WO2020248501A1 - 活性酯化合物、树脂组合物及具有其的半固化片、绝缘薄膜、覆金属箔层压板、印制线路板 - Google Patents

活性酯化合物、树脂组合物及具有其的半固化片、绝缘薄膜、覆金属箔层压板、印制线路板 Download PDF

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WO2020248501A1
WO2020248501A1 PCT/CN2019/118497 CN2019118497W WO2020248501A1 WO 2020248501 A1 WO2020248501 A1 WO 2020248501A1 CN 2019118497 W CN2019118497 W CN 2019118497W WO 2020248501 A1 WO2020248501 A1 WO 2020248501A1
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weight
resin
parts
resin composition
epoxy resin
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PCT/CN2019/118497
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English (en)
French (fr)
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崔春梅
戴善凯
陈诚
何继亮
杨宋
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苏州生益科技有限公司
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Publication of WO2020248501A1 publication Critical patent/WO2020248501A1/zh

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    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C69/00—Esters of carboxylic acids; Esters of carbonic or haloformic acids
    • C07C69/76—Esters of carboxylic acids having a carboxyl group bound to a carbon atom of a six-membered aromatic ring
    • C07C69/80—Phthalic acid esters
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B15/00—Layered products comprising a layer of metal
    • B32B15/04—Layered products comprising a layer of metal comprising metal as the main or only constituent of a layer, which is next to another layer of the same or of a different material
    • B32B15/08—Layered products comprising a layer of metal comprising metal as the main or only constituent of a layer, which is next to another layer of the same or of a different material of synthetic resin
    • B32B15/09—Layered products comprising a layer of metal comprising metal as the main or only constituent of a layer, which is next to another layer of the same or of a different material of synthetic resin comprising polyesters
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B15/00—Layered products comprising a layer of metal
    • B32B15/20—Layered products comprising a layer of metal comprising aluminium or copper
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B27/00—Layered products comprising a layer of synthetic resin
    • B32B27/06—Layered products comprising a layer of synthetic resin as the main or only constituent of a layer, which is next to another layer of the same or of a different material
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B27/00—Layered products comprising a layer of synthetic resin
    • B32B27/36—Layered products comprising a layer of synthetic resin comprising polyesters
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B33/00—Layered products characterised by particular properties or particular surface features, e.g. particular surface coatings; Layered products designed for particular purposes not covered by another single class
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B7/00—Layered products characterised by the relation between layers; Layered products characterised by the relative orientation of features between layers, or by the relative values of a measurable parameter between layers, i.e. products comprising layers having different physical, chemical or physicochemical properties; Layered products characterised by the interconnection of layers
    • B32B7/04—Interconnection of layers
    • B32B7/12—Interconnection of layers using interposed adhesives or interposed materials with bonding properties
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C67/00—Preparation of carboxylic acid esters
    • C07C67/08—Preparation of carboxylic acid esters by reacting carboxylic acids or symmetrical anhydrides with the hydroxy or O-metal group of organic compounds
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G59/00—Polycondensates containing more than one epoxy group per molecule; Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups
    • C08G59/18—Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups ; e.g. general methods of curing
    • C08G59/40—Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups ; e.g. general methods of curing characterised by the curing agents used
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G59/00—Polycondensates containing more than one epoxy group per molecule; Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups
    • C08G59/18—Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups ; e.g. general methods of curing
    • C08G59/40—Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups ; e.g. general methods of curing characterised by the curing agents used
    • C08G59/42—Polycarboxylic acids; Anhydrides, halides or low molecular weight esters thereof
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G59/00—Polycondensates containing more than one epoxy group per molecule; Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups
    • C08G59/18—Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups ; e.g. general methods of curing
    • C08G59/40—Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups ; e.g. general methods of curing characterised by the curing agents used
    • C08G59/42—Polycarboxylic acids; Anhydrides, halides or low molecular weight esters thereof
    • C08G59/4223—Polycarboxylic acids; Anhydrides, halides or low molecular weight esters thereof aromatic
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L63/00—Compositions of epoxy resins; Compositions of derivatives of epoxy resins
    • H—ELECTRICITY
    • H05—ELECTRIC TECHNIQUES NOT OTHERWISE PROVIDED FOR
    • H05K—PRINTED CIRCUITS; CASINGS OR CONSTRUCTIONAL DETAILS OF ELECTRIC APPARATUS; MANUFACTURE OF ASSEMBLAGES OF ELECTRICAL COMPONENTS
    • H05K1/00—Printed circuits
    • H05K1/02—Details
    • H05K1/03—Use of materials for the substrate
    • H—ELECTRICITY
    • H05—ELECTRIC TECHNIQUES NOT OTHERWISE PROVIDED FOR
    • H05K—PRINTED CIRCUITS; CASINGS OR CONSTRUCTIONAL DETAILS OF ELECTRIC APPARATUS; MANUFACTURE OF ASSEMBLAGES OF ELECTRICAL COMPONENTS
    • H05K1/00—Printed circuits
    • H05K1/02—Details
    • H05K1/03—Use of materials for the substrate
    • H05K1/0313—Organic insulating material
    • H05K1/0353—Organic insulating material consisting of two or more materials, e.g. two or more polymers, polymer + filler, + reinforcement
    • H05K1/0373—Organic insulating material consisting of two or more materials, e.g. two or more polymers, polymer + filler, + reinforcement containing additives, e.g. fillers
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B15/00—Layered products comprising a layer of metal
    • B32B15/04—Layered products comprising a layer of metal comprising metal as the main or only constituent of a layer, which is next to another layer of the same or of a different material
    • B32B15/08—Layered products comprising a layer of metal comprising metal as the main or only constituent of a layer, which is next to another layer of the same or of a different material of synthetic resin
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B2255/00—Coating on the layer surface
    • B32B2255/26—Polymeric coating
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B2307/00—Properties of the layers or laminate
    • B32B2307/20—Properties of the layers or laminate having particular electrical or magnetic properties, e.g. piezoelectric
    • B32B2307/206—Insulating
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B2457/00—Electrical equipment
    • B32B2457/08—PCBs, i.e. printed circuit boards
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B27/00—Layered products comprising a layer of synthetic resin
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C2603/00—Systems containing at least three condensed rings
    • C07C2603/56—Ring systems containing bridged rings
    • C07C2603/58—Ring systems containing bridged rings containing three rings
    • C07C2603/60—Ring systems containing bridged rings containing three rings containing at least one ring with less than six members
    • C07C2603/66—Ring systems containing bridged rings containing three rings containing at least one ring with less than six members containing five-membered rings
    • C07C2603/68—Dicyclopentadienes; Hydrogenated dicyclopentadienes

Definitions

  • the present invention relates to the technical field of polymer materials, in particular to an active ester compound with low dielectric constant and low dielectric loss, a resin composition and a prepreg, insulating film, metal-clad laminate, and printed circuit board with the same .
  • thermosetting resin composition The printed circuit board material made of this thermosetting resin composition can exhibit a sufficiently low low dielectric constant and low dielectric constant during the high-speed and high-frequency signal transmission process. Loss tangent.
  • materials prepared from thermosetting resin compositions with epoxy resin and its curing agents as essential components have the advantages of good heat resistance, insulation, processability and low cost, so they are widely used in semiconductors and printing In electronic materials such as circuit boards.
  • Commonly used curing agents for epoxy resins include polyamines, acid anhydrides, and phenolic resins.
  • curing agents containing active hydrogen in molecular structures such as amines and phenolic resins, there are a large number of hydroxyl groups in the cured epoxy resin, which will cause the water absorption of the cured product to increase, and the heat resistance and dielectric properties of the cured product will decrease.
  • active esters are a promising epoxy curing agent. Active ester can react with epoxy resin under relatively mild conditions; at the same time, epoxy resin cured by active ester does not contain hydroxyl groups, instead of ester groups, epoxy resins with excellent moisture and heat resistance and dielectric properties can be obtained. Resin cured product.
  • Japanese Patent Laid-Open Nos. JP2002012650A, JP2003082063A, JP2004155990A, JP2009235165A and JP2012246367A disclose a series of active ester resins, which are used as epoxy resin curing agents to appropriately reduce the dielectric constant and dielectric loss of the cured epoxy resin.
  • the dielectric constant reaches between 2.8-3.3, and the dielectric loss value reaches between 0.002-0.005.
  • bismaleimide resin, benzoxazine resin or phosphorus-containing flame retardant are added to the resin composition. And other components, so the final dielectric constant of the substrate material still fails to meet the requirements of high-frequency and high-speed substrates.
  • the object of the present invention is to provide an active ester compound with low dielectric constant and low dielectric loss, low roughness and high toughness, resin composition, and prepregs, insulating films, metal-clad laminates, And printed circuit boards.
  • An active ester compound the structural formula is: structural formula (1)
  • R 1 represents hydrogen or a C1-C5 alkyl group
  • m is an integer of 1-10
  • A is one of the following groups:
  • R 10 , R 11 , R 12 , and R 13 are respectively selected from hydrogen, C1-C5 alkyl, or C6-C10 aryl or aralkyl.
  • aromatic phenol resin aromatic diformyl halide compound, vinyl phenol
  • a resin composition comprising 20-100 parts by weight of an epoxy resin, 1-100 parts by weight of a curing agent, and 0.001-5 parts by weight of a curing accelerator; wherein the curing agent at least contains as described above The active ester compound.
  • a prepreg comprising a reinforcing material and a resin composition attached to the surface of the reinforcing material, the resin composition being the resin composition described in any one of the above.
  • an insulating film comprising a carrier film and a resin composition coated on the surface of the carrier film, the resin composition being the resin composition described in any one of the above.
  • a metal-clad laminate comprising at least one prepreg as described above and a metal foil formed on at least one side of the prepreg.
  • a printed wiring board comprising at least one prepreg as described above or at least one insulating film as described above.
  • the active ester compound of the present invention is an active ester compound containing two reactive groups, wherein the active ester group can react with epoxy resin without generating a strong hydroxyl group, thereby obtaining a low dielectric after the reaction Constant and low dielectric loss value.
  • the carbon-carbon double bond at the end undergoes free radical polymerization, which further reduces the dielectric constant and dielectric loss of the cured product, so that very low dielectric constant and dielectric loss values are obtained, and free radical polymerization
  • the combination with active ester groups solves the problems of coarseness and toughness.
  • compositions comprising and “containing” in this specification mean that in addition to the aforementioned components, other components can be included, and these other components can impart different characteristics to the resin composition.
  • R 1 represents hydrogen or a C1-C5 alkyl group
  • m is an integer of 1-10
  • A is one of the following groups:
  • R 10 , R 11 , R 12 , and R 13 are respectively selected from hydrogen, C1-C5 alkyl, or C6-C10 aryl or aralkyl.
  • the active ester compound represented by the structural formula (1) in the curing agent of the present invention is an active ester compound containing two reactive groups, wherein the active ester group does not generate a polar hydroxyl group when reacting with the epoxy resin, so that after the reaction Obtain a low dielectric constant and low dielectric loss.
  • the carbon-carbon double bond at the end undergoes free radical polymerization, which further reduces the dielectric constant and dielectric loss of the cured product, thus obtaining a very low dielectric constant and dielectric loss value.
  • the combination of radical polymerization and active ester groups further obtains a final cured product with low roughness and high toughness.
  • the active ester compound is well applied to polyphenylene ether resin, maleimide resin or hydrocarbon resin containing carbon-carbon double bond.
  • the R 1 may be hydrogen, methyl, ethyl, propyl, tert-butyl or pentyl, and more preferably, the R 1 may be hydrogen or methyl.
  • the R 10 , R 11 , R 12 and R 13 are independently selected from hydrogen, methyl, ethyl, propyl, tert-butyl or pentyl, or phenyl, biphenyl or naphthyl, and more Preferably, it is hydrogen, methyl or phenyl, and more preferably, said R 10 , R 11 , R 12 and R 13 are each independently hydrogen, methyl or phenyl.
  • a in the active ester compound represented by the structural formula (1) contains dicyclopentadienyl, tricyclopentadienyl or naphthyl.
  • the active ester compound represented by structural formula (1) is a dicyclopentadiene active ester, and its structural formula is as follows:
  • the active ester compound represented by structural formula (1) is a naphthalene active ester, and its structural formula is as follows:
  • the active ester compound is a dicyclopentadienyl group-containing active ester represented by structural formula (2).
  • the preparation method of the active ester compound represented by the structural formula (1) in the present invention is: the aromatic phenol resin, the aromatic dicarboxylic acid or the aromatic diformyl halide compound and the vinyl phenol are reacted to obtain the reaction
  • the molar ratio is as follows:
  • the aromatic diformyl halide compound is aromatic diformyl chloride, aromatic diformyl bromide or aromatic diformyl fluoride, preferably terephthaloyl chloride.
  • the vinyl phenol is p-vinyl phenol, m-vinyl phenol or o-vinyl phenol, preferably p-vinyl phenol.
  • the active ester compound represented by structural formula (1) in the present invention can also be prepared by the following preparation method:
  • aromatic diformyl chloride can also be replaced with other aromatic diformyl halide compounds, and the reaction mechanism is the same as the above, so it will not be repeated here.
  • This application also provides a resin composition, comprising 20-100 parts by weight of epoxy resin, 1-100 parts by weight of curing agent, and 0.001-5 parts by weight of curing accelerator; the curing agent at least contains as shown in structural formula (1) The active ester compound.
  • the content of the active ester compound represented by the structural formula (1) in the curing agent is 1-100% by weight. More preferably, it is 5-50% by weight; for example, 1% by weight, 2% by weight, 3% by weight, 4% by weight, 5% by weight, 6% by weight, 7% by weight, 8% by weight, 9% by weight, 10% by weight, 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 %, 24% by weight, 25% by weight, 26% by weight, 27% by weight, 28% by weight, 29% by weight, 30% by weight, 31% by weight, 32% by weight, 33% by weight, 34% by weight, 35% by weight, 36% by weight, 37% by weight, 38% by weight, 39% by weight, 30% by weight, 31% by
  • the curing agent further contains at least one of an amine compound, an amide compound, an acid anhydride compound, a phenol compound, and an active ester compound different from the structural formula (1).
  • the content is based on 100 parts by weight of the total curing agent, containing 0-99 parts by weight, preferably 5-60 parts by weight, such as 0 parts by weight, 5 parts by weight, 10 parts by weight, 25 parts by weight, 35 parts by weight, 60 parts by weight Parts by weight, 70 parts by weight, 85 parts by weight, 99 parts by weight, and specific points between the above values are limited to space and for the sake of brevity.
  • the present invention will not exhaust the specific points included in the range.
  • the amine compound may be diaminodiphenylmethane, diaminodiphenylsulfone, diethylenetriamine, biscarboxyphthalimide, imidazole, etc., preferably diaminodiphenyl Methane and diaminodiphenyl sulfone;
  • the amide compound may be dicyandiamide, low molecular polyamide, etc., preferably dicyandiamide;
  • the acid anhydride compound may be phthalic anhydride, trimellitic anhydride, homo Pyromellitic dianhydride, maleic anhydride, hydrogenated phthalic anhydride, Nadic anhydride, etc., preferably styrene-maleic anhydride;
  • the phenolic compound may be bisphenol A phenol resin, phenol phenol resin, naphthol Phenolic resin, biphenol phenol resin, biphenol naphthol resin, dicyclopentadiene phenol addition molding resin, phenol aralkyl resin
  • X is phenyl or naphthyl; j is 0 or 1; k is 0 or 1; n represents a repeating unit and is 0.25 to 1.25.
  • the epoxy resin is selected from the group consisting of bisphenol A epoxy resin, bisphenol F epoxy resin, bisphenol S type epoxy resin, bisphenol E type epoxy resin, phosphorus-containing epoxy resin, Nitrogen-containing epoxy resin, o-cresol novolac epoxy resin, bisphenol A novolac epoxy resin, phenol novolac epoxy resin, cresol novolac epoxy resin, triphenylmethane epoxy resin, tetraphenylethane epoxy resin , Biphenyl epoxy resin, naphthalene ring epoxy resin, dicyclopentadiene epoxy resin, isocyanate epoxy resin, aralkyl novolac epoxy resin, cycloaliphatic epoxy resin, glycidyl amine One or more of type epoxy resin, glycidyl ether type epoxy resin and glycidyl ester type epoxy resin.
  • the epoxy resin may be a naphthalene ring type epoxy resin, a biphenyl type epoxy resin or a dicyclopentadiene type epoxy resin, and the structural formula of the naphthalene ring type epoxy resin is as shown in the structural formula (5).
  • the structural formula of the biphenyl epoxy resin is shown in the structural formula (6)
  • the structural formula of the dicyclopentadiene epoxy resin is shown in the structural formula (7):
  • p is an integer of 1-10;
  • n is an integer of 1-10;
  • n is an integer of 1-10.
  • the curing accelerator is selected from at least one of 4-dimethylaminopyridine, 2-methylimidazole, 2-methyl4-ethylimidazole, 2-phenylimidazole, and zinc isooctanoate,
  • 4-dimethylaminopyridine 2-methylimidazole
  • 2-methyl4-ethylimidazole 2-phenylimidazole
  • zinc isooctanoate 2-methyl
  • the mixture of methylimidazole, 2-methyl-4-ethylimidazole and 2-phenylimidazole is not limited thereto.
  • the content of the curing accelerator is 0.001 to 5 parts by weight, for example, 0.001 parts by weight, 0.01 parts by weight, 1 part by weight, 2.5 parts by weight, 5 parts by weight, and the aforementioned values
  • the specific point values between are limited to space and for the sake of brevity, the present invention will not exhaustively list specific point values included in the range.
  • the content of the curing accelerator is 0.01 to 1 part by weight.
  • the resin composition further includes a filler. Based on 100 parts by weight of the resin composition, the filler is 0-200 parts by weight. It is understood that the resin composition can be The filler may be contained or not.
  • the content of the filler is 10-100 parts by weight, more preferably 30-70 parts by weight, for example, 10 parts by weight.
  • the filler is an organic filler or an inorganic filler, wherein the inorganic filler is selected from one of non-metal oxides, metal nitrides, non-metal nitrides, inorganic hydrates, inorganic salts, metal hydrates or inorganic phosphorus Or a mixture of at least any two; the organic filler is selected from at least one of polytetrafluoroethylene powder, polyphenylene sulfide, and polyethersulfone powder.
  • the inorganic filler is selected from fused silica, crystalline silica, spherical silica, hollow silica, aluminum hydroxide, alumina, talc, aluminum nitride, boron nitride, At least one of silicon carbide, barium sulfate, barium titanate, strontium titanate, calcium carbonate, calcium silicate, mica, and glass fiber powder.
  • the filler is silica, more preferably, surface-treated spherical silica.
  • the median particle size of the filler is 1 to 15 ⁇ m, for example, 1 ⁇ m, 2 ⁇ m, 5 ⁇ m, 8 ⁇ m, 10 ⁇ m, 11 ⁇ m, 12 ⁇ m, 13 ⁇ m, 14 ⁇ m or 15 ⁇ m, and specific points between the above values, and the space is limited. And for the sake of simplicity, the present invention will not exhaustively list the specific points included in the range.
  • the median particle size of the filler is 1-10 ⁇ m.
  • the surface treatment agent used to treat the silica is a silane coupling agent, such as an epoxy silane coupling agent or an amino silane coupling agent.
  • the resin composition further includes an initiator selected from the group consisting of diacyl peroxides, peroxy ketals, peroxycarbonates, peroxy esters, ketone peroxides, and dialkyl peroxides.
  • an initiator selected from the group consisting of diacyl peroxides, peroxy ketals, peroxycarbonates, peroxy esters, ketone peroxides, and dialkyl peroxides.
  • diacyl peroxide is selected from isononanoyl peroxide, decanoyl peroxide, lauroyl peroxide, p-chlorobenzoyl peroxide
  • the peroxy ketal is selected from 2,2-bis(4,4-bis-(two) -Tertiary butylperoxy) cyclohexyl) propane
  • the peroxycarbonate is selected from one or both of di-3-methoxybutylperoxydicarbonate and dicyclohexylperoxydicarbonate Species
  • the resin composition further includes a flame retardant to improve the flame retardancy of the finally formed cured product.
  • the cured product can be understood as a prepreg, an insulating film, a metal-clad laminate, and a printed circuit. Board etc.
  • the content of the flame retardant is 1 to 80 parts by weight, for example, 1 part by weight, 5 parts by weight, 10 parts by weight, 20 parts by weight, 50 parts by weight, 70 parts by weight Parts, 80 parts by weight, and specific points between the above values are limited to space and for the sake of brevity. The present invention will not exhaustively list specific points included in the range.
  • the content of the flame retardant is 5-50 parts by weight.
  • the flame retardant may be a brominated flame retardant, a phosphorus flame retardant, a nitrogen flame retardant, a silicone flame retardant, an organic metal salt flame retardant, an inorganic flame retardant, and the like.
  • the brominated flame retardant may be decabromodiphenyl ether, decabromodiphenylethane, brominated styrene or tetrabromophthalamide.
  • Phosphorus-based flame retardants can be inorganic phosphorus, phosphate compounds, phosphonic acid compounds, phosphinic acid compounds, phosphine oxide compounds, and 9,10-dihydro-9oxa-10-phosphaphenanthrene-10-oxide, 10-(2,5 dihydroxyphenyl)-9,10-dihydro-9oxa-10-phosphaphenanthrene-10-oxide, 10-phenyl-9,10-dihydro-9-oxa -10-Phosphophenanthrene-10-oxide, tris(2,6-dimethylphenyl)phosphine, phosphazene and other organic phosphorus compounds.
  • the nitrogen-based flame retardant may be a triazine compound, a cyanuric acid compound, an isocyanate compound, a phenothiazine, or the like.
  • the silicone flame retardant can be silicone oil, silicone rubber, silicone resin and the like.
  • the organic metal salt flame retardant may be ferrocene, acetylacetone metal complex, organic metal carbonyl compound, and the like.
  • the inorganic flame retardant may be aluminum hydroxide, magnesium hydroxide, aluminum oxide, barium oxide, and the like.
  • the type of flame retardant is not limited to this. It can be understood that the flame retardant added can be selected according to the specific application field of the laminate.
  • the application field that requires halogen, preferably non- Halogen flame retardants, such as phosphorous or nitrogen-containing flame retardants, are more preferably phosphazene, DOPO or DOPO-HQ.
  • the phosphorus-containing flame retardant when selected, it can form a nitrogen and phosphorus synergistic flame retardant with the nitrogen element of the active ester compound in the curing agent to improve the flame retardant efficiency.
  • the resin composition further includes 0-5 parts of other auxiliary agents.
  • the other auxiliary agents include coupling agents, dispersants, and dyes.
  • the coupling agent is a silane coupling agent, such as epoxy silane coupling agent or amino silane coupling agent;
  • the dispersing agent is ⁇ -aminopropyl triethoxy silane, N- ⁇ -(aminoethyl) -Gamma-aminopropyltrimethoxysilane and other amino-based silane compounds having an amino group and a hydrolyzable group or hydroxyl group, 3-acryloxypropyltrimethoxysilane, etc.
  • the agent having an epoxy group and a hydrolyzable group Or hydroxy epoxy silane compounds, ⁇ -methacryloxypropyl trimethoxysilane and other vinyl silane compounds with hydrolyzable groups or hydroxyl groups, such as vinyl silane compounds, cationic silane coupling agents, dispersed Disperbyk-110, 111, 118, 180, 161, 2009, BYK-W996, W9010, W903 (all product names) made by BYK can be used as the agent;
  • the dyes are fluorescent dyes and black dyes, and the fluorescent dye is pyrazoline Etc.
  • the black dye is carbon black (liquid or powdered), pyridine complex, azo complex, nigrosine, black talc, cobalt chromium chromium metal oxide, azine, phthalocyanine and the like.
  • the preparation method of the resin composition of the present invention is a conventional technical means in the field, specifically: take a container, first put the solid component into it, then add the liquid organic solvent, stir until completely dissolved, add the liquid resin and filler And the curing accelerator, continue to stir evenly, and finally adjust the liquid solid content to 50-80% with a solvent to make a glue, where the solid content is by weight.
  • the organic solvent and the solvent in the present invention are not specifically limited.
  • the organic solvent can be selected from acetone, methyl ethyl ketone, toluene, methyl isobutyl ketone, N, N-dimethylformamide, N, N-dimethylacetamide, ethylene glycol methyl ether, propylene glycol methyl ether, benzene , Toluene, cyclohexane or any combination of several.
  • the addition amount of the solvent is selected by those skilled in the art according to their own experience, as long as the obtained glue can reach a viscosity suitable for use.
  • the present invention also provides a prepreg comprising a reinforcing material and the above-mentioned resin composition attached to the surface of the reinforcing material.
  • the reinforcing material is natural fiber, organic synthetic fiber, organic fabric or inorganic fabric, inorganic fabric.
  • the reinforcing material is glass fiber cloth, and the glass fiber cloth preferably uses open fiber cloth or flat cloth.
  • the glass fiber cloth when used as the reinforcing material, the glass fiber cloth generally needs to be chemically treated to improve the interface between the resin composition and the glass fiber cloth.
  • the main method of the chemical treatment is coupling agent treatment.
  • the coupling agent used is preferably epoxy silane or amino silane to provide good water resistance and heat resistance.
  • the preparation method of the prepreg is as follows: immerse the reinforcing material in the above resin composition glue solution, and then bake the impregnated reinforcing material at 50-170°C for 1-10 min, and dry it to obtain the present invention Prepreg.
  • the present invention also provides an insulating film comprising a carrier film and the above-mentioned resin composition coated on the surface of the carrier film.
  • the preparation method of the insulating film is as follows: adding the above resin composition into a solvent, dissolving it into a glue solution, coating the glue solution on a carrier film, heating and drying the carrier film coated with the glue solution, The insulating resin layer is formed by the liquid, and the insulating film can be obtained.
  • the solvent is selected from the group consisting of acetone, methyl ethyl ketone, toluene, methyl isobutyl ketone, N, N-dimethylformamide, N, N-dimethylacetamide, ethylene glycol methyl ether, and propylene glycol methyl ether One or more.
  • the carrier film may be polyethylene terephthalate (PET) film, release film, copper foil, aluminum foil, etc., and the carrier film is preferably a PET film.
  • PET polyethylene terephthalate
  • the above heating and drying conditions are baking at 50-170°C for 1-10 minutes, of course, it is not limited to this.
  • the side of the insulating resin layer facing away from the carrier film is covered with a protective film to protect the insulating resin layer.
  • the material of the protective film is the same as the material of the carrier film, of course, it is not limited thereto.
  • the present invention also provides a metal-clad laminate comprising at least one prepreg as described above and a metal foil formed on at least one side of the prepreg.
  • the metal-clad laminate refers to bonding one or two of the above-mentioned prepregs together by heating and pressing to form a laminate, and then bonding the metal foil on one or both sides of the laminate by heating and pressing.
  • the preparation steps of the metal-clad laminate are as follows: one or both sides of the above-mentioned prepreg are covered with metal foil, or after at least two above-mentioned prepregs are superimposed, one or both sides are covered with metal foil, Hot press forming, you can get the metal foil laminate.
  • the pressing conditions of the above-mentioned metal foil and laminate are pressing at a pressure of 0.2-2 MPa and a temperature of 180-250°C for 2 to 4 hours.
  • the number of the prepregs can be determined according to the thickness of the required laminate, and one or more sheets can be used.
  • the metal foil may be copper foil or aluminum foil, and the material is not limited; the thickness of the metal foil is also not particularly limited, such as 5 ⁇ m, 8 ⁇ m, 12 ⁇ m, 18 ⁇ m, 35 ⁇ m, or 70 ⁇ m.
  • the present invention also provides a printed circuit board, which includes at least one prepreg or at least one insulating film as described above.
  • the epoxy resin, the active ester compound obtained in the synthesis example, curing agent, curing accelerator, filler, flame retardant and appropriate methyl ethyl ketone solvent are stirred and mixed to obtain a solid content of 65% by weight.
  • glue methyl ethyl ketone
  • the glue was dipped and coated on E glass fiber cloth (7628), and dried in an oven at 160°C for 5 minutes to prepare a prepreg.
  • the glue was coated on a PET carrier and dried in an oven at 160°C for 5 minutes to prepare an insulating film.
  • the specific pressing process is pressing at a pressure of 1.5Mpa and a temperature of 220°C for 2 hours.
  • the specific pressing process is pressing at a pressure of 1.5Mpa and a temperature of 220°C for 2 hours.
  • Roughness Use laminate b and non-contact surface roughness meter to test 10 point values, and calculate the average roughness (Ra) value.
  • Dielectric constant Use the laminate a, and use the plate method in accordance with IPC-TM-650 2.5.5.9 to measure the dielectric constant at 1 GHz.
  • Dielectric loss tangent Use laminate a, and use the plate method in accordance with IPC-TM-650 2.5.5.9 to measure the dielectric loss factor at 1 GHz.
  • Example 1 has a lower dielectric constant and dielectric loss value than Comparative Example 1 (the prior art active ester).

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Abstract

本发明提供了一种活性酯化合物、树脂组合物及具有其的半固化片、绝缘薄膜、覆金属箔层压板以及印制线路板。活性酯化合物为含有两个反应基的活性酯化合物，其中活性酯基与环氧树脂发生反应时不产生极性较强的羟基，从而反应后获得具有低介电常数和低介质损耗。

Description

活性酯化合物、树脂组合物及具有其的半固化片、绝缘薄膜、覆金属箔层压板、印制线路板 技术领域
本发明涉及高分子材料技术领域，尤其涉及一种具有低介电常数、低介质损耗的活性酯化合物、树脂组合物及具有其的半固化片、绝缘薄膜、覆金属箔层压板、以及印制线路板。
背景技术
汽车市场、智能手机等消费类电子市场，随着技术的升级，对PCB提出了新的需求，而到了2018年5G商用上市以后，对PCB基材的介电性能方面的要求更上一层台阶，高频高速覆铜板是5G时代不可或缺的电子基材之一。简单来说，即PCB基板材料需要具备较低的介电常数和介电损耗正切，以减少高速传输时信号的延迟、失真和损耗，以及信号之间的干扰。因此，期望提供一种热固性树脂组合物，使用这种热固性树脂组合物制作的印制电路板材料在高速化、高频化的信号传输过程能表现出充分低的低介电常数和低介电损耗正切。
现有技术中，以环氧树脂及其固化剂为必需成分的热固性树脂组合物制备的材料具有良好的耐热性、绝缘性、加工性和成本低廉等优点，因此广泛应用于半导体、印制电路板等电子材料中。环氧树脂常用的固化剂有多胺、酸酐、酚醛树脂等。如胺类、酚醛树脂这类分子结构中含有活性氢的固化剂，其固化的环氧树脂中存在大量的羟基，这会导致固化物的吸水率上升，耐湿热性能和介电性能下降。为了解决常用固化剂固化环氧树脂时出现的上述问题，人们发现活性酯是一种很有前景的环氧树脂固化剂。活性酯在较温和的条件下就可以和环氧树脂发生反应；同时，活性酯固化的环氧树脂，不含有羟基，取而代之的是酯基，可以得到耐湿热性能和介电性能优良的环氧树脂固化产物。日本专利特开JP2002012650A，JP2003082063A，JP2004155990A，JP2009235165A及JP2012246367A中公开了一系列活性酯树脂，将其用作环氧树脂固化剂，可以适当降低环氧树脂固化物的介电常数和介电损耗，一般介电常数达到2.8-3.3之间，介电损耗值达到0.002-0.005之间。但是制备高频高速用高性能基板时，为了改善耐热性、热膨胀系数或阻燃性，在树脂组合物中还添加双马来酰亚胺树脂、苯并噁嗪树脂或含磷阻燃剂等其他组分，因此最终获得的基板材料的介电常数还是未能很好地满足高频高速基板要求。
有鉴于此，有必要提供一种新的活性酯化合物、树脂组合物及具有其的半固化片、绝缘薄膜、覆金属箔层压板、以及印制线路板以解决上述问题。
发明内容
本发明的目的在于提供一种具有低介电常数和低介质损耗、低粗化度和高韧性的活性酯化合物、树脂组合物、以及使用其制备的半固化片、绝缘薄膜、覆金属箔层压板、以及印制线路板。
为实现上述发明目的，本发明采用如下技术方案：
一种活性酯化合物，结构式为：结构式(1)
Figure PCTCN2019118497-appb-000001
其中，R 1表示氢或C1-C5的烷基，m为1-10的整数，A为以下基团中的一种：
Figure PCTCN2019118497-appb-000002
其中，R 10、R 11、R 12、R 13分别选自氢、C1-C5的烷基，或C6-C10的芳基或芳烷基。
另一技术方案为：一种活性酯化合物的制备方法，
将芳香族酚树脂、芳香族二羧酸、乙烯基苯酚发生反应；
或将芳香族酚树脂、芳香族二甲酰卤化合物、乙烯基苯酚发生反应；
或先将芳香族酚树脂与芳香族二羧酸发生反应，再加入乙烯基苯酚继续发生反应；
或先将芳香族酚树脂与芳香族二甲酰卤化合物发生反应，再加入乙烯基苯酚继续发生反应。
另一技术方案为：一种树脂组合物，包括环氧树脂20-100重量份、固化剂1-100重量 份、固化促进剂0.001-5重量份；其中，所述固化剂至少包含如上所述的活性酯化合物。
另一技术方案为：一种半固化片，包括增强材料、附着于所述增强材料表面的树脂组合物，所述树脂组合物为上述任意一项所述的树脂组合物。
另一技术方案为：一种绝缘薄膜，包括载体膜、涂覆于载体膜表面的树脂组合物，所述树脂组合物为如上任意一项所述的树脂组合物。
另一技术方案为：一种覆金属箔层压板，包括至少一张如上所述的半固化片、成形于所述半固化片的至少一面的金属箔。
另一技术方案为：一种印制线路板，包括至少一张如上所述的半固化片、或者至少一张如上所述的绝缘薄膜。
有益效果：本发明所述的活性酯化合物为含有两个反应基的活性酯化合物，其中活性酯基能够与环氧树脂发生反应时不产生极性较强的羟基，从而反应后获得低介电常数和低介质损耗值，同时末端的碳碳双键发生自由基聚合反应，进一步降低固化物的介电常数和介质损耗，因此获得非常低的介电常数和介质损耗值，同时自由基聚合反应和活性酯基的组合解决了粗化度和韧性问题。
具体实施例
以下所述是本发明实施例的具体实施方式，应当指出，对于本领域的普通技术人员来说，在不脱离本发明实施例原理的前提下，还可以做出若干改进和润饰，这些改进和润饰也视为本发明实施例的保护范围。
本说明书中的“包含”、“含有”，意指除所述组分外，还可以包含其他组分，这些其他组分能够赋予树脂组合物不同的特性。
本说明书中的“以树脂组合物100重量份计”意思是除了阻燃剂、填料、催化剂、助剂和引发剂以外的组分总量为100重量份计。
为实现上述发明目的，本发明采用如下技术方案：
一种活性酯化合物，如结构式(1)所示：
Figure PCTCN2019118497-appb-000003
其中，R 1表示氢或C1-C5的烷基，m为1-10的整数，A为以下基团中的一种：
Figure PCTCN2019118497-appb-000004
Figure PCTCN2019118497-appb-000005
其中，R 10、R 11、R 12、R 13分别选自氢、C1-C5的烷基，或C6-C10的芳基或芳烷基。
本发明固化剂中如结构式(1)所示的活性酯化合物为含有两个反应基的活性酯化合物，其中活性酯基与环氧树脂发生反应时不产生极性较强的羟基，从而反应后获得具有低介电常数和低介质损耗，同时末端的碳碳双键发生自由基聚合反应，进一步降低固化物的介电常数和介质损耗，因此获得非常低的介电常数和介质损耗值，同时自由基聚合反应和活性酯基的组合进一步获得低粗化度和高韧性的最终固化物。该活性酯化合物很好的应用于含碳碳双键的聚苯醚树脂、马来酰亚胺树脂或碳氢树脂中。
优选地，所述R 1可以是氢、甲基、乙基、丙基、叔丁基或戊基，更优选地，所述R 1可以为氢或甲基。
优选地，所述R 10、R 11、R 12、R 13分别独立地选氢、甲基、乙基、丙基、叔丁基或戊基，或苯基、联苯基或萘基，更优选为氢、甲基或苯基，更优选地，所述R 10、R 11、R 12、R 13分别独立地氢、甲基或苯基。
优选地，所述结构式(1)所示的活性酯化合物中的A中含有双环戊二烯基、三环戊二烯基或萘基。
例如，在所述R 1为氢、m为1、A为双环戊二烯基时，结构式(1)所示的活性酯化合物为双环戊二烯活性酯，其结构式如下所示：
Figure PCTCN2019118497-appb-000006
例如，在所述R 1为氢、m为1、A为萘基时，结构式(1)所示的活性酯化合物为萘活性酯，其结构式如下所示：
Figure PCTCN2019118497-appb-000007
更优选地，所述活性酯化合物是结构式(2)所示的含双环戊二烯基活性酯。
本发明中的如结构式(1)所示的活性酯化合物的制备方法为：将芳香族酚树脂、芳香族二羧酸或芳香族二甲酰卤化合物和、乙烯基苯酚发生反应获得，其反应摩尔比为如下所示：
芳香族酚树脂：芳香族二羧酸或芳香族二甲酰卤化合物＝0.5-0.98；
芳香族酚树脂：乙烯基苯酚＝0.5-9.5；
所述芳香族二甲酰卤化合物为芳香族二甲酰氯、芳香族二甲酰溴或芳香族二甲酰氟，优选为对苯二甲酰氯。
所述乙烯基苯酚为对乙烯基苯酚、间乙烯基苯酚或邻乙烯基苯酚，优选为对乙烯基苯酚。
下面以双环戊二烯活性酯的制备为例，其反应机理如下所示：
Figure PCTCN2019118497-appb-000008
或者，本发明中的如结构式(1)所示的活性酯化合物还可以采用如下制备方法：
先将芳香族酚树脂、芳香族二羧酸发生反应，再加入对乙烯基苯酚继续发生反应，获得所述活性酯化合物，下面以双环戊二烯活性酯的制备为例，其反应机理如下所示：
第一步：
Figure PCTCN2019118497-appb-000009
第二步：
Figure PCTCN2019118497-appb-000010
或先将芳香族酚树脂、芳香族二甲酰氯发生反应，再加入对乙烯基苯酚继续发生反应，获得所述活性酯化合物，下面以双环戊二烯活性酯的制备为例，其反应机理如下所示：
第一步：
Figure PCTCN2019118497-appb-000011
第二步：
Figure PCTCN2019118497-appb-000012
其中，芳香族二甲酰氯也可以替换为其他芳香族二甲酰卤化合物，反应机理同上，于此不再逐一赘述。
当然，并不以此为限，也可以采用其他方法制备出如结构式(1)所示的活性酯化合物，即，所有能够制备出如结构式(1)所示的活性酯化合物的方法均在本发明的保护范围之内。
本申请还提供一种树脂组合物，包括环氧树脂20-100重量份、固化剂1-100重量份、固化促进剂0.001-5重量份；所述固化剂至少包含如结构式(1)所示的活性酯化合物。
作为本发明的进一步改进，所述固化剂中如结构式(1)所示的活性酯化合物的含量为1-100重量％。更优选为5-50重量％；例如1重量％、2重量％、3重量％、4重量％、5重量％、6重量％、7重量％、8重量％、9重量％、10重量％、11重量％、12重量％、13重量％、14重量％、15重量％、16重量％、17重量％、18重量％、19重量％、20重 量％、21重量％、22重量％、23重量％、24重量％、25重量％、26重量％、27重量％、28重量％、29重量％、30重量％、31重量％、32重量％、33重量％、34重量％、35重量％、36重量％、37重量％、38重量％、39重量％、40重量％、41重量％、42重量％、43重量％、44重量％、45重量％、46重量％、47重量％、48重量％、49重量％、50重量％、51重量％、52重量％、53重量％、54重量％、55重量％、56重量％、57重量％、58重量％、59重量％、60重量％、61重量％、62重量％、63重量％、64重量％、65重量％、66重量％、67重量％、68重量％、69重量％、70重量％、71重量％、72重量％、73重量％、74重量％、75重量％、76重量％、77重量％、78重量％、79重量％、80重量％、81重量％、82重量％、83重量％、84重量％、85重量％、86重量％、87重量％、88重量％、89重量％、90重量％、91重量％、92重量％、93重量％、94重量％、95重量％、96重量％、97重量％、98重量％、99重量％或100重量％，以及上述数值之间的具体点值，限于篇幅以及处于简明的考虑，本发明不再穷尽列举所述范围包括的具体点值。
作为本发明的进一步改进，所述固化剂中还含有胺系化合物、酰胺系化合物、酸酐系化合物、酚系化合物、不同于结构式(1)的活性酯类化合物中的至少一种。其含量为以固化剂总量100重量份计，含有0-99重量份，优选为5-60重量份，例如0重量份、5重量份、10重量份、25重量份、35重量份、60重量份、70重量份、85重量份、99重量份，以及上述数值之间的具体点值，限于篇幅以及处于简明的考虑，本发明不再穷尽列举所述范围包括的具体点值。
具体地，所述胺系化合物可以是二氨基二苯基甲烷、二氨基二苯砜、二亚乙基三胺、双羧基邻苯二甲酰亚胺、咪唑等，优选为二氨基二苯基甲烷和二氨基二苯砜；所述酰胺系化合物可以是双氰胺、低分子聚酰胺等，优选为双氰胺；所述酸酐系化合物可以是邻苯二甲酸酐、偏苯三甲酸酐、均苯四甲酸二酐、马来酸酐、氢化邻苯二甲酸酐、纳迪克酸酐等，优选为苯乙烯-马来酸酐；所述酚系化合物可以是双酚A酚醛树脂、苯酚酚醛树脂、萘酚酚醛树脂、联苯苯酚型酚醛树脂、联苯苯酚型萘酚树脂、双环戊二烯苯酚加成型树脂、苯酚芳烷基树脂、萘酚芳烷基树脂、三羟甲基甲烷树脂等；不同于结构式(1)的活性酯类化合物可以选结构式(4)所示的化合物：
Figure PCTCN2019118497-appb-000013
其中，X为苯基或者萘基；j为0或1；k为0或1；n表示重复单元，为0.25～1.25。
当然，并不以此为限，可以理解的是，不同于结构式(1)的活性酯类化合物也可以选择其他地活性酯类化合物。
作为本发明地进一步改进，所述环氧树脂选自双酚A环氧树脂、双酚F环氧树脂、双酚S型环氧树脂、双酚E型环氧树脂、含磷环氧树脂、含氮环氧树脂、邻甲酚醛环氧树脂、双酚A酚醛环氧树脂、苯酚酚醛环氧树脂、甲酚酚醛环氧树脂、三苯基甲烷环氧树脂、四苯基乙烷环氧树脂、联苯型环氧树脂、萘环型环氧树脂、双环戊二烯型环氧树脂、异氰酸酯型环氧树脂、芳烷基线型酚醛环氧树脂、脂环族类环氧树脂、缩水甘油胺型环氧树脂、缩水甘油醚型环氧树脂、缩水甘油酯型环氧树脂中的一种或几种。
更优选地，所述环氧树脂可以为萘环型环氧树脂、联苯型环氧树脂或双环戊二烯型环氧树脂，所述萘环型环氧树脂的结构式如结构式(5)所示，所述联苯型环氧树脂的结构式如结构式(6)所示，所述双环戊二烯型环氧树脂的结构式结构式(7)所示：
Figure PCTCN2019118497-appb-000014
其中，p为1-10的整数；
Figure PCTCN2019118497-appb-000015
其中，n为1-10的整数；
Figure PCTCN2019118497-appb-000016
Figure PCTCN2019118497-appb-000017
其中，m为1-10的整数。
本发明中，所述固化促进剂选自4-二甲氨基吡啶、2-甲基咪唑、2-甲基4-乙基咪唑、2-苯基咪唑、以及异辛酸锌中的至少一种，例如：4-二甲氨基吡啶和2-甲基咪唑的混合物，2-甲基咪唑和2-甲基4-乙基咪唑的混合物，2-苯基咪唑和异辛酸锌的混合物，2-甲基咪唑、2-甲基4-乙基咪唑和2-苯基咪唑的混合物，当然，并不以此为限。
在所述环氧树脂按100重量份计时，所述固化促进剂的含量为0.001-5重量份，例如0.001重量份、0.01重量份、1重量份、2.5重量份、5重量份、以及上述数值之间的具体点值，限于篇幅以及处于简明的考虑，本发明不再穷尽列举所述范围包括的具体点值。
更优选地，所述固化促进剂含量为0.01-1重量份。
作为本发明的进一步改进，所述树脂组合物还包括填料，以所述树脂组合物按100重量份计，所述填料为0-200重量份，可以理解的是，所述树脂组合物中可以含有所述填料，也可以不含有所述填料。
在所述树脂组合物中含有填料时，以所述环氧树脂100重量份计，优选地，所述填料含量为10-100重量份，更优选地，为30-70重量份，例如为10重量份、20重量份、30重量份、40重量份、50重量份、60重量份、70重量份、80重量份、90重量份、100重量份、110重量份、120重量份、130重量份、140重量份、150重量份、160重量份、170重量份、180重量份、190重量份或200重量份；以及上述数值之间的具体点值，限于篇幅以及处于简明的考虑，本发明不再穷尽列举所述范围包括的具体点值。
具体地，所述填料为有机填料或无机填料，其中，无机填料选自非金属氧化物、金属氮化物、非金属氮化物、无机水合物、无机盐、金属水合物或无机磷中的一种或者至少任意两种的混合物；所述有机填料选自聚四氟乙烯粉末、聚苯硫醚、聚醚砜粉末中的至少一种。
更优选地，所述无机填料选自熔融二氧化硅、结晶型二氧化硅、球型二氧化硅、空心二氧化硅、氢氧化铝、氧化铝、滑石粉、氮化铝、氮化硼、碳化硅、硫酸钡、钛酸钡、钛酸锶、碳酸钙、硅酸钙、云母、玻璃纤维粉中的至少一种。
优选地，所述填料为二氧化硅，更优选地，为经表面处理的球形二氧化硅。
优选地，所述填料的粒径中度值为1～15μm，例如1μm、2μm、5μm、8μm、10μm、11μm、12μm、13μm、14μm或15μm，以及上述数值之间的具体点值，限于篇幅以及处于简明的考虑，本发明不再穷尽列举所述范围包括的具体点值。
更优选地，所述填料的粒径中度值为1～10μm。
具体地，用于处理所述二氧化硅的表面处理剂为硅烷偶联剂，如环氧硅烷偶联剂或氨基硅烷偶联剂。
本发明中，所述树脂组合物还包括引发剂，所述引发剂选自二酰基过氧化物、过氧基缩酮、过氧化碳酸酯、过氧酯、酮过氧化物、二烷基过氧化物及氢过氧化物中的一种或几种，其中，该二酰基过氧化物选自异壬酰基过氧化物、癸酰基过氧化物、月桂酰基过氧化物、对氯苯甲酰基过氧化物及二(3,5,5-三甲基己酰基)过氧化物中的一种或几种；该过氧基缩酮选自2,2-二(4,4-二-(二-第三丁基过氧基)环己基)丙烷；该过氧化碳酸酯选自二-3-甲氧基丁基过氧二碳酸酯及二环己基过氧二碳酸酯中的一种或两种；该过氧酯选自第三丁基过氧苯甲酸酯、第三丁基过氧乙酸酯、第三丁基过氧-2-乙基己酸酯、第三丁基过氧异丁酸酯、第三丁基过氧戊酸酯、第三丁基二过氧己二酸酯、异丙苯基过氧新癸酸酯、第三丁基过氧苯甲酸酯、1,1,3,3-四甲基过氧基-2-乙基己酸酯及2,5-二甲基-2,5-二(苯甲酰基过氧基)己烷中的一种或几种；该酮过氧化物选自甲基乙基酮过氧化物及环己酮过氧化物中的一种或两种；该二烷基过氧化物选自二-第三丁基过氧化物、二异丙苯基过氧化物、第三丁基异丙苯基过氧化物、1,1-二(第三己基过氧基)-3,3,5-三甲基环己烷、二-第三己基过氧化物及二(2-第三丁基过氧基异丙基)苯中的一种或几种；该氢过氧化物选自异丙苯羟基过氧化物、第三丁基过氧化氢及对-薄荷烷过氧化氢中的一种或几种。其含量为以树脂组合物100重量份计，含有0.001-3重量份。
根据本发明，所述树脂组合物进一步还包括阻燃剂，以提高最终形成的固化物的阻燃性，所述固化物可以理解为半固化片、绝缘薄膜、覆金属箔层压板、以及印制线路板等。
进一步地，以环氧树脂100重量份计，所述阻燃剂的含量为1～80重量份，例如，1重量份、5重量份、10重量份、20重量份、50重量份、70重量份、80重量份、以及上述数值之间的具体点值，限于篇幅以及处于简明的考虑，本发明不再穷尽列举所述范围包括的具体点值。
优选地，所述阻燃剂的含量为5～50重量份。
具体地，所述阻燃剂可以是溴系阻燃剂、磷系阻燃剂、氮系阻燃剂、有机硅阻燃剂、有机金属盐阻燃剂、无机系阻燃剂等。其中，溴系阻燃剂可以是十溴二苯醚、十溴二苯乙烷、溴化苯乙烯或者四溴邻苯二甲酰胺。磷系阻燃剂可以是无机磷、磷酸酯化合物、膦酸化合物、次膦酸化合物、氧化膦化合物、以及9,10-二氢-9氧杂-10-膦杂菲-10-氧化物、10-(2，5二 羟基苯基)-9,10-二氢-9氧杂-10-膦杂菲-10-氧化物、10-苯基-9,10-二氢-9-氧杂-10-膦菲-10-氧化物、三(2,6二甲基苯基)膦、膦腈等有机含磷化合物。氮系阻燃剂可以是三嗪化合物、氰尿酸化合物、异氰酸化合物、吩噻嗪等。有机硅阻燃剂可以是有机硅油、有机硅橡胶、有机硅树脂等。有机金属盐阻燃剂可以是二茂铁、乙酰丙酮金属络合物、有机金属羰基化合物等。无机阻燃剂可以是氢氧化铝、氢氧化镁、氧化铝、氧化钡等。
当然，所述阻燃剂地种类并不以此为限，可以理解的是，所添加的阻燃剂可以根据层压板的具体应用领域而选择，如，对卤素有要求的应用领域，优选非卤阻燃剂，如含磷或者含氮的阻燃剂，更优选为磷腈、DOPO或DOPO-HQ。
优选地，在选择含磷阻燃剂时，可以与固化剂中的活性酯化合物的氮元素形成氮磷协同阻燃，提高阻燃效率。
根据本发明，最终产品的不同要求，在所述树脂组合物进一步还包括0～5份其他助剂。
所述其他助剂包括偶联剂、分散剂、染料。所述偶联剂为硅烷偶联剂，如环氧硅烷偶联剂或氨基硅烷偶联剂；所述分散剂为γ-氨基丙基三乙氧基硅烷、N-β-(氨基乙基)-γ-氨基丙基三甲氧基硅烷等具有氨基且具有水解性基团或羟基的氨基系硅烷化合物、3-丙烯酰氧基丙基三甲氧基硅烷等具有环氧基且具有水解性基团或羟基的环氧系硅烷化合物、γ-甲基丙烯酰氧基丙基三甲氧基硅烷等具有乙烯基且具有水解性基团或羟基的乙烯基系硅烷化合物、阳离子系硅烷偶联剂，分散剂可用BYK制的Disperbyk-110、111、118、180、161、2009、BYK-W996、W9010、W903(均为产品名)；所述染料为荧光染料和黑色染料，其中荧光染料为吡唑啉等，所述黑色染料为炭黑(液态或粉末状)、吡啶络合物、偶氮络合物、苯胺黑、黑滑石粉、钴铬铬金属氧化物、吖嗪、酞菁等。
本发明中的树脂组合物的制作方法为本领域的常规技术手段，具体为：取一容器，先将固体组分放入，然后加入液体有机溶剂，搅拌直至完全溶解后，加入液体树脂、填料和固化促进剂，继续搅拌均匀即可，最后用溶剂调整液体固含量至50～80％而制成胶液，其中，固含量是以重量来计的。
作为本发明中的有机溶剂以及溶剂并不作具体限定。例如有机溶剂可以选自丙酮、丁酮、甲苯、甲基异丁酮、N、N-二甲基甲酰胺、N、N-二甲基乙酰胺、乙二醇甲醚、丙二醇甲醚、苯、甲苯、环己烷中的一种或任意几种的组合。
所述溶剂的添加量由本领域技术人员根据自己的经验来选择，只要能够使得得到的胶液达到适合使用的粘度即可。
为实现上述发明目的，本发明还提供一种半固化片，包括增强材料、附着于所述增强材料表面的上述的树脂组合物。
其中，所述增强材料为天然纤维、有机合成纤维、有机织物或者无机织物，无机织物，优选地，所述增强材料采用玻璃纤维布，而，玻璃纤维布中优选使用开纤布或扁平布。
此外，在所述增强材料采用玻璃纤维布时，所述玻璃纤维布一般都需要进行化学处理， 以改善树脂组合物与玻璃纤维布的界面之间结合。所述化学处理主要方法是偶联剂处理。所用偶联剂优选用环氧硅烷或者氨基硅烷等，以提供良好的耐水性和耐热性。
所述半固化片的制备方法为：将增强材料浸渍在上述的树脂组合物胶液中，然后将浸渍后的增强材料在50-170℃环境下烘烤1-10min，干燥后即可得本发明中的半固化片。
为实现上述发明目的，本发明还提供一种绝缘薄膜，包括载体膜、涂覆于载体膜表面的上述的树脂组合物。
所述绝缘薄膜的制备方法为：将上述的树脂组合物加入溶剂中，溶解制成胶液，将所述胶液涂覆于载体膜上，将涂覆胶液的载体膜加热干燥后，胶液形成绝缘树脂层，即可得到所述绝缘薄膜。
所述的溶剂选自丙酮、丁酮、甲苯、甲基异丁酮、N、N-二甲基甲酰胺、N、N-二甲基乙酰胺、乙二醇甲醚、丙二醇甲醚中的一种或几种。
所述载体膜可为聚乙烯对苯二甲酸酯(PET)膜、离型膜、铜箔、铝箔等，所述载体膜优选为PET膜。
上述的加热干燥条件为在50-170℃下烘烤1-10分钟，当然，并不以此为限。
进一步地，所述绝缘树脂层背离所述载体膜的一侧覆盖有保护膜，以保护绝缘树脂层。
具体地，所述保护膜的材料与所述载体膜的材料相同，当然，并不以此为限。
为实现上述发明目的，本发明还提供一种覆金属箔层压板，包括至少一张上述的半固化片、成形于所述半固化片的至少一面的金属箔。
所述覆金属箔层压板即是指将一张或者两张上述的半固化片通过加热加压粘合在一起形成层压板，然后再层压板的一面或者双面通过加热加压粘合金属箔。
所述覆金属箔层压板的制备步骤如下：在一张上述半固化片的单面或双面覆上金属箔，或者将至少2张上述半固化片叠加后，在其单面或双面覆上金属箔，热压成形，即可得到金属箔层压板。
上述金属箔和层压板的压制条件为，在0.2～2MPa压力和180～250℃温度下压制2～4小时。
具体地，所述半固化片的数量可根据需要的层压板的厚度来确定，可用一张或多张。
所述金属箔，可以是铜箔，也可以是铝箔，其材质不限；所述金属箔的厚度也没有特别限制，如5μm、8μm、12μm、18μm、35μm或70μm均可。
为实现上述发明目的，本发明还提供一种印制线路板，所述印制线路板包括至少一张上述的半固化片、或者至少一张上述的绝缘薄膜。
下面分多个实施例对本发明的实施方式进行进一步的说明。可以理解的是，本发明的实施例并不限于以下的具体实施例。在不改变权利要求的范围内，可以适当地进行变更实施。
合成例1：合成双环戊二烯基活性酯化合物
取双环戊二烯酚树脂和苯二羧酸，在甲苯溶剂中搅拌溶解均匀，在60℃的温度条件下， 同时通入氮气，加入四丁基溴化铵催化剂，然后慢慢滴入浓度为20％的氢氧化钠水溶液，反应4小时，然后添加对乙烯基苯酚，继续反应1小时，反应结束且经过数次洗涤后，在80℃的真空条件下，干燥3h，获得所述双环戊二烯基活性酯化合物，记为活性酯A。
合成例2：合成三环戊二烯基活性酯化合物
取三环戊二烯酚树脂和苯二羧酸，在甲苯溶剂中搅拌溶解均匀，在60℃的温度条件下，同时通入氮气，加入四丁基溴化铵催化剂，然后慢慢滴入浓度为20％的氢氧化钠水溶液，反应4小时，然后添加对乙烯基苯酚，继续反应1小时，反应结束且经过数次洗涤后，在80℃的真空条件下，干燥3h，获得所述三环戊二烯基活性酯化合物，记为活性酯B。
合成例3：合成萘基活性酯化合物
取萘酚树脂和苯二羧酸，在甲苯溶剂中搅拌溶解均匀，在60℃的温度条件下，同时通入氮气，加入四丁基溴化铵催化剂，然后慢慢滴入浓度为20％的氢氧化钠水溶液，反应4小时，然后添加对乙烯基苯酚，继续反应1小时，反应结束且经过数次洗涤后，在80℃的真空条件下，干燥3h，获得所述萘基活性酯化合物，记为活性酯C。
合成例4：合成双环戊二烯萘基活性酯化合物
取双环戊二烯萘酚树脂和苯二羧酸，在甲苯溶剂中搅拌溶解均匀，在60℃的温度条件下，同时通入氮气，加入四丁基溴化铵催化剂，然后慢慢滴入浓度为20％的氢氧化钠水溶液，反应4小时，然后添加对乙烯基苯酚，继续反应1小时，反应结束且经过数次洗涤后，在80℃的真空条件下，干燥3h，获得所述萘基活性酯化合物，记为活性酯D。
实施例1-7及比较例1：
实施例1-7及比较例1的树脂组合物的组分及含量如下表1中所示：
表1
Figure PCTCN2019118497-appb-000018
Figure PCTCN2019118497-appb-000019
上述组分的具体明细为如下：
表2
Figure PCTCN2019118497-appb-000020
实施例：
按照表1中组分含量将环氧树脂、合成例中所得的活性酯化合物，固化剂、固化促进剂、填料、阻燃剂及适量的丁酮溶剂，搅拌混合均匀得到固体含量为65重量％的胶液。
将该胶液浸渍并涂布在E玻纤布(7628)上，并在160℃烘箱中烘5min制得半固化片。
将该胶液涂覆在PET载体上，并在160℃烘箱中烘5min制得绝缘薄膜。
制备性能评估样品层压板：
(1)制备层压板a
将上述制得的半固化片，上下各放一张18μm金属铜箔，置于真空热压机中压制得到层压板a。具体的压合工艺为在1.5Mpa压力，220℃温度下压合2小时。
(2)制备层压板b
取一张芯板，在其上下两面各放一张上述制得的绝缘薄膜，置于真空热压机中压制，剥离PET载体。具体的压合工艺为在1.5Mpa压力，220℃温度下压合2小时。
然后用高锰酸钾法将表面绝缘薄膜层进行粗化处理，其步骤为如下：
(1)将板材浸渍在膨润液(二甘醇一丁基醚溶液)中，经10min后取出；
(2)取出的板材再浸渍在氧化剂(高锰酸钾溶液)溶液中，经20min后取出；
(3)取出的板材再浸渍在中和溶液(硫酸羟胺水溶液)中，经10min后取出；
(4)在80℃下干燥30min，获得层压板b，待测试粗化度。
性能评估方法：
(1)玻璃转化温度Tg(℃)：根据差示扫描量热法，按照IPC-TM-650 2.4.25所规定的DSC方法进行测定。
(2)剥离强度(PS)：用层压板a，按照IPC-TM-650方法中的“热应力后”实验条件，测试金属盖层的剥离强度。
(3)粗化度：用层压板b，用非接触式表面粗化度计，测试10个点值，计算平均粗化度(Ra)值。
(4)介电常数：用层压板a，按照IPC-TM-650 2.5.5.9使用平板法，测定1GHz下的介电常数。
(5)介质损耗角正切：用层压板a，按照IPC-TM-650 2.5.5.9使用平板法，测定1GHz下的介电损耗因子。
获得的层压板性能如表3所示。
表3
Figure PCTCN2019118497-appb-000021
通过上述实施例中可知，用本发明活性酯的实施例获得较低介电常数和低介质损耗，同时较优异的剥离强度和粗化度。特别是，实施例1相比对比例1(现有技术活性酯)，具有更加低的介电常数和介质损耗值。
应当理解，虽然本说明书按照实施方式加以描述，但并非每个实施方式仅包含一个独立的技术方案，说明书的这种叙述方式仅仅是为清楚起见，本领域技术人员应当将说明书作为一个整体，各实施方式中的技术方案也可以经适当组合，形成本领域技术人员可以理解的其他实施方式。
上文所列出的一系列的详细说明仅仅是针对本申请的可行性实施方式的具体说明，它们并非用以限制本申请的保护范围，凡未脱离本申请技艺精神所作的等效实施方式或变更均应包含在本申请的保护范围之内。

Claims (10)

  1. 一种活性酯化合物，其特征在于，结构式为：结构式(1)
    Figure PCTCN2019118497-appb-100001
    其中，R 1表示氢或C1-C5的烷基，m为1-10的整数，A为以下基团中的一种：
    Figure PCTCN2019118497-appb-100002
    其中，R 10、R 11、R 12、R 13分别选自氢、C1-C5的烷基，或C6-C10的芳基或芳烷基。
  2. 如权利要求1所述的活性酯化合物，其特征在于：所述结构式(1)所示的活性酯化合物中的A中含有双环戊二烯基、三环戊二烯基或萘基；
    和/或，所述R 1是氢、甲基、乙基、丙基、叔丁基或戊基；
    和/或，所述R 10、R 11、R 12、R 13分别独立地选自氢、甲基、乙基、丙基、叔丁基、戊基、苯基、联苯基或萘基；
    进一步地，所述R 1为氢，m为1，A为双环戊二烯基；
    或，所述R 1为氢，m为1，A为萘基。
  3. 一种活性酯化合物的制备方法，其特征在于，
    将芳香族酚树脂、芳香族二羧酸、乙烯基苯酚发生反应；
    或将芳香族酚树脂、芳香族二甲酰卤化合物、乙烯基苯酚发生反应；
    或先将芳香族酚树脂与芳香族二羧酸发生反应，再加入乙烯基苯酚继续发生反应；
    或先将芳香族酚树脂与芳香族二甲酰卤化合物发生反应，再加入乙烯基苯酚继续发生反应。
  4. 一种树脂组合物，其特征在于：包括环氧树脂20-100重量份、固化剂1-100重量份、固化促进剂0.001-5重量份；其中，所述固化剂至少包含权利要求1所述的活性酯化合物。
  5. 如权利要求4所述的树脂组合物，其特征在于：所述固化剂中如结构式(1)所示的活性酯化合物的含量为1-100重量％；优选为5-50重量％；
    或，所述固化剂中还含有胺系化合物、酰胺系化合物、酸酐系化合物、酚系化合物、不同于结构式(1)的活性酯类化合物中的至少一种；
    优选地，以固化剂总量100重量份计，固化剂中含有的至少一种上述化合物的含量为0-99重量份，优选为5-60重量份；
    优选地，胺系化合物选自二氨基二苯基甲烷、二氨基二苯砜、二亚乙基三胺、双羧基邻苯二甲酰亚胺或咪唑；
    优选地，所述酰胺系化合物选自双氰胺或低分子聚酰胺；
    优选地，所述酸酐系化合物选自邻苯二甲酸酐、偏苯三甲酸酐、均苯四甲酸二酐、马来酸酐、氢化邻苯二甲酸酐、纳迪克酸酐或苯乙烯-马来酸酐；
    优选地，所述酚系化合物选自双酚A酚醛树脂、苯酚酚醛树脂、萘酚酚醛树脂、联苯苯酚型酚醛树脂、联苯苯酚型萘酚树脂、双环戊二烯苯酚加成型树脂、苯酚芳烷基树脂、萘酚芳烷基树脂或三羟甲基甲烷树脂；
    优选地，不同于结构式(1)的活性酯类化合物选结构式(4)所示的化合物：
    Figure PCTCN2019118497-appb-100003
    其中，X为苯基或者萘基；j为0或1；k为0或1；n表示重复单元，为0.25～1.25；
    和/或，所述环氧树脂选自双酚A环氧树脂、双酚F环氧树脂、双酚S型环氧树脂、双酚E型环氧树脂、含磷环氧树脂、含氮环氧树脂、邻甲酚醛环氧树脂、双酚A酚醛环氧树脂、苯酚酚醛环氧树脂、甲酚酚醛环氧树脂、三苯基甲烷环氧树脂、四苯基乙烷环氧树脂、 联苯型环氧树脂、萘环型环氧树脂、双环戊二烯型环氧树脂、异氰酸酯型环氧树脂、芳烷基线型酚醛环氧树脂、脂环族类环氧树脂、缩水甘油胺型环氧树脂、缩水甘油醚型环氧树脂、缩水甘油酯型环氧树脂中的一种或几种；
    和/或，所述固化促进剂选自4-二甲氨基吡啶、2-甲基咪唑、2-甲基4-乙基咪唑、2-苯基咪唑、以及异辛酸锌中的至少一种；
    优选地，以所述树脂组合物按100重量份计，所述固化促进剂含量为0.01-1重量份。。
  6. 如权利要求4所述的树脂组合物，其特征在于：所述树脂组合物还包括填料，所述树脂组合物按100重量份计，所述填料为0-200重量份，
    所述填料为有机填料或无机填料，其中，
    无机填料选自非金属氧化物、金属氮化物、非金属氮化物、无机水合物、无机盐、金属水合物或无机磷中的一种或者至少任意两种的混合物，优选熔融二氧化硅、结晶型二氧化硅、球型二氧化硅、空心二氧化硅、氢氧化铝、氧化铝、滑石粉、氮化铝、氮化硼、碳化硅、硫酸钡、钛酸钡、钛酸锶、碳酸钙、硅酸钙、云母、玻璃纤维粉中的至少一种；
    所述有机填料选自聚四氟乙烯粉末、聚苯硫醚、聚醚砜粉末中的至少一种；
    和/或，所树脂组合物还包括阻燃剂；
    优选地，所述阻燃剂选自溴系阻燃剂、磷系阻燃剂、氮系阻燃剂、有机硅阻燃剂、有机金属阻燃剂、无机系阻燃剂中的至少一种；
    优选地，以所述树脂组合物按100重量份计，所述阻燃剂的含量为1～80重量份，优选5～50重量份；
    和/或，所树脂组合物还包括其他助剂；
    优选地，所述其他助剂包括偶联剂、分散剂、染料中的至少一种；
    优选地，以所述树脂组合物按100重量份计，所述其他助剂的含量为0～5重量份；
    和/或，所树脂组合物还包括含碳碳双键的聚苯醚树脂或碳氢树脂；
    优选地，以所述树脂组合物按100重量份计，所述聚苯醚树脂的含量为10～70重量份；
    优选地，以所述树脂组合物按100重量份计，所述碳氢树脂的含量为10～90重量份；
    和/或，所树脂组合物还包括引发剂；
    优选地，以所述树脂组合物按100重量份计，所述引发剂的含量为0.001-3重量份。
  7. 一种半固化片，其特征在于：所述半固化片包括增强材料、附着于所述增强材料表面的树脂组合物，所述树脂组合物为权利要求4所述的树脂组合物。
  8. 一种绝缘薄膜，其特征在于：所述绝缘薄膜包括载体膜、涂覆于载体膜表面的树脂组合物，所述树脂组合物为权利要求4所述的树脂组合物。
  9. 一种覆金属箔层压板，其特征在于：所述覆金属箔层压板包括至少一张如权利要求7所述的半固化片、成形于所述半固化片的至少一面的金属箔。
  10. 一种印制线路板，其特征在于：所述印制线路板包括至少一张如权利要求7所述的 半固化片、或者至少一张如权利要求8所述的绝缘薄膜。
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