WO2020133337A1 - 热固性树脂组合物及含有它的预浸料、层压板和高频电路基板 - Google Patents

热固性树脂组合物及含有它的预浸料、层压板和高频电路基板 Download PDF

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WO2020133337A1
WO2020133337A1 PCT/CN2018/125308 CN2018125308W WO2020133337A1 WO 2020133337 A1 WO2020133337 A1 WO 2020133337A1 CN 2018125308 W CN2018125308 W CN 2018125308W WO 2020133337 A1 WO2020133337 A1 WO 2020133337A1
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weight
parts
substituted
integer
unsubstituted
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PCT/CN2018/125308
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English (en)
French (fr)
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黄天辉
林伟
游江
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广东生益科技股份有限公司
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Priority to PCT/CN2018/125308 priority Critical patent/WO2020133337A1/zh
Publication of WO2020133337A1 publication Critical patent/WO2020133337A1/zh

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    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B27/00—Layered products comprising a layer of synthetic resin
    • B32B27/06—Layered products comprising a layer of synthetic resin as the main or only constituent of a layer, which is next to another layer of the same or of a different material
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B27/00—Layered products comprising a layer of synthetic resin
    • B32B27/38—Layered products comprising a layer of synthetic resin comprising epoxy resins
    • 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
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L79/00—Compositions of macromolecular compounds obtained by reactions forming in the main chain of the macromolecule a linkage containing nitrogen with or without oxygen or carbon only, not provided for in groups C08L61/00 - C08L77/00
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L85/00—Compositions of macromolecular compounds obtained by reactions forming a linkage in the main chain of the macromolecule containing atoms other than silicon, sulfur, nitrogen, oxygen and carbon; Compositions of derivatives of such polymers
    • C08L85/02—Compositions of macromolecular compounds obtained by reactions forming a linkage in the main chain of the macromolecule containing atoms other than silicon, sulfur, nitrogen, oxygen and carbon; Compositions of derivatives of such polymers containing phosphorus

Definitions

  • the invention belongs to the technical field of thermosetting resin compositions, and relates to a thermosetting resin composition, a prepreg, a laminate and a high-frequency circuit board using the same.
  • Phenolic resins have been adopted as curing agents for epoxy resins.
  • Phenolic resins have a high-density benzene ring structure, so the heat resistance of the system after epoxy curing Excellent, but at the same time the dielectric properties of the cured product tend to be deteriorated.
  • CN1795223A discloses a polyphosphonate flame retardant curing agent for epoxy resin, which includes epoxy resin and epoxy active polyphosphonate as general curing agent (1) which is an effective curing agent.
  • CN106459559A discloses an epoxy composition comprising oligomeric phosphonate, carbodiimide, carbodiimide, phenolic antioxidant or phosphonite antioxidant, oligophosphonic acid Esters and carbodiimides, or oligophosphonates, carbodiimides and phenolic antioxidants or phosphonite antioxidants, which improve the flame retardant properties of the material and the glass transition temperature of the composition.
  • thermosetting resin composition with excellent dielectric properties, high heat resistance, low water absorption, and good processability to prepare laminates and the like.
  • the object of the present invention is to provide a thermosetting resin composition and a prepreg, laminate and high-frequency circuit substrate using the same; a prepreg, a laminate and a high-frequency circuit substrate prepared from the thermosetting resin composition provided by the present invention It has excellent dielectric properties, high heat resistance, low water absorption and good processing performance, and its flame retardancy can reach UL94 V-0 level.
  • the present invention uses the following technical solutions:
  • thermosetting resin composition comprising the following components in parts by weight:
  • Epoxy resin 30-70 parts by weight, 30-70 parts by weight;
  • Hydroxy-containing polyphosphonate and/or hydroxyl-containing phosphonate-carbonate copolymer 5-40 parts by weight.
  • the melting point of the aromatic polycarbodiimide is 100-160°C, such as 105°C, 110°C, 115°C, 120°C, 125°C, 130°C, 135°C, 140°C, 145°C, 150°C, 155°C etc.
  • the use of aromatic polycarbodiimide and hydroxyl-containing polyphosphonate and/or hydroxyl-containing phosphonate-carbonate copolymer as the co-curing agent of epoxy resin ensures that the hydroxyl-containing Polyphosphonate and/or hydroxy-containing phosphonate-carbonate copolymer electrical properties while ensuring that the final cured system has a high cross-linking density and good heat and humidity resistance, while aromatic carbodiimide It also has the function of preventing the hydrolysis of ester groups, which can further improve the hydrolysis resistance of ester-cured epoxy resins.
  • hydroxyl-containing polyphosphonates and/or hydroxyl-containing phosphonate-carbonate copolymers also have The function of the flame retardant, without adding other flame retardants, the flame retardant of the cured product of the present invention can reach UL94 V-0 level.
  • Adding a certain amount of aromatic polycarbodiimide with a melting point of 100-160°C in the resin composition of the present invention can greatly improve the electrical performance of the resin composition, and at the same time make the resin composition have a better T g and can Reduce the PCT water absorption rate of the board.
  • the melting point of the aromatic polycarbodiimide is too low, there is volatilization during the sizing process, and the cured product has poor heat resistance, and does not contribute much to the dielectric properties; but if the melting point is too high, there are solubility problems .
  • the weight part of the aromatic polycarbodiimide is 5-15 parts by weight, for example, 6 parts by weight, 8 parts by weight, 9 parts by weight, 10 parts by weight, 12 parts by weight, 14 parts by weight, and the like.
  • the aromatic polycarbodiimide is selected from 1,3-di-p-tolylpolycarbodiimide, N,N′-bis(2-methylphenyl)carbodiimide, N-(tert-butyl Radical)-N-[1-(2-chlorophenyl)-1-methylethyl]polycarbodiimide or N,N′-benzyl-N-cyclohexyl polycarbodiimide Species or a combination of at least two.
  • the parts by weight of the epoxy resin are 30-70 parts by weight, such as 35 parts by weight, 40 parts by weight, 45 parts by weight, 50 parts by weight, 55 parts by weight, 60 parts by weight, 65 parts by weight, and the like.
  • the epoxy resin includes bisphenol A epoxy resin, bisphenol F epoxy resin, o-cresol novolac epoxy resin, bisphenol A novolac epoxy resin, triphenol novolac epoxy resin , Dicyclopentadiene novolac epoxy resin, biphenyl novolac epoxy resin, alkylbenzene novolac epoxy resin or naphthol novolac epoxy resin, or a combination of at least two of them.
  • the epoxy resin is an epoxy resin having the structure of formula I:
  • X 1 , X 2 and X 3 are each independently selected from R 1 is selected from any one of a hydrogen atom, a substituted or unsubstituted C1-C5 linear alkyl group or a substituted or unsubstituted C1-C5 branched chain alkyl group.
  • Y 1 and Y 2 are each independently selected from a single bond, -CH 2 -,
  • R2 is selected from a hydrogen atom, a substituted or unsubstituted C1-C5 linear alkyl group or a substituted or unsubstituted C1-C5 branched chain alkyl group.
  • a is an integer of 1-10, for example 1, 2, 3, 4, 5, 6, 7, 8, 9, 10, etc.
  • the weight part of the hydroxyl group-containing polyphosphonate and/or hydroxyl group-containing phosphonate-carbonate copolymer is 5-40 parts by weight, such as 8 parts by weight, 10 parts by weight, and 15 parts by weight , 18 parts by weight, 20 parts by weight, 25 parts by weight, 28 parts by weight, 30 parts by weight, 35 parts by weight, 38 parts by weight, etc., more preferably 10-25 parts by weight.
  • the structure of the polyphosphonate is as shown in formula II:
  • Ar is an aryl group
  • the -O-Ar-O- group is selected from resorcinol active groups, hydroquinone active groups, bisphenol A active groups, bisphenol F active groups, 4,4′-diphenol active group, phenolphthalein active group, 4,4′-thiodiphenol active group, 4,4′-sulfonyl diphenol active group or 3,3,5-trimethyl Any one of the active groups based on cyclohexyl diphenol.
  • X is C1-C20 substituted or unsubstituted linear alkyl, C1-C20 substituted or unsubstituted branched alkyl, C2-C20 substituted or unsubstituted linear alkenyl, C2-C20 substituted or Unsubstituted branched alkenyl group, C2-C20 substituted or unsubstituted linear alkylene group, C2-C20 substituted or unsubstituted branched alkylene group, C5-C20 substituted or unsubstituted cycloalkyl group Or any one of C6-C20 substituted or unsubstituted aryl groups.
  • the C1-C20 described in the present invention may be C2, C3, C4, C5, C8, C9, C10, C12, C14, C16, C18, C19 and so on.
  • n is any integer from 1 to 75, such as 5, 10, 15, 18, 20, 25, 30, 35, 40, 45, 50, 55, 60, 65, 70, etc.
  • the phosphonate-carbonate copolymer has a structure represented by Formula III or Formula IV:
  • Ar 1 , Ar 2 and Ar 3 are each independently selected from aryl groups, and said -O-Ar 3 -O- is selected from resorcinol active groups, hydroquinone active groups, bisphenol A Active group, bisphenol F active group, 4,4′-diphenol active group, phenolphthalein active group, 4,4′-thiodiphenol active group, 4,4′-sulfonyl diphenol activity Either group or 3,3,5-trimethylcyclohexyl diphenol active group.
  • X 1 and X 2 are each independently a C1-C20 substituted or unsubstituted linear alkyl group, a C1-C20 substituted or unsubstituted branched chain alkyl group, a C2-C20 substituted or unsubstituted linear alkyl group , C2-C20 substituted or unsubstituted branched chain alkenyl group, C2-C20 substituted or unsubstituted linear alkylene group, C2-C20 substituted or unsubstituted branched chain alkylene group, C5-C20 substitution Or unsubstituted cycloalkyl or C6-C20 substituted or unsubstituted aryl.
  • n is any integer from 1 to 100, such as 5, 10, 15, 20, 25, 30, 35, 40, 45, 50, 55, 60, 65, 70, 75, 80, 85, 90, 95, etc., preferably Any integer from 5 to 100, further preferably any integer from 10 to 100.
  • n 1 and n 2 are each independently an arbitrary integer of 1-75, such as 5, 10, 15, 20, 25, 30, 35, 40, 45, 50, 55, 60, 65, 70, etc., preferably 5-75 Any integer of, more preferably any integer of 10-75.
  • p is any integer of 2-50, such as 5, 10, 15, 20, 25, 30, 35, 40, 45, etc., preferably any integer of 5-50, further preferably any integer of 10-50.
  • R 1 and R 2 are each independently selected from a substituted or unsubstituted aliphatic or aromatic hydrocarbon group, preferably an unsubstituted aliphatic or aromatic hydrocarbon group.
  • aryl refers to any functional group or substituent derived from an aromatic ring.
  • aromatic rings include toluene, ethylbenzene, n-propylbenzene, cumene, styrene, phenol, acetophenone, benzophenone Ether, phenethyl ether, benzyl alcohol, benzaldehyde, benzoyl, benzoyl chloride, benzoic acid, benzyl cyanide, nitrobenzene, nitrosobenzene, aniline, fluorobenzene, chlorobenzene, bromobenzene, iodobenzene, benzene Sulfonic acid, diphenyl ketone, diphenyl ethanedione, phenylacetic acid, mandelic acid, cinnamic acid, acetanilide, phenethylamine, azobenzene, diazobenzene chloride,
  • the polyphosphonate or/and phosphonate-carbonate copolymer is selected from Any one or a combination of at least two of them.
  • R 3 and R 4 are each independently selected from a substituted or unsubstituted aliphatic or aromatic hydrocarbon group, preferably an unsubstituted aliphatic or aromatic hydrocarbon group.
  • m 1 is any integer from 1 to 100, such as 5, 10, 15, 20, 25, 30, 35, 40, 45, 50, 55, 60, 65, 70, 75, 80, 85, 90, 95, etc., Any integer of 5-100 is preferred, and any integer of 10-100 is further preferred.
  • n 3 , n 4 , n 5 are each independently an arbitrary integer of 1-75, such as 5, 10, 15, 20, 25, 30, 35, 40 , 45 , 50 , 55 , 60, 65, 70, etc., preferably Any integer from 5 to 75, further preferably from 10 to 75.
  • p 1 is an arbitrary integer of 2-50, such as 5, 10, 15, 20, 25, 30, 35, 40, 45, etc., preferably an integer of 5-50, further preferably an integer of 10-50.
  • the weight average molecular weights of the polyphosphonate and phosphonate-carbonate copolymers are independently 1000 to 60,000 (the test method for molecular weight is GB/T 21863-2008, weight average molecular weight, such as Styrene calibration based on gel permeation chromatography), for example 2000, 3000, 3500, 4000, 4500, 5000, 7000, 8000, 10000, 15000, 20000, 25000, 30000, 35000, 40000, 45000, 50000, 55000 etc., preferably 2000-50000, further preferably 2500-10000.
  • the test method for molecular weight is GB/T 21863-2008, weight average molecular weight, such as Styrene calibration based on gel permeation chromatography
  • 2000, 3000, 3500, 4000, 4500, 5000, 7000, 8000, 10000, 15000, 20000, 25000, 30000, 35000, 40000, 45000, 50000, 55000 etc. preferably 2000-50000
  • the cured product When the weight average molecular weight is less than 1,000, the cured product has a low T g and poor heat resistance; when the weight average molecular weight is greater than 60,000, the polyphosphonate or/and phosphonate-carbonate copolymer dissolves in an organic solvent The performance is poor, and a good and uniform glue cannot be obtained, which makes it difficult to meet the technological requirements of copper clad laminates.
  • the addition amount of the polyphosphonate or/and phosphonate-carbonate copolymer described in the present invention can make the cured product flame retardant to UL94 V-0 level.
  • thermosetting resin composition of the present invention further includes a curing accelerator.
  • the curing promotion is based on a total weight of aromatic polycarbodiimide, epoxy resin, hydroxyl-containing polyphosphonate and/or hydroxyl-containing phosphonate-carbonate copolymer of 100 parts by weight
  • the added amount of the agent is 0.01-1 parts by weight, for example, 0.02 parts by weight, 0.05 parts by weight, 0.1 parts by weight, 0.5 parts by weight, 0.8 parts by weight, etc., more preferably 0.05-0.8 parts by weight, still more preferably 0.05-0.6 parts by weight.
  • the curing accelerator is not particularly limited, as long as it can catalyze the reaction of the epoxy functional group and lower the reaction temperature of the curing system; preferably, the curing accelerator is selected from imidazole curing agents and their derivatives, Lewis acids, Any one of triphenylphosphine or piperidine accelerator or a combination of at least two.
  • the imidazole curing agent is selected from any one or at least two of 2-methylimidazole, 2-ethyl-4-methylimidazole, 2-phenylimidazole or 2-undecylimidazole The combination.
  • thermosetting resin composition of the present invention further includes a filler.
  • the filler based on the total weight of aromatic polycarbodiimide, epoxy resin, hydroxyl-containing polyphosphonate and/or hydroxyl-containing phosphonate-carbonate copolymer as 100 parts by weight, the filler The added amount is 5-300 parts by weight, such as 10 parts by weight, 15 parts by weight, 20 parts by weight, 50 parts by weight, 80 parts by weight, 100 parts by weight, 150 parts by weight, 180 parts by weight, 250 parts by weight, 280 parts by weight, etc. It is further preferably 5-200 parts by weight, still more preferably 5-150 parts by weight.
  • the median particle size of the filler is 0.01-50 ⁇ m, such as 0.02 ⁇ m, 0.05 ⁇ m, 0.15 ⁇ m, 0.2 ⁇ m, 0.5 ⁇ m, 0.8 ⁇ m, 1 ⁇ m, 1.5 ⁇ m, 2 ⁇ m, 5 ⁇ m, 8 ⁇ m, 10 ⁇ m, 15 ⁇ m, 25 ⁇ m, 30 ⁇ m, 40 ⁇ m, 45 ⁇ m, etc., more preferably 0.01-20 ⁇ m, still more preferably 0.1-10 ⁇ m.
  • the filler is selected from organic fillers or inorganic fillers, further preferably inorganic fillers, still more preferably surface-treated inorganic fillers, most preferably surface-treated silica.
  • the surface-treated surface treatment agent is selected from any one of silane coupling agent, silicone oligomer or titanate coupling agent or a combination of at least two.
  • the amount of the surface treatment agent is 0.1-5.0 parts by weight based on 100 parts by weight of the inorganic filler, such as 0.2 parts by weight, 0.5 parts by weight, 0.8 parts by weight, 1.0 parts by weight, 1.2 parts by weight, and 1.5 parts by weight , 2.0 parts by weight, 2.5 parts by weight, 3.5 parts by weight, 4 parts by weight, 4.5 parts by weight, etc., further preferably 0.5-3.0 parts by weight, still more preferably 0.75-2.0 parts by weight.
  • the inorganic filler is selected from any one of non-metal oxides, metal nitrides, non-metal nitrides, inorganic hydrates or inorganic salts (such as inorganic phosphorus) or a combination of at least two, further preferably molten two Silicon oxide, crystalline silica, spherical silica, hollow silica, aluminum hydroxide, alumina, talc, aluminum nitride, boron nitride, silicon carbide, barium sulfate, barium titanate, titanic acid Any one or a combination of at least two of strontium, calcium carbonate, calcium silicate or mica.
  • the organic filler is selected from any one of polytetrafluoroethylene, polyphenylene sulfide or polyether sulfone or a combination of at least two.
  • the present invention provides a resin glue solution obtained by dissolving or dispersing the thermosetting resin composition as described in the first aspect in a solvent.
  • the conventional preparation method of the resin glue solution of the present invention is as follows: first put the solid material, then add a liquid solvent, stir until the solid material is completely dissolved, then add the liquid resin and the accelerator, and continue to stir evenly.
  • the solvent in the present invention is not particularly limited, and specific examples include alcohols such as methanol, ethanol, and butanol, ethyl cellosolve, butyl cellosolve, ethylene glycol methyl ether, carbitol, butyl alcohol Ethers such as carbitol, ketones such as acetone, methyl ethyl ketone, methyl ethyl ketone, cyclohexanone, aromatic hydrocarbons such as toluene and xylene, esters such as ethyl acetate and ethoxyethyl acetate Type, N,N-dimethylformamide, N,N-dimethylacetamide and other nitrogen-containing solvents; the above solvents can be used alone or in combination of two or more; preferably acetone, butanone, Ketone solvents such as methyl ethyl ketone and cyclohexanone.
  • alcohols such as methanol, ethanol, and butan
  • the present invention provides a prepreg comprising a reinforcing material and the thermosetting resin composition as described in the first aspect attached thereto after being dried by dipping.
  • the reinforcing material is organic fiber cloth, inorganic fiber woven cloth or non-woven cloth.
  • the organic fiber is aramid non-woven fabric.
  • the inorganic fiber woven cloth is E-glass fiber 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 0.01-0.2 mm, such as 0.02 mm, 0.05 mm, 0.08 mm, 0.1 mm, 0.12 mm, 0.15 mm, 0.18 mm, and the like.
  • the reinforcing material is subjected to fiber opening treatment and surface treatment with a silane coupling agent;
  • the silane coupling agent is any one of epoxy silane coupling agent, amino silane coupling agent or vinyl silane coupling agent Or a mixture of at least two.
  • the preparation method of the prepreg is: impregnating the above-mentioned thermosetting resin composition with a reinforcing material, and then baking at a temperature of 100-250°C for 1-15 minutes to obtain the prepreg.
  • the present invention provides a laminate including at least one prepreg according to the third aspect.
  • the method for preparing the laminate is a laminate made by heating and pressurizing one or more prepregs together.
  • the laminate is cured in a hot press, the curing temperature is 150-250°C, and the curing pressure is 10-60Kg/cm 2 .
  • the present invention provides a high-frequency circuit substrate comprising at least one prepreg according to the third aspect and covering one or both sides of the laminated prepreg Metal foil.
  • the metal foil is copper foil, nickel foil, aluminum foil, SUS foil, or the like.
  • the present invention has the following beneficial effects:
  • the present invention uses aromatic polycarbodiimide and hydroxyl-containing polyphosphonate and/or hydroxyl-containing phosphonate-carbonate copolymer as a co-curing agent for epoxy resin, ensuring Polyphosphonate and/or hydroxy-containing phosphonate-carbonate copolymer electrical properties while ensuring that the resulting cured system has a high cross-linking density and good heat and humidity resistance, while aromatic polycarbodiimide It also has the function of preventing the hydrolysis of ester groups, which in turn can improve the hydrolysis resistance of ester-cured epoxy resins, and the hydroxyl-containing polyphosphonates and/or hydroxyl-containing phosphonate-carbonate copolymers also have resistance Without the addition of other flame retardants, the flame retardant of the cured product of the present invention can achieve UL94 V-0 level.
  • A-1 Aromatic polycarbodiimide Statabaxol P100 (line chemical, melting point 100-120 °C);
  • A-2 Aromatic polycarbodiimide HYDROSTAB 2 (Laian Chemicals, softening point 140°C);
  • A-3 Aromatic carbodiimide monomer HYDROSTAB I (Laian Chemicals, softening point 50°C);
  • A-4 Aromatic polycarbodiimide Statabaxol P (line chemical, softening point 60-90°C);
  • A-5 Non-aromatic polycarbodiimide (Rhein chemistry, liquid);
  • B-2 Biphenyl novolac epoxy resin NC-3000H (Japanese chemical, EEW: 288g/eq);
  • C-2 hydroxy-terminated bisphenol a polyphosphonate FRX OL5001 (US FRX Polymers, phosphorus content 10%, molecular weight 5000);
  • E-1 2-phenylimidazole (Japan Shikoku Chemicals);
  • F-1 Fused silica (average particle size is 1-10 ⁇ m, purity is more than 99%);
  • thermosetting resin composition is formulated according to the components shown in Table 1, and the laminate samples are prepared according to the following laminate manufacturing method:
  • the prepreg is made, and several prepregs are stacked together, and copper foil is stacked on the upper and lower sides of the prepreg.
  • the curing temperature is 190-200°C
  • the curing pressure is 30-60Kg/cm 2
  • the curing time is 90-120min
  • the copper clad laminate is made under the conditions.
  • thermosetting resin composition was prepared according to the components shown in Table 2, and a laminate sample was prepared according to the manufacturing method of the laminate described in the examples.
  • T g Glass transition temperature: measured according to the differential scanning calorimetry (DSC), according to the DSC method specified in IPC-TM-6502.4.25;
  • Dielectric constant (Dk) and dielectric loss factor (Df) According to the resonance method using a strip line, the dielectric loss and dielectric loss factor at 1 GHz are measured according to the method of IPC-TM-650 2.5.5.5 ;
  • the copper clad laminate prepared by the thermosetting resin composition provided by the present invention has excellent dielectric properties, high heat resistance, low water absorption rate and good processing performance, and the flame retardancy can reach UL94 V-0 level.
  • Example 1-2 Comparative Example 1-2 that the addition of an aromatic polycarbodiimide with a melting point of 100-160°C can significantly improve the final addition to the addition of an aromatic polycarbodiimide with a low melting point.
  • the resulting CCL T g while reducing the dielectric loss, and PCT water absorption, and can increase the burst plate and PCT solder dip resistance 288 °C limit time.
  • Example 1-2 and Comparative Example 3 compared with the addition of non-aromatic polycarbodiimide, the addition of aromatic polycarbodiimide with a melting point of 100-160°C can significantly improve the final copper clad laminate T g , while reducing its dielectric loss and PCT water absorption rate, and can increase the PCT burst plate and dip soldering resistance 288 °C limit time.
  • the aromatic polycarbodiimide and the hydroxyl-terminated phosphonate-carbonate copolymer as the co-curing agent jointly cure the epoxy resin, which can make the final
  • the obtained copper-clad laminate has high cross-linking density and good heat and humidity resistance.
  • the aromatic polycarbodiimide also has the function of preventing hydrolysis of the ester group, thereby further improving the hydrolysis resistance of the copper-clad laminate.
  • Example 2 Comparative Example 5
  • the polyphosphate ester containing hydroxyl groups selected in Example 2 and the polyphosphate ester containing no hydroxyl groups selected in Comparative Example 5 have the same molecular structure and molecular weight except that they do not contain terminal hydroxyl groups
  • the polyphosphate without hydroxyl group can reduce the dielectric loss of the system, it greatly damages the performance of the system such as Tg , PCT and the 288°C limit of dip soldering resistance.
  • hydroxyl polyphosphate can be improved while reducing the dielectric loss system T g of the system, reducing the water absorption of PCT, PCT improve burst resistance and solder dip plate 288 °C limit time effect.
  • the amount of aromatic polycarbodiimide should be within the scope of the present invention, if the amount of aromatic polycarbodiimide is too high Low, the effect of reducing dielectric loss is small; if the amount of aromatic polycarbodiimide added is too high, it will instead increase the dielectric loss, only within the scope of the present invention, the final copper clad laminate Has a low dielectric loss value.
  • the resin composition of the present invention requires not only the combination of epoxy resin, aromatic polycarbodiimide, hydroxyl-containing polyphosphonate and/or hydroxyl-containing phosphonate-carbonate copolymer, but also The proportion of each component can produce a copper clad laminate with excellent performance.
  • the present invention illustrates the thermosetting resin composition of the present invention and the prepregs, laminates and high-frequency circuit substrates containing the same through the above examples, but the present invention is not limited to the above detailed method, which does not mean The present invention can only be implemented by relying on the above detailed methods. Those skilled in the art should understand that any improvement to the present invention, equivalent replacement of various raw materials of the product of the present invention, addition of auxiliary components, choice of specific modes, etc., fall within the scope of protection and disclosure of the present invention.

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Abstract

一种热固性树脂组合物及含有它的预浸料、层压板和高频电路基板，所述热固性组合物按重量份数包括如下组分：芳香族聚碳化二亚胺5-15重量份；环氧树脂30-70重量份；含羟基的聚膦酸酯和/或含羟基的膦酸酯-碳酸酯共聚物5-40重量份；其中，所述芳香族聚碳化二亚胺的熔点为100-160℃。由所述热固性树脂组合物制备得到的预浸料、层压板以及高频电路基板具有较优异的介电性能、高耐热性能以及较低的吸水率和良好的加工性能，且阻燃能达到UL94 V-0级。

Description

热固性树脂组合物及含有它的预浸料、层压板和高频电路基板 技术领域
本发明属于热固性树脂组合物技术领域，涉及一种热固性树脂组合物及使用它的预浸料、层压板和高频电路基板。
背景技术
随着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，除了对层压板材料的耐热性有更高的要求外，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。
随着消费电子产品对环保的要求越来越高，覆铜箔层压板无卤化的趋势也日趋普遍而且因此降低Dk/Df已成为基板业者的追逐热点。
CN1795223A公开了一种用与环氧树脂的聚膦酸酯阻燃固化剂，其包括环氧树脂和作为有效固化剂且为通式(1)的环氧活性聚膦酸酯。CN106459559A公开了一种环氧组合物，所述环氧树脂组合物包括低聚膦酸酯、碳二亚胺、碳二亚胺和酚类抗氧化剂或亚膦酸酯抗氧化剂，低聚膦酸酯和碳二亚胺，或低聚膦酸酯、碳二亚胺和酚类抗氧化剂或亚膦酸酯抗氧化剂，其改善了材料的阻燃性能以及组合物的玻璃化转变温度。但是当聚膦酸酯或/和膦酸酯-碳酸酯共聚物类作为环氧树脂的固化剂时，为了实现更好的电性能，其端羟基会采用芳香族 酰氯或酚类进行封端，导致其交联密度下降，T g降低，耐热性不足等缺点，但不进行端羟基封端又会极大影响电性能。
因此希望开发一种具有较优异的介电性能、高耐热性能以及较低的吸水率和良好的加工性能的热固性树脂组合物来制备层压板等。
发明内容
本发明的目的在于提供一种热固性树脂组合物及使用它的预浸料、层压板和高频电路基板；由本发明提供的热固性树脂组合物制备得到的预浸料、层压板以及高频电路基板具有较优异的介电性能、高耐热性能以及较低的吸水率和良好的加工性能，且阻燃能达到UL94 V-0级。
为达此目的，本发明采用以下技术方案：
第一方面，本发明提供了一种热固性树脂组合物，所述热固性组合物按重量份数包括如下组分：
芳香族聚碳化二亚胺                                5-15重量份；
环氧树脂                                          30-70重量份；
含羟基的聚膦酸酯和/或含羟基的膦酸酯-碳酸酯共聚物  5-40重量份。
其中，所述芳香族聚碳化二亚胺的熔点为100-160℃，例如105℃、110℃、115℃、120℃、125℃、130℃、135℃、140℃、145℃、150℃、155℃等。
在本发明中，采用芳香族聚碳化二亚胺和含羟基的聚膦酸酯和/或含羟基的膦酸酯-碳酸酯共聚物作为环氧树脂的共固化剂，在保证了含羟基的聚膦酸酯和/或含羟基的膦酸酯-碳酸酯共聚物电性能的同时保证最后得到的固化体系具有较高的交联密度以及良好的耐湿热性，同时芳香族的碳化二亚胺又具有防止酯类基团水解的功能，进而可以提高酯类固化环氧树脂的耐水解性，同时，含羟基的聚膦酸酯和/或含羟基的膦酸酯-碳酸酯共聚物还具有阻燃剂的功能，在不添 加其他阻燃剂的情况下，本发明的固化物的阻燃可以达到UL94 V-0级。
本发明的树脂组合物添加一定量的熔点为100-160℃的芳香族聚碳化二亚胺，可以极大的改善树脂组合物的电性能，同时使树脂组合物具有较好的T g以及可以降低板材的PCT吸水率。当芳香族聚碳化二亚胺的熔点过低时，在上胶过程中存在挥发，并且其固化物耐热性较差，对介电性能贡献不大；但如果熔点过高又存在溶解性问题。
在本发明中，所述芳香族聚碳化二亚胺的重量份为5-15重量份，例如6重量份、8重量份、9重量份、10重量份、12重量份、14重量份等。
所述芳香族聚碳化二亚胺选自1，3-二-对甲苯基聚碳二亚胺、N，N′-双(2-甲基苯基)碳二亚胺、N-(叔丁基)-N-[1-(2-氯苯基)-1-甲基乙基]聚碳二亚胺或N，N′-苄基-N-环己基聚碳二亚胺中的任意一种或至少两种的组合。
在本发明中，所述环氧树脂的重量份为30-70重量份，例如35重量份、40重量份、45重量份、50重量份、55重量份、60重量份、65重量份等。
优选地，所述的环氧树脂包括双酚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组合。
优选地，所述环氧树脂为具有式I结构的环氧树脂：
Figure PCTCN2018125308-appb-000001
其中，X 1、X 2、X 3各自独立地选自
Figure PCTCN2018125308-appb-000002
R 1选自氢原子、取代或未取代的C1-C5直链烷基或取代或未取代的C1-C5支链烷基中的任意一种。
Y 1、Y 2各自独立地选自单键、-CH 2-、
Figure PCTCN2018125308-appb-000003
Figure PCTCN2018125308-appb-000004
中的任意一种，R2选自氢原子、取代或未取代的C1-C5直链烷基或取代或未取代的C1-C5支链烷基中的任意一种。
a为1-10的整数，例如1、2、3、4、5、6、7、8、9、10等。
在本发明中，所述含羟基的聚膦酸酯和/或含羟基的膦酸酯-碳酸酯共聚物的重量份为5-40重量份，例如8重量份、10重量份、15重量份、18重量份、20重量份、25重量份、28重量份、30重量份、35重量份、38重量份等，进一步优选10-25重量份。
优选地，所述聚膦酸酯的结构如式II所示：
Figure PCTCN2018125308-appb-000005
其中，Ar为芳基，所述-O-Ar-O-基团选自间苯二酚活性基团、对苯二酚活性基团、双酚A活性基团、双酚F活性基团、4，4′-二苯酚活性基团、酚酞活性 基团、4，4′-硫代二酚活性基团、4，4′-磺酰二酚活性基团或3，3，5-三甲基环己基二苯酚活性基团中的任意一种。
X为C1-C20的取代或未取代的直链烷基、C1-C20的取代或未取代的支链烷基、C2-C20的取代或未取代的直链烯烃基、C2-C20的取代或未取代的支链烯烃基、C2-C20的取代或未取代的直链亚烷基、C2-C20的取代或未取代的支链亚烷基、C5-C20的取代或未取代的环烷基或C6-C20取代或未取代的芳基中的任意一种。
本发明所述的C1-C20可以是C2、C3、C4、C5、C8、C9、C10、C12、C14、C16、C18、C19等。
n为1-75的任意整数，例如5、10、15、18、20、25、30、35、40、45、50、55、60、65、70等。
优选地，所述膦酸酯-碳酸酯共聚物具有式III或式IV所示结构：
Figure PCTCN2018125308-appb-000006
其中，Ar 1、Ar 2、Ar 3各自独立地选自芳基，所述的-O-Ar 3-O-选自间苯二酚活性基团、对苯二酚活性基团、双酚A活性基团、双酚F活性基团、4，4′-二苯酚活性基团、酚酞活性基团、4，4′-硫代二酚活性基团、4，4′-磺酰二酚活性基团或 3，3，5-三甲基环己基二苯酚活性基团中的任意一种。
X 1、X 2各自独立地为C1-C20的取代或未取代的直链烷基、C1-C20的取代或未取代的支链烷基、C2-C20的取代或未取代的直链烯烃基、C2-C20的取代或未取代的支链烯烃基、C2-C20的取代或未取代的直链亚烷基、C2-C20的取代或未取代的支链亚烷基、C5-C20的取代或未取代的环烷基或C6-C20取代或未取代的芳基。
m为1-100的任意整数，例如5、10、15、20、25、30、35、40、45、50、55、60、65、70、75、80、85、90、95等，优选5-100的任意整数，进一步优选10-100的任意整数。
n 1、n 2各自独立地为1-75的任意整数，例如5、10、15、20、25、30、35、40、45、50、55、60、65、70等，优选5-75的任意整数，进一步优选10-75的任意整数。
p为2-50的任意整数，例如5、10、15、20、25、30、35、40、45等，优选5-50的任意整数，进一步优选10-50的任意整数。
R 1、R 2各自独立地选自取代或未取代的脂肪族或芳香族烃基，优选为未取代的脂肪族或芳香族烃基。
在本发明中，芳基指任何从芳香环衍生出的官能团或取代基，示例性的芳香环有甲苯、乙苯、正丙苯、异丙苯、苯乙烯、苯酚、苯乙酮、苯甲醚、苯乙醚、苯甲醇、苯甲醛、苯甲酰、苯甲酰氯、苯甲酸、苯甲氰、硝基苯、亚硝基苯、苯胺、氟苯、氯苯、溴苯、碘苯、苯磺酸、二苯基甲酮、二苯基乙二酮、苯乙酸、扁桃酸、肉桂酸、乙酰苯胺、苯乙胺、偶氮苯、氯化重氮苯、过氧化苯甲酰、氯化苄、苯磺酰氯、二苯甲烷、三苯甲烷、三苯甲醇、三苯氯甲烷、四苯甲烷、二甲苯(邻二甲苯、间二甲苯、对二甲苯)、苯二酚(邻苯二酚、间 苯二酚、对苯二酚)、苯二甲酸(邻苯二甲酸、间苯二甲酸、对苯二甲酸)、苯二胺(邻苯二胺、间苯二胺、对苯二胺)、甲苯胺(邻甲苯胺、见甲苯胺、对甲苯胺)、间苯二磺酸、对甲苯磺酸、对氨基苯甲酸、水杨酸、乙酰水杨酸、对乙酰氨基酚、间氯过氧苯甲酸、均三甲苯、偏三甲苯、连苯三酚、苦味酸、三硝基甲苯、三溴苯酚、五氯酚、苯六甲酸、联苯、三联苯、萘、蒽、菲、苯醌(邻苯醌、对苯醌)等，所述芳基可以为上述任何芳香环衍生出来的官能团或取代基。
优选地，所述聚膦酸酯或/和膦酸酯-碳酸酯共聚物选自
Figure PCTCN2018125308-appb-000007
中的任意一种或至少两种的组合。
其中，R 3、R 4各自独立地选自取代或未取代的脂肪族或芳香族烃基，优选未取代的脂肪族或芳香族烃基。
m 1为1-100的任意整数，例如5、10、15、20、25、30、35、40、45、50、 55、60、65、70、75、80、85、90、95等，优选5-100的任意整数，进一步优选10-100的任意整数。
n 3、n 4、n 5各自独立地为1-75的任意整数，例如5、10、15、20、25、30、35、40、45、50、55、60、65、70等，优选5-75的任意整数，进一步优选10-75的任意整数。
p 1为2-50的任意整数，例如5、10、15、20、25、30、35、40、45等，优选5-50的任意整数，进一步优选10-50的任意整数。
优选地，所述聚膦酸酯、膦酸酯-碳酸酯共聚物的重均分子量各自独立的为1000-60000(分子量的测试方法为GB/T 21863-2008，重均分子量，如可以以聚苯乙烯校准为基础通过凝胶渗透色谱法所测定)，例如2000、3000、3500、4000、4500、5000、7000、8000、10000、15000、20000、25000、30000、35000、40000、45000、50000、55000等，优选为2000-50000，进一步优选为2500-10000。
当重均分子量小于1000时，固化物T g低、耐热性差；当重均分子量大于60000时，所述的聚膦酸酯或/和膦酸酯-碳酸酯共聚物在有机溶剂中的溶解性较差，无法得到良好、均一的胶液，从而难以满足覆铜板的工艺要求。
本发明中所述的聚膦酸酯或/和膦酸酯-碳酸酯共聚物添加量可以使固化物阻燃达到UL94 V-0级。
如有需要，本发明的所述热固性树脂组合物还包括固化促进剂。
优选地，以芳香族聚碳化二亚胺、环氧树脂、含羟基的聚膦酸酯和/或含羟基的膦酸酯-碳酸酯共聚物的总重量为100重量份计，所述固化促进剂的添加量为0.01-1重量份，例如0.02重量份、0.05重量份、0.1重量份、0.5重量份、0.8重量份等，进一步优选0.05-0.8重量份，更进一步优选0.05-0.6重量份。
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、降低固化 体系的反应温度即可；优选地，所述的固化促进剂选自咪唑类固化剂及其衍生物、路易斯酸、三苯基膦或哌啶类促进剂中的任意一种或至少两种的组合。
优选地，所述咪唑类固化剂选自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组合。
如有需要，本发明的所述热固性树脂组合物还包括填料。
优选地，以芳香族聚碳化二亚胺、环氧树脂、含羟基的聚膦酸酯和/或含羟基的膦酸酯-碳酸酯共聚物的总重量为100重量份计，所述填料的添加量为5-300重量份，例如10重量份、15重量份、20重量份、50重量份、80重量份、100重量份、150重量份、180重量份、250重量份、280重量份等，进一步优选5-200重量份，更进一步优选5-150重量份。
优选地，所述填料的中位粒径为0.01-50μm，例如0.02μm、0.05μm、0.15μm、0.2μm、0.5μm、0.8μm、1μm、1.5μm、2μm、5μm、8μm、10μm、15μm、25μm、30μm、40μm、45μm等，进一步优选0.01-20μm，更进一步优选0.1-10μm。
优选地，所述填料选自有机填料或无机填料，进一步优选无机填料，更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组合。
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，例如0.2重量份、0.5重量份、0.8重量份、1.0重量份、1.2重量份、1.5重量份、2.0重量份、2.5重量份、3.5重量份、4重量份、4.5重量份等，进一步优选0.5-3.0重量份，更进一步优选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、 无机水合物或无机盐(如无机磷)中的任意一种或者至少两种的组合，进一步优选熔融二氧化硅、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、硅酸钙或云母中的任意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、聚苯硫醚或聚醚砜中的任意一种或至少两种的组合。
第二方面，本发明提供了一种树脂胶液，所述树脂胶液是将如第一方面所述的热固性树脂组合物溶解或分散在溶剂中得到。
本发明的树脂胶液常规制备方法为：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、环己酮等酮类溶剂。
第三方面，本发明提供了一种预浸料，所述预浸料包括增强材料及通过浸渍干燥后附着其上的如第一方面所述的热固性树脂组合物。
优选地，所述增强材料为有机纤维布、无机纤维编织布或无纺布。
优选地，所述有机纤维为芳纶无纺布。
优选地，所述无机纤维编织布为E-玻纤布、D-玻纤布、S-玻纤布、T玻纤布、NE-玻纤布或石英布。
优选地，所述增强材料的厚度为0.01-0.2mm，例如0.02mm、0.05mm、 0.08mm、0.1mm、0.12mm、0.15mm、0.18mm等。
优选地，所述增强材料经过开纤处理及硅烷偶联剂表面处理；所述硅烷偶联剂为环氧硅烷偶联剂、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。
优选地，所述预浸料的制备方法为：将增强材料含浸上述的热固性树脂组合物，然后在100-250℃条件下，烘烤1-15min得到所述预浸料。
第四方面，本发明提供了一种层压板，所述层压板包括至少一张如第三方面所述的预浸料。
优选地，所述层压板的制备方法为通过加热和加压，使一片或两片以上的预浸料粘合在一起而制成的层压板。
优选地，所述的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/cm 2。
第五方面，本发明提供了一种高频电路基板，所述高频电路基板含有至少一张如第三方面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。
优选地，所述金属箔为铜箔、镍箔、铝箔或SUS箔等。
相对于现有技术，本发明具有以下有益效果：
(1)本发明以芳香族聚碳化二亚胺和含羟基的聚膦酸酯和/或含羟基的膦酸酯-碳酸酯共聚物作为环氧树脂的共固化剂，在保证了含羟基的聚膦酸酯和/或含羟基的膦酸酯-碳酸酯共聚物电性能的同时保证最后得到的固化体系具有较高的交联密度以及良好的耐湿热性，同时芳香族聚碳化二亚胺又具有防止酯类基团水解的功能，进而可以提高酯类固化环氧树脂的耐水解性，而含羟基的聚膦酸酯和/或含羟基的膦酸酯-碳酸酯共聚物还具有阻燃剂的功能，在不添加其他阻燃剂的情况下，本发明的固化物的阻燃可以达到UL94 V-0级。
(2)本发明的树脂组合物添加一定量的熔点为100-160℃的芳香族聚碳化二亚胺，可以极大的改善树脂组合物的电性能，同时使树脂组合物具有较好的T g以及可以降低板材的PCT吸水率。
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。
下述实施例和对比例所涉及的材料及牌号信息如下：
(A)芳香族聚碳化二亚胺
A-1：芳香族聚碳化二亚胺Stabaxol P100(莱恩化学，熔点100-120℃)；
A-2：芳香族聚碳化二亚胺HYDROSTAB 2(莱安化学，软化点140℃)；
A-3：芳香族碳化二亚胺单体HYDROSTAB I(莱安化学，软化点50℃)；
A-4：芳香族聚碳化二亚胺Stabaxol P(莱恩化学，软化点60-90℃)；
A-5：非芳香族聚碳化二亚胺(莱茵化学，液体)；
(B)环氧树脂
B-1：双环戊二烯型环氧树脂DNE260A75(台湾长春，EEW：265g/eq)；
B-2：联苯型酚醛环氧树脂NC-3000H(日本化药，EEW：288g/eq)；
B-3：邻甲酚型环氧树脂Epon 164(momentIve，EEW：200g/eq)；
(C)含羟基的聚膦酸酯和/或含羟基的膦酸酯-碳酸酯共聚物
C-1：含端羟基双酚a型聚膦酸酯FRX OL3001(美国FRX Polymers，磷含量10％，分子量3000)；
C-2：含端羟基双酚a型聚膦酸酯FRX OL5001(美国FRX Polymers，磷含量10％，分子量5000)；
C-3：含端羟基双酚a型聚膦酸酯FRX HM1100(美国FRX Polymers，磷含 量10％，分子量11000)；
C-4：含端羟基的膦酸酯-碳酸酯共聚物FRX CO95(美国FRX Polymers，磷含量10.6％，分子量25000)；
C-5：含端羟基联苯型聚膦酸酯(美国FRX Polymers，磷含量10％，分子量15000)；
C-6：不含端羟基聚膦酸酯FRX OL3000(美国FRX Polymers，磷含量10％)；
(D)阻燃剂
D-1：含磷阻燃剂XP-7866(美国雅宝，磷含量13.5％)
D-2：BT-93W(美国雅宝，溴含量67.2％)
(E)促进剂
E-1：2-苯基咪唑(日本四国化成)；
(F)填料
F-1：熔融二氧化硅(平均粒径为1-10μm，纯度99％以上)；
F-2：勃姆石。
实施例1-11
按表1所示组分配制热固性树脂组合物，并按照如下层压板的制作方法制作层压板样品：
将配方量的各组分在溶剂中混合均匀，控制胶液固含量为65％，用2116玻纤布浸渍上述胶液，控制合适厚度，然后在145-175℃的烘箱中烘烤2-15min制成预浸料，然后数张预浸料叠在一起，在其上下两面叠上铜箔，在固化温度为190-200℃，固化压力为30-60Kg/cm 2，固化时间为90-120min条件下制成覆铜板。
对比例1-8
按表2所示组分配制热固性树脂组合物，按照实施例中所述层压板的制作方法制作层压板样品。
表1
Figure PCTCN2018125308-appb-000008
表2
Figure PCTCN2018125308-appb-000009
Figure PCTCN2018125308-appb-000010
性能测试
对实施例1-11和对比例1-8提供的层压板进行性能测试，测试方法如下：
(1)玻璃化转变温度(T g)：根据差示扫描量热法(DSC)，按照IPC-TM-6502.4.25所规定的DSC方法进行测定；
(2)介电常数(Dk)和介电损耗因子(Df)：根据使用条状线的共振法，按照IPC-TM-650 2.5.5.5的方法测定1GHz下的介电损耗、介电损耗因素；
(3)PCT以及PCT吸水率：按照IPC-TM-650 2.6.16的方法进行测定；
(4)耐浸焊性：按照IPC-TM-650 2.4.13.1的方法观察分层起泡时间；
(5)难燃烧性；按照UL 94标准方法进行。
对实施例1-11和对比例1-8提供的层压板的测试结果见表3：
表3
Figure PCTCN2018125308-appb-000011
Figure PCTCN2018125308-appb-000012
由实施例和性能测试可知，由本发明提供的热固性树脂组合物制备得到的覆铜板具有较优异的介电性能、高耐热性能以及较低的吸水率和良好的加工性能，且阻燃能达到UL94 V-0级。
由实施例3-6可知，选择不同分子量以及不同结构的含羟基膦酸酯以及添加熔点为140℃的芳香族聚碳化二亚胺，最后得到的覆铜板表现出较好T g、较低介电损耗同时具有较低PCT吸水率，较好PCT爆板和耐浸焊288℃极限时间性能。
由实施例1-2和对比例1-2的对比可知，相比于添加低熔点的芳香族聚碳化二亚胺，添加熔点在100-160℃的芳香族聚碳化二亚胺可以显著提高最后得到的覆铜板的T g，同时降低其介电损耗以及PCT吸水率，并且可以提高PCT爆板和耐浸焊288℃极限时间。
由实施例1-2和对比例3的对比可知，相比于添加非芳香族聚碳化二亚胺，添加熔点在100-160℃的芳香族聚碳化二亚胺可以显著提高最后得到的覆铜板的T g，同时降低其介电损耗以及PCT吸水率，并且可以提高PCT爆板和耐浸焊288℃极限时间。
由实施例5和对比例4的对比可知，在本发明中，芳香族聚碳化二亚胺和含端羟基的膦酸酯-碳酸酯共聚物作为共固化剂共同固化环氧树脂，可以使最后 得到的覆铜板具有较高的交联密度且具有良好的耐湿热性，同时芳香族聚碳化二亚胺又具有防止酯类基团水解的功能，进而可以提高覆铜板的耐水解性。
由实施例2和对比例5的对比可知，实施例2选用的含端羟基的聚磷酸酯与对比例5选用的不含羟基的聚磷酸酯除了不含端羟基外，分子结构与分子量均相同，由此对比可知，不含羟基的聚磷酸酯虽然可以降低体系的介电损耗，但是却极大的损伤了体系的T g、PCT以及耐浸焊288℃极限等性能，而本发明选用含端羟基的聚磷酸酯可以在降低体系介电损耗的同时提高体系的T g，降低其PCT吸水率，提高PCT爆板和耐浸焊288℃极限时间的效果。
由实施例8-10和对比例6-8的对比可知，在本发明中，芳香族聚碳化二亚胺的添加量应在本发明范围内，若芳香族聚碳化二亚胺的添加量过低，则对介电损耗的降低效果较小；若芳香族聚碳化二亚胺的添加量过高，则反而会使介电损耗有所增加，只有在本发明范围内，最后得到的覆铜板的介电损耗值较低。
因此，本发明的树脂组合物不仅要求环氧树脂、芳香族聚碳化二亚胺、含羟基的聚膦酸酯和/或含羟基的膦酸酯-碳酸酯共聚物等的搭配，还要求满足各组分的配比，才能制得具有优异性能的覆铜板。
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含有它的预浸料、层压板和高频电路基板，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. 一种热固性树脂组合物，其特征在于，所述热固性组合物按重量份数包括如下组分：
    芳香族聚碳化二亚胺                                      5-15重量份；
    环氧树脂                                                30-70重量份；
    含羟基的聚膦酸酯和/或含羟基的膦酸酯-碳酸酯共聚物        5-40重量份；
    其中，所述芳香族聚碳化二亚胺的熔点为100-160℃。
  2. 根据权利要求1所述的热固性树脂组合物，其特征在于，所述芳香族聚碳化二亚胺选自1，3-二-对甲苯基聚碳二亚胺、N，N′-双(2-甲基苯基)碳二亚胺、N-(叔丁基)-N-[1-(2-氯苯基)-1-甲基乙基]聚碳二亚胺或N，N′-苄基-N-环己基聚碳二亚胺中的任意一种或至少两种的组合；
    优选地，所述的环氧树脂包括双酚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组合；
    优选地，所述环氧树脂为具有式I结构的环氧树脂：
    Figure PCTCN2018125308-appb-100001
    其中，X 1、X 2、X 3各自独立地选自
    Figure PCTCN2018125308-appb-100002
    R 1选自氢原子、取代或未取代的C1-C5直链烷基或取代或未取代的C1-C5支链烷基中的 任意一种；
    Y 1、Y 2各自独立地选自单键、-CH 2-、
    Figure PCTCN2018125308-appb-100003
    Figure PCTCN2018125308-appb-100004
    中的任意一种，R 2选自氢原子、取代或未取代的C1-C5直链烷基或取代或未取代的C1-C5支链烷基中的任意一种；
    a为1～10的整数。
  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，所述聚膦酸酯的结构如式II所示：
    Figure PCTCN2018125308-appb-100005
    其中，Ar为芳基，所述-O-Ar-O-基团选自间苯二酚活性基团、对苯二酚活性基团、双酚A活性基团、双酚F活性基团、4，4′-二苯酚活性基团、酚酞活性基团、4，4′-硫代二酚活性基团、4，4′-磺酰二酚活性基团或3，3，5-三甲基环己基二苯酚活性基团中的任意一种；
    X为C1-C20的取代或未取代的直链烷基、C1-C20的取代或未取代的支链烷基、C2-C20的取代或未取代的直链烯烃基、C2-C20的取代或未取代的支链烯烃基、C2-C20的取代或未取代的直链亚烷基、C2-C20的取代或未取代的支链亚烷基、C5-C20的取代或未取代的环烷基或C6-C20取代或未取代的芳基中 的任意一种；
    n为1-75的任意整数；
    优选地，所述膦酸酯-碳酸酯共聚物具有式III或式IV所示结构：
    Figure PCTCN2018125308-appb-100006
    其中，Ar 1、Ar 2、Ar 3各自独立地选自芳基，所述的-O-Ar 3-O-选自间苯二酚活性基团、对苯二酚活性基团、双酚A活性基团、双酚F活性基团、4，4′-二苯酚活性基团、酚酞活性基团、4，4′-硫代二酚活性基团、4，4′-磺酰二酚活性基团或3，3，5-三甲基环己基二苯酚活性基团中的任意一种；
    X 1、X 2各自独立地为C1-C20的取代或未取代的直链烷基、C1-C20的取代或未取代的支链烷基、C2-C20的取代或未取代的直链烯烃基、C2-C20的取代或未取代的支链烯烃基、C2-C20的取代或未取代的直链亚烷基、C2-C20的取代或未取代的支链亚烷基、C5-C20的取代或未取代的环烷基或C6-C20取代或未取代的芳基；
    m为1-100的任意整数，优选5-100的任意整数，进一步优选10-100的任意整数；
    n 1、n 2各自独立地为1-75的任意整数，优选5-75的任意整数，进一步优选 10-75的任意整数；
    p为2-50的任意整数，优选5-50的任意整数，进一步优选10-50的任意整数；
    R 1、R 2各自独立地选自取代或未取代的脂肪族或芳香族烃基，优选为未取代的脂肪族或芳香族烃基；
    优选地，所述聚膦酸酯或/和膦酸酯-碳酸酯共聚物选自
    Figure PCTCN2018125308-appb-100007
    中的任意一种或至少两种的组合；
    其中，R 3、R 4各自独立地选自取代或未取代的脂肪族或芳香族烃基，优选未取代的脂肪族或芳香族烃基；
    m 1为1-100的任意整数，优选5-100的任意整数，进一步优选10-100的任意整数；
    n 3、n 4、n 5各自独立地为1-75的任意整数，优选5-75的任意整数，进一步 优选10-75的任意整数；
    p 1为2-50的任意整数，优选5-50的任意整数，进一步优选10-50的任意整数。
  4. 根据权利要求1-3中的任一项所述的热固性树脂组合物，其特征在于，所述聚膦酸酯、膦酸酯-碳酸酯共聚物的重均分子量各自独立的为1000-60000，优选为2000-50000，进一步优选为2500-10000。
  5. 根据权利要求1-4中的任一项所述的热固性树脂组合物，其特征在于，所述热固性树脂组合物还包括固化促进剂；
    优选地，以芳香族聚碳化二亚胺、环氧树脂、含羟基的聚膦酸酯和/或含羟基的膦酸酯-碳酸酯共聚物的总重量为100重量份计，所述固化促进剂的添加量为0.01-1重量份，进一步优选0.05-0.8重量份，更进一步优选0.05-0.6重量份；
    优选地，所述的固化促进剂选自咪唑类固化剂及其衍生物、路易斯酸、三苯基膦或哌啶类促进剂中的任意一种或至少两种的组合；
    优选地，所述咪唑类固化剂选自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组合。
  6. 根据权利要求1-5中的任一项所述的热固性树脂组合物，其特征在于，所述热固性树脂组合物还包括填料；
    优选地，以芳香族聚碳化二亚胺、环氧树脂、含羟基的聚膦酸酯和/或含羟基的膦酸酯-碳酸酯共聚物的总重量为100重量份计，所述填料的添加量为5-300重量份，进一步优选5-200重量份，更进一步优选5-150重量份；
    优选地，所述填料的中位粒径为0.01-50μm，进一步优选0.01-20μm，更进一步优选0.1-10μm；
    优选地，所述填料选自有机填料或无机填料，进一步优选无机填料，更进 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组合；
    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，进一步优选0.5-3.0重量份，更进一步优选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、无机水合物或无机盐中的任意一种或者至少两种的组合，进一步优选熔融二氧化硅、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、硅酸钙或云母中的任意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、聚苯硫醚或聚醚砜中的任意一种或至少两种的组合。
  7. 一种树脂胶液，其特征在于，所述树脂胶液是将如权利要求1-6中任一项所述的热固性树脂组合物溶解或分散在溶剂中得到。
  8. 一种预浸料，其特征在于，所述预浸料包括增强材料及通过浸渍干燥后附着其上的如权利要求1-6中任一项所述的热固性树脂组合物。
  9. 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8所述的预浸料。
  10. 一种高频电路基板，其特征在于，所述高频电路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。
PCT/CN2018/125308 2018-12-29 2018-12-29 热固性树脂组合物及含有它的预浸料、层压板和高频电路基板 WO2020133337A1 (zh)

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CN103384674A (zh) * 2010-12-22 2013-11-06 Frx聚合物股份有限公司 寡聚的膦酸酯及包括所述寡聚的膦酸酯的组合物
CN103694642A (zh) * 2013-12-27 2014-04-02 广东生益科技股份有限公司 一种热固性树脂组合物及其用途
WO2015134600A1 (en) * 2014-03-04 2015-09-11 Frx Polymers, Inc. Epoxy compositions
CN104910585A (zh) * 2015-06-10 2015-09-16 苏州生益科技有限公司 热固性树脂组合物及使用其制作的半固化片及层压板
CN109705530A (zh) * 2018-12-29 2019-05-03 广东生益科技股份有限公司 热固性树脂组合物及含有它的预浸料、层压板和高频电路基板

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CN103384674A (zh) * 2010-12-22 2013-11-06 Frx聚合物股份有限公司 寡聚的膦酸酯及包括所述寡聚的膦酸酯的组合物
CN102911631A (zh) * 2011-08-05 2013-02-06 汉高股份有限公司 单组分环氧结构粘合剂组合物
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