WO2019024255A1 - 一种热固性树脂组合物及使用其制作的半固化片与覆金属箔层压板 - Google Patents

一种热固性树脂组合物及使用其制作的半固化片与覆金属箔层压板 Download PDF

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Publication number
WO2019024255A1
WO2019024255A1 PCT/CN2017/106830 CN2017106830W WO2019024255A1 WO 2019024255 A1 WO2019024255 A1 WO 2019024255A1 CN 2017106830 W CN2017106830 W CN 2017106830W WO 2019024255 A1 WO2019024255 A1 WO 2019024255A1
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Prior art keywords
weight
resin composition
component
thermosetting resin
parts
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PCT/CN2017/106830
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English (en)
French (fr)
Inventor
曾宪平
关迟记
陈广兵
徐浩晟
Original Assignee
广东生益科技股份有限公司
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Application filed by 广东生益科技股份有限公司 filed Critical 广东生益科技股份有限公司
Priority to EP17920511.7A priority Critical patent/EP3663348A4/en
Priority to KR1020207000065A priority patent/KR20200015930A/ko
Priority to US16/632,005 priority patent/US20210070980A1/en
Priority to JP2019554844A priority patent/JP6861843B2/ja
Publication of WO2019024255A1 publication Critical patent/WO2019024255A1/zh

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    • C—CHEMISTRY; METALLURGY
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    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L2203/00—Applications
    • C08L2203/20—Applications use in electrical or conductive gadgets
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
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    • 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
    • H05K1/0213—Electrical arrangements not otherwise provided for
    • H05K1/0237—High frequency adaptations
    • 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
    • H05K2201/00—Indexing scheme relating to printed circuits covered by H05K1/00
    • H05K2201/02—Fillers; Particles; Fibers; Reinforcement materials
    • H05K2201/0203—Fillers and particles
    • H05K2201/0206—Materials
    • H05K2201/0209—Inorganic, non-metallic particles

Definitions

  • the invention belongs to the technical field of copper clad laminates, and relates to a thermosetting resin composition and a prepreg and a metal foil-clad laminate prepared using the same.
  • the epoxy resin circuit board generally has a high dielectric constant and dielectric loss tangent (dielectric constant Dk is greater than 4, dielectric loss tangent Df is about 0.02), and high frequency characteristics are insufficient, which cannot meet the requirements of high frequency signal. . Therefore, it is necessary to develop a resin excellent in dielectric properties, that is, a resin having a low dielectric constant and a dielectric loss tangent.
  • thermosetting polyphenylene ether resins bismaleimide resins, vinyl benzyl ether resins, hydrocarbon resins and the like which have good dielectric properties; well known, curable crosslinking
  • the hydrocarbon resin polyolefin resin
  • Df dielectric loss tangent
  • TW200536862A discloses that in the presence of a Lewis acid catalyst and an initiator in an organic solvent system, 20 to 100 mol% of a divinyl aromatic compound and, if necessary, other monomers (such as B) are added at a reaction temperature of 20 to 120 °C. Polymerization of other monomers such as vinyl aromatic compounds, preparation A soluble polyfunctional vinyl aromatic copolymer having a controlled molecular weight.
  • the resin can be used in high friction fields related to electronic substrates and the like, and has good heat resistance and processability. Although the electronic circuit substrate prepared by using the copolymer has better dielectric properties and better heat resistance, it also has obvious defects of large brittleness.
  • the large brittleness has a large negative impact on subsequent PCB processing (serious wear of the drill, delamination of the sheet, and large halo after drilling, resulting in poor CAF), which cannot meet the requirements for the fabrication of high-layer printed circuit boards.
  • CN1914239A copolymerizes a terminal vinyl-modified polyphenylene ether and a soluble polyfunctional vinyl aromatic copolymer to produce a copper clad laminate having excellent chemical resistance, dielectric properties and heat resistance.
  • one or two or more thermoplastic resins may be added, but the addition of a thermoplastic resin will greatly lower the glass transition temperature of the substrate, and in addition, the thermoplastic resin and the cured product may not appear.
  • CN103172803A After curing using a composition of a soluble polyfunctional copolymer, an acryl-containing silicone resin, and an initiator, an optical article having excellent optical properties such as a refractive index and a high light transmittance, heat resistance, and processability is prepared.
  • the resin composition can be used for a copper clad laminate and a prepreg, that is, a copper clad laminate is produced by curing the resin composition, and dielectric properties (dielectric loss tangent Df) are remarkably deteriorated (the resin composition is contained in the resin composition)
  • the acryl-based silicone resin, and the acryl-containing silicone resin is relatively polar, cannot meet the high-frequency signal transmission requirements.
  • thermosetting resin composition and a prepreg and a metal foil-clad laminate produced using the same.
  • the present invention provides a thermosetting resin composition
  • the molar fraction of the vinyl group-containing structural unit derived from the divinyl aromatic compound (a) represented by the following formulas (a 1 ) and (a 2 ) satisfies (a 1 )/[(a 1 )+ (a 2)] ⁇ 0.5, and measured by gel permeation chromatography on a polystyrene equivalent number-average molecular weight M n of 600 to 30,000, a weight-average molecular weight M w to the number average molecular weight M n ratio of M w / M n less than Equal
  • R 13 is an aromatic hydrocarbon group having 6 to 30 carbon atoms
  • R 14 is an aromatic hydrocarbon group having 6 to 30 carbon atoms
  • the resin component of the thermosetting resin composition of the present invention does not contain a polar hydroxyl group, and does not generate a polar group such as a secondary hydroxyl group during the curing process, thereby ensuring low water absorption of the circuit substrate and excellent intermediation.
  • Electrical properties, using the olefin resin as a cross-linking agent of a solvent-soluble polyfunctional vinyl aromatic copolymer the resin composition has a high crosslink density after curing, and the solubility of the soluble polyfunctional vinyl aromatic copolymer is obviously improved.
  • the brittleness of the prepared circuit substrate is better, and the drilling processability of the PCB is improved, which is advantageous for improving the reliability of the multilayer printed circuit board.
  • the olefin resin is a butadiene-styrene copolymer and/or a butadiene-styrene-divinylbenzene copolymer.
  • the compounding amount of the component (A) is from 10 to 98% by weight (for example, 10% by weight, 15% by weight, 20% by weight, based on the total of the components (A) and (B). 25 wt%, 28 wt%, 30 wt%, 35 wt%, 38 wt%, 40 wt%, 50 wt%, 60 wt%, 70 wt%, 80 wt%, 90 wt%, 95 wt% or 98 wt%), the compounding amount of the component (B) is 2 ⁇ 90 wt% (e.g., 2 wt%, 5 wt%, 8 wt%, 10 wt%, 15 wt%, 20 wt%, 25 wt%, 30 wt%, 40 wt%, 50 wt%, 60 wt%, 70 wt%, 80 wt%, or 90 wt%).
  • the compounding amount of the component (B) is 2 ⁇
  • the component (A) is a soluble polyfunctional vinyl aromatic copolymer having a general formula in the main chain skeleton of the polyfunctional vinyl aromatic copolymer. Incomplete structure shown in (a 3 )
  • W represents a saturated or unsaturated aliphatic hydrocarbon group or an aromatic hydrocarbon group or an aromatic ring or a substituted aromatic ring fused to a benzene ring
  • Z is an integer of 0 to 4.
  • the component (A) is a soluble polyfunctional vinyl aromatic copolymer which contains a monovinyl group other than the ethyl vinyl aromatic compound (b) in the polyfunctional vinyl aromatic copolymer.
  • the copolymer contains the structural unit represented by the above (a 1 ), (a 2 ) and (a 3 ) as a repeating unit derived from the divinyl aromatic compound (a).
  • R 13 , R 14 , W and Z in the structural units represented by the above (a 1 ), (a 2 ) and (a 3 ) have the same meanings as described above, but the proportion of each structural unit in the copolymer depends on the used
  • the reaction conditions such as the type of the divinyl aromatic compound (a), the ethyl vinyl aromatic compound (b), the reaction catalyst, and the reaction temperature.
  • the divinyl aromatic compound (a) to be used for example, m-divinylbenzene, p-divinylbenzene, 1,2-diisopropenylbenzene, or 1,3-diiso can be used.
  • divinylbenzene both meta and para isomers
  • Divinylbiphenyl (including each isomer) and divinylnaphthalene (including each isomer) are preferred. More preferred are divinylbenzene (both meta and para isomers) and divinylbiphenyl (including isomers).
  • divinylbenzene (both meta and para isomers) is most preferably used.
  • divinylbiphenyl (including each isomer) and divinylnaphthalene (including each isomer) are particularly preferable.
  • an ethyl group which is used as a component (b) which provides a structural unit which adjusts the compatibility with the vinyl silicone resin as the component (B) and improves solvent solubility and processability.
  • the vinyl aromatic compound o-ethylvinylbenzene, m-ethylvinylbenzene, p-ethylvinylbenzene, 2-vinyl-2'-ethylbiphenyl, 2-vinyl-3'- can be used.
  • a structural unit derived from the component (b) into the polyfunctional vinyl aromatic copolymer, not only gelation of the copolymer but also solubility in a solvent can be prevented.
  • ethyl vinylbenzene both meta and para isomers
  • ethyl vinyl are exemplified in terms of cost, prevention of gelation, and heat resistance of the obtained cured product.
  • Biphenyl including each isomer and the like.
  • a monovinyl aromatic compound other than the ethylvinyl aromatic compound (b) to be added may be added.
  • styrene substituted with an alkyl group on the ring for example, an alkyl-substituted styrene such as methyl styrene, ethyl styrene or butyl styrene can be used.
  • styrene substituted with an alkyl group in the ring may be methoxystyrene, ethoxystyrene or butoxystyrene. Further, phenoxystyrene or the like can also be used.
  • aromatic vinyl compound for example, 2-vinylbiphenyl, 3-vinylbiphenyl, 4-vinylbiphenyl, 1-vinylnaphthalene or 1-vinylnaphthalene can be used.
  • aromatic vinyl compound substituted with an alkyl group in the ring for example, vinyl-propylbiphenyl or vinyl-propylnaphthalene or the like can be used.
  • ⁇ -alkyl substituted styrene for example, ⁇ -methylstyrene or ⁇ -ethylstyrene can be used. Alkene and the like.
  • anthracene derivative in addition to hydrazine, an alkyl group such as methyl hydrazine, ethyl hydrazine, propyl hydrazine or butyl hydrazine may be used instead of hydrazine. Further, an alkoxy fluorene such as methoxy hydrazine, ethoxy hydrazine or butoxy hydrazine may also be used.
  • an alkyl group such as methyl hydrazine or ethyl hydrazine may be used to substitute an anthracene; a halogenated anthracene such as chloro anthracene or bromo hydrazine; a phenyl hydrazine or the like.
  • these monovinyl aromatic compounds as the component (c) are not limited to these compounds. These may be used singly or in combination of two or more.
  • styrene ⁇ -alkyl substituted styrene, ⁇ -alkyl group
  • styrene, ⁇ -alkyl substituted styrene, ⁇ -alkyl group from the viewpoint of a large amount of incomplete structure formation in the skeleton of the polymer
  • Substituted aromatic vinyl compounds are preferred.
  • styrene, ⁇ -methylstyrene, 4-isopropene, and biphenyl are mentioned from the viewpoint of the cost and the heat resistance of the obtained polymer.
  • the amount of the divinyl aromatic compound as the component (a) relative to the sum of the monomers composed of the component (a), the component (b), and the component (c) 20 to 99.5 mol%, for example, 20 mol%, 25 mol%, 28 mol%, 30 mol%, 35 mol%, 38 mol%, 40 mol%, 45 mol%, 50 mol%, 55 mol%, 60 mol% %, 65 mol%, 70 mol%, 80 mol%, 90 mol%, 95 mol% or 99 mol%, preferably 33 to 99 mol%, more preferably 45 to 95 mol%, particularly preferably 50 to 85 mol% %.
  • the content of the divinyl aromatic compound (a) is less than 20% by mole, when the resulting soluble polyfunctional vinyl aromatic copolymer is cured, heat resistance tends to be lowered, which is not preferable.
  • the total amount of the ethyl vinyl aromatic compound as the component (b) relative to the monomer composed of the component (a), the component (b), and the component (c) And the amount used is 0.5 to 80 mol%, for example, 0.5 mol%, 0.8 mol%, 1 mol%, 5 mol%, 10 mol%, 15 mol%, 20 mol%, 25 mol%, 30 mol%, 35 mol% %, 40 mol%, 45 mol%, 50 mol%, 55 mol%, 60 mol%, 65 mol%, 70 mol%, 75 mol% or 80 mol%, preferably 1 to 70 mol%, more preferably 5 ⁇ 60 mol%, particularly preferably 15 to 50 mol%.
  • the content of the ethyl vinyl aromatic compound (b) is more than 80% by mole, when the resulting soluble polyfunctional vinyl aromatic copolymer is cured, heat resistance tends to be lowered, which
  • the monovinyl aromatic compound as the component (c) is used in combination with the monomer composed of the components (a), (b) and (c).
  • the amount is less than 40% by mole, for example, 38% by mole, 35% by mole, 33% by mole, 30% by mole, 28% by mole, 25% by mole, 23% by mole, 20% by mole, 18% by mole, 15% by mole, and 13 moles %, 10 mol%, 8 mol%, 5 mol%, 3 mol% or 1 mol%, preferably less than 30 mol%, more preferably less than 25 mol%, particularly preferably less than 20 mol%.
  • the content of the monovinyl aromatic compound (c) is 40% by mole or more, when the resulting soluble polyfunctional vinyl aromatic copolymer is cured, heat resistance tends to be lowered, which is not preferable.
  • the mole fraction of the vinyl group-containing structural unit derived from the divinyl aromatic compound (a) represented by the above formulas (a 1 ) and (a 2 ) must satisfy (a) 1 ) / [(a 1 ) + (a 2 )] ⁇ 0.5, for example, the mole fraction is 0.5, 0.6, 0.7, 0.8, 0.9, 0.95, 0.98, and the like.
  • the mole fraction is greater than or equal to 0.7, and particularly preferably greater than or equal to 0.9. If it is less than 0.5, the heat resistance of the cured product of the resulting copolymer is lowered, and curing takes a long time, which is not preferable.
  • W has an unsaturated aliphatic hydrocarbon group such as a vinyl group, an aromatic hydrocarbon group such as a phenyl group, a substituent of these hydrocarbon groups, and the like, and these may be substituted with 0 to 4 substituents.
  • W may form a second-order hydrocarbon group such as a naphthalene ring by forming a fused ring with a benzene ring of an indane structure, and the second-order hydrocarbon group may have a substituent.
  • the indane structure represented by the formula (a 3 ) is a structural unit which further improves the heat resistance of the soluble polyfunctional vinyl aromatic copolymer and solubility in a solvent, and is produced by producing a polyfunctional vinyl aromatic
  • the active site at the end of the growing polymer chain attacks the structural unit derived from the divinyl aromatic compound and the monovinyl aromatic compound by being produced under conditions of preparation of a specific solvent, catalyst, temperature, and the like.
  • Aromatic ring is a structural unit which further improves the heat resistance of the soluble polyfunctional vinyl aromatic copolymer and solubility in a solvent, and is produced by producing a polyfunctional vinyl aromatic
  • the indane structure is present in an amount of 0.01 mol% or more, for example, 0.01 mol%, 0.03 mol%, 0.05 mol%, 0.08 mol%, 0.1 mol%, 0.2 mol%, 0.5 mol%, based on the total structural units of the monomers.
  • the upper limit is preferably 20% by mole or less, more preferably 15% by mole or less.
  • the number average molecular weight Mn (in terms of polystyrene measured by gel permeation chromatography) of the soluble polyfunctional vinyl aromatic copolymer is preferably 600 to 30,000, for example, 600, 800, 1000, 1500, 2000, 4000, 6000, 8000. 10,000, 15,000, 20,000, 25,000 or 30,000, more preferably 600 to 10,000, most preferably 700 to 5,000.
  • Mn is less than 600, since the viscosity of the soluble polyfunctional vinyl aromatic copolymer is too low, it is difficult to apply a thick film or form a thick film, and workability is lowered, which is not preferable.
  • Mn is more than 30,000, the gel is easily produced, the compatibility with other resin components is lowered, and the appearance and physical properties are lowered in the case of sizing or film formation, which is not preferable.
  • the value of the number average molecular weight distribution (M w /M n ) of the soluble polyfunctional vinyl aromatic copolymer may be 20 or less, for example, 20, 18, 15, 10, 8, 6, 4, 2, 1, and the like. It is preferably 15 or less, more preferably 10 or less, and most preferably 5 or less.
  • M w /M n exceeds 20, the viscosity of the thermosetting resin composition of the present invention increases, resulting in deterioration of processing characteristics and a decrease in compatibility with other resin components, which is accompanied by appearance and Problems such as the decline in physical properties.
  • the soluble polyfunctional vinyl aromatic copolymer used as the component (A) has a metal ion content of preferably 500 ppm or less, for example, 500 ppm, 400 ppm, 300 ppm, 200 ppm, 100 ppm, 50 ppm, 30 ppm, 20 ppm, 10 ppm, 8 ppm, for each metal ion. 5 ppm, 3 ppm or 1 ppm, more preferably 100 ppm or less, further preferably 20 ppm or less, and most preferably 1 ppm or less.
  • the soluble polyfunctional vinyl aromatic copolymer may further use a trivinyl aromatic compound or other divinyl compound in addition to the above components (a), (b) and (c) without impairing the effects of the present invention. And a substance obtained by copolymerization of a monovinyl compound.
  • trivinyl aromatic compound examples include 1,2,4-trivinylbenzene, 1,3,5-trivinylbenzene, 1,2,4-triisopropylbenzene, and 1, 3,5-triisopropylbenzene, 1,3,5-trivinylnaphthalene, 3,5,4'-trivinylbiphenyl, and the like.
  • examples of the other divinyl compound include diene compounds such as butadiene and isoprene.
  • examples of the other monovinyl compound include an alkyl vinyl ether, an aromatic vinyl ether, isobutylene, and diisobutylene. These may be used alone or in combination of two or more. The amount of these other monomers used is less than 30% by mole based on the total amount of the monomers of the monovinyl aromatic compound containing the divinyl aromatic compound (a), the component (b), and the component (c). .
  • the soluble polyfunctional vinyl aromatic copolymer can be obtained by, for example, containing a divinyl aromatic compound (a), an ethyl vinyl aromatic compound (b), and an ethyl vinyl aromatic compound (b) a monomer component of the monovinyl aromatic compound (c) other than the compound represented by the following formula (a 4 ) in one or more organic solvents having a dielectric constant of 2 to 15 in the Lewis acid catalyst and the following formula (a 4 )
  • the polymerization is carried out at a temperature of from 20 to 100 ° C in the presence of an initiator.
  • R 15 represents a hydrogen atom or a monovalent hydrocarbon group having 1 to 6 carbon atoms
  • R 16 represents an E-valent aromatic hydrocarbon group or an aliphatic hydrocarbon group
  • D represents a halogen atom and an alkoxy group having 1 to 6 carbon atoms. Or an acyloxy group
  • E is an integer of 1-6. In the case where there are a plurality of R 15 and D in one molecule, they may be the same or different, respectively.
  • the method of recovering the copolymer after the polymerization reaction is stopped is not particularly limited, and for example, a method generally used such as a stripping method or precipitation in a poor solvent can be used.
  • the component (B) as the thermosetting resin composition of the present invention is selected from the group consisting of a number average molecular weight of 500 to 10,000 (for example, 500, 800, 1000, 1300, 1500, 2000, 3000, 4000, 5000, 6000, 7000, 8000, 9000).
  • an olefin having a styrene structure in a weight ratio of 10 to 50% for example, 10%, 13%, 15%, 20%, 25%, 30%, 35%, 40%, 45%, or 50%
  • Resin, and its molecular structure contains a 1,2-added butadiene structure, which can be copolymerized with a polyfunctional vinyl aromatic copolymer to form a crosslinked network, providing good dielectric properties and effectively improving The problem of high brittleness of the self-curing of the functional vinyl aromatic copolymer.
  • the styrene segment contained in the olefin resin structure can have good compatibility with the soluble polyfunctional vinyl aromatic copolymer, and the functionalized polyphenylene ether resin when the styrene weight ratio is less than 10% Poor compatibility with cross-linking curing agent, can not form a uniform stable solution, the glue liquid is easy to produce phase separation during the placement process; when the styrene weight ratio exceeds 50%, the butadiene unit structure ratio is too small, and can not Provide enough unsaturated double bonds The effect of good cross-linking curing is not achieved, and the heat resistance of the cured system is lowered, and the styrene structure is excessive, the brittleness of the cured system is increased, and the workability is deteriorated.
  • the olefin resin used in the present invention has a butadiene weight ratio of 1,2-position addition in the molecule of not less than 20%, preferably more than or equal to 30%; and the olefin resin passes through 1, 2 in its molecule
  • the addition-added butadiene-based unsaturated double bond can be cross-linked and cured well with the polyfunctional vinyl aromatic copolymer to form a three-dimensional network, which effectively improves the heat resistance of the final laminate material.
  • the olefin resin has a butadiene group weight ratio of addition of 1,2 position in the molecule of preferably 50% or more, and further preferably, the olefin resin is a butadiene group added at the 1,2 position in the molecule.
  • the weight ratio content is preferably greater than or equal to 70%.
  • the olefin resin may be one of a butadiene-styrene copolymer, a styrene-isoprene copolymer, a butadiene-styrene-divinylbenzene copolymer, or a mixture thereof, and is available for selection.
  • Commercial products such as SARTOMER's Ricon 100, Ricon 181, Ricon 184, Ricon 104, Ricon 104H, Ricon 250, R257, but are not limited to the products listed above.
  • the compounding ratio of the above components (A) and (B) for forming the thermosetting resin composition of the present invention may vary within a wide range, but the compounding amount (wt%) of the component (A) and the component (B) must be The conditions of the following formula are satisfied: the compounding amount of the component (A) is 10 to 98% by weight, and the compounding amount of the component (B) is 2 to 90% by weight.
  • the compounding amount of the component (A) is preferably from 30 to 90% by weight, and the compounding amount of the component (B) is from 10 to 70% by weight.
  • the compounding amount of the component (B) when the compounding amount of the component (B) is less than 2% by weight, the toughness of the thermosetting resin composition after curing is poor, and if it exceeds 90% by weight, the crosslinking density after curing of the thermosetting resin composition is insufficient, and the glass transition temperature is lowered. Since both the polyfunctional vinyl aromatic copolymer and the olefin resin used in the present invention have excellent dielectric properties, a cured product excellent in dielectric properties can be formed.
  • the initiator (C) is contained in an amount of 0.1 part by weight to 10 parts by weight, based on 100 parts by weight of the component (A) and (B), and is, for example, 0.1 part by weight, 0.5 part by weight, or 0.8 part by weight. Parts, 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, preferably 0.5 to 8 parts by weight, More preferably, it is 1-5 weight part.
  • the thermosetting resin composition contains an initiator as the component (C) for the purpose of improving the crosslinking curing effect.
  • an initiator as the component (C) for the purpose of improving the crosslinking curing effect.
  • the half-life temperature t 1/2 of the (C) component initiator is not less than 130 ° C; the initiator is a radical initiator.
  • the initiator is selected from the group consisting of dicumyl peroxide, tert-butyl peroxybenzoate, 2,5-di(2-ethylhexanoylperoxy)-2,5-dimethylhexane, Di-(tert-butylperoxyisopropyl)benzene, (2,4-dichlorobenzoyl) peroxide, 2,5-dimethyl-2,5-bis(tert-butylperoxy)hexane , tert-butyl peroxy-2-ethylhexyl carbonate, 2,5-dimethyl-2,5-bis(tert-butylperoxy)-3-hexyne, 4,4-di(tert-butyl Oxidation) butyl valerate, 1,1-bis(tert-butylperoxy)-3,3,5-trimethylcyclohexane, 3,3,5,7,7-pentamethyl-1,2 A combination of one or
  • the initiator as the component (C) may be used singly or in combination, and a synergistic effect can be achieved by mixing.
  • thermosetting resin composition further includes a filler including an organic filler and/or an inorganic filler.
  • the inorganic filler is selected from the group consisting of crystalline silica, fused silica, spherical silica, hollow silica, glass frit, aluminum nitride, boron nitride, silicon carbide, silicon aluminum silicate, and hydroxide.
  • Aluminum, magnesium hydroxide, titanium dioxide, barium titanate, barium titanate, zinc oxide, zirconium oxide, aluminum oxide, oxidation A combination of one or at least two of cerium, magnesium oxide, barium sulfate, talc, clay, calcium silicate, calcium carbonate or mica.
  • the organic filler is selected from one or a combination of at least two of polytetrafluoroethylene powder, polyphenylene sulfide, polyetherimide, polyphenylene ether or polyethersulfone powder.
  • the present invention does not limit the shape and particle diameter of the inorganic filler, and generally has a particle diameter of 0.01 to 50 ⁇ m, for example, 0.01 ⁇ m, 0.05 ⁇ m, 0.08 ⁇ m, 0.1 ⁇ m, 0.2 ⁇ m, 0.5 ⁇ m, 1 ⁇ m, 3 ⁇ m, 5 ⁇ m, 8 ⁇ m, 10 ⁇ m, 15 ⁇ m, 20 ⁇ m, 25 ⁇ m, 30 ⁇ m, 35 ⁇ m, 40 ⁇ m, 45 ⁇ m or 50 ⁇ m, etc., preferably 0.01 to 20 ⁇ m, more preferably 0.01 to 10 ⁇ m, and the inorganic filler having such a particle diameter range is more easily dispersed in the resin liquid.
  • the amount of the filler to be used in the thermosetting resin composition of the present invention is not particularly limited, and the filler is preferably used in an amount of 5 to 400 parts by weight, based on 100 parts by weight of the component (A) + (B), for example, 5 , 10, 20, 30, 40, 50, 60, 70, 80, 90, 100, 110, 120, 130, 140 or 150, 200, 250 parts, 300 parts, 350 parts or 400 parts, more preferably 5 to 200 parts by weight, still more preferably 5 to 150 parts by weight.
  • thermosetting resin composition of the present invention further comprises a flame retardant, and the flame retardant may be a bromine-containing flame retardant or a halogen-free flame retardant.
  • the inclusion of the flame retardant in the thermosetting resin composition of the present invention is determined by the necessity of flame retardancy, and the cured resin product has flame retardant properties and meets the requirements of UL 94 V-0.
  • the flame retardant to be added as needed is not particularly limited, and it is preferred that the dielectric properties are not affected.
  • the bromine-containing flame retardant is one or at least two of decabromodiphenyl ether, decabromodiphenylethane, ethylene bistetrabromophthalimide or brominated polycarbonate.
  • the optional commercial bromine-based flame retardants are HT-93, HT-93W, HP-8010 or HP-3010, but are not limited to the above categories.
  • the halogen-free flame retardant is a phosphorus-containing halogen-free flame retardant, a nitrogen-containing halogen-free flame retardant, and a silicon-containing halogen-free flame retardant One or a combination of at least two of the flame retardants.
  • the halogen-free flame retardant is tris(2,6-dimethylphenyl)phosphine, 10-(2,5-dihydroxyphenyl)-9,10-dihydro-9-oxa- 10-phosphaphenanthrene-10-oxide, 2,6-bis(2,6-dimethylphenyl)phosphinobenzene or 10-phenyl-9,10-dihydro-9-oxa-10-phosphine
  • Optional commercial halogen-free flame retardants are SP-100, PK-200, PK-202, LR-202, LR-700, OP-930, OP-935, LP-2200, but are not limited to the above categories .
  • the amount of the flame retardant is determined according to the UL 94 V-0 level of the cured product, and is not particularly limited.
  • the flame retardant is used in an amount of 5 to 80 parts by weight, such as 5, based on 100 parts by weight of the component (A) + (B), without sacrificing heat resistance, dielectric properties, and hygroscopicity of the cured product.
  • the thermosetting resin composition further comprises an additive introduced to solve certain problems, the additive being an antioxidant, a heat stabilizer, a light stabilizer, a plasticizer, a lubricant, a flow modifier, and an anti-drip.
  • the additive being an antioxidant, a heat stabilizer, a light stabilizer, a plasticizer, a lubricant, a flow modifier, and an anti-drip.
  • the amount of the additive is not particularly limited, and the amount of the additive is preferably 0.1 to 10 parts by weight, based on 100 parts by weight of the component (A) + (B), for example, 0.1 parts by weight, 0.5 parts by weight, 0.8 parts by weight, 1 part by weight, 2 parts by weight, 3 parts by weight, 4 The 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, still more preferably 1 to 5 parts by weight.
  • the present invention provides a method for producing a thermosetting resin composition as described above, which can be blended, stirred, and mixed with a soluble polyfunctional vinyl aromatic copolymer or an olefin resin by a known method. , a free radical initiator, a powder filler, and various flame retardants, various additives, to prepare.
  • the present invention provides a resin glue obtained by dissolving or dispersing a resin composition as described above in a solvent.
  • the solvent in the present invention is not particularly limited, and specific examples thereof include alcohols such as methanol, ethanol, and butanol, ethyl cellosolve, butyl cellosolve, ethylene glycol-methyl ether, carbitol, and butyl.
  • Ethers such as carbitol, ketones such as acetone, methyl ethyl ketone, methyl ethyl ketone, methyl isobutyl ketone, and cyclohexanone; aromatic hydrocarbons such as toluene, xylene, and mesitylene; An ester such as ethyl acetate or ethyl acetate; a nitrogen-containing solvent such as N,N-dimethylformamide, N,N-dimethylacetamide or N-methyl-2-pyrrolidone. These solvents may be used alone or in combination of two or more.
  • aromatic hydrocarbon solvents such as toluene, xylene, and mesitylene, and acetone, methyl ethyl ketone, methyl ethyl ketone, and methyl group.
  • a ketone flux such as butyl ketone or cyclohexanone is used in combination.
  • the amount of the solvent to be used can be selected by a person skilled in the art according to his own experience, so that the obtained resin glue can reach a viscosity suitable for use.
  • An emulsifier may be added during the process of dissolving or dispersing the resin composition as described above in a solvent. By dispersing by an emulsifier, the powder filler or the like can be uniformly dispersed in the glue.
  • the present invention provides a prepreg comprising a substrate and a thermosetting resin composition as described above adhered to the substrate by impregnation and drying.
  • the prepreg according to the present invention may also be referred to as a prepreg, which may also be a method in which a resin glue as described above is impregnated into a substrate, and then heated and dried to remove an organic solvent and partially cure the resin in the substrate.
  • the composition gives a prepreg.
  • the substrate described in the present invention may also be referred to as a reinforcing material.
  • the substrate is a woven or non-woven fabric made of organic fibers, carbon fibers or inorganic fibers.
  • the organic fibers comprise aramid fibers such as Kevlar fibers from DuPont.
  • the woven fabric or the non-woven fabric obtained from the inorganic fibers is not particularly limited.
  • the inorganic fiber-made woven fabric or non-woven fabric component contains 50 to 99.9% by weight (for example, 50%, 55%, or the like).
  • SiO 2 SiO 2 , weight ratio 0 to 30% (eg 0%, 5%) , 10%, 15%, 20%, 25% or 30%) of CaO, weight ratio of 0 to 20% (for example, 0%, 5%, 10%, 15% or 20%) of Al 2 O 3 , weight ratio 0 to 25% (for example, 0%, 5%, 10%, 15%, 20% or 25%) of B 2 O 3 , and a weight ratio of 0 to 5% (for example, 0%, 0.5%, 1%, 2%) , 3%, 4% or 5%) of MgO is not limited to the above components.
  • the substrate is preferably a braided fiber cloth, optionally E-Glass, T-Glass, NE-Glass, L-Glass, Q-Glass, D-Glass, particularly preferably NE-Glass .
  • the thickness of the substrate to be used is also not particularly limited.
  • the content of the resin used to impregnate the above substrate is preferably 30% by mass or more, such as 30% by mass, 35% by mass, 40% by mass, 50% by mass, 60% by mass or more, of the resin content in the semi-curing. . Since the dielectric constant of the substrate tends to be higher than that of the resin composition, in order to lower the dielectric constant of the laminate obtained from these prepregs, the content of the resin composition component in the prepreg is preferably the above content.
  • the prepreg described above has a drying temperature of 80 to 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;
  • the drying time is 1 to 30 minutes, for example, 1 minute, 5 minutes, 8 minutes, 13 minutes, 17 minutes, 21 minutes, 24 minutes, 28 minutes or 30 minutes.
  • the invention provides a laminate comprising at least one prepreg as described above.
  • the present invention provides a metal foil-clad laminate comprising one or at least two laminated prepregs as described above, and one or both of the prepreg sheets after lamination Side metal foil.
  • the metal foil is a copper foil.
  • the copper foil is an electrolytic copper foil or a rolled copper foil having a surface roughness of less than 5 microns, such as less than 4 microns, less than 3 microns, less than 2 microns, less than 1 micron, less than 0.8 microns, less than 0.5 microns, and the like. It can improve and improve the signal loss of laminate materials used in high frequency and high speed printed circuit boards.
  • the copper foil is chemically treated with a silane coupling agent, and the silane coupling agent used is an epoxy silane coupling agent, vinyl silane coupling One or a mixture of at least two of the acrylate or silane-based silane coupling agents.
  • the present invention provides a high frequency high speed circuit board comprising one or at least two laminated prepregs as described above.
  • the high speed circuit board of the present invention is produced by the following method:
  • At least one prepreg as described above is overlapped, and a copper foil is placed on the upper and lower sides of the prepreg, and is formed by lamination molding.
  • the overlap preferably employs an automated stacking operation to make the process operation easier.
  • the laminate molding is preferably vacuum lamination molding, and the vacuum lamination molding can be carried out by a vacuum laminator.
  • the lamination time is 70-120 min, such as 70 min, 75 min, 80 min, 85 min, 90 min, 95 min, 100 min, 105 min, 110 min, 115 min or 120 min, etc.;
  • the lamination temperature is 180-220 ° C, for example 180 ° C 185 ° C, 190 ° C, 195 ° C, 200 ° C, 205 ° C, 210 ° C, 215 ° C or 220 ° C;
  • the pressure of the lamination 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 and the like.
  • the electronic circuit substrate prepared by the method of the invention has good toughness and maintains high glass transition temperature, low water absorption, excellent dielectric properties and excellent heat and humidity resistance, and is very suitable for high-multilayer printing. Circuit board processing.
  • the copper foil used may be selected from an electrolytic copper foil or a rolled copper foil, and the surface roughness thereof is less than 5 ⁇ m.
  • the copper foil can also be chemically treated with a silane coupling agent, and the silane used.
  • the coupling agent is a mixture of one or more of an epoxy silane coupling agent, a vinyl silane coupling agent, and an acrylate-based silane coupling agent, and the purpose is to provide a bonding force between the copper foil and the substrate to prevent The risk of dropping or dropping the pad during the use of the printed circuit board.
  • the present invention has the following beneficial effects:
  • the resin composition has a high crosslink density after curing, can provide a high glass transition temperature of the circuit substrate, and significantly improve solubility.
  • the brittleness of the polyfunctional vinyl aromatic copolymer after curing, the prepared circuit substrate has better toughness, improves the drilling processability of the PCB, and is advantageous for improving the reliability of the high multilayer printed circuit board, and further, the olefin
  • the molecule of the resin does not contain a polar group, and the circuit board can ensure low water absorption and excellent dielectric properties.
  • a circuit prepared by using the resin composition of the olefin resin and the soluble polyfunctional vinyl aromatic copolymer.
  • the substrate has good toughness and maintains high glass transition temperature, low water absorption, excellent dielectric properties and heat and humidity resistance, and is suitable for high frequency and high speed printed circuit board applications, and is suitable for multilayer printing. Circuit board processing.
  • the obtained polymer VOD-A had Mw of 4,180, Mn of 2560, and Mw/Mn of 1.6.
  • the polymer VOD-A was found to contain 52 mol% of structural units derived from divinylbenzene and 48 mol% of structural units derived from ethylvinylbenzene by a JNM-LA600 type nuclear magnetic resonance spectroscopic device manufactured by JEOL. Further, it is understood that there is an incomplete structure in the copolymer VOD-A.
  • the indane structure is present in an amount of 7.5 mole percent relative to the structural units of all monomers. Further, the molar fraction of the structural unit represented by the formula (a 1 ) is 0.99 with respect to the total amount of the structural units represented by the above formulas (a 1 ) and (a 2 ).
  • the copolymer VOD-A was soluble in toluene, xylene, THF, dichloromethane, dichloroethane, chloroform, and no gel formation was observed.
  • the obtained polymer VOD-B had Mw of 7,670, Mn of 3,680 and Mw/Mn of 2.1.
  • the polymer VOD-B was found to contain 51 mol% of structural units derived from divinylbenzene and 49 mol% of structural units derived from ethylvinylbenzene by a JNM-LA600 type nuclear magnetic resonance spectroscopic device manufactured by JEOL. Further, it is understood that there is an incomplete structure in the copolymer VOD-B.
  • the indane structure is present in an amount of 7.5 mole percent relative to the structural units of all monomers. Further, the molar fraction of the structural unit represented by the formula (a 1 ) is 0.99 with respect to the total amount of the structural units represented by the above formulas (a 1 ) and (a 2 ).
  • the copolymer VOD-B was soluble in toluene, xylene, THF, dichloromethane, dichloroethane, chloroform, and no gel formation was observed.
  • the obtained polymer VOD-C contained a gel and was only soluble in a THF solvent, and had Mw of 94600, Mn of 12,800 and Mw/Mn of 7.4.
  • the polymer VOD-C was found to contain 58 mol% of structural units derived from divinylbenzene and 42 mol% of structural units derived from ethylvinylbenzene by a JNM-LA600 type nuclear magnetic resonance spectroscopic device manufactured by JEOL.
  • the copolymer VOD-C does not contain an indane structure.
  • the molar fraction of the structural unit represented by the formula (a 1 ) is 0.25 with respect to the total amount of the structural units represented by the above formulas (a 1 ) and (a 2 ).
  • Table 1 shows the materials used in the examples and comparative examples.
  • the ratio of the polyfunctional vinyl aromatic copolymer VOD-A and the styrene-butadiene copolymer Ricon 100 was changed from the original weight ratio of 80:20 to 50:50. .
  • Example 2 The procedure of Example 1, but the composition of the olefin resin, was replaced by a styrene-butadiene copolymer Ricon 181 (Sartomer, styrene content 28%). The physical properties of the prepared copper foil substrate were tested, and the results are shown in Table 2.
  • Example 2 The procedure of Example 1, but the composition of the olefin resin, was replaced by a styrene-butadiene-divinylbenzene copolymer Ricon 250 (Sartomer, styrene content 35%). The physical properties of the prepared copper foil substrate were tested, and the results are shown in Table 2.
  • the ratio of the polyfunctional vinyl aromatic copolymer VOD-A and the styrene-butadiene-divinylbenzene copolymer Ricon 250 was changed from the original weight ratio of 80:20. It becomes 50:50.
  • the ratio of the polyfunctional vinyl aromatic copolymer VOD-A and the styrene-butadiene copolymer Ricon 100 was changed from the original weight ratio of 80:20 to 13:87. .
  • the ratio of the polyfunctional vinyl aromatic copolymer VOD-A and the styrene-butadiene copolymer Ricon 100 was changed from the original weight ratio of 80:20 to 93:7. .
  • the physical properties of the prepared copper foil substrate were tested, and the results are shown in Table 2.
  • the resin glue was impregnated with NE-glass cloth (Nittobo, model 2116NE), controlled by a single-axis, and dried in an oven to remove the toluene solvent to prepare a prepreg of 2116.
  • 6 sheets of 2116 prepreg and 12 sheets of 2116 prepreg were respectively overlapped, and the upper and lower sides were coated with a copper foil of 1OZ thickness, vacuum laminated and cured for 120 min in a press, the curing pressure was 50 kg/cm 2 , and the curing temperature was 200 ° C.
  • a high-speed circuit board with a thickness specification (6*2116-0.76mm board for testing comprehensive performance, 12*2116-1.52mm thick board for testing mechanical properties).
  • the resin glue was impregnated with NE-glass cloth (Nittobo, model 2116NE), controlled by a single-axis, and dried in an oven to remove the toluene solvent to prepare a prepreg of 2116.
  • 6 sheets of 2116 prepreg and 12 sheets of 2116 prepreg were respectively overlapped, and the upper and lower sides were coated with a copper foil of 1OZ thickness, vacuum laminated and cured for 120 min in a press, the curing pressure was 50 kg/cm 2 , and the curing temperature was 200 ° C.
  • a high-speed circuit board with a thickness specification (6*2116-0.76mm board for testing comprehensive performance, 12*2116-1.52mm thick board for testing mechanical properties).
  • the physical properties of the prepared copper foil substrate were tested, and the results are shown in Table 3.
  • Tg Glass transition temperature
  • Td-5% loss Thermal decomposition temperature (Td-5% loss): According to the thermogravimetric analysis (TGA), the temperature Td at 5% of the weight loss of the laminate is measured according to the TGA method specified in IPC-TM-650 2.4.24.6. .
  • PCT water absorption rate After etching the copper foil on the surface of the copper clad laminate, the substrate is dried and weighed, and then placed in a pressure cooker, treated at 120 ° C, 150 KPa for two hours, and taken out with a dry cloth. Wipe dry, weigh the sample after water absorption, PCT water absorption (weight after cooking - weight before cooking) / weight before cooking.
  • Dielectric constant Dk and dielectric loss factor Df Tested according to the SPDR (Split Post Dielectric Resonator) method, the test frequency is 10 GHz.
  • Pendulum impact strength Using a simple-supported beam non-metallic material pendulum impact tester, a laminate of about 1.6 mm is made into 120 mm*10 mm notched samples (notch depth 2 mm), and the pendulum is 3.8 m/ The speed of s impacts the sample. After the sample breaks, the absorption work of the pendulum impact tester is read, and finally the pendulum impact strength is calculated.
  • Drop hammer impact toughness using the drop hammer impact tester, the impact gauge drop weight is 100cm, the weight of the drop weight is 1Kg, the toughness is good or bad.
  • the cross is clear, indicating that the product toughness is better, represented by the character ⁇ ; the cross is blurred, indicating The product has poor toughness and brittleness, and is represented by the character ⁇ ; the clarity of the cross is between clear and fuzzy, indicating that the toughness of the product is generally indicated by the character ⁇ .
  • PCT After etching the copper foil on the surface of the copper clad plate, the substrate is placed in a pressure cooker, treated at 120 ° C, 150 KPa for two hours, and then immersed in a tin furnace at 288 ° C, when the substrate is layered, Record the corresponding time; the evaluation can be ended when the substrate has not appeared bubbles or delamination in the tin furnace for more than 5 minutes.
  • Comparative Example 4 the cage-type silsesquioxane A having a terminal (meth)acryloyl group introduced as a crosslinking agent was inferior in dielectric properties due to its large polarity.
  • the styrene-butadiene copolymer used had a styrene content of more than 50%, resulting in a significant decrease in the toughness of the substrate; in Comparative Example 6, the maleated polybutadiene Ricon 130MA8 was used.
  • Such a polyolefin resin has a polar structure, so that the dielectric properties of the prepared substrate are deteriorated and the toughness is also lowered.
  • Examples 1 to 8 an olefin resin (styrene-butadiene copolymer) was used as the polyfunctional vinyl aromatic copolymer VOD-A/VOD-B, and the substrate had good toughness after curing, and maintained its high. Glass transition temperature, low water absorption, excellent dielectric properties and heat and humidity resistance.
  • the circuit substrate of the present invention has good toughness as compared with a general laminate, and maintains its high glass transition temperature, low water absorption, excellent dielectric properties, and moist heat resistance.
  • the present invention describes the thermosetting resin composition of the present invention and the prepreg and copper clad laminate produced using the same according to the above embodiments, but the present invention is not limited to the above embodiment, that is, it does not mean that the present invention is necessary It can be implemented depending on the above embodiment. It should be apparent to those skilled in the art that any modifications of the present invention, equivalent substitution of the various materials of the products of the present invention, addition of auxiliary components, selection of specific means, and the like, are all within the scope of the present invention.

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Abstract

本发明提供了一种热固性树脂组合物及使用其制作的半固化片与覆金属箔层压板，所述热固性树脂组合物包括(A)成分：溶剂可溶性的多官能乙烯基芳香族共聚物，是具有来自于包括二乙烯基芳香族化合物(a)及乙基乙烯基芳香族化合物(b)的单体的结构单元的多官能乙烯基芳香族共聚物；和(B)成分：选自数均分子量为500～10000的含有10～50％重量比的苯乙烯结构的烯烃树脂，且其分子中含有1，2位加成的丁二烯结构。本发明的热固性树脂组合物制作的半固化片及覆铜箔层压板具有良好的韧性，且保持了其高的玻璃化转变温度、低的吸水率、优异的介电特性和耐湿热性，适合高频高速印制线路板领域使用，并适合于多层印制线路板加工。

Description

一种热固性树脂组合物及使用其制作的半固化片与覆金属箔层压板 技术领域
本发明属于覆铜板技术领域，涉及一种热固性树脂组合物及使用其制作的半固化片与覆金属箔层压板。
背景技术
近年来，随着计算机和信息通讯设备高性能化、高功能化以及网络化的发展，为了高速传输及处理大容量信息，操作信号趋向于高频化，因而对电路基板的材料提出了要求，尤其是在那些使用宽带的电子设备如移动通信装置上有迅速的发展。
现有的用于印制电路基板的材料中，广泛使用粘接特性优异的环氧树脂。然而，环氧树脂电路基板一般介电常数和介质损耗角正切较高(介电常数Dk大于4，介质损耗角正切Df在0.02左右)，高频特性不充分，不能适应信号高频化的要求。因此必须研制介电特性优异的树脂，即介电常数和介质损耗角正切低的树脂。长期以来本领域的技术人员对介电性能很好的热固性的聚苯醚树脂、双马来酰亚胺树脂、乙烯基苄基醚树脂、碳氢树脂等进行了研究；众所周知，可固化交联的碳氢树脂(聚烯烃树脂)具有较低的介质损耗角正切Df(可以与聚四氟乙烯树脂媲美)、且流动性较好，进而吸引了广大技术人员对其进行了大量的深入研究，但由于其耐热性不足，无法满足高多层印制线路板的工艺制作要求，需要与其他耐热性好的树脂搭配使用。
TW200536862A公开了在有机溶剂体系中，存在路易斯酸催化剂和引发剂的情况下，在20～120℃反应温度下使20～100摩尔％的二乙烯芳香族化合物及必要时添加其他单体(如乙基乙烯芳香族化合物等其他单体)成分聚合，制备 出分子量可控的可溶性的多官能乙烯基芳香族共聚物。该树脂可用于电子基材等相关的高摩擦领域，具有较好的耐热性和加工性。虽然使用该共聚物制备的电子电路基材，其介电性能较好，且耐热性较佳，但同时也存在脆性大的明显缺陷。脆性大对后续PCB加工产生较大的负面影响(钻刀磨损严重，板材分层，钻孔后晕圈大，导致CAF差)，无法满足高多层印制线路板的工艺制作要求。
CN1914239A利用端乙烯基改性聚苯醚和可溶性的多官能乙烯基芳香族共聚物进行共聚，制造出具有优异耐化学性、介电特性和耐热性的覆铜板。为改善覆铜板的韧性，指出可以加入一种或两种或多种的热塑性树脂，但是添加热塑性的树脂，将会大大降低基材的玻璃化转变温度，另外，热塑性树脂和固化物会出现不相容，导致基材分相，大大恶化基材的耐湿热性，使高多层印制电路板在无铅回流焊的热处理后出现分层爆板，无法使用。
CN103172803A使用可溶性多官能共聚物、含丙烯酰基的有机硅树脂和引发剂的组合物固化后，制备具有折射率、高光线透过率等优异的光学特性、耐热性及加工性的光学物品。其未指出该树脂组合物可用于覆铜板和半固化片，即使用该树脂组合物固化后制作覆铜板，其介电特性(介质损耗角正切Df)将出现明显的恶化(该树脂组合物使用了含丙烯酰基的有机硅树脂，而含丙烯酰基的有机硅树脂极性较大)，无法满足高频信号传输需求。
因此，在本领域期望获得一种使覆铜板具有韧性、介电性能以及耐湿热性等良好综合性能的树脂组合物。
发明内容
针对现有技术的不足，本发明的目的在于提供一种热固性树脂组合物及使用其制作的半固化片与覆金属箔层压板。
为达此目的，本发明采用以下技术方案：
一方面，本发明提供一种热固性树脂组合物，所述热固性树脂组合物包括(A)成分：溶剂可溶性的多官能乙烯基芳香族共聚物，该共聚物是具有来自于包括二乙烯基芳香族化合物(a)及乙基乙烯基芳香族化合物(b)的单体的结构单元的多官能乙烯基芳香族共聚物，含有大于等于20摩尔％来自于二乙烯基芳香族化合物(a)的重复单元，且下述式(a1)及(a2)所示的来自二乙烯基芳香族化合物(a)的含有乙烯基的结构单元的摩尔分数满足(a1)/[(a1)+(a2)]≥0.5，且用凝胶渗透色谱测定的聚苯乙烯换算的数均分子量Mn为600～30000，重均分子量Mw与数均分子量Mn之比Mw/Mn小于等于20.0，
Figure PCTCN2017106830-appb-000001
其中，R13为碳原子数6～30的芳香族烃基，R14为碳原子数6～30的芳香族烃基；和
(B)成分：选自数均分子量为500～10000的含有10～50％重量比的苯乙烯结构的烯烃树脂，且其分子中含有1，2位加成的丁二烯结构。
本发明所述的热固性树脂组合物的树脂成分不含有极性的羟基基团，并且在固化加工过程中不会产生二次羟基等极性基团，可保证电路基板低吸水率以及优异的介电性能，采用所述烯烃树脂作为溶剂可溶性的多官能乙烯基芳香族共聚物的交联剂，树脂组合物固化后交联密度大，明显改善可溶性的多官能乙烯基芳香族共聚物固化后的脆性，所制备的电路基板韧性较佳，改善PCB的钻孔加工性，有利于提高多层印制电路板的可靠性。
优选地，所述烯烃树脂为丁二烯-苯乙烯共聚物和/或丁二烯-苯乙烯-二乙烯基苯共聚物。
优选地，在所述热固性树脂组合物中，相对于(A)成分及(B)成分的总和，(A)成分的混配量为10～98wt％(例如10wt％、15wt％、20wt％、25wt％、28wt％、30wt％、35wt％、38wt％、40wt％、50wt％、60wt％、70wt％、80wt％、90wt％、95wt％或98wt％)，(B)成分的混配量为2～90wt％(例如2wt％、5wt％、8wt％、10wt％、15wt％、20wt％、25wt％、30wt％、40wt％、50wt％、60wt％、70wt％、80wt％或90wt％)。
本发明提供的热固性树脂组合物中，(A)成分是可溶性的多官能乙烯基芳香族共聚物，该共聚物中，在多官能乙烯基芳香族共聚物的主链骨架中具有下述通式(a3)所示的茚满结构
Figure PCTCN2017106830-appb-000002
其中，W表示饱和或不饱和的脂肪族烃基或芳香族烃基或稠合于苯环的芳香环或取代芳香环，Z为0～4的整数。
优选地，(A)成分为如下的可溶性多官能乙烯基芳香族共聚物，即，在多官能乙烯基芳香族共聚物中，含有来自乙基乙烯基芳香族化合物(b)以外的单乙烯基芳香族化合物(c)的结构单元。
该共聚物含有上述(a1)、(a2)及(a3)表示的结构单元作为来自二乙烯基芳香族化合物(a)的重复单元。上述(a1)、(a2)及(a3)表示的结构单元中R13、R14、W和Z与上述意义相同，但各结构单元在共聚物中的存在比例取决于所使用的二乙烯基芳香族化合物(a)、乙基乙烯基芳香族化合物(b)的种 类及反应催化剂、反应温度等反应条件。
在本发明中，作为所使用的二乙烯基芳香族化合物(a)，例如可以使用间二乙烯基苯、对二乙烯基苯、1，2-二异丙烯基苯、1，3-二异丙烯基苯、1，4-二异丙烯基苯、1，3-二异丙烯基萘、1，4-二异丙烯基萘、1，5-二异丙烯基萘、1，8-二异丙烯基萘、2，3-二异丙烯基萘、2，6-二异丙烯基萘、2，7-二异丙烯基萘、4，4’-二乙烯基联苯、4，3’-二乙烯基联苯、4，2’-二乙烯基联苯、3，2’-二乙烯基联苯、3，3’-二乙烯基联苯、2，2’-二乙烯基联苯、2，4-二乙烯基联苯、1，2-二乙烯基-3，4-二甲基苯、1，3-二乙烯基-4，5，8-三丁基萘或2，2’-二乙烯基-4-乙基-4’-丙基联苯中的任意一种或至少两种的组合，但不局限于这些物质，并且这些物质可以单独使用或两种以上组合使用。
作为所使用的二乙烯基芳香族化合物(a)的优选具体例，从成本及所获得的聚合物的耐热性来看，二乙烯基苯(间位及对位异构体两者)、二乙烯基联苯(包含各异构体)及二乙烯基萘(包含各异构体)是优选的。更优选二乙烯基苯(间位及对位异构体两者)、二乙烯基联苯(包含各异构体)。特别是二乙烯基苯(间位及对位异构体两者)为最优选使用的。在需要更高耐热性的领域中，特别优选二乙烯基联苯(包含各异构体)及二乙烯基萘(包含各异构体)。
在多官能乙烯基芳香族共聚物中，作为提供调节与作为(B)成分的乙烯基有机硅树脂的相容性、改善溶剂可溶性及加工性的结构单元的(b)成分而使用的乙基乙烯基芳香族化合物，可以使用邻乙基乙烯基苯、间乙基乙烯基苯、对乙基乙烯基苯、2-乙烯基-2′-乙基联苯、2-乙烯基-3′-乙基联苯、2-乙烯基-4′-乙基联苯、3-乙烯基-2’-乙基联苯、3-乙烯基-3′-乙基联苯、3-乙烯基-4′-乙基联苯、4-乙烯基-2′-乙基联苯、4-乙烯基-3′-乙基联苯、4-乙烯基-4′-乙基联苯、1-乙烯基-2-乙基萘、1-乙烯基-3-乙基萘、1-乙烯基-4-乙基萘、1-乙烯基-5-乙基萘、1- 乙烯基-6-乙基萘、1-乙烯基-7-乙基萘、1-乙烯基-8-乙基萘、2-乙烯基-1-乙基萘、2-乙烯基-3-乙基萘、2-乙烯基-4-乙基萘、2-乙烯基-5-乙基萘、2-乙烯基-6-乙基萘、2-乙烯基-7-乙基萘、2-乙烯基-8-乙基萘等，但不局限与这些物质。这些物质可以单独使用或两种以上组合使用。通过将衍生自(b)成分的结构单元引入多官能乙烯基芳香族共聚物中，不仅能防止共聚物的凝胶化、提高在溶剂的溶解性。作为优选的具体例，从成本、防止凝胶化及所获得的固化物的耐热性来看，可以列举乙基乙烯基苯(间位及对位异构体两者)及乙基乙烯基联苯(包含各异构体)等。
为提高本发明的热固性树脂组合物的固化物的耐热性，或改善与其他树脂的相容性，可以添加所加入的乙基乙烯基芳香族化合物(b)以外的单乙烯基芳香族化合物(c)，优选苯乙烯、乙基乙烯基芳香族化合物以外的环上被烷基取代的苯乙烯、乙基乙烯基芳香族化合物以外的环上被烷基取代的芳香族乙烯基化合物、α-烷基取代苯乙烯、α-烷基取代芳香族乙烯基化合物、β-烷基取代苯乙烯、烷基取代芳香族乙烯基化合物、茚衍生物及苊衍生物等。
作为环上被烷基取代的苯乙烯，例如可以使用甲基苯乙烯、乙基苯乙烯、丁基苯乙烯等烷基取代的苯乙烯。
另外环上被烷基取代的苯乙烯，可以使用甲氧基苯乙烯、乙氧基苯乙烯、丁氧基苯乙烯。另外，也可以使用苯氧基苯乙烯等。
作为芳香族乙烯基化合物，例如可以使用2-乙烯基联苯、3-乙烯基联苯、4-乙烯基联苯、1-乙烯基萘或1-乙烯基萘。
作为环上被烷基取代的芳香族乙烯基化合物，例如可以使用乙烯基-丙基联苯或乙烯基-丙基萘等。
另外，作为α-烷基取代苯乙烯，例如可以使用α-甲基苯乙烯、α-乙基苯乙 烯等。
作为茚衍生物，除了茚外，可以使用甲基茚、乙基茚、丙基茚、丁基茚等烷基取代茚等。另外，还可以使用甲氧基茚、乙氧基茚、丁氧基茚等烷氧基茚等。
作为苊衍生物，除了茚外，可以使用甲基苊、乙基苊等烷基取代苊类；氯代苊、溴代苊等卤代苊类；苯基苊类等。
对于可溶性多官能乙烯基芳香族共聚物来说，这些作为(c)成分的单乙烯基芳香族化合物并不局限于这些化合物。这些物质可以单独使用或将两者或多种组合使用。
在这些作为(c)成分的单乙烯基芳香族化合物中，从聚合物的骨架中的茚满结构生成量大的方面来看，苯乙烯、α-烷基取代的苯乙烯、α-烷基取代的芳香族乙烯基化合物是优选的。作为最优选的具体例，从成本及所获得的聚合物的耐热性方面来看，可以列举苯乙烯、α-甲基苯乙烯及4-异丙烯及联苯。
对于可溶性多官能乙烯基芳香族共聚物来说，作为(a)成分的二乙烯基芳香族化合物相对于由(a)成分、(b)成分及(c)成分组成的单体总和的使用量为20～99.5摩尔％，例如20摩尔％、25摩尔％、28摩尔％、30摩尔％、35摩尔％、38摩尔％、40摩尔％、45摩尔％、50摩尔％、55摩尔％、60摩尔％、65摩尔％、70摩尔％、80摩尔％、90摩尔％、95摩尔％或99摩尔％，优选为33～99摩尔％，更优选为45～95摩尔％，特别优选为50～85摩尔％。如果二乙烯基芳香族化合物(a)的含量不足20摩尔％，则使生成的可溶性多官能乙烯基芳香族共聚物固化时，存在耐热性降低的倾向，因而不优选。
另外，对于可溶性多官能乙烯基芳香族共聚物来说，作为(b)成分的乙基乙烯基芳香族化合物相对于由(a)成分、(b)成分及(c)成分组成的单体总 和的使用量为0.5～80摩尔％，例如0.5摩尔％、0.8摩尔％、1摩尔％、5摩尔％、10摩尔％、15摩尔％、20摩尔％、25摩尔％、30摩尔％、35摩尔％、40摩尔％、45摩尔％、50摩尔％、55摩尔％、60摩尔％、65摩尔％、70摩尔％、75摩尔％或80摩尔％，优选为1～70摩尔％，更优选为5～60摩尔％，特别优选为15～50摩尔％。如果乙基乙烯基芳香族化合物(b)的含量大于80摩尔％，则使生成的可溶性多官能乙烯基芳香族共聚物固化时，存在耐热性降低的倾向，因而不优选。
另外，对于可溶性多官能乙烯基芳香族共聚物来说，作为(c)成分的单乙烯基芳香族化合物相对于由(a)成分、(b)成分及(c)成分组成的单体总和使用量为不足40摩尔％，例如38摩尔％、35摩尔％、33摩尔％、30摩尔％、28摩尔％、25摩尔％、23摩尔％、20摩尔％、18摩尔％、15摩尔％、13摩尔％、10摩尔％、8摩尔％、5摩尔％、3摩尔％或1摩尔％，优选为小于30摩尔％，更优选为小于25摩尔％，特别优选小于20摩尔％。如果单乙烯基芳香族化合物(c)的含量大于等于40摩尔％，则使生成的可溶性多官能乙烯基芳香族共聚物固化时，存在耐热性降低的倾向，因而不优选。
在可溶性的多官能乙烯基芳香族共聚物中，上述式(a1)及(a2)表示的来自二乙烯基芳香族化合物(a)的含有乙烯基的结构单元的摩尔分数必须满足(a1)/[(a1)+(a2)]≥0.5，例如该摩尔分数为0.5、0.6、0.7、0.8、0.9、0.95、0.98等。优选该摩尔分数大于等于0.7，特别优选大于等于0.9。如果不足0.5，则生成的共聚物的固化物的耐热性降低，固化需要较长时间，因而不优选。
另外，可溶性的多官能乙烯基芳香族共聚物的主骨架上必须具有上述通式(a3)所示的茚满结构。在通式(a3)中，W具有乙烯基等不饱和脂肪族烃基、苯基等芳香族烃基、这些烃基的取代体等，它们可以进行0～4个取代。另外， W也可以是通过与茚满结构的苯环形成稠合环从而形成萘环等2阶烃基，该2阶烃基可以具有取代基。
通式(a3)所示的茚满结构是进一步提高可溶性多官能乙烯基芳香族共聚物的耐热性及对溶剂的可溶性的结构单元，其通过以下方式生成：在制造多官能乙烯基芳香族共聚物时，通过在特定的溶剂、催化剂、温度等制备条件下进行制造，使成长聚合物链末端的活性点攻击来自于二乙烯基芳香族化合物及单乙烯基芳香族化合物的结构单元的芳香环。优选茚满结构相对于全部单体的结构单元的存在量大于等于0.01摩尔％，例如0.01摩尔％、0.03摩尔％、0.05摩尔％、0.08摩尔％、0.1摩尔％、0.2摩尔％、0.5摩尔％、0.8摩尔％、1摩尔％、1.3摩尔％、1.5摩尔％、1.8摩尔％、2摩尔％、5摩尔％、10摩尔％、15摩尔％、20摩尔％、25摩尔％或30摩尔％，更优选为大于等于0.1摩尔％，进一步优选为大于等于1摩尔％，特别优选为大于等于3摩尔％，最优选为大于等于5摩尔％。上限优选为小于等于20摩尔％，更优选为小于等于15摩尔％。如果多官能乙烯基芳香族共聚物的主链骨架中不存在上述茚满结构，则耐热性及对溶剂的可溶性不足，因此不优选。
可溶性多官能乙烯基芳香族共聚物的数均分子量Mn(使用凝胶渗透色谱测定的聚苯乙烯换算的)优选为600～30000，例如600、800、1000、1500、2000、4000、6000、8000、10000、15000、20000、25000或30000，更优选为600～10000，最优选为700～5000。如果Mn不足600，则由于可溶性多官能乙烯基芳香族共聚物的粘度过低，难以上胶或形成厚膜，加工性降低，因而不优选。另外，如果Mn大于30000，则易生产凝胶，与其他树脂成分的相容性降低，在上胶或成膜等情况下，导致外观及物性下降，因而不优选。
另外，可溶性多官能乙烯基芳香族共聚物的数均分子量分布(Mw/Mn)的 值可以小于等于20，例如20、18、15、10、8、6、4、2、1等，优选为小于等于15，更优选为小于等于10，最优选为小于等于5。如果Mw/Mn超过20，则伴随着本发明的热固性树脂组合物的粘度上升，将会导致加工特性变差，与其他树脂成分的相容性下降，伴之而来的是产生外观和物性下降等问题。
作为(A)成分使用的可溶性多官能乙烯基芳香族共聚物的金属离子含量为各金属离子优选小于等于500ppm，例如500ppm、400ppm、300ppm、200ppm、100ppm、50ppm、30ppm、20ppm、10ppm、8ppm、5ppm、3ppm或1ppm，更优选小于等于100ppm，进一步优选小于等于20ppm，最优选小于等于1ppm。
可溶性多官能乙烯基芳香族共聚物还可以除了上述(a)、(b)和(c)成分外，在不损害本发明的效果范围内使用三乙烯基芳香族化合物、其他的二乙烯基化合物及单乙烯基化合物进行共聚而获得的物质。
作为三乙烯基芳香族化合物的具体例子，例如可以列举1，2，4-三乙烯基苯、1，3，5-三乙烯基苯、1，2，4-三异丙基苯、1，3，5-三异丙基苯、1，3，5-三乙烯基萘、3，5，4′-三乙烯基联苯等。另外，作为其他的二乙烯基化合物，可以列举丁二烯、异戊二烯等二烯化合物。作为其他的单乙烯基化合物，可以列举烷基乙烯基醚、芳香族乙烯基醚、异丁烯、二异丁烯等。这些可以单独使用或将2种或多种组合使用。相对于包含二乙烯基芳香族化合物(a)、(b)成分及(c)成分的单乙烯基芳香族化合物的单体总量，这些其他单体的使用量为不足30摩尔％的范围内。
该可溶性多官能乙烯基芳香族共聚物可通过以下方式获得：例如，将含有二乙烯基芳香族化合物(a)、乙基乙烯基本芳香族化合物(b)及乙基乙烯基芳香族化合物(b)以外的单乙烯基芳香族化合物(c)的单体成分在介电常数 为2～15的一种或多种有机溶剂中，在路易斯酸催化剂及下述通式(a4)所示的引发剂的存在下，在20～100℃的温度下进行聚合。
Figure PCTCN2017106830-appb-000003
其中，R15表示氢原子或碳原子数为1～6的1价烃基，R16表示E价的芳香族烃基或脂肪族烃基，D表示卤原子、碳原子数为1～6的烷氧基或酰氧基，E为1～6的整数。在一分子中具有多个R15和D的情况下，可以分别相同或不同。
聚合反应停止后，回收共聚物的方法没有特别限定，例如可以使用汽提法、在不良溶剂中的析出等通用使用的方法。
作为本发明的热固性树脂组合物的(B)成分为选自数均分子量为500～10000(例如500、800、1000、1300、1500、2000、3000、4000、5000、6000、7000、8000、9000或10000)的含有10～50％(例如10％、13％、15％、20％、25％、30％、35％、40％、45％、或50％)重量比的苯乙烯结构的烯烃树脂，且其分子中含有1，2位加成的丁二烯结构，可以和多官能乙烯基芳香族共聚物进行共聚反应，形成交联网络，提供良好的介电性能，并有效地改善多官能乙烯基芳香族共聚物自固化的脆性大的问题。所述烯烃树脂结构中含有的苯乙烯链段可以使其与可溶性多官能乙烯基芳香族共聚物具有较好的相容性，当苯乙烯重量比含量小于10％时，官能化聚苯醚树脂和交联固化剂相容性差，无法形成均一稳定的溶液，胶液在放置过程中容易产生分相；当苯乙烯重量比含量超过50％的时候，丁二烯单元结构比例太少，又无法提供足够的不饱和双键，而起 不到良好交联固化的作用，导致固化体系的耐热性降低，且苯乙烯结构过多，固化体系的脆性增大，可加工性变差。
另外，本发明中使用的烯烃树脂，其分子中1，2-位加成的丁二烯重量比含量不小于20％，优选大于或等于30％；所述烯烃树脂通过其分子中1，2位加成的丁二烯基不饱和双键，可以很好地和多官能乙烯基芳香族共聚物进行交联固化，形成三维网络，有效地提高了最终层压板材料的耐热性。更优选的，烯烃树脂为分子中1，2位加成的丁二烯基重量比含量优选大于或等于50％，进一步优选的，烯烃树脂为分子中1，2位加成的丁二烯基重量比含量优选大于或等于70％。当分子中1，2-位加成的丁二烯基重量比含量不足20％时，无法提供足够的不饱和双键进行交联反应，从而带来固化产物的耐热性低下。所述的烯烃树脂可以为丁二烯-苯乙烯共聚物、苯乙烯-异戊二烯共聚物、丁二烯-苯乙烯-二乙烯基苯共聚物中的一种或其混合物，可供选择的商品化产品，如SARTOMER公司的Ricon 100、Ricon 181、Ricon 184、Ricon 104、Ricon 104H、Ricon 250、R257，但不局限于以上所列举的产品。
用于形成本发明的热固性树脂组合物的上述(A)及(B)成分的混配比可以在宽范围内变化，但(A)成分及(B)成分的混配量(wt％)必须满足下述式条件：(A)成分的混配量为10～98wt％，(B)成分的混配量为2～90wt％。优选(A)成分混配量为30～90wt％，(B)成分混配量为10～70wt％。
在本发明中，如果(B)成分混配量不足2wt％，热固性树脂组合物固化后的韧性差，如果超过90wt％，热固性树脂组合物固化后的交联密度不足，玻璃化转变温度降低。由于本发明使用的多官能乙烯基芳香族共聚物和烯烃树脂都具有较优的介电特性，因而可形成介电特性优异的固化物。
在本发明所述的热固性树脂组合物中，除了(A)成分和(B)成分外，还 含有作为(C)成分的引发剂，以(A)成分+(B)成分为100重量份计算，(C)成分的用量为0.1～10重量份，例如0.1重量份、0.5重量份、0.8重量份、1重量份、2重量份、3重量份、4重量份、5重量份、6重量份、7重量份、8重量份、9重量份或10重量份，优选为0.5～8重量份，进一步优选为1～5重量份。
在本发明中，热固性树脂组合物含有作为(C)成分的引发剂的目的在于提高交联固化效果。虽然多官能乙烯基芳香族共聚物和烯烃树脂也可以在加热加温条件下进行固化，但是引入引发剂可以大幅度提高工艺效率，降低加工成本。
在本发明中，所述(C)成分引发剂的半衰期温度t1/2不小于130℃；所述引发剂为自由基引发剂。
优选地，所述引发剂选自过氧化二异丙苯、过氧化苯甲酸叔丁酯、2，5-二(2-乙基己酰过氧)-2，5-二甲基己烷、二-(叔丁基过氧异丙基)苯、过氧化(2，4-二氯苯甲酰)、2，5-二甲基-2，5-双(叔丁基过氧)己烷、过氧化-2-乙基己基碳酸叔丁酯、2，5-二甲基-2，5-双(叔丁基过氧)-3-己炔、4，4-二(叔丁基过氧化)戊酸丁酯、1，1-双(叔丁基过氧化)-3，3，5-三甲基环己烷、3，3，5，7，7-五甲基-1，2，4-三氧杂环庚烷、二叔丁基过氧化物或叔丁基过氧化异丙苯中的一种或至少两种的组合。
在本发明所述树脂组合物中，作为(C)成分的引发剂可以单独使用，也可以混合使用，混合使用可以达到更好的协同效果。
在本发明中，所述热固性树脂组合物还包括填料，所述填料包括有机填料和/或无机填料。
优选地，所述无机填料选自结晶型二氧化硅、熔融二氧化硅、球形二氧化硅、空心二氧化硅、玻璃粉、氮化铝、氮化硼、碳化硅、碳化硅铝、氢氧化铝、氢氧化镁、二氧化钛、钛酸锶、钛酸钡、氧化锌、氧化锆、氧化铝、氧化 铍、氧化镁、硫酸钡、滑石粉、粘土、硅酸钙、碳酸钙或云母中的一种或至少两种的组合。
优选地，所述有机填料选自聚四氟乙烯粉末、聚苯硫醚、聚醚酰亚胺、聚苯醚或聚醚砜粉末中的一种或至少两种的组合。
另外，本发明对无机填料的形状和粒径不作限定，通常使用的粒径为0.01-50μm，例如0.01μm、0.05μm、0.08μm、0.1μm、0.2μm、0.5μm、1μm、3μm、5μm、8μm、10μm、15μm、20μm、25μm、30μm、35μm、40μm、45μm或50μm等，优选为0.01～20μm，更优选为0.01～10μm，这种粒径范围的无机填料在树脂液中更易分散。
再者，本发明对填料在热固性树脂组合物中的用量也无特定限定，以成分(A)+(B)为100重量份计，所述填料的用量优选为5～400重量份，例如5份、10份、20份、30份、40份、50份、60份、70份、80份、90份、100份、110份、120份、130份、140份或150份、200份、250份、300份、350份或400份，更优选为5～200重量份，进一步优选为5～150重量份。
优选地，本发明所述热固性树脂组合物还包括阻燃剂，所述阻燃剂可以为含溴阻燃剂或无卤阻燃剂。
在本发明的热固性树脂组合物中包含阻燃剂是由阻燃性的需要而决定的，使树脂固化物具有阻燃特性，符合UL 94 V-0要求。对视需要而添加的阻燃剂并无特别限定，以不影响介电性能为佳。
优选地，所述含溴阻燃剂为十溴二苯醚、十溴二苯乙烷、乙撑双四溴邻苯二甲酰亚胺或溴化聚碳酸酯中的一种或至少两种的组合。可选的商品化的溴系阻燃剂有HT-93、HT-93W、HP-8010或HP-3010，但并不限于以上种类。
优选地，所述无卤阻燃剂为含磷无卤阻燃剂、含氮无卤阻燃剂及含硅无卤 阻燃剂中的一种或至少两种的组合。
优选地，所述无卤阻燃剂为三(2，6-二甲基苯基)膦、10-(2，5-二羟基苯基)-9，10-二氢-9-氧杂-10-膦菲-10-氧化物、2，6-二(2，6-二甲基苯基)膦基苯或10-苯基-9，10-二氢-9-氧杂-10-膦菲-10-氧化物、苯氧基膦氰化合物、磷酸酯或聚磷酸酯中的一种或至少两种的组合。
可选的商品化的无卤阻燃剂有SP-100、PK-200、PK-202、LR-202、LR-700、OP-930、OP-935、LP-2200，但并不限于以上种类。
在本发明中，所述阻燃剂的用量根据固化产物达到UL 94 V-0级别要求而定，并没有特别的限制。从不牺牲固化产物的耐热性、介电性能、吸湿性方面考虑，以成分(A)+(B)为100重量份计，所述阻燃剂的用量为5～80重量份，例如5重量份、8重量份、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重量份或80重量份，优选为10～60重量份，更优选为15～40重量份。当阻燃剂添加量不足时，无法达到很好的阻燃效果；当阻燃剂添加量大于80份时，会带来体系的耐热性下降、吸水率增加的风险，另外体系的介电性能也会被恶化。
优选地，所述热固性树脂组合物还包含为了解决某些问题而引进的添加剂，所述添加剂为抗氧化剂、热稳定剂、光稳定剂、增塑剂、润滑剂、流动改性剂、防滴剂、防粘连剂、抗静电剂、流动促进剂、加工助剂、基板粘合剂、脱模剂、增韧剂、低收缩添加剂或应力消除添加剂中的一种或至少两种的组合。
在本发明所述的热固性树脂组合物中，所述添加剂的用量无特别限定，以成分(A)+(B)为100重量份计，所述添加剂的用量优选为0.1～10重量份，例如0.1重量份、0.5重量份、0.8重量份、1重量份、2重量份、3重量份、4 重量份、5重量份、6重量份、7重量份、8重量份、9重量份或10重量份，更优选为0.5～8重量份，进一步优选为1～5重量份。
另一方面，本发明提供了如上所述的热固性树脂组合物的制备方法，所述制备方法可以采用公知的方法来配合、搅拌、混合所述的可溶性多官能乙烯基芳香族共聚物、烯烃树脂、自由基引发剂、粉末填料，以及各种阻燃剂、各种添加剂，来制备。
另一方面，本发明提供一种树脂胶液，其是将如上所述的树脂组合物溶解或分散在溶剂中得到。
作为本发明中的溶剂，没有特别限定，作为具体例，可以举出甲醇、乙醇、丁醇等醇类，乙基溶纤剂、丁基溶纤剂、乙二醇-甲醚、卡必醇、丁基卡必醇等醚类，丙酮、丁酮、甲基乙基甲酮、甲基异丁基甲酮、环己酮等酮类，甲苯、二甲苯、均三甲苯等芳香族烃类，乙氧基乙基乙酸酯、醋酸乙酯等酯类，N，N-二甲基甲酰胺、N，N-二甲基乙酰胺、N-甲基-2-吡咯烷酮等含氮类溶剂。上述溶剂可以单独使用一种，也可以两种或者两种以上混合使用，优选甲苯、二甲苯、均三甲苯等芳香族烃类溶剂与丙酮、丁酮、甲基乙基甲酮、甲基异丁基甲酮、环己酮等酮类熔剂混合使用。所述溶剂的使用量本领域技术人员可以根据自己的经验来选择，使得到的树脂胶液达到适于使用的粘度即可。
在如上所述的树脂组合物溶解或分散在溶剂的过程中，可以添加乳化剂。通过乳化剂进行分散，可以使粉末填料等在胶液中分散均匀。
另一方面，本发明提供一种半固化片，所述半固化片包括基材及通过含浸干燥后附着于基材上的如上所述热固性树脂组合物。
本发明所述半固化片也可称之为预浸料，其也可以是将如上所述的树脂胶液浸渍基材，而后对其进行加热烘干以除去有机溶剂并部分固化基材内的树脂 组合物，便得到半固化片。在本发明中所述基材也可以称之为增强材料。
优选地，所述基材为有机纤维、碳纤维或无机纤维制得的纺织物或无纺织物。
优选地，所述有机纤维包括芳纶纤维，如杜邦公司的Kevlar纤维。
对无机纤维制得纺织物或无纺织物无特别的限定，优选地，所述无机纤维制得纺织物或无纺织物的成分中包含有重量比50～99.9％(例如50％、55％、58％、60％、65％、70％、75％、80％、85％、88％、90％、95％或99％)的SiO2、重量比0～30％(例如0％、5％、10％、15％、20％、25％或30％)的CaO、重量比0～20％(例如0％、5％、10％、15％或20％)的Al2O3、重量比0～25％(例如0％、5％、10％、15％、20％或25％)的B2O3、及重量比0～5％(例如0％、0.5％、1％、2％、3％、4％或5％)的MgO，并不局限于以上组分。优选地，所述基材(增强材料)优选为编制纤维布，可选为E-Glass、T-Glass、NE-Glass、L-Glass，Q-Glass、D-Glass，特别优选为NE-Glass。对使用的基材的厚度也没有特别的限定。
用来浸渍上述基材的树脂含量，优选为使得半固化中的树脂含量的30质量％或更高，例如30质量％、35质量％、40质量％、50质量％、60质量％或更高。由于基材的介电常数往往要高于树脂组合物，为了降低由这些半固化片制得的层压板的介电常数，树脂组合物成分在半固化片中的含量优选于上述含量。
优选地，以上所述的半固化片的干燥温度为80～200℃，例如80℃、90℃、110℃、120℃、130℃、140℃、150℃、170℃、190℃或200℃等；所述干燥时间为1～30min，例如1min、5min、8min、13min、17min、21min、24min、28min或30min等。
另一方面，本发明提供一种层压板，所述层压板包括至少一张如上所述的半固化片。
另一方面，本发明提供一种覆金属箔层压板，所述覆金属箔层压板包括一张或至少两张叠合的如上所述的半固化片，以及位于叠合后的半固化片的一侧或两侧的金属箔。
优选地，所述金属箔为铜箔。优选地，所述铜箔为电解铜箔或压延铜箔，其表面粗糙度小于5微米，例如小于4微米、小于3微米、小于2微米、小于1微米、小于0.8微米、小于0.5微米等。可以改善及提高层压板材料在高频高速印制线路板使用的信号损失。
同时，为了提高铜箔半固化片一面的粘合力，进一步优选地，所述铜箔使用硅烷偶联剂进行化学处理，所用的硅烷偶联剂为环氧基硅烷偶联剂、乙烯基硅烷偶联剂或丙烯酸酯基硅烷偶联剂中的一种或至少两种的混合物。
另一方面，本发明提供一种高频高速电路板，所述高频高速电路板包括一张或至少两张叠合的如上所述的半固化片。
具体地，本发明所述高速电路板是通过以下方法制得的：
重叠至少一张如上所述的半固化片，在重叠半固化片的上下两侧放置铜箔，进行层压成型制备得到。所述重叠优选采用自动堆叠操作，从而使工艺操作更加简便。
所述层压成型优选真空层压成型，真空层压成型可以通过真空层压机实现。所述层压的时间为70～120min，例如70min、75min、80min、85min、90min、95min、100min、105min、110min、115min或120min等；所述层压的温度为180～220℃，例如180℃、185℃、190℃、195℃、200℃、205℃、210℃、215℃或220℃；所述层压的压力为20～60kg/cm2，例如20kg/cm2、25kg/cm2、30kg/cm2、35kg/cm2、40kg/cm2、45kg/cm2、50kg/cm2、55kg/cm2、58kg/cm2或60kg/cm2等。
用本发明所述的方法制备出的电子电路基材韧性好，且保持了玻璃化转变温度高、吸水率低、介电性能优异和优异的耐湿热性等优点，非常适合高多层印制电路板加工使用。
此外，为了进一步提高材料在高频高速领域的应用，在本发明的覆铜箔层压板生产中，使用的铜箔，可以选择电解铜箔或压延铜箔，其表面粗糙度小于5微米，可以改善及提高层压板材料在高频高速印制线路板使用的信号损失；同时，为了提高铜箔半固化片一面的粘合力，所述铜箔还可以使用硅烷偶联剂进行化学处理，所用的硅烷偶联剂为环氧基硅烷偶联剂、乙烯基硅烷偶联剂及丙烯酸酯基硅烷偶联剂中的一种或多种的混合物，目的是提供铜箔和基材的结合力，防止在印制线路板使用过程中发生掉线、掉焊盘等风险。
相对于现有技术，本发明具有以下有益效果：
采用本发明所述的烯烃树脂作为可溶性的多官能乙烯基芳香族共聚物的交联剂，树脂组合物固化后交联密度大，可提供电路基板的高玻璃化转变温度；并且明显改善可溶性的多官能乙烯基芳香族共聚物固化后的脆性，所制备的电路基板韧性较佳，改善PCB的钻孔加工性，有利于提高高多层印制电路板的可靠性，此外，所述的烯烃树脂的分子不含极性基团，可保证电路基板低吸水率及优异的介电性能，总之，采用所述的烯烃树脂和可溶性的多官能乙烯基芳香族共聚物的树脂组合物制备的电路基板的韧性好，且保持了高的玻璃化转变温度、低的吸水率、优异的介电特性和耐湿热性等优点，适合高频高速印制线路板领域使用，并适合于多层印制线路板加工。
具体实施方式
下面通过具体实施方式来进一步说明本发明的技术方案。本领域技术人员应该明了，所述实施例仅仅是帮助理解本发明，不应视为对本发明的具体限 制。
制备例1
将乙烯基苯0.481摩尔(68.4mL)、乙基乙烯基苯0.0362摩尔(5.16mL)、1-氯乙烯基苯(40mmol)的二氯乙烷溶液(浓度：0.634mmol/mL)63mL、溴化四正丁基铵(1.5mmol)的二氯乙烷溶液(浓度：0.135mmol/mL)11mL、及二氯乙烷500mL投入到1000mL的烧瓶内，在70℃下添加1.5mmol的SnCl4的二氯乙烷溶液(浓度：0.068mmol/mL)1.5mL，反应时间1小时。通过用氮气进行了发泡的少量甲醇终止聚合反应后，在室温下降反应混合液投入大量的甲醇中，使聚合物析出，用甲醇清洗得到的聚合物，进行过滤、干燥、称量，得到共聚物VOD-A共54.6g(收率49.8wt％)。
所得的聚合物VOD-A的Mw为4180，Mn为2560，Mw/Mn为1.6。通过日本电子制造的JNM-LA600型核磁共振分光装置测得聚合物VOD-A含有52摩尔％来自二乙烯基苯的结构单元，48摩尔％来自乙基乙烯基苯的结构单元。另外可知，共聚物VOD-A中存在茚满结构。茚满结构的存在量相对于全部单体的结构单元的7.5摩尔％。而且，相对于上述通式(a1)及(a2)所示结构单元的总量，通式(a1)所示结构单元的摩尔分数为0.99。
共聚物VOD-A可溶于甲苯、二甲苯、THF、二氯甲烷、二氯乙烷、氯仿，未发现凝胶生成。
制备例2
将乙烯基苯0.481摩尔(68mL)、乙基乙烯基苯0.362摩尔(52mL)、1-氯乙烯基苯(30mmol)的二氯乙烷溶液(浓度：0.634mmol/mL)47mL、氯化四正丁基铵(2.25mmol)的二氯乙烷溶液(浓度：0.035mmol/mL)65mL、及二氯乙烷500mL投入到1000mL的烧瓶内，在70℃下添加1.5mmol的SnCl4的二 氯乙烷溶液(浓度：0.068mmol/mL)22mL，反应时间1小时。通过用氮气进行了发泡的少量甲醇终止聚合反应后，在室温下降反应混合液投入大量的甲醇中，使聚合物析出，用甲醇清洗得到的聚合物，进行过滤、干燥、称量，得到共聚物VOD-B共67.4g(收率61.4wt％)。
所得的聚合物VOD-B的Mw为7670，Mn为3680，Mw/Mn为2.1。通过日本电子制造的JNM-LA600型核磁共振分光装置测得聚合物VOD-B含有51摩尔％来自二乙烯基苯的结构单元，49摩尔％来自乙基乙烯基苯的结构单元。另外可知，共聚物VOD-B中存在茚满结构。茚满结构的存在量相对于全部单体的结构单元的7.5摩尔％。而且，相对于上述通式(a1)及(a2)所示结构单元的总量，通式(a1)所示结构单元的摩尔分数为0.99。
共聚物VOD-B可溶于甲苯、二甲苯、THF、二氯甲烷、二氯乙烷、氯仿，未发现凝胶生成。
制备例3
将乙烯基苯0.0481摩尔(6.84mL)、乙基乙烯基苯0.0362摩尔(5.16mL)、下列通式(a5)
Figure PCTCN2017106830-appb-000004
(式中，R30为异丙基，Py为吡啶基)
所示钴系链转移剂12.0mg及四氢呋喃150ml投入300ml烧瓶中，50℃下再加入 2，2’-偶氮双(2，4-二甲基戊腈)方应72小时。在室温下降反应混合液投入大量的甲醇中，使聚合物析出，用甲醇清洗得到的聚合物，进行过滤、干燥、称量，得到共聚物VOD-C共3.15g(收率28.7wt％)。
所得的聚合物VOD-C含有凝胶，故仅溶于THF溶剂，其Mw为94600，Mn为12800，Mw/Mn为7.4。通过日本电子制造的JNM-LA600型核磁共振分光装置测得聚合物VOD-C含有58摩尔％来自二乙烯基苯的结构单元，42摩尔％来自乙基乙烯基苯的结构单元。另外可知，共聚物VOD-C中不含茚满结构。而且，相对于上述通式(a1)及(a2)所示结构单元的总量，通式(a1)所示结构单元的摩尔分数为0.25。
表1所示为实施例及比较例所用原料。
表1
Figure PCTCN2017106830-appb-000005
实施例1
将80.0重量份的多官能乙烯基芳香族共聚物VOD-A，20.0重量份的苯乙烯-丁二烯共聚物Ricon 100(Sartomer公司，苯乙烯含量25％)，3.0重量份的自由基引发剂DCP，25重量份的溴阻燃剂BT-93W，60重量份的硅微粉S0-C2，溶解于甲苯溶剂中，并调节至适合粘度。用NE-玻纤布(Nittobo，型号2116NE)浸润树脂胶液，过夹轴控制适合单重，并在烘箱中干燥，除去甲苯溶剂，制得2116的半固化片。将6张2116半固化片和12张2116半固化片分别重叠，上下两面配以1OZ厚度的铜箔，在压机中真空层压固化120min，固化压力为50kg/cm2，固化温度为200℃，制得两种厚度规格(6*2116-0.76mm板用于测试综合性能，12*2116-1.52mm厚板用于测试机械性能)的高速电路基板。
测试所制成的铜箔基板的物性，其结果详见表2。
实施例2
如同实施例1的制法，但多官能乙烯基芳香族共聚物VOD-A和苯乙烯-丁二烯共聚物Ricon 100的配比有所变化，由原来重量比80∶20变为50∶50。
测试所制成的铜箔基板的物性，其结果详见表2。
实施例3
如同实施例1的制法，但烯烃树脂的成分，以苯乙烯-丁二烯共聚物Ricon 181(Sartomer公司，苯乙烯含量28％)取代。测试所制成的铜箔基板的物性，其结果详见表2。
实施例4
如同实施例1的制法，但烯烃树脂的成分，以苯乙烯-丁二烯-二乙烯基苯共聚物Ricon 250(Sartomer公司，苯乙烯含量35％)取代。测试所制成的铜箔基板的物性，其结果详见表2。
实施例5
如同实施例4的制法，但多官能乙烯基芳香族共聚物VOD-A和苯乙烯-丁二烯-二乙烯基苯共聚物Ricon 250的配比有所变化，由原来重量比80∶20变为50∶50。
测试所制成的铜箔基板的物性，其结果详见表2。
实施例6
如同实施例1的制法，但多官能乙烯基芳香族共聚物VOD-A和苯乙烯-丁二烯共聚物Ricon 100的配比有所变化，由原来重量比80∶20变为13∶87。
测试所制成的铜箔基板的物性，其结果详见表2。
实施例7
如同实施例1的制法，但多官能乙烯基芳香族共聚物VOD-A和苯乙烯-丁二烯共聚物Ricon 100的配比有所变化，由原来重量比80∶20变为93∶7。测试所制成的铜箔基板的物性，其结果详见表2。
实施例8
如同实施例1的制法，但多官能乙烯基芳香族共聚物VOD-A，以多官能乙烯基芳香族共聚物VOD-B取代。测试所制成的铜箔基板的物性，其结果详见表2。
比较例1
将100重量份的多官能乙烯基芳香族共聚物VOD-A，3.0重量份的自由基引发剂DCP，25重量份的溴阻燃剂BT-93W，60重量份的硅微粉S0-C2，溶解于甲苯溶剂中，并调节至适合粘度。用NE-玻纤布(Nittobo，型号2116NE)浸润树脂胶液，过夹轴控制适合单重，并在烘箱中干燥，除去甲苯溶剂，制得2116的半固化片。将6张2116半固化片和12张2116半固化片分别重叠，上下两面配以1OZ厚度的铜箔，在压机中真空层压固化120min，固化压力为50kg/cm2，固化温度为200℃，制得两种厚度规格(6*2116-0.76mm板用于测试综合性能，12*2116-1.52mm厚板用于测试机械性能)的高速电路基板。测试所制成的铜箔 基板的物性，其结果详见表3。
比较例2
将80.0重量份的多官能乙烯基芳香族共聚物VOD-C，20.0重量份的苯乙烯-丁二烯共聚物Ricon 100(Sartomer公司，苯乙烯含量25％)，3.0重量份的自由基引发剂DCP，25重量份的溴阻燃剂BT-93W，60重量份的硅微粉S0-C2，溶解于四氢呋喃与甲苯的混合溶剂中，并调节至适合粘度。用NE-玻纤布(Nittobo，型号2116NE)浸润树脂胶液，过夹轴控制适合单重，并在烘箱中干燥，除去甲苯溶剂，制得2116的半固化片。将6张2116半固化片和12张2116半固化片分别重叠，上下两面配以1OZ厚度的铜箔，在压机中真空层压固化120min，固化压力为50kg/cm2，固化温度为200℃，制得两种厚度规格(6*2116-0.76mm板用于测试综合性能，12*2116-1.52mm厚板用于测试机械性能)的高速电路基板。
测试所制成的铜箔基板的物性，其结果详见表3。
比较例3
将48重量份的多官能乙烯基芳香族共聚物VOD-A，12重量份的乙烯基改性聚苯醚树脂OPE-2ST-1，40重量份的氢化苯乙烯丁二烯嵌段共聚物H1041，3.0重量份的自由基引发剂DCP，25重量份的溴阻燃剂BT-93W，60重量份的硅微粉S0-C2，溶解于甲苯溶剂中，并调节至适合粘度。用NE-玻纤布(Nittobo，型号2116NE)浸润树脂胶液，过夹轴控制适合单重，并在烘箱中干燥，除去甲苯溶剂，制得2116的半固化片。将6张2116半固化片和12张2116半固化片分别重叠，上下两面配以1OZ厚度的铜箔，在压机中真空层压固化120min，固化压力为50kg/cm2，固化温度为200℃，制得两种厚度规格(6*2116-0.76mm板用于测试综合性能，12*2116-1.52mm厚板用于测试机械性能)的高速电路基板。测试所制成的铜箔基板的物性，其结果详见表3。
比较例4
将80重量份的多官能乙烯基芳香族共聚物VOD-A，20重量份的端(甲基)丙烯酰基的笼型倍半硅氧烷A，3.0重量份的自由基引发剂DCP，25重量份的溴阻燃剂BT-93W，60重量份的硅微粉S0-C2，溶解于甲苯溶剂中，并调节至适合粘度。用NE-玻纤布(Nittobo，型号2116NE)浸润树脂胶液，过夹轴控制适合单重，并在烘箱中干燥，除去甲苯溶剂，制得2116的半固化片。将6张2116半固化片和12张2116半固化片分别重叠，上下两面配以1OZ厚度的铜箔，在压机中真空层压固化120min，固化压力为50kg/cm2，固化温度为200℃，制得两种厚度规格(6*2116-0.76mm板用于测试综合性能，12*2116-1.52mm厚板用于测试机械性能)的高速电路基板。测试所制成的铜箔基板的物性，其结果详见表3。
比较例5
将80.0重量份的多官能乙烯基芳香族共聚物VOD-A，20.0重量份的苯乙烯-丁二烯共聚物D4272(Kraton公司，苯乙烯含量53％)，3.0重量份的自由基引发剂DCP，25重量份的溴阻燃剂BT-93W，60重量份的硅微粉S0-C2，溶解于甲苯溶剂中，并调节至适合粘度。用NE-玻纤布(Nittobo，型号2116NE)浸润树脂胶液，过夹轴控制适合单重，并在烘箱中干燥，除去甲苯溶剂，制得2116的半固化片。将6张2116半固化片和12张2116半固化片分别重叠，上下两面配以1OZ厚度的铜箔，在压机中真空层压固化120min，固化压力为50kg/cm2，固化温度为200℃，制得两种厚度规格(6*2116-0.76mm板用于测试综合性能，12*2116-1.52mm厚板用于测试机械性能)的高速电路基板。
测试所制成的铜箔基板的物性，其结果详见表3。
比较例6
如同比较例5的制法，但烯烃树脂的成分，以马来酸酐化的聚丁二烯Ricon  130MA8(Sartomer公司，苯乙烯含量35％)取代。测试所制成的铜箔基板的物性，其结果详见表3。
表2
Figure PCTCN2017106830-appb-000006
表3
Figure PCTCN2017106830-appb-000007
Figure PCTCN2017106830-appb-000008
以上特性的测试方法如下：
1)玻璃化转变温度(Tg)：根据动态热机械分析法(DMA)，按照IPC-TM-650 2.4.24.4所规定的DMA方法进行测定层压板的Tg。
2)热分解温度温度(Td-5％loss)：根据热重分析法(TGA)，按照IPC-TM-650 2.4.24.6所规定的TGA方法进行测定层压板的5％热失重时的温度Td。
3)PCT吸水率：将覆铜板表面的铜箔蚀刻后，将基材烘干称量原始重量，再将基板放置压力锅中，在120℃、150KPa条件下，处理两个小时，取出用干布擦干，称量吸水后的样品重量，PCT吸水率为(蒸煮后重量-蒸煮前重量)/蒸煮前重量。
4)介电常数Dk和介电损耗因子Df：根据分离介质柱谐振腔SPDR(Split Post Dielectric Resonator)方法测试，测试频率为10GHz。
5)摆锤冲击强度：使用简支梁非金属材料摆锤式冲击试验机，将约1.6mm的层压板制成120mm*10mm带缺口样品数条(缺口深度2mm)，摆锤以3.8m/s的速度冲击样品，样品断裂后，读取摆锤式冲击试验机的吸收功，最后计算出摆锤冲击强度。
6)落锤冲击韧性：使用落锤冲击仪，冲击仪落锤高度100cm，下落重锤重量为1Kg，韧性好坏评价：十字架清晰，说明产品韧性越好，以字符◎表示；十字架模糊，说明产品的韧性差、脆性大，以字符△表示；十字架清晰程度介于清晰和模糊之间，说明产品的韧性一般，以字符○表示。
7)PCT：将覆铜板表面的铜箔蚀刻后，将基板放置压力锅中，在120℃、150KPa条件下，处理两个小时，后浸渍于288℃的锡炉中，当基材分层时，记录相应时间；当基板在锡炉中超过5min还没出现气泡或分层时即可结束评价。物性分析：
从表2和表3的物性数据对比可知，比较例1中，采用多官能乙烯基芳香族共聚物VOD-A自固化后，基材的玻璃化转变温度较高、电性能较好、吸水率较低，但其韧性极差；比较例2中使用多官能乙烯基芳香族共聚物VOD-C，在该共聚物中相对于通式(a1)及(a2)所示结构单元的总量，通式(a1)所示结构单元的摩尔分数为0.25，即(a1)/[(a1)+(a2)]＝0.25，此时，基材的耐热性降低，并且韧性较差；比较例3中，加入氢化苯乙烯丁二烯嵌段共聚物后，基材的韧性得到一定改善，但玻璃化转变温度明显降低，且出现分层爆板，耐湿热性较差；而比较例4中，引入端(甲基)丙烯酰基的笼型倍半硅氧烷A作为交联剂，由于其极性较大，介电性能较差。比较例5中，使用的苯乙烯-丁二烯共聚物中苯乙烯含量高于50％，导致基材的韧性显著降低；比较例6中，使用马来酸酐化的聚丁二烯Ricon 130MA8，这种聚烯烃树脂具有极性结构，使得其制备得到的基材的介电性能变 差，韧性也有所降低。实施例1～8中采用烯烃树脂(苯乙烯-丁二烯共聚物)作为多官能乙烯基芳香族共聚物VOD-A/VOD-B，固化后基材具有良好的韧性，且保持了其高的玻璃化转变温度、低的吸水率、优异的介电特性和耐湿热性。
如上所述，与一般的层压板相比，本发明的电路基板具有良好的韧性，且保持了其高的玻璃化转变温度、低的吸水率、优异的介电特性和耐湿热性。
申请人声明，本发明通过上述实施例来说明本发明的热固性树脂组合物及使用其制作的半固化片与覆铜箔层压板，但本发明并不局限于上述实施例，即不意味着本发明必须依赖上述实施例才能实施。所属技术领域的技术人员应该明了，对本发明的任何改进，对本发明产品各原料的等效替换及辅助成分的添加、具体方式的选择等，均落在本发明的保护范围和公开范围之内。

Claims (10)

  1. 一种热固性树脂组合物，其特征在于，所述热固性树脂组合物包括(A)成分：溶剂可溶性的多官能乙烯基芳香族共聚物，该共聚物是具有来自于包括二乙烯基芳香族化合物(a)及乙基乙烯基芳香族化合物(b)的单体的结构单元的多官能乙烯基芳香族共聚物，含有大于等于20摩尔％来自于二乙烯基芳香族化合物(a)的重复单元，且下述式(a1)及(a2)所示的来自二乙烯基芳香族化合物(a)的含有乙烯基的结构单元的摩尔分数满足(a1)/[(a1)+(a2)]≥0.5，且用凝胶渗透色谱测定的聚苯乙烯换算的数均分子量Mn为600～30000，重均分子量Mw与数均分子量Mn之比Mw/Mn小于等于20.0，
    Figure PCTCN2017106830-appb-100001
    其中，R13为碳原子数6～30的芳香族烃基，R14为碳原子数6～30的芳香族烃基；和
    (B)成分：选自数均分子量为500～10000的含有10～50％重量比的苯乙烯结构的烯烃树脂，且其分子中含有1，2位加成的丁二烯结构。
  2. 根据权利要求1所述的热固性树脂组合物，其特征在于，所述烯烃树脂为丁二烯-苯乙烯共聚物和/或丁二烯-苯乙烯-二乙烯基苯共聚物。
  3. 根据权利要求1或2所述的热固性树脂组合物，其特征在于，在所述热固性树脂组合物中，相对于(A)成分及(B)成分的总和，(A)成分的混配量为10～98wt％，(B)成分的混配量为2～90wt％，优选(A)成分混配量为30～90wt％，(B)成分混配量为10～70wt％；
    优选地，所述可溶性的多官能乙烯基芳香族共聚物的主链骨架中具有下述 通式(a3)所示的茚满结构
    Figure PCTCN2017106830-appb-100002
    其中，W表示饱和或不饱和的脂肪族烃基或芳香族烃基或稠合于苯环的芳香环或取代芳香环，Z为0～4的整数；
    优选地，所述可溶性多官能乙烯基芳香族共聚物的数均分子量Mn为600～10000，最优选为700～5000；
    优选地，所述可溶性多官能乙烯基芳香族共聚物的数均分子量分布Mw/Mn的值小于等于15，更优选为小于等于10，最优选为小于等于5；
    优选地，所述可溶性多官能乙烯基芳香族共聚物的金属离子含量为各金属离子含量之和小于等于500ppm，更优选小于等于100ppm，进一步优选小于等于20ppm，最优选小于等于1ppm。
  4. 根据权利要求1-3中任一项所述的热固性树脂组合物，其特征在于，(A)成分为如下的可溶性多官能乙烯基芳香族共聚物，即，在多官能乙烯基芳香族共聚物中，含有来自乙基乙烯基芳香族化合物(b)以外的单乙烯基芳香族化合物(c)的结构单元。
  5. 根据权利要求1-4中任一项所述的热固性树脂组合物，其特征在于，除了(A)成分和(B)成分外，还含有作为(C)成分的引发剂，以(A)成分+(B)成分为100重量份计算，(C)成分的用量为0.1～10重量份，优选为0.5～8重量份，进一步优选为1～5重量份；
    优选地，所述(C)成分引发剂的半衰期温度t1/2不小于130℃；所述引发剂为自由基引发剂；
    优选地，所述引发剂选自过氧化二异丙苯、过氧化苯甲酸叔丁酯、2，5-二(2-乙基己酰过氧)-2，5-二甲基己烷、二-(叔丁基过氧异丙基)苯、过氧化(2，4-二氯苯甲酰)、2，5-二甲基-2，5-双(叔丁基过氧)己烷、过氧化-2-乙基己基碳酸叔丁酯、2，5-二甲基-2，5-双(叔丁基过氧)-3-己炔、4，4-二(叔丁基过氧化)戊酸丁酯、1，1-双(叔丁基过氧化)-3，3，5-三甲基环己烷、3，3，5，7，7-五甲基-1，2，4-三氧杂环庚烷、二叔丁基过氧化物或叔丁基过氧化异丙苯中的一种或至少两种的组合；
    优选地，所述热固性树脂组合物还包括填料，所述填料包括有机填料和/或无机填料；
    优选地，所述无机填料选自结晶型二氧化硅、熔融二氧化硅、球形二氧化硅、空心二氧化硅、玻璃粉、氮化铝、氮化硼、碳化硅、碳化硅铝、氢氧化铝、氢氧化镁、二氧化钛、钛酸锶、钛酸钡、氧化锌、氧化锆、氧化铝、氧化铍、氧化镁、硫酸钡、滑石粉、粘土、硅酸钙、碳酸钙或云母中的一种或至少两种的组合；
    优选地，所述有机填料选自聚四氟乙烯粉末、聚苯硫醚、聚醚酰亚胺、聚苯醚或聚醚砜粉末中的一种或至少两种的组合；
    优选地，所述热固性树脂组合物还包括阻燃剂，所述阻燃剂可以为含溴阻燃剂或无卤阻燃剂；
    优选地，所述含溴阻燃剂为十溴二苯醚、十溴二苯乙烷、乙撑双四溴邻苯二甲酰亚胺或溴化聚碳酸酯中的一种或至少两种的组合；
    优选地，所述无卤阻燃剂为含磷无卤阻燃剂、含氮无卤阻燃剂及含硅无卤阻燃剂中的一种或至少两种的组合；
    优选地，所述无卤阻燃剂为三(2，6-二甲基苯基)膦、10-(2，5-二羟基苯基)-9，10-二氢-9-氧杂-10-膦菲-10-氧化物、2，6-二(2，6-二甲基苯基)膦基苯或10- 苯基-9，10-二氢-9-氧杂-10-膦菲-10-氧化物、苯氧基膦氰化合物、磷酸酯或聚磷酸酯中的一种或至少两种的组合；
    优选地，以成分(A)+(B)为100重量份计，所述阻燃剂的用量为5～80重量份，优选为10～60重量份，更优选为15～40重量份；
    优选地，所述热固性树脂组合物还包含抗氧化剂、热稳定剂、光稳定剂、增塑剂、润滑剂、流动改性剂、防滴剂、防粘连剂、抗静电剂、流动促进剂、加工助剂、基板粘合剂、脱模剂、增韧剂、低收缩添加剂或应力消除添加剂中的一种或至少两种的组合。
  6. 一种树脂胶液，其特征在于，其是将如权利要求1-5中任一项所述的树脂组合物溶解或分散在溶剂中得到。
  7. 一种半固化片，其特征在于，所述半固化片包括基材及通过含浸干燥后附着于基材上的如权利要求1-5中任一项所述热固性树脂组合物；
    优选地，所述基材为有机纤维、碳纤维或无机纤维制得的纺织物或无纺织物。
  8. 一种层压板，其特征在于，所述层压板包括至少一张如权利要求7所述的半固化片。
  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一张或至少两张叠合的如权利要求7所述的半固化片，以及位于叠合后的半固化片的一侧或两侧的金属箔。
  10. 一种高频高速电路板，所述高频高速电路板包括一张或至少两张叠合的如权利要求7所述的半固化片。
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