WO2016107066A1 - 一种无卤热固性树脂组合物及使用它的预浸料以及印制电路用层压板 - Google Patents

一种无卤热固性树脂组合物及使用它的预浸料以及印制电路用层压板 Download PDF

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WO2016107066A1
WO2016107066A1 PCT/CN2015/080538 CN2015080538W WO2016107066A1 WO 2016107066 A1 WO2016107066 A1 WO 2016107066A1 CN 2015080538 W CN2015080538 W CN 2015080538W WO 2016107066 A1 WO2016107066 A1 WO 2016107066A1
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weight
parts
halogen
component
resin composition
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PCT/CN2015/080538
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English (en)
French (fr)
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游江
黄天辉
杨中强
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广东生益科技股份有限公司
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Publication of WO2016107066A1 publication Critical patent/WO2016107066A1/zh

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    • 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
    • C08L63/04—Epoxynovolacs
    • 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
    • C08G59/4007—Curing agents not provided for by the groups C08G59/42 - C08G59/66
    • C08G59/4071—Curing agents not provided for by the groups C08G59/42 - C08G59/66 phosphorus containing 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
    • C08G59/62—Alcohols or phenols
    • C08G59/621—Phenols
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J5/00—Manufacture of articles or shaped materials containing macromolecular substances
    • C08J5/24—Impregnating materials with prepolymers which can be polymerised in situ, e.g. manufacture of prepregs
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K5/00—Use of organic ingredients
    • C08K5/0008—Organic ingredients according to more than one of the "one dot" groups of C08K5/01 - C08K5/59
    • C08K5/0025—Crosslinking or vulcanising agents; including accelerators
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K5/00—Use of organic ingredients
    • C08K5/0008—Organic ingredients according to more than one of the "one dot" groups of C08K5/01 - C08K5/59
    • C08K5/0066—Flame-proofing or flame-retarding additives
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K5/00—Use of organic ingredients
    • C08K5/49—Phosphorus-containing compounds
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K5/00—Use of organic ingredients
    • C08K5/49—Phosphorus-containing compounds
    • C08K5/51—Phosphorus bound to oxygen
    • C08K5/53—Phosphorus bound to oxygen bound to oxygen and to carbon only
    • C08K5/5317—Phosphonic compounds, e.g. R—P(:O)(OR')2
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K5/00—Use of organic ingredients
    • C08K5/49—Phosphorus-containing compounds
    • C08K5/51—Phosphorus bound to oxygen
    • C08K5/53—Phosphorus bound to oxygen bound to oxygen and to carbon only
    • C08K5/5317—Phosphonic compounds, e.g. R—P(:O)(OR')2
    • C08K5/5333—Esters of phosphonic acids
    • 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
    • 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
    • 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
    • C08G59/20—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 epoxy compounds used
    • C08G59/32—Epoxy compounds containing three or more epoxy groups
    • C08G59/3218—Carbocyclic compounds
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J2363/00—Characterised by the use of epoxy resins; Derivatives of epoxy resins
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J2363/00—Characterised by the use of epoxy resins; Derivatives of epoxy resins
    • C08J2363/04—Epoxynovolacs

Definitions

  • the present invention relates to a halogen-free thermosetting resin composition, and to a prepreg made of the halogen-free thermosetting resin composition and a laminate for a printed circuit.
  • the application frequency is constantly increasing.
  • the dielectric constant and dielectric loss values are required to be lower and lower, thus reducing Dk/Df.
  • Conventional FR-4 materials use dicyandiamide as a curing agent.
  • This curing agent has a tertiary reaction amine and has good process operability.
  • due to its weak CN bond it is easily cracked at high temperatures, resulting in a cured product.
  • the thermal decomposition temperature is low and cannot meet the heat resistance requirements of the lead-free process.
  • phenolic resin was used as a curing agent for epoxy in the industry.
  • the phenolic resin has a high-density benzene ring structure, so the heat resistance of the system after curing with epoxy Excellent, but at the same time the dielectric properties of the cured product tend to deteriorate.
  • phosphorus-containing bisphenol can be used as a curing agent for epoxy resin.
  • the reactive group includes hydroxyl groups and phosphorus units at both ends, and the reaction does not produce secondary hydroxyl groups.
  • the cured glass has high glass transition temperature and dielectric properties. Excellent heat resistance.
  • the phosphorus-containing bisphenol has a high phosphorus content, and has a halogen-free flame retardant effect as a curing agent, thereby greatly reducing the amount of the flame retardant added.
  • one of the objects of the present invention is to provide a halogen-free thermosetting resin composition, and a prepreg and a laminate for printed circuit board using the same.
  • the printed circuit board laminate produced by using the resin composition has high glass transition temperature, excellent dielectric properties, low water absorption, high heat resistance, and good processability, and can realize halogen-free flame retardant. UL94V-0.
  • the present inventors conducted intensive studies to achieve the above object, and as a result, found that a halogen-free epoxy resin, a phosphorus-containing bisphenol, a dicyclopentadiene type phenol, a phosphorus-containing flame retardant, and optionally other substances are appropriately mixed.
  • the composition can achieve the above purpose.
  • thermosetting resin composition containing the following four substances as essential components, and the organic solid matter is 100 parts by weight, which comprises:
  • (C) second curing agent biscyclopentadiene type phenolic 5 to 30 parts by weight
  • the halogen-free thermosetting resin composition of the present invention uses a halogen-free epoxy resin having a specific molecular structure, has high functionality and good dielectric properties, and has a high Tg of a cured product and a low water absorption rate.
  • the halogen-free thermosetting resin composition of the present invention uses phosphorus-containing bisphenol as the first curing agent, and the phosphorus-containing bisphenol has high structural symmetry, and the phosphorus in the molecule can react with the secondary hydroxyl group of the epoxy resin, and the cured product has a high Tg.
  • the dielectric properties are excellent; in addition, the phosphorus-containing bisphenol has a high phosphorus content and has a halogen-free flame retardant effect.
  • the halogen-free thermosetting resin composition of the present invention has a dicyclopentadiene type phenol aldehyde as a second curing agent, and fully exerts its points.
  • the present invention utilizes the synergistic effect between the phosphorus-containing bisphenol and the dicyclopentadiene-type phenolic, and can significantly improve the glass transition temperature and heat resistance of the prepreg prepared using the resin composition and the laminate for printed circuit boards. And it has excellent dielectric properties, low water absorption and good processability, and achieves halogen-free flame retardant, reaching UL94V-0.
  • the curing reaction rate of phosphorus-containing bisphenol and epoxy resin is fast, while the curing reaction rate of dicyclopentadiene type phenolic resin and epoxy resin is slow, and the epoxy resin is cured with phosphorus-containing bisphenol and dicyclopentadiene type phenolic compound.
  • the resin makes the curing reaction rate moderate and easy to control, greatly reducing the difficulty of production and processing.
  • the component (A) in the present invention is a halogen-free epoxy resin, and it is preferably used in an amount of 30 to 60 parts by weight, for example, 32 parts by weight, 34 parts by weight, 36 parts by weight, 38 parts by weight, and 40 parts by weight. Parts, 42 parts by weight, 44 parts by weight, 46 parts by weight, 48 parts by weight, 50 parts by weight, 52 parts by weight, 54 parts by weight, 56 parts by weight or 58 parts by weight.
  • the halogen-free epoxy resin comprises bisphenol A epoxy resin, bisphenol F epoxy resin, o-cresol novolac epoxy resin, bisphenol A novolac epoxy resin, trisphenol novolac epoxy resin Any one or a mixture of at least two of a resin, a dicyclopentadiene novolac epoxy resin, a biphenyl type novolac epoxy resin, an alkylbenzene type novolac epoxy resin or a naphthol type novolac epoxy resin.
  • the above epoxy resins are all halogen-free epoxy resins.
  • the halogen-free epoxy resin is selected from the group consisting of epoxy resins having the following structure:
  • X 1 , X 2 and X 3 are each independently selected from or R 1 is selected from a hydrogen atom, a substituted or unsubstituted C1-C5 (e.g., C2, C3 or C4) linear alkyl group or a substituted or unsubstituted C1-C5 (e.g., C2, C3 or C4) branched alkyl group. Any one;
  • Y 1 and Y 2 are each independently selected from a single bond, -CH 2 -, or Any one of them, n 1 is any integer from 1 to 10, such as 2, 3, 4, 5, 6, 7, 8, or 9, and R 2 is selected from a hydrogen atom, a substituted or unsubstituted C1-C5 (for example, A C2, C3 or C4) linear alkyl group or a substituted or unsubstituted C1-C5 (e.g., C2, C3 or C4) branched alkyl group.
  • a substituted or unsubstituted C1-C5 for example, A C2, C3 or C4 linear alkyl group or a substituted or unsubstituted C1-C5 (e.g., C2, C3 or C4) branched alkyl group.
  • the halogen-free thermosetting resin composition of the present invention employs the above-mentioned specific molecular structure halogen-free epoxy resin, which has high functionality and good dielectric properties, and has a high Tg of cured product and low water absorption.
  • the component (B) described in the present invention is a phosphorus-containing bisphenol curing agent.
  • the phosphorus-containing bisphenol has the following structure:
  • n 2 is any integer from 2 to 20, such as 3, 4, 5, 6, 7, 8, 9, 10, 11, 12, 13, 14, 15, 16, 17, 18 or 19, preferably n 2 It is any integer from 3 to 10.
  • the phosphorus-containing bisphenol has a weight average molecular weight of from 1,000 to 6,500, preferably from 1,000 to 4,500, more preferably from 1,000 to 3,000.
  • the weight average molecular weight is less than 1000, the cured product has a low Tg and poor heat resistance; when the weight average molecular weight is more than 6,500, the solubility of the phosphorus-containing bisphenol in an organic solvent is poor, and cannot be obtained.
  • a good and uniform glue is difficult to meet the process requirements of the copper clad laminate.
  • the phosphorus-containing bisphenol is preferably added in an amount of 5 to 30 parts by weight, for example, 6 parts by weight, 7 parts by weight, 9 parts by weight, 11 parts by weight, 12 parts by weight, 13 parts by weight, 15 parts by weight, 17 parts by weight, 18 parts by weight, 19 parts by weight, 21 parts by weight, 23 parts by weight, 24 parts by weight, 25 parts by weight, 27 parts by weight, 29 parts by weight or 30 parts by weight. If the addition is too small, the effect of increasing the glass transition temperature and dielectric properties of the cured product is not significant; if too much is added, the water absorption of the cured product is high.
  • component (C) is the second curing agent dicyclopentadiene type phenol no.
  • the biscyclopentadiene type phenolic resin has the following structure:
  • Z 1 , Z 2 and Z 3 are independently selected from -H, -CH 3 , -C 2 H 5 or -C(CH 3 ) 3 , and n 3 is selected from any integer from 0 to 7, for example 1 , 2, 3, 4, 5 or 6.
  • the component (C) dicyclopentadiene type phenolic curing agent in the present invention is preferably added in an amount of 10 to 30 parts by weight, for example, 5 parts by weight, 7 parts by weight, 8 parts by weight, 9 parts by weight, 11 parts by weight, and 13 parts by weight. 14 parts by weight, 15 parts by weight, 17 parts by weight, 19 parts by weight, 20 parts by weight, 21 parts by weight, 23 parts by weight, 25 parts by weight, 26 parts by weight, 27 parts by weight or 29 parts by weight.
  • the dicyclopentadiene type phenolic structure the dicyclopentadiene ring has excellent dielectric properties but low adhesion and is easy to burn. If the addition is too small, the dielectric properties of the cured product are poor, and the water absorption rate is high. If too much is added, the cured product is cured. Low adhesion and poor flame retardancy.
  • the (D) component described in the present invention that is, the phosphorus-containing flame retardant, imparts flame retardant properties to the resin composition and meets UL 94V-0 requirements.
  • the amount of the flame retardant added is not particularly limited as long as the flame retardancy of the cured product reaches the UL 94V-0 level.
  • the component (D) phosphorus-containing flame retardant is added in an amount of 5 to 50 parts by weight, for example, 6 parts by weight, 11 parts by weight, 16 parts by weight, 21 parts by weight, and 26 parts by weight, based on 100 parts by weight. 31 parts by weight, 36 parts by weight, 41 parts by weight or 46 parts by weight, preferably 10 to 30 parts by weight.
  • the phosphorus-containing flame retardant is tris(2,6-dimethylphenyl)phosphine, 10-(2,5-dihydroxyphenyl)-9,10-dihydro-9-oxa- 10-phosphinophen-10-oxide, 2,6-bis(2,6-dimethylphenyl)phosphinobenzene, 10-phenyl-9,10-dihydro-9-oxa-10-phosphine Any one or a mixture of at least two of a phenanthrene-10-oxide, a phenoxyphosphazene compound, a phosphate, a polyphosphate, a polyphosphonate or a phosphonate-carbonate copolymer.
  • the halogen-free thermosetting resin composition of the present invention further comprises a component (E) curing accelerator, and the curing accelerator is not particularly limited as long as it can catalyze an epoxy functional group reaction and lower the reaction temperature of the curing system.
  • a component (E) curing accelerator is not particularly limited as long as it can catalyze an epoxy functional group reaction and lower the reaction temperature of the curing system.
  • a mixture of an imidazole compound, a derivative of an imidazole compound, a piperidine compound, a Lewis acid or a triphenylphosphine, or a mixture of at least two is preferable.
  • the imidazole compound may, for example, be any one of a mixture of 2-methylimidazole, 2-ethyl-4-methylimidazole, 2-phenylimidazole or 2-undecylimidazole or a mixture of at least two.
  • the piperidine compound may, for example, be 2,3-diaminopiperidine, 2,5-diaminopiperidine, 2,6-diaminopiperidine, 2-amino-3-methylpiperidine or 2-amino Any one or at least -4-methylpiperidine, 2-amino-3-nitropiperidine, 2-amino-5-nitropiperidine or 2-amino-4,4-dimethylpiperidine a mixture of two.
  • the addition of the component (A) curing accelerator is based on 100 parts by weight of the sum of the addition amounts of the component (A), the component (B), the component (C) and the component (D).
  • the amount is 0.01 to 1 part by weight, for example, 0.05 part by weight, 0.1 part by weight, 0.15 part by weight, 0.2 part by weight, 0.25 part by weight, 0.3 part by weight, 0.35 part by weight, 0.4 part by weight, 0.45 part by weight, 0.5 part by weight, 0.55.
  • Parts by weight 0.6 parts by weight, 0.65 parts by weight, 0.7 parts by weight, 0.75 parts by weight, 0.8 parts by weight, 0.85 parts by weight, 0.9 parts by weight or 0.95 parts by weight, preferably 0.05 to 0.8 parts by weight, further preferably 0.05 to 0.6 parts by weight.
  • the halogen-free thermosetting resin composition of the present invention further comprises a component (F) filler, and the filler is as needed
  • the amount of addition is not particularly limited, and the filler is selected from the group consisting of an organic filler and an inorganic filler, preferably an inorganic filler, further preferably a surface-treated inorganic filler, and most preferably a surface-treated silica.
  • the surface-treated surface treatment agent is selected from any one or a mixture of at least two of a silane coupling agent, a silicone oligomer, or a titanate coupling agent.
  • the surface treatment agent is used in an amount of 0.1 to 5.0 parts by weight, such as 0.4 parts by weight, 0.8 parts by weight, 1.2 parts by weight, 1.6 parts by weight, 2 parts by weight, 2.4 parts by weight, and 2.8 parts by weight based on 100 parts by weight of the inorganic filler.
  • Parts, 3.2 parts by weight, 3.6 parts by weight, 4 parts by weight, 4.4 parts by weight or 4.8 parts by weight preferably 0.5 to 3.0 parts by weight, more preferably 0.75 to 2.0 parts by weight.
  • the inorganic filler is selected from any one of a non-metal oxide, a metal nitride, a non-metal nitride, an inorganic hydrate, an inorganic salt, a metal hydrate or an inorganic phosphorus or a mixture of at least two, preferably molten Silica, crystalline silica, spherical silica, hollow silica, aluminum hydroxide, alumina, talc, aluminum nitride, boron nitride, silicon carbide, barium sulfate, barium titanate, titanium A mixture of one or at least two of acid strontium, calcium carbonate, calcium silicate or mica.
  • the organic filler is selected from any one or a mixture of at least two of polytetrafluoroethylene powder, polyphenylene sulfide or polyethersulfone powder.
  • the shape and particle diameter of the filler are not particularly limited, and it is preferable that the filler has a median diameter of 0.01 to 50 ⁇ m, for example, 1 ⁇ m, 6 ⁇ m, 11 ⁇ m, 16 ⁇ m, 21 ⁇ m, 26 ⁇ m, 31 ⁇ m, 36 ⁇ m, 41 ⁇ m or 46 ⁇ m.
  • it is 0.01 to 20 ⁇ m, further preferably 0.1 to 10 ⁇ m, and the filler of such a particle size range is more easily dispersed in the gum solution.
  • the addition amount of the component (F) filler is also not particularly limited, and the sum of the addition amounts of the component (A), the component (B), the component (C), and the component (D) is 100 parts by weight.
  • the component (F) filler is added in an amount of 5 to 300 parts by weight, for example, 10 parts by weight, 30 parts by weight, 50 parts by weight, 70 parts by weight, 90 parts by weight, 110 parts by weight, 130 parts by weight, 150 parts by weight, 170 parts by weight, 190 parts by weight, 210 parts by weight, 230 parts by weight, 250 parts by weight, 270 parts by weight or 290 parts by weight, preferably 5 to 200 parts by weight Further, it is preferably 5 to 150 parts by weight.
  • the halogen-free thermosetting resin composition may further contain various additives, and specific examples thereof include an antioxidant, a heat stabilizer, an antistatic agent, an ultraviolet absorber, a pigment, a colorant, a lubricant, and the like. These various additives may be used singly or in combination of two or more kinds.
  • the halogen-free thermosetting resin composition of the present invention is conventionally prepared by first placing a solid substance, then adding a liquid solvent, stirring until the solid substance is completely dissolved, and then adding a liquid resin and a promoter, and continuing to stir uniformly.
  • 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, and cyclohexanone; aromatic hydrocarbons such as toluene and xylene; esters such as ethyl acetate and ethoxyethyl acetate
  • a nitrogen-containing solvent such as N,N-dimethylformamide or N,N-dimethylacetamide.
  • the above solvents may be used singly or in combination of two or more. Preference is given to ketones such as acetone, methyl ethyl ketone, methyl ethyl ketone and cyclohexanone.
  • the amount of the solvent to be added is selected by those skilled in the art based on his own experience, so that the resin glue can reach a viscosity suitable for use.
  • Another object of the present invention is to provide a prepreg comprising a reinforcing material and a halogen-free thermosetting resin composition as described above adhered thereto by dipping and drying.
  • the reinforcing material to be used is not particularly limited and may be an organic fiber, an inorganic fiber woven cloth or a nonwoven fabric.
  • the organic fiber may be selected from aramid nonwoven fabric, and the inorganic fiber woven fabric may be E- Fiberglass cloth, D-glass fiber cloth, S-glass fiber cloth, T glass fiber cloth, NE-glass fiber cloth or quartz cloth.
  • the thickness of the reinforcing material is not particularly limited, and the thickness of the woven fabric and the nonwoven fabric is preferably 0.01 to 0.2 mm, and preferably the fiber-opening treatment and the silane coupling agent are considered.
  • the silane coupling agent is preferably any one or at least two of an epoxy silane coupling agent, an amino silane coupling agent or a vinyl silane coupling agent.
  • the prepreg is obtained by impregnating the above-mentioned halogen-free thermosetting resin composition by baking at 100 to 250 ° C for 1 to 15 minutes.
  • a third object of the present invention is to provide a laminate comprising at least one prepreg as described above.
  • the laminate is obtained by bonding at least one prepreg together by heat and pressure.
  • the laminate is obtained by curing in a hot press at a curing temperature of 150 ° C to 250 ° C and a curing pressure of 10 to 60 kg / cm 2 .
  • a fourth object of the present invention is to provide a halogen-free high-frequency circuit substrate comprising at least one prepreg as described above and a metal foil covering one side or both sides of the laminated prepreg.
  • the metal foil is copper foil, nickel foil, aluminum foil, SUS foil, etc., and the material thereof is not limited.
  • the present invention has the following beneficial effects:
  • the halogen-free thermosetting resin composition of the present invention uses phosphorus-containing bisphenol as the first curing agent, and the phosphorus-containing bisphenol has high structural symmetry, and the phosphorus in the molecule can react with the secondary hydroxyl group of the epoxy resin, and the cured product has a high Tg.
  • the dielectric properties are excellent; in addition, the phosphorus-containing bisphenol has a high phosphorus content and has a halogen-free flame retardant effect.
  • the halogen-free thermosetting resin composition of the present invention has a dicyclopentadiene type phenol aldehyde as a second curing agent, and has an advantage of having a large dicyclopentadiene structure in its molecule and having a low dielectric property and a low water absorption rate.
  • the water absorption rate of the cured product is greatly reduced without sacrificing the Tg of the cured product and the dielectric properties.
  • the invention utilizes the synergistic effect between the phosphorus-containing bisphenol and the dicyclopentadiene type phenolic resin, and can Significantly improve the glass transition temperature and heat resistance of the prepreg prepared by using the resin composition and the laminate for printed circuit, and have excellent dielectric properties, low water absorption, and good processability, and are realized Halogen-free flame retardant, reaching UL94V-0.
  • the prepreg, printed circuit board laminate prepared using the resin composition has high glass transition temperature, excellent dielectric properties, high heat resistance, low water absorption rate, and realizes halogen-free flame retardancy, and is flame-retardant. Can reach UL94V-0 level.
  • the glass transition temperature, dielectric constant, dielectric loss factor, peel strength, and water absorption were tested for the printed circuit board laminate (8 prepregs, reinforcing material type 2116, thickness 0.08 mm).
  • the properties such as heat resistance, flame retardancy and the like are further described and described in detail in the following examples.
  • the structure is as follows:
  • Fused silica (average particle size 1 to 10 ⁇ m, purity 99% or more)
  • Tg Glass transition temperature: Measured according to the differential scanning calorimetry (DSC) according to the DSC method specified in IPC-TM-650 2.4.25.
  • the dielectric loss and dielectric loss factor at 1 GHz were measured in accordance with IPC-TM-650 2.5.5.5.
  • the peel strength of the metal cap layer was tested in accordance with the experimental conditions of "after thermal stress" in the IPC-TM-650 2.4.8 method.
  • the stratified foaming time was observed according to IPC-TM-650 2.4.13.1.
  • Comparative Example 1 and Comparative Example 7 From the physical property data of Table 1, Table 2, and Table 3, it was found that in Comparative Example 1 and Comparative Example 7, the dicyclopentadiene type epoxy resin was separately cured using phosphorus-containing bisphenol, and the obtained laminate had a high Tg and dielectric properties and peeling. It is excellent in strength and flame retardancy, but has high water absorption and poor heat resistance.
  • Comparative Example 2 and Comparative Example 8 a dicyclopentadiene type epoxy resin was separately cured using a dicyclopentadiene type phenol aldehyde, and the obtained laminate Tg was high.
  • the ratio is high and the heat resistance is poor; in the comparative example 8, the dicyclopentadiene type epoxy resin is separately cured with the dicyclopentadiene type phenol aldehyde, and the obtained laminate has a high glass transition temperature, a good dielectric property, and a low water absorption rate. Good heat resistance, but peel strength Lower and poor flame retardancy.
  • Examples 1-8 are mainly composed of a halogen-free epoxy resin, and after co-curing using phosphorus-containing bisphenol and dicyclopentadiene-type phenolic, the obtained laminate has high glass transition temperature, excellent dielectric properties, and high heat resistance. It has low water absorption and achieves halogen-free flame retardant, and its flame retardant can reach UL94V-0.
  • the laminate for printed circuit of the present invention has a higher glass transition temperature, more excellent dielectric properties, moisture resistance, and heat resistance than a general laminate, and is suitable for use in a high frequency field.
  • the halogen content can meet the V-0 standard in the flame retardancy test UL94 within the requirements of the JPCA halogen-free standard, and it has environmental protection effects.

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Abstract

本发明涉及一种无卤热固性树脂组合物及使用它的预浸料及印制电路用层压板。所述无卤热固性树脂组合物，有机固化物按100重量份计，包含(A)无卤环氧树脂30～60重量份；(B)第一固化剂：含磷双酚5～30重量份；(C)第二固化剂：双环戊二烯型酚醛5～30重量份；(D)含磷阻燃剂。本发明所提供的无卤热固性树脂组合物制成的预浸料及印制电路用层压板，具有高玻璃化转变温度、优异的介电性能、低吸水率、高耐热性和良好的工艺加工性，并能实现无卤阻燃，达到UL94V-0。

Description

一种无卤热固性树脂组合物及使用它的预浸料以及印制电路用层压板 技术领域
本发明涉及一种无卤热固性树脂组合物，还涉及该无卤热固性树脂组合物制成的预浸料及印制电路用层压板。
背景技术
传统的印制电路用层压板通常采用溴系阻燃剂来实现阻燃，特别是采用四溴双酚A型环氧树脂，这种溴化环氧树脂具有良好的阻燃性，但它在燃烧时会产生溴化氢气体。此外，近年来在含溴、氯等卤素的电子电气设备废弃物的燃烧产物中已检测出二噁英、二苯并呋喃等致癌物质，因此溴化环氧树脂的应用受到限制。2006年7月1日，欧盟的两份环保指令《关于报废电气电子设备指令》和《关于在电气电子设备中限制使用某些有害物质指令》正式实施，无卤阻燃覆铜箔层压板的开发成为业界的热点，各覆铜箔层压板厂家都纷纷推出自己的无卤阻燃覆铜箔层压板。
同时随着消费电子产品信息处理的高速化和多功能化，应用频率不断提高，除了环保的要求越来越高外，要求介电常数和介电损耗值越来越低，因此降低Dk/Df已成为基板业者的追逐热点。传统的FR-4材料多采用双氰胺作为固化剂，这种固化剂具有三级反应胺，具有良好的工艺操作性，但由于其C-N键较弱，在高温下容易裂解，导致固化物的热分解温度较低，无法满足无铅制程的耐热要求。在此背景下，随着2006年无铅工艺的大范围实施，行内开始采用酚醛树脂作为环氧的固化剂，酚醛树脂具有高密度的苯环结构，所以和环氧固化后体系的耐热性优异，但同时固化物的介电性能有被恶化的趋势。
发明内容
经发明人研究发现，含磷双酚可用作环氧树脂的固化剂，反应基团包括两端羟基和磷单元，且反应不产生二次羟基，固化物玻璃化转变温度高、介电性能和耐热性优异。此外，含磷双酚磷含量高，在用作固化剂的同时还有无卤阻燃的功效，大大地降低了阻燃剂的添加量。
基于此，本发明的目的之一在于提供一种无卤热固性树脂组合物，以及使用它的预浸料和印制电路用层压板。使用该树脂组合物制作的印制电路用层压板具有高玻璃化转变温度、优异的介电性能、低吸水率、高耐热性和良好的工艺加工性，并能实现无卤阻燃，达到UL94V-0。
本发明人为实现上述目的，进行了反复深入的研究，结果发现：将无卤环氧树脂、含磷双酚、双环戊二烯型酚醛、含磷阻燃剂及任选地其他物质适当混合得到的组合物，可达到上述目的。
即，本发明采用如下技术方案：一种无卤热固性树脂组合物，含有以下四种物质作为必要组分，有机固形物按100重量份计，其包含：
(A)无卤环氧树脂：30～60重量份；
(B)第一固化剂：含磷双酚5～30重量份；
(C)第二固化剂：双环戊二烯型酚醛5～30重量份；
(D)含磷阻燃剂。
本发明的无卤热固性树脂组合物采用了特定分子结构的无卤环氧树脂，具有较高的官能度和良好的介电性能，其固化物Tg较高，吸水率低。
本发明的无卤热固性树脂组合物以含磷双酚为第一固化剂，该含磷双酚结构对称性高，且分子中的磷可以与环氧树脂的二次羟基反应，固化物Tg高、介电性能优异；此外，该含磷双酚磷含量高，有无卤阻燃的功效。此外，本发明的无卤热固性树脂组合物以双环戊二烯型酚醛为第二固化剂，充分发挥了其分 子中有较多双环戊二烯结构从而介电性能优异吸水率低的优势，在不牺牲固化物Tg、介电性能前提下大大降低固化物吸水率。本发明利用含磷双酚和双环戊二烯型酚醛两者之间的协同效应，可以显著提高使用该树脂组合物制作的预浸料以及印制电路用层压板的玻璃化温度和耐热性，并使其具有优异的介电性能、低吸水率以及良好的工艺加工性，并实现无卤阻燃，达到UL94V-0。此外，含磷双酚与环氧树脂的固化反应速率快，而双环戊二烯型酚醛与环氧树脂的固化反应速率缓慢，同时用含磷双酚和双环戊二烯型酚醛复合固化环氧树脂使得固化反应速率适中容易控制，大大降低了生产和加工工艺的难度。
下面对各组分进行详细说明。
本发明中的组分(A)，即为无卤环氧树脂，使用量建议为30到60重量份为宜，例如为32重量份、34重量份、36重量份、38重量份、40重量份、42重量份、44重量份、46重量份、48重量份、50重量份、52重量份、54重量份、56重量份或58重量份。
优选地，所述无卤环氧树脂包括双酚A型环氧树脂、双酚F型环氧树脂、邻甲酚酚醛环氧树脂、双酚A型酚醛环氧树脂、三酚型酚醛环氧树脂、双环戊二烯酚醛环氧树脂、联苯型酚醛环氧树脂、烷基苯型酚醛环氧树脂或萘酚型酚醛环氧树脂中的任意一种或至少两种的混合物。上述环氧树脂均为无卤的环氧树脂。
优选地，所述无卤环氧树脂选自具有如下结构的环氧树脂：
Figure PCTCN2015080538-appb-000001
其中，X1、X2和X3各自独立地选自
Figure PCTCN2015080538-appb-000002
或
Figure PCTCN2015080538-appb-000003
R1选自氢原子、取代或未取代的C1-C5(例如C2、C3或C4)直链烷基或者取代或未取代的C1-C5(例如C2、C3或C4)支链烷基中的任意一种；
Y1和Y2各自独立地选自单键、-CH2-、
Figure PCTCN2015080538-appb-000004
Figure PCTCN2015080538-appb-000005
或
Figure PCTCN2015080538-appb-000006
中的任意一种，n1为1～10的任意整数，例如2、3、4、5、6、7、8或9，R2选自氢原子、取代或未取代的C1-C5(例如C2、C3或C4)直链烷基或者取代或未取代的C1-C5(例如C2、C3或C4)支链烷基中的任意一种。
本发明无卤热固性树脂组合物采用上述特定分子结构的无卤环氧树脂，其具有较高的官能度和良好的介电性能，其固化物Tg较高，吸水率低。
本发明中所述的(B)组分，即为含磷双酚固化剂。
优选地，所述含磷双酚具有如下结构：
Figure PCTCN2015080538-appb-000007
其中，n2为2～20的任意整数，例如3、4、5、6、7、8、9、10、11、12、13、14、15、16、17、18或19，优选n2为3～10的任意整数。
优选地，所述含磷双酚的重均分子量为1000～6500，优选为1000～4500，进一步优选为1000～3000。当重均分子量小于1000时，固化物Tg低、耐热性差；当重均分子量大于6500时，所述含磷双酚在有机溶剂中的溶解性较差，无法得 到良好和均一的胶液，从而难以满足覆铜板的工艺要求。
本发明中含磷双酚建议添加量为5～30重量份，例如6重量份、7重量份、9重量份、11重量份、12重量份、13重量份、15重量份、17重量份、18重量份、19重量份、21重量份、23重量份、24重量份、25重量份、27重量份、29重量份或30重量份。若添加过少，提高固化物玻璃化转变温度和介电性能的效果不明显；若添加过多，固化物吸水率较高。
本发明中组分(C)即为第二固化剂双环戊二烯型酚醛。
优选地，所述的双环戊二烯型酚醛树脂具有如下结构：
Figure PCTCN2015080538-appb-000008
式中，Z1、Z2和Z3独立地选自-H、-CH3、-C2H5或-C(CH3)3，n3选自0～7中的任意整数，例如1、2、3、4、5或6。
本发明中组分(C)双环戊二烯型酚醛固化剂建议添加量为10～30重量份，例如5重量份、7重量份、8重量份、9重量份、11重量份、13重量份、14重量份、15重量份、17重量份、19重量份、20重量份、21重量份、23重量份、25重量份、26重量份、27重量份或29重量份。双环戊二烯型酚醛结构中双环戊二烯环介电性能优异但粘合力低且易燃烧，若添加过少则固化物介电性能较差，吸水率高，若添加过多则固化物粘合力低，阻燃性较差。
本发明中所述的(D)组分，即含磷阻燃剂，使树脂组合物具有阻燃特性，符合UL 94V-0要求。阻燃剂的添加量根据固化物阻燃性达到UL 94V-0级别要求而定，并没有特别的限制。优选地，以组分(A)、组分(B)和组分(C)的 添加量之和为100重量份计，组分(D)含磷阻燃剂的添加量为5-50重量份，例如6重量份、11重量份、16重量份、21重量份、26重量份、31重量份、36重量份、41重量份或46重量份，优选10～30重量份。
优选地，所述含磷阻燃剂为三(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、10-苯基-9，10-二氢-9-氧杂-10-膦菲-10-氧化物、苯氧基磷腈化合物、磷酸酯、聚磷酸酯、聚膦酸酯或膦酸酯-碳酸酯共聚物中的任意一种或者至少两种的混合物。
优选地，本发明的无卤热固性树脂组合物还包括组分(E)固化促进剂，所述固化促进剂没有特别的限定，只要能催化环氧官能团反应并降低固化体系的反应温度即可，优选咪唑类化合物、咪唑类化合物的衍生物、哌啶类化合物、路易斯酸或三苯基膦中的任意一种或至少两种的混合物。所述咪唑类化合物可以列举有2-甲基咪唑、2-乙基-4-甲基咪唑、2-苯基咪唑或2-十一烷基咪唑中的任意一种或至少两种的混合物。所述哌啶类化合物可以列举有2，3-二氨基哌啶、2，5-二氨基哌啶、2，6-二氨基哌啶、2-氨基-3-甲基哌啶、2-氨基-4-甲基哌啶、2-氨基-3-硝基哌啶、2-氨基-5-硝基哌啶或2-氨基-4，4-二甲基哌啶中的任意一种或至少两种的混合物。
优选地，以组分(A)、组分(B)、组分(C)和组分(D)的添加量之和为100重量份计，所述组分(E)固化促进剂的添加量为0.01～1重量份，例如0.05重量份、0.1重量份、0.15重量份、0.2重量份、0.25重量份、0.3重量份、0.35重量份、0.4重量份、0.45重量份、0.5重量份、0.55重量份、0.6重量份、0.65重量份、0.7重量份、0.75重量份、0.8重量份、0.85重量份、0.9重量份或0.95重量份，优选0.05～0.8重量份，进一步优选0.05～0.6重量份。
优选地，本发明的无卤热固性树脂组合物还包括组分(F)填料，填料视需 要添加，添加量并没有特别的限定，所述填料选自有机填料和无机填料，优选无机填料，进一步优选经过表面处理的无机填料，最优选经过表面处理的二氧化硅。
所述表面处理的表面处理剂选自硅烷偶联剂、有机硅低聚物或钛酸酯偶联剂中的任意一种或至少两种的混合物。
以无机填料为100重量份计，所述表面处理剂的用量为0.1～5.0重量份，例如0.4重量份、0.8重量份、1.2重量份、1.6重量份、2重量份、2.4重量份、2.8重量份、3.2重量份、3.6重量份、4重量份、4.4重量份或4.8重量份，优选0.5～3.0重量份，更优选0.75～2.0重量份。
优选地，所述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任意一种或者至少两种的混合物，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、硅酸钙或云母中的一种或至少两种的混合物。
优选地，所述有机填料选自聚四氟乙烯粉末、聚苯硫醚或聚醚砜粉末中的任意一种或至少两种的混合物。
优选地，所述填料的形状和粒径无特别的限定，优选所述填料的中位粒径为0.01～50μm，例如1μm、6μm、11μm、16μm、21μm、26μm、31μm、36μm、41μm或46μm，优选0.01～20μm，进一步优选0.1～10μm，这种粒径范围的填料在胶液中更容易分散。
此外，组分(F)填料的添加量也无特别的限定，以组分(A)、组分(B)、组分(C)和组分(D)的添加量之和为100重量份计，所述组分(F)填料的添加量为5～300重量份，例如10重量份、30重量份、50重量份、70重量份、 90重量份、110重量份、130重量份、150重量份、170重量份、190重量份、210重量份、230重量份、250重量份、270重量份或290重量份，优选5～200重量份，进一步优选5～150重量份。
本发明所述的“包括”，意指其除所述组份外，还可以包括其他组份，这些其他组份赋予所述无卤热固性树脂组合物不同的特性。除此之外，本发明所述的“包括”，还可以替换为封闭式的“为”或“由……组成”。
例如，所述无卤热固性树脂组合物还可以含有各种添加剂，作为具体例，可以举出抗氧剂、热稳定剂、抗静电剂、紫外线吸收剂、颜料、着色剂或润滑剂等。这些各种添加剂可以单独使用，也可以两种或者两种以上混合使用。
本发明的无卤热固性树脂组合物常规制备方法为：先将固形物放入，然后加入液态溶剂，搅拌至固形物完全溶解后，再加入液态树脂和促进剂，继续搅拌均匀即可。
作为本发明中的溶剂，没有特别的限定，作为具体例，可以列举出甲醇、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、环己酮等酮类，甲苯、二甲苯等芳香烃类，醋酸乙酯、乙氧基乙基乙酸酯等酯类，N，N-二甲基甲酰胺、N，N-二甲基乙酰胺等含氮类溶剂。以上溶剂可单独使用，也可两种或两种以上混合使用。优选丙酮、丁酮、甲基乙基甲酮、环己酮等酮类。所述溶剂的添加量由本领域技术人员根据自己经验来选择，使得树脂胶液达到适合使用的粘度即可。
本发明的目的之二在于提供一种预浸料，其包括增强材料及通过浸渍干燥后附着在其上的如上所述的无卤热固性树脂组合物。
所使用的增强材料无特别的限定，可以为有机纤维、无机纤维编织布或无纺布。所述的有机纤维可以选择芳纶无纺布，所述的无机纤维编织布可以为E- 玻纤布、D-玻纤布、S-玻纤布、T玻纤布、NE-玻纤布或石英布。所述增强材料的厚度无特别限定，处于层压板有良好的尺寸稳定性的考虑，所述编织布及无纺布厚度优选0.01～0.2mm，且最好是经过开纤处理及硅烷偶联剂表面处理的，为了提供良好的耐水性和耐热性，所述硅烷偶联剂优选为环氧硅烷偶联剂、氨基硅烷偶联剂或乙烯基硅烷偶联剂中的任意一种或至少两种的混合物。将增强材料通过含浸上述的无卤热固性树脂组合物，在100～250℃条件下，烘烤1～15分钟得到所述预浸料。
本发明的目的之三在于提供一种层压板，所述层压板含有至少一张如上所述的预浸料。该层压板通过加热和加压使至少一张以上的预浸料粘合在一起而得到。
所述层压板是在热压机中固化制得，固化温度为150℃～250℃，固化压力为10～60Kg/cm2。
本发明的目的之四在于提供一种无卤高频电路基板，所述基板含有至少一张如上所述的预浸料以及覆于叠合后的预浸料一侧或两侧的金属箔。
所述的金属箔为铜箔、镍箔、铝箔及SUS箔等，其材质不限。
与已有技术相比，本发明具有如下有益效果：
本发明的无卤热固性树脂组合物以含磷双酚为第一固化剂，该含磷双酚结构对称性高，且分子中的磷可以与环氧树脂的二次羟基反应，固化物Tg高、介电性能优异；此外，该含磷双酚磷含量高，有无卤阻燃的功效。
而且，本发明的无卤热固性树脂组合物以双环戊二烯型酚醛为第二固化剂，充分发挥了其分子中有较多双环戊二烯结构从而介电性能优异吸水率低的优势，在不牺牲固化物Tg、介电性能前提下大大降低固化物吸水率。
本发明利用含磷双酚和双环戊二烯型酚醛树脂两者之间的协同效应，可以 显著提高使用该树脂组合物制作的预浸料以及印制电路用层压板的玻璃化温度和耐热性，并使其具有优异的介电性能、低吸水率以及良好的工艺加工性，并实现无卤阻燃，达到UL94V-0。
使用该树脂组合物制成的预浸料、印制电路用层压板具有高玻璃化转变温度、优异的介电性能、高耐热性、低吸水率并实现了无卤阻燃，且阻燃能达到UL94V-0级。
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。
针对上述制成的印制电路用层压板(8片预浸料，增强材料型号为2116，厚度为0.08mm)测试其玻璃化转变温度、介电常数、介电损耗因素、剥离强度、吸水性、耐热性、阻燃性等性能，如下实施例进一步详细说明与描述。
请参阅实施例1-8和比较例1-8。下文中无特别说明，其份代表重量份，其％代表“重量％”。
(A)无卤环氧树脂
(A-1)双环戊二烯型环氧树脂HP-7200H(日本DIC商品名，EEW：275g/eq)
(A-2)联苯型酚醛环氧树脂NC-3000H(日本化药商品名，EEW：288g/eq)
(B)第一固化剂
(B-1)含磷双酚OL1001(美国FRX Polymers商品名，磷含量8.5％)
(B-2)聚膦酸酯OL5000(美国FRX Polymers商品名，磷含量10.8％)
结构式如下：
Figure PCTCN2015080538-appb-000009
(C)第二固化剂
(C-1)双环戊二烯型酚醛DP9110A70(台湾长春商品名)
(C-2)活性酯固化剂HPC-8000-65T(大日本油墨商品名)
(C-3)线性酚醛2812(韩国MOMENTIVE商品名)
(D)含磷阻燃剂
含磷酚醛XZ92741(美国DOW商品名，磷含量9％)
(E)促进剂
2-乙基-4-甲基咪唑(日本四国化成)
(F)填料
熔融二氧化硅(平均粒径为1至10μm，纯度99％以上)
表1、各实施例的配方组成及其物性数据
Figure PCTCN2015080538-appb-000010
Figure PCTCN2015080538-appb-000011
表2、比较例1～6的配方组成及其物性数据
Figure PCTCN2015080538-appb-000012
Figure PCTCN2015080538-appb-000013
表3、比较例7～8的配方组成及其物性数据
Figure PCTCN2015080538-appb-000014
Figure PCTCN2015080538-appb-000015
以上特性的测试方法如下：
(a)玻璃化转变温度(Tg)：根据差示扫描量热法(DSC)，按照IPC-TM-650 2.4.25所规定的DSC方法进行测定。
(b)介电常数、介电损耗因素
根据使用条状线的共振法，按照IPC-TM-650 2.5.5.5测定1GHz下的介电损耗、介电损耗因素。
(c)剥离强度
按照IPC-TM-650 2.4.8方法中的“热应力后”的实验条件，测试金属盖层的剥离强度。
(d)吸水性
按照IPC-TM-650 2.6.2.1方法进行测定。
(e)耐浸焊性
按照IPC-TM-650 2.4.13.1观察分层起泡时间。
(f)难燃烧性
依据UL 94垂直燃烧法测定。
从表1、表2和表3的物性数据可知，比较例1和比较例7中使用含磷双酚单独固化双环戊二烯型环氧树脂，得到的层压板Tg高且介电性能、剥离强度、阻燃性优异，但吸水率高、耐热性差；比较例2和比较例8中使用双环戊二烯型酚醛单独固化双环戊二烯型环氧树脂，得到的层压板Tg高、介电性能和耐热 性优异、吸水率低，但剥离强度低、阻燃性差；比较例3中使用含磷双酚和活性酯共固化双环戊二烯型环氧树脂，得到的层压板Tg较高、介电性能良好，但吸水率高；比较例4中使用含磷双酚和线性酚醛共固化双环戊二烯型环氧树脂，板材介电常数和介电损耗均较高，难以满足热固性高速领域层压板对介电性能的要求；比较例5和6中使用聚膦酸酯和双环戊二烯型酚醛分别共固化双环戊二烯型环氧树脂和联苯型酚醛环氧树脂，得到的层压板Tg较低、介电性能差且吸水率较高；比较例7中用含磷双酚单独固化双环戊二烯型环氧树脂，得到的层压板玻璃化转变温度高、介电性能优异，但同时吸水率高、耐热性差；比较例8中用双环戊二烯型酚醛单独固化双环戊二烯型环氧树脂，得到的层压板玻璃化转变温度较高、介电性能较好、吸水率低且耐热性好，但剥离强度较低且阻燃性差。实施例1-8以无卤环氧树脂为主体，使用含磷双酚和双环戊二烯型酚醛共固化后，得到的层压板具有高玻璃化转变温度、优异的介电性能、高耐热性、低吸水率并实现了无卤阻燃，且阻燃能达到UL94V-0级。
如上所述，与一般的层压板相比，本发明的印制电路用层压板具有更高的玻璃化转变温度、更优异的介电性能、耐湿性、耐热性，适用于高频领域。另外卤素含量在JPCA无卤标准要求范围内能达到难燃性试验UL94中的V-0标准，有环保的功效。
申请人声明，本发明通过上述实施例来说明本发明的详细方法，但本发明并不局限于上述详细方法，即不意味着本发明必须依赖上述详细方法才能实施。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. 一种无卤热固性树脂组合物，有机固形物按100重量份计，其包含：
    (A)无卤环氧树脂：30～60重量份；
    (B)第一固化剂：含磷双酚5～30重量份；
    (C)第二固化剂：双环戊二烯型酚醛5～30重量份；
    (D)含磷阻燃剂。
  2. 如权利要求1所述的无卤热固性树脂组合物，其特征在于，所述无卤环氧树脂为双酚A型环氧树脂、双酚F型环氧树脂、邻甲酚酚醛环氧树脂、双酚A型酚醛环氧树脂、三酚型酚醛环氧树脂、双环戊二烯酚醛环氧树脂、联苯型酚醛环氧树脂、烷基苯型酚醛环氧树脂或萘酚型酚醛环氧树脂中的任意一种或至少两种的混合物；
    优选地，所述无卤环氧树脂选自具有如下结构的环氧树脂：
    Figure PCTCN2015080538-appb-100001
    其中，X1、X2和X3各自独立地选自
    Figure PCTCN2015080538-appb-100002
    R1选自氢原子、取代或未取代的C1-C5直链烷基或者取代或未取代的C1-C5支链烷基中的任意一种；
    Y1和Y2各自独立地选自单键、-CH2-、
    Figure PCTCN2015080538-appb-100003
    Figure PCTCN2015080538-appb-100004
    和的任意一种，n1为1～10 的任意整数，R2选自氢原子、取代或未取代的C1-C5直链烷基或者取代或未取代的C1-C5支链烷基中的任意一种。
  3. 如权利要求1或2所述的无卤热固性树脂组合物，其特征在于，所述含磷双酚具有如下结构：
    Figure PCTCN2015080538-appb-100005
    其中，n2为2～20的任意整数，优选n2为3～10的任意整数；
    优选地，所述含磷双酚的重均分子量为1000～6500，优选为1000～4500，进一步优选为1000～3000。
  4. 如权利要求1-3之一所述的无卤热固性树脂组合物，其特征在于，所述双环戊二烯型酚醛具有如下结构：
    Figure PCTCN2015080538-appb-100006
    式中，Z1、Z2和Z3独立地选自-H、-CH3、-C2H5或-C(CH3)3，n3选自0～7中的任意整数。
  5. 如权利要求1-4之一所述的无卤热固性树脂组合物，其特征在于，以组分(A)、组分(B)和组分(C)的添加量之和为100重量份计，组分(D)含磷阻燃剂的添加量为5-50重量份，优选10～30重量份；
    优选地，所述含磷阻燃剂为三(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、10-苯基-9，10-二氢-9-氧杂-10-膦菲-10-氧化物、苯氧基磷腈化合物、磷酸酯、聚磷 酸酯、聚膦酸酯或膦酸酯-碳酸酯共聚物中的任意一种或者至少两种的混合物。
  6. 如权利要求1-5之一所述的无卤热固性树脂组合物，其特征在于，所述无卤热固性树脂组合物还包括组分(E)固化促进剂；
    优选地，所述固化促进剂选自咪唑类化合物、咪唑类化合物的衍生物、哌啶类化合物、路易斯酸或三苯基膦中的任意一种或至少两种的混合物；
    优选地，所述咪唑类化合物为2-甲基咪唑、2-乙基-4-甲基咪唑、2-苯基咪唑或2-十一烷基咪唑中的任意一种或至少两种的混合物；
    优选地，所述哌啶类化合物为2，3-二氨基哌啶、2，5-二氨基哌啶、2，6-二氨基哌啶、2-氨基-3-甲基哌啶、2-氨基-4-甲基哌啶、2-氨基-3-硝基哌啶、2-氨基-5-硝基哌啶或2-氨基-4，4-二甲基哌啶中的任意一种或至少两种的混合物；
    优选地，以组分(A)、组分(B)、组分(C)和组分(D)的添加量之和为100重量份计，所述组分(E)固化促进剂的添加量为0.01～1重量份，优选0.05～0.8重量份，进一步优选0.05～0.6重量份。
  7. 如权利要求1-6之一所述的无卤热固性树脂组合物，其特征在于，无卤热固性树脂组合物还包括组分(F)填料；
    优选地，所述填料选自有机填料和无机填料，优选无机填料，进一步优选经过表面处理的无机填料，最优选经过表面处理的二氧化硅；
    优选地，所述表面处理的表面处理剂选自硅烷偶联剂、有机硅低聚物或钛酸酯偶联剂中的任意一种或至少两种的混合物；
    优选地，以无机填料为100重量份计，所述表面处理剂的用量为0.1～5.0重量份，优选0.5～3.0重量份，更优选0.75～2.0重量份；
    优选地，所述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任意一种或者至少两种的混合 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、硅酸钙或云母中的一种或至少两种的混合物；
    优选地，所述有机填料选自聚四氟乙烯粉末、聚苯硫醚或聚醚砜粉末中的任意一种或至少两种的混合物；
    优选地，所述填料的中位粒径为0.01～50μm，优选0.01～20μm，进一步优选0.1～10μm；
    优选地，以组分(A)、组分(B)、组分(C)和组分(D)的添加量之和为100重量份计，所述组分(F)填料的添加量为5～300重量份，优选5～200重量份，进一步优选5～150重量份。
  8. 一种预浸料，其包括增强材料及通过浸渍干燥后附着在其上的如权利要求1-7之一所述的无卤热固性树脂组合物。
  9. 一种层压板，所述层压板含有至少一张如权利要求8所述的预浸料。
  10. 一种无卤高频电路基板，所述基板含有至少一张如权利要求8所述的预浸料以及覆于叠合后的预浸料一侧或两侧的金属箔。
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