, It is prepared from the prepreg described in claim 12.

14. A printed circuit board, characterized in that, It comprises the prepreg of claim 12 or the metal-clad laminate of claim 13.

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