WO2015188377A1 - 一种苯氧基环三磷腈活性酯、无卤树脂组合物及其用途 - Google Patents

一种苯氧基环三磷腈活性酯、无卤树脂组合物及其用途 Download PDF

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WO2015188377A1
WO2015188377A1 PCT/CN2014/079854 CN2014079854W WO2015188377A1 WO 2015188377 A1 WO2015188377 A1 WO 2015188377A1 CN 2014079854 W CN2014079854 W CN 2014079854W WO 2015188377 A1 WO2015188377 A1 WO 2015188377A1
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Prior art keywords
resin
parts
weight
halogen
free
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PCT/CN2014/079854
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English (en)
French (fr)
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何岳山
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广东生益科技股份有限公司
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Priority to US15/027,369 priority Critical patent/US20160244471A1/en
Priority to KR1020167021440A priority patent/KR20160106673A/ko
Priority to EP14894791.4A priority patent/EP3037475A4/en
Priority to PCT/CN2014/079854 priority patent/WO2015188377A1/zh
Publication of WO2015188377A1 publication Critical patent/WO2015188377A1/zh

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    • C07F9/00—Compounds containing elements of Groups 5 or 15 of the Periodic System
    • C07F9/02—Phosphorus compounds
    • C07F9/547—Heterocyclic compounds, e.g. containing phosphorus as a ring hetero atom
    • C07F9/6564—Heterocyclic compounds, e.g. containing phosphorus as a ring hetero atom having phosphorus atoms, with or without nitrogen, oxygen, sulfur, selenium or tellurium atoms, as ring hetero atoms
    • C07F9/6581—Heterocyclic compounds, e.g. containing phosphorus as a ring hetero atom having phosphorus atoms, with or without nitrogen, oxygen, sulfur, selenium or tellurium atoms, as ring hetero atoms having phosphorus and nitrogen atoms with or without oxygen or sulfur atoms, as ring hetero atoms
    • C07F9/65812—Cyclic phosphazenes [P=N-]n, n>=3
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    • C07F9/02—Phosphorus compounds
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    • C07F9/65812—Cyclic phosphazenes [P=N-]n, n>=3
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    • C09K21/00—Fireproofing materials
    • C09K21/14—Macromolecular materials
    • 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
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Definitions

  • the present invention relates to a phenoxycyclotriphosphazene active ester, a resin-free composition for use in the preparation of a prepreg, a laminate, and a printed wiring board, and a use thereof.
  • a printed wiring board is developed toward a higher-order multilayer printed wiring board while being more precisely wired.
  • an effective method is to lower the dielectric constant of the material used.
  • an effective method is to use a material having a lower dielectric loss tangent (dielectric loss).
  • one of the objects of the present invention is to provide a phenoxycyclotriphosphazene activity.
  • the ester is introduced into the thermosetting resin, and the reactive group carried by it reacts with a specific thermosetting resin or the like without generating a hydroxyl group, which satisfies the halogen-free flame retardant requirement and does not change the dielectric constant and dielectric loss.
  • the corner tangent improves the electrical performance, making it possible to halogen-free high-frequency high-speed substrate materials.
  • the at least 65% is, for example, 66%, 67%, 68%, 69%, 70%, 71%, 72%, 73%,
  • n is, for example, 0.28, 0.35, 0.42, 0.5, 0.6, 0.7, 0.8, 0.9, 1, 1.1, 1.2.
  • An exemplary method for preparing an active ester of phenoxycyclotriphosphazene is as follows:
  • the solvent, the hydroxy-containing phenoxycyclotriphosphazene (the molar ratio of the two hydroxyl groups is more than 65%), the acid binding agent and the catalyst are added to the reaction device, stirred, and protected by nitrogen gas, less than 20 ° C A certain amount of p-benzoyl chloride is gradually added dropwise. After reacting for 1 to 8 hours, an excess of phenol is added, the reaction is continued for 1 to 8 hours, cooled to room temperature, suction filtered, and the filtrate is subjected to pressure distillation to evaporate the solvent to obtain a viscous product. , that is, phenoxycyclotriphosphazene active ester.
  • the phenoxycyclotriphosphazene active ester prepared by this method is a mixture which inevitably contains other components such as impurities, wherein it contains at least 65% of the substance having the above structural formula.
  • Another object of the present invention is to provide a halogen-free resin composition
  • a halogen-free resin composition comprising, by weight: by weight:
  • thermosetting resin is selected from any one or at least two of an epoxy resin, a benzoxazine resin, a cyanate resin, a bismaleimide resin, a reactive polyphenylene ether resin or a hydrocarbon resin. mixture.
  • the reactive polyphenylene ether resin is a polyphenylene ether resin which is crosslinked with a reactive group in the main chain.
  • the parts by weight of the phenoxycyclotriphosphazene active ester are, for example, 7 parts by weight, 9 parts by weight, 11 parts by weight, 13 parts by weight, 15 parts by weight, 17 parts by weight, 19 parts by weight, 21 parts by weight, 23 Parts by weight, 25 parts by weight, 27 parts by weight, 29 parts by weight, 31 parts by weight, 35 parts by weight, 37 parts by weight, 39 parts by weight, 41 parts by weight, 43 parts by weight, 45 parts by weight, 47 parts by weight or 49 parts by weight .
  • the parts by weight of the thermosetting resin are, for example, 18 parts by weight, 21 parts by weight, 24 parts by weight, 27 parts by weight, 30 parts by weight, 33 parts by weight, 36 parts by weight, 39 parts by weight, 42 parts by weight, 45 parts by weight, 48 parts by weight, 51 parts by weight, 54 parts by weight, 57 parts by weight, 60 parts by weight, 63 parts by weight, 66 parts by weight, 69 parts by weight, 72 parts by weight, 75 parts by weight, 78 parts by weight, 81 parts by weight or 84% by weight Share.
  • the parts by weight of the curing agent are, for example, 2 parts by weight, 4 parts by weight, 6 parts by weight, 8 parts by weight, 10 parts by weight, 12 parts by weight, 14 parts by weight, 16 parts by weight, 18 parts by weight, 20 parts by weight, 22 parts by weight, 24 parts by weight, 26 parts by weight, 28 parts by weight, 30 parts by weight, 32 parts by weight or 34 parts by weight.
  • the part by weight of the curing accelerator is, for example, 0.2 parts by weight, 0.5 parts by weight, 0.8 parts by weight, 1.1 parts by weight, 1.4 parts by weight, 1.7 parts by weight, 2 parts by weight, 2.3 parts by weight, 2.6 parts by weight, 2.9 parts by weight, 3.2 parts by weight, 3.5 parts by weight, 3.8 parts by weight, 4.1 parts by weight, 4.4 parts by weight, 4.6 parts by weight Parts or 4.8 parts by weight.
  • the parts by weight of the inorganic filler are, for example, 4 parts by weight, 8 parts by weight, 12 parts by weight, 16 parts by weight, 20 parts by weight, 24 parts by weight, 28 parts by weight, 32 parts by weight, 36 parts by weight, 40 parts by weight, 44 parts by weight, 48 parts by weight, 52 parts by weight, 56 parts by weight, 60 parts by weight, 64 parts by weight, 68 parts by weight, 72 parts by weight, 76 parts by weight, 80 parts by weight, 84 parts by weight, 88 parts by weight, 92 parts by weight Parts, 96 parts by weight or 98 parts by weight, preferably 25 to 100 parts by weight.
  • the invention introduces phenoxycyclotriphosphazene active ester into the thermosetting resin, and reacts the active ester with the epoxy resin to generate no hydroxyl group, thereby satisfying the halogen-free flame retardant requirement and improving the electrical properties of the system (reducing and stabilizing) Dk and Df) make it possible to halogen-free high-frequency high-speed substrate materials.
  • the thermosetting resin has a dicyclopentadiene, a biphenyl or a naphthalene ring, and its dielectric properties are superior to those of other structures of thermosetting resins because of its containing dicyclopentadiene, biphenyl or naphthalene ring groups.
  • the epoxy resin is selected from the group consisting of bisphenol A epoxy resin, bisphenol F epoxy resin, DCPD epoxy resin, trisphenol epoxy resin, biphenyl epoxy resin or naphthol epoxy resin. Any one or a mixture of at least two.
  • the mixture is, for example, a mixture of a bisphenol A type epoxy resin and a bisphenol F type epoxy resin, a mixture of a DCPD epoxy resin and a trisphenol epoxy resin, a mixture of a biphenyl epoxy resin and a naphthol epoxy resin, A mixture of a phenolic A type epoxy resin, a bisphenol F type epoxy resin and a DCPD epoxy resin, a mixture of a trisphenol epoxy resin, a biphenyl epoxy resin, and a naphthol epoxy resin.
  • the epoxy resin has a phosphorus content of 1.5-6.0 wt% (for example, 1.8 wt%, 2.1 wt%, 2.4 wt%, 2.7 wt%, 3 wt%, 3.3 wt%, 3.6 wt%, 3.9 wt%). , 4.2 wt%, 4.5 wt%, 4.8 wt%, 5.1 wt%, 5.4 wt% or 5.7 wt%) of phosphorus-containing epoxy resin.
  • the benzoxazine resin is selected from the group consisting of bisphenol A type benzoxazine resin, bisphenol F type benzoxazole Any one or a mixture of at least two of a azine resin, a DCPD type benzoxazine resin or a phenolphthalein type benzoxazine resin.
  • the mixture is, for example, a mixture of a bisphenol A type benzoxazine resin and a bisphenol F type benzoxazine resin, a mixture of a DCPD type benzoxazine resin and a phenolphthalein type benzoxazine resin, and a bisphenol A type benzoate.
  • the cyanate resin is selected from any one or a mixture of at least two of a bisphenol A type cyanate resin, a DCPD type cyanate resin or a phenol type cyanate resin.
  • the mixture is, for example, a mixture of a bisphenol A type cyanate resin and a DCPD type cyanate resin, a mixture of a phenolic type cyanate resin and a bisphenol A type cyanate resin, a DCPD type cyanate resin and a novolac type cyanide.
  • the bismaleimide resin comprises 4,4'-diphenylmethane bismaleimide or / and allyl-modified diphenylmethane bismaleimide.
  • the reactive polyphenylene ether resin has a number average molecular weight of from 1,000 to 7,000 and a reactive group of a hydroxyl group or a/double bond.
  • the hydrocarbon resin is selected from a vinyl styrene-butadiene resin having a number average molecular weight of 11,000 or less, a vinyl polybutadiene resin having a polar group, or a maleic anhydride grafted butadiene and a styrene resin. Any one or at least two copolymers.
  • the curing agent is selected from any one or a mixture of at least two of dicyandiamide, an aromatic amine, an acid anhydride, a phenolic compound, a triallylene isocyanurate or a phosphorus-containing phenolic aldehyde.
  • the mixture is, for example, a mixture of dicyandiamide and an aromatic amine, a mixture of an acid anhydride and a phenolic compound, a mixture of a trienyl isocyanurate and a phosphorus-containing phenolic aldehyde, a mixture of dicyandiamide, an aromatic amine and an acid anhydride, a phenolic compound, and a different Trienyl cyanurate And a mixture of phosphorus-containing phenolic aldehydes.
  • the curing accelerator is selected from the group consisting of 2-methylimidazole, 2-ethyl-4-methylimidazole, 2-phenylimidazole, pyridine, DMP-30, hexamethylenetetramine, diisopropyl peroxide Any one of benzene, tert-butyl peroxybenzoate, 2,5-di(2-ethylhexanoylperoxy)-2,5-dimethylhexane, acetylacetonate or zincate or a mixture of at least two.
  • the mixture is, for example, a mixture of 2-methylimidazole and 2-ethyl-4-methylimidazole, a mixture of 2-phenylimidazole and pyridine, a mixture of DMP-30 and hexamethylenetetramine, diisopropyl peroxide a mixture of benzene and tert-butyl peroxybenzoate, a mixture of 2,5-bis(2-ethylhexanoylperoxy)-2,5-dimethylhexane, acetylacetonate and zincate, 2 a mixture of methylimidazole, 2-ethyl-4-methylimidazole and 2-phenylimidazole, a mixture of pyridine, DMP-30 and hexamethylenetetramine, dicumyl peroxide, benzoic acid benzoate Mixture of butyl ester, 2,5-bis(2-ethylhexanoylperoxy)-2,5-dimethylhexane
  • the inorganic filler is selected from any one or at least two of aluminum hydroxide, magnesium hydroxide, zeolite, wollastonite, silica, magnesia, calcium silicate, calcium carbonate, clay, talc or mica.
  • aluminum hydroxide magnesium hydroxide
  • zeolite zeolite
  • wollastonite silica
  • magnesia calcium silicate
  • calcium carbonate clay
  • talc talc or mica
  • the mixture for example a mixture of aluminum hydroxide and magnesium hydroxide, a mixture of zeolite and wollastonite, a mixture of silica and magnesia, a mixture of calcium silicate and calcium carbonate, a mixture of clay, talc and mica, hydroxide A mixture of aluminum, magnesium hydroxide and zeolite, a mixture of wollastonite, silica, magnesia and calcium silicate, a mixture of calcium carbonate, clay, talc and mica.
  • the term “comprising” as used in the present invention means that it may include other components in addition to the components, and these other components impart different characteristics to the halogen-free resin composition.
  • the "including” of the present invention may be replaced by a closed “for” or “consisting of”.
  • the halogen-free 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.
  • a third object of the present invention is to provide a prepreg comprising a reinforcing material and a resin composition as described above adhered thereto by dipping and drying.
  • a fourth object of the present invention is to provide a laminate comprising at least one prepreg as described above.
  • a fifth object of the present invention is to provide a printed wiring board comprising at least one prepreg as described above.
  • An exemplary method of preparing a laminate includes the following steps:
  • the prepreg is cut into suitable sizes, neatly superimposed, and a piece of copper foil is placed on the upper and lower sides and placed in a vacuum hot press for pressing to obtain a copper clad laminate.
  • the baking temperature of the step (2) is set according to the boiling point of the solvent used for the glue, the temperature is generally 85 to 175 ° C, and the baking time is generally 5 to 20 minutes.
  • the pressing process adopts a stepwise pressing (step heating and boosting) method, and the specific steps are as follows: 15 minutes from room temperature to 150 ° C for 30 min, then 5 min to 180 ° C for 2 hr, and finally 30min cooling room temperature; pressure Imin from zero to 0.6MPa for 20min, then Imin rose to l.OMPa holding pressure 2.5hr; post-treatment conditions of 200 ⁇ 245 °C for l ⁇ 5hr.
  • the present invention has the following beneficial effects:
  • the invention introduces phenoxycyclotriphosphazene active ester into the thermosetting resin, and reacts the active ester with the epoxy resin to generate no hydroxyl group, thereby satisfying the halogen-free flame retardant requirement and improving the electrical performance of the system.
  • Low, stable Dk and Df) make it possible to halogen-free high-frequency high-speed substrate materials.
  • an active ester of phenoxycyclotriphosphazene and an epoxy resin a benzoxazine resin, a cyanate resin, a bismaleimide resin, a small molecule polyphenylene ether resin, a hydrocarbon resin It is compounded with thermosetting resin, cured with a composite curing agent, mixed with some organic and inorganic fillers, glued, laminated, and laminated to obtain a copper clad laminate.
  • the obtained copper clad laminate meets halogen-free requirements, excellent heat resistance and moisture resistance, and dielectric loss. Low advantage.
  • the solvent, the hydroxy-containing phenoxycyclotriphosphazene (the ratio of the two hydroxyl groups is more than 65%), the acid binding agent and the catalyst are added to the reaction device, stirred, and protected by nitrogen gas, and a certain amount is gradually added at a low temperature.
  • an appropriate amount of phenol is added, the reaction is continued for 1 to 8 hours, cooled to room temperature, suction filtered, and the filtrate is subjected to pressure distillation, and the solvent is evaporated to give a viscous product.
  • DCPD epoxy resin selected DCPD epoxy resin was HP-7200H (DIC), equivalent 275-280), an appropriate amount of imidazole and pyridine were added, and the mixture was stirred and mixed to obtain a gum solution.
  • a 300 X 300 cm, smooth, flat E-glass cloth was applied, and the above glue was uniformly applied and baked in an oven at 155 ° C for 7 min to obtain a bonded sheet.
  • Stepwise (step-by-step heating and boosting) program is used, in which 15 minutes from room temperature to 150 ° C for 30 min, then 5 min to 180 ° C for 2 hr, last 30 min to cool room temperature; pressure Imin rises from zero to The pressure was maintained at 0.6 MPa for 20 min, and then Imin was raised to 1.0 MPa for 2.5 hr.
  • the basic performance is shown in Table 1.
  • the solvent, the hydroxy-containing phenoxycyclotriphosphazene (the ratio of the two hydroxyl groups is more than 65%), the acid binding agent and the catalyst are added to the reaction device, stirred, and protected by nitrogen gas, and a certain amount is gradually added at a low temperature.
  • an appropriate amount of phenol is added, the reaction is continued for 1 to 8 hours, cooled to room temperature, suction filtered, and the filtrate is subjected to pressure distillation, and the solvent is evaporated to give a viscous product.
  • DCPD benzoxazine 40 g selected DCPD benzoxazine is LZ8260 (Huntsman)
  • DCPD epoxy resin 20 g selected DCPD epoxy resin is HP-7200H (DIC) ), equivalent 275-280
  • styrene/maleic anhydride 10g selected anhydride is EF-30, Sartomer
  • appropriate amount of imidazole and pyridine stirred and mixed to obtain a glue.
  • a 300 X 300 cm, smooth, flat E-glass cloth was applied, and the above glue was uniformly applied and baked in an oven at 155 ° C for 7 min to obtain a bonded sheet.
  • Stepwise (step-by-step heating and boosting) program suppression in which 15 minutes from room temperature to 150 ° C for 30 min, then 5 min to 190 ° C for 2 hr, the last 30 min to cool room temperature; pressure Imin rose from zero to The pressure was maintained at 0.6 MPa for 20 min, and then Imin was raised to 1.0 MPa for 2.5 hr.
  • the basic performance is shown in Table 1.
  • the solvent, the hydroxy-containing phenoxycyclotriphosphazene (the ratio of the two hydroxyl groups is more than 65%), the acid binding agent and the catalyst are added to the reaction device, stirred, and protected by nitrogen gas, and a certain amount is gradually added at a low temperature.
  • an appropriate amount of phenol is added, the reaction is continued for 1 to 8 hours, cooled to room temperature, suction filtered, and the filtrate is subjected to pressure distillation, and the solvent is evaporated to give a viscous product.
  • a 300 X 300 cm, smooth, flat E-glass cloth was applied, and the above glue was uniformly applied and baked in an oven at 155 ° C for 7 min to obtain a bonded sheet.
  • Step-by-step (step-by-step heating and boosting) program suppression in which 15 minutes from room temperature to 150 ° C for 30 min, then 5 min to 210 ° C for 2 hr, the last 30 min to cool the room temperature; pressure Imin rose from zero to The pressure was maintained at 0.6 MPa for 20 min, and then Imin was raised to 1.0 MPa for 2.5 hr.
  • Table 1 The basic performance is shown in Table 1.
  • the solvent, the hydroxy-containing phenoxycyclotriphosphazene (the ratio of the two hydroxyl groups is more than 65%), the acid binding agent and the catalyst are added to the reaction device, stirred, and protected by nitrogen gas, and a certain amount is gradually added at a low temperature.
  • an appropriate amount of phenol is added, the reaction is continued for 1 to 8 hours, cooled to room temperature, suction filtered, and the filtrate is subjected to pressure distillation, and the solvent is evaporated to give a viscous product.
  • a 300 X 300 cm, smooth, flat E-glass cloth was applied, and the above glue was uniformly applied and baked in an oven at 155 ° C for 7 min to obtain a bonded sheet.
  • the solvent, the hydroxy-containing phenoxycyclotriphosphazene (the ratio of the two hydroxyl groups is more than 65%), the acid binding agent and the catalyst are added to the reaction device, stirred, and protected by nitrogen gas, and a certain amount is gradually added at a low temperature.
  • an appropriate amount of phenol is added, the reaction is continued for 1 to 8 hours, cooled to room temperature, suction filtered, and the filtrate is subjected to pressure distillation, and the solvent is evaporated to give a viscous product.
  • cyanate ester selected cyanate ester is LONZA-Primaset BA-230s
  • naphthol epoxy resin 5 g HPC-9500 (DIC)
  • appropriate amount of aluminum acetylacetonate is added.
  • pyridine stirring and mixing to obtain a glue.
  • a 300 X 300 cm, smooth, flat E-glass cloth was applied, and the above glue was uniformly applied and baked in an oven at 155 ° C for 7 min to obtain a bonded sheet.
  • Step-by-step (step-by-step heating and boosting) program suppression in which 15 minutes from room temperature to 150 ° C for 30 min, then 5 min to 210 ° C for 2 hr, the last 30 min to cool the room temperature; pressure Imin rose from zero to The pressure was maintained at 0.6 MPa for 20 min, and then Imin was raised to 1.0 MPa for 2.5 hr.
  • Table 1 The basic performance is shown in Table 1.
  • the solvent, the hydroxy-containing phenoxycyclotriphosphazene (the ratio of which contains 2 hydroxyl groups is more than 65%), the acid binding agent and the catalyst are added to the reaction device, stirred, and protected by nitrogen gas, and gradually added at a low temperature.
  • the amount of p-benzoyl chloride is adjusted, and after reacting for 1 to 8 hours, an appropriate amount of phenol is added, the reaction is continued for 1 to 8 hours, cooled to room temperature, suction filtered, and the filtrate is subjected to pressure distillation to evaporate the solvent to obtain a viscous product.
  • DCPD epoxy resin selected DCPD epoxy resin was HP-7200H (DIC), equivalent 275-280), an appropriate amount of imidazole and pyridine were added, and the mixture was stirred and mixed to obtain a gum solution.
  • a 300 X 300 cm, smooth, flat E-glass cloth was applied, and the above glue was uniformly applied and baked in an oven at 155 ° C for 7 min to obtain a bonded sheet.
  • a piece of bonded embossed sheet was superposed, and 18 ⁇ of copper foil was attached to the upper and lower sides, and pressed in a vacuum hot press to obtain a copper clad laminate.
  • Stepwise (step-by-step heating and boosting) program is used, in which 15 minutes from room temperature to 150 ° C for 30 min, then 5 min to 180 ° C for 2 hr, last 30 min to cool room temperature; pressure Imin rises from zero to The pressure was maintained at 0.6 MPa for 20 min, and then Imin was raised to 1.0 MPa for 2.5 hr.
  • the basic performance is shown in Table 1.
  • Example 3 30 g of the phenoxycyclotriphosphazene active ester in Example 3 was replaced with 30 g of the phosphorus-containing phenolic aldehyde (the selected phosphorus-containing phenolic aldehyde was Dow Chemical XZ92741), and the remainder remained unchanged.
  • Example 4 30 g of the phenoxycyclotriphosphazene active ester in Example 4 was replaced with 30 g of the phosphorus-containing phenolic aldehyde (the selected phosphorus-containing phenolic aldehyde was Dow Chemical XZ92741), and the rest remained unchanged.
  • Example 1 30 g of the phenoxycyclotriphosphazene active ester in Example 1 was replaced with 30 g of the active ester (DIC company HP8000), and the rest remained unchanged.
  • R is a phenyl group
  • R1 is an azophosphine skeleton
  • R2 is a phenyl group.
  • the symbols in the table indicate no change, ⁇ indicates white spots, and X indicates stratification.
  • the dielectric loss factor at 1 GHz was measured according to IPC-TM-650 2.5.5.5 according to the resonance method using a strip line.
  • a 1.60 mm thick substrate was placed on a die of a certain pattern for punching, and the human eye was observed by the naked eye (hi), there was no white circle at the edge of the hole, (h2) a white circle was formed at the edge of the hole, and (h3) the edge of the hole was split, and the table was respectively separated.
  • the active ester of phenoxycyclotriphosphazene is used, and the antimony and antimony atoms are more effective than the DIC 8000 active ester, and the flame retardant effect is better; and the active ester phase containing the phosphate ester of Comparative Example 4 Compared with the low water absorption rate, the present invention adopts phenoxycyclotriphosphazene active ester, which can achieve halogen-free flame retardant (halogen content within the requirements of JPCA halogen-free standard) without lowering the dielectric properties, and has excellent It has good heat resistance and good processability.
  • halogen-free flame retardant halogen content within the requirements of JPCA halogen-free standard

Abstract

一种苯氧基环三磷腈活性酯、无卤树脂组合物及其用途。所述苯氧基环三磷腈活性酯含有至少65％摩尔比的具有如下结构式的物质。该无卤树脂组合物按重量份数包括：5～50重量份的苯氧基环三磷腈活性酯、15～85重量份的热固性树脂、1～35重量份的固化剂、0～5重量份的固化促进剂以及0～100份的无机填料。通过在热固性树脂中引入苯氧基环三磷腈活性酯，利用活性酯与环氧树脂等热固性树脂反应不产生羟基，既能满足无卤阻燃要求，又能改良体系电性能(降低、稳定Dk和Df)，使高频高速基板材料无卤化成为可能。

Description

一种苯氧基环三磷腈活性酯、 无卤树脂组合物及其用途 技术领域
本发明涉及一种苯氧基环三磷腈活性酯、 无^树脂组合物及其用途， 所述 无卤树脂组合物用于制备预浸料、 层压板以及印制线路板。
背景技术
近年来， 随着电子设备、 高密度电子仪器组件和高密度印刷线路板布线中 用到的半导体器件的集成技术、 接合技术和装配技术的发展， 电子设备得到了 不断进步， 尤其是在那些使用宽带的电子设备如移动通信装置上有了快速的发 展。
印刷线路板作为这种电子设备的一个构成， 向着更高成都的多层印刷线路 板的同时更为精密布线发展。 为了将信号传输速度提高到加速信息处理所需要 的水平， 有效方法是降低所使用材料的介电常数， 为了降低传输损耗， 有效办 法是使用较低介电损耗正切 （介电损耗） 的材料。
电子技术迅速发展的同时， 人们也越来越最求环境保护， 但传统的高频高 速材料基本上是使用卤化物、 锑化物等来达到阻燃目的， 含卤化物的覆铜板着 火燃烧时， 不但发烟量大， 气味难闻， 而且会放出毒性大、 腐蚀性强的卤化氢 气体， 不仅污染环境， 也危害人体健康； 目前工业上普遍使用含磷有菲型化合 物 DOPO或 ODOPB对应的环氧树脂来实现普通 FR-4来达到阻燃， 但是含磷有 菲型化合物 DOPO 或 ODOPB 依然有较大的吸水率对高频高速材料的介电常 数， 介质损耗角正切有极大的影响。
发明内容
针对已有技术的问题， 本发明的目的之一在于提供一种苯氧基环三磷腈活 性酯， 将其引入热固性树脂中， 利用其带有的反应性基团与特定的热固性树脂 等反应不产生羟基， 既能满足无卤阻燃要求， 又不太大改变介电常数和介质损 耗角正切， 实现电性能的改良， 使高频高速基板材料无卤化成为可能。
为了达到上述目的， 本发明采用了如下技术方案：
一 三磷腈活性酯， 其含有至少 65%的具有如下结构式的物质：
Figure imgf000003_0001
所述至少 65%例如为 66%、 67%、 68%、 69%、 70%、 71%、 72%、 73%、
74%、 75%、 76%、 77%、 78%、 79%、 80%、 81%、 82%、 83%、 84%、 85%、
86%、 87%、 88%、 89%、 90%、 91%、 92%、 93%、 94%、 95%、 96%、 97%、
98%或 99%。
所述 n例如为 0.28、 0.35、 0.42、 0.5、 0.6、 0.7、 0.8、 0.9、 1、 1.1、 . 1.2、
1.3、 1.4、 1.5、 1.6、 1.7、 1.8、 1.9、 2、 2.1、 2.2、 2.3、 2.4、 2.5、 2.6、 2.7、
2.8或 2.9。
示例性的苯氧基环三磷腈活性酯的制备方法如下所示：
将溶剂、 含有羟基的苯氧基环三磷腈 （其中含 2个羟基的摩尔比比例大于 65%) 、 缚酸剂和催化剂加入反应装置内， 搅拌， 通入氮气保护， 小于 20°C下 逐步滴加一定量对苯甲酰氯， 反应 1〜8 小时后， 加入过量的苯酚， 继续反应 1〜8 小时冷却至室温， 抽滤， 对滤液进行加压蒸馏， 蒸发溶剂， 得到粘稠状产 物， 即苯氧基环三磷腈活性酯。 由该方法制备得到的苯氧基环三磷腈活性酯是一混合物， 其不可避免的包 含其他组分如杂质， 其中， 其含有至少 65%的具有上述结构式的物质。
本发明的目的之二在于提供一种无卤树脂组合物， 所述无卤树脂组合物按 重量份数包括：
5-50重量份的苯氧基环三磷腈活性酯、 15〜85重量份的热固性树脂、 1〜35 重量份的固化剂、 0〜5重量份的固化促进剂以及 0〜100份的无机填料；
其中， 所述热固性树脂选自环氧树脂、 苯并噁嗪树脂、 氰酸酯树脂、 双马 来酰亚胺树脂、 反应性聚苯醚树脂或碳氢树脂中的任意一种或者至少两种的混 合物。
所述反应性聚苯醚树脂即主链上弓 I入交联反应性基团的聚苯醚树脂。
所述苯氧基环三磷腈活性酯的重量份数例如为 7重量份、 9重量份、 11重 量份、 13重量份、 15重量份、 17重量份、 19重量份、 21重量份、 23重量份、 25重量份、 27重量份、 29重量份、 31重量份、 35重量份、 37重量份、 39重 量份、 41重量份、 43重量份、 45重量份、 47重量份或 49重量份。
所述热固性树脂的重量份数例如为 18重量份、 21重量份、 24重量份、 27 重量份、 30重量份、 33重量份、 36重量份、 39重量份、 42重量份、 45重量 份、 48重量份、 51重量份、 54重量份、 57重量份、 60重量份、 63重量份、 66 重量份、 69重量份、 72重量份、 75重量份、 78重量份、 81重量份或 84重量 份。
所述固化剂的重量份数例如为 2重量份、 4重量份、 6重量份、 8重量份、 10重量份、 12重量份、 14重量份、 16重量份、 18重量份、 20重量份、 22重 量份、 24重量份、 26重量份、 28重量份、 30重量份、 32重量份或 34重量份。
所述固化促进剂的重量份数例如为 0.2重量份、 0.5重量份、 0.8重量份、 1.1重量份、 1.4重量份、 1.7重量份、 2重量份、 2.3重量份、 2.6重量份、 2.9 重量份、 3.2重量份、 3.5重量份、 3.8重量份、 4.1重量份、 4.4重量份、 4.6重 量份或 4.8重量份。
所述无机填料的重量份数例如为 4重量份、 8重量份、 12重量份、 16重量 份、 20重量份、 24重量份、 28重量份、 32重量份、 36重量份、 40重量份、 44 重量份、 48重量份、 52重量份、 56重量份、 60重量份、 64重量份、 68重量 份、 72重量份、 76重量份、 80重量份、 84重量份、 88重量份、 92重量份、 96 重量份或 98重量份， 优选 25〜100重量份。
本发明通过在热固性树脂中引入苯氧基环三磷腈活性酯， 利用活性酯与环 氧树脂等反应不产生羟基， 既能满足无卤阻燃要求， 又能改良体系电性能 （降 低、 稳定 Dk和 Df) ， 使高频高速基板材料无卤化成为可能。
优选地， 热固性树脂具有双环戊二烯、 联苯或萘环， 因含双环戊二烯、 联 苯基或萘环基团， 其介电性能比其它结构的热固性树脂更优越。
优选地， 所述环氧树脂选自双酚 A型环氧树脂、 双酚 F 型环氧树脂、 DCPD 环氧树脂、 三酚环氧树脂、 联苯环氧树脂或萘酚环氧树脂中的任意一种 或者至少两种的混合物。 所述混合物例如双酚 A型环氧树脂和双酚 F型环氧树 脂的混合物， DCPD 环氧树脂和三酚环氧树脂的混合物， 联苯环氧树脂和萘酚 环氧树脂的混合物， 双酚 A型环氧树脂、 双酚 F型环氧树脂和 DCPD环氧树脂 的混合物， 三酚环氧树脂、 联苯环氧树脂和萘酚环氧树脂的混合物。
优选地， 所述环氧树脂为磷含量在 1.5-6.0wt% (例如 1.8 wt%、 2.1 wt%、 2.4 wt%、 2.7 wt%, 3 wt%、 3.3 wt%、 3.6 wt%、 3.9 wt%、 4.2 wt%、 4.5 wt%、 4.8 wt%、 5.1 wt%, 5.4 wt%或5.7 wt%) 的含磷环氧树脂。
优选地， 所述苯并噁嗪树脂选自双酚 A型苯并噁嗪树脂、 双酚 F型苯并噁 嗪树脂、 DCPD 型苯并噁嗪树脂或酚酞型苯并噁嗪树脂中的任意一种或者至少 两种的混合物。 所述混合物例如双酚 A型苯并噁嗪树脂和双酚 F型苯并噁嗪树 脂的混合物， DCPD型苯并噁嗪树脂和酚酞型苯并噁嗪树脂的混合物， 双酚 A 型苯并噁嗪树脂、 双酚 F型苯并噁嗪树脂和 DCPD型苯并噁嗪树脂的混合物， 酚酞型苯并噁嗪树脂、 双酚 A 型苯并噁嗪树脂、 双酚 F 型苯并噁嗪树脂、 DCPD型苯并噁嗪树脂和酚酞型苯并噁嗪树脂的混合物。
优选地， 所述氰酸酯树脂选自双酚 A型氰酸酯树脂、 DCPD型氰酸酯树脂 或酚醛型氰酸酯树脂中的任意一种或者至少两种的混合物。 所述混合物例如双 酚 A型氰酸酯树脂和 DCPD型氰酸酯树脂的混合物， 酚醛型氰酸酯树脂和双酚 A 型氰酸酯树脂的混合物， DCPD 型氰酸酯树脂和酚醛型氰酸酯树脂的混合 物， 双酚 A型氰酸酯树脂、 DCPD 型氰酸酯树脂和酚醛型氰酸酯树脂的混合 物。
优选地， 所述双马来酰亚胺树脂包括 4,4'-二苯甲烷双马来酰亚胺或 /和烯 丙基改性二苯甲烷双马来酰亚胺。
优选地， 所述反应性聚苯醚树脂的数均分子量在 1000〜7000， 其反应基团 为羟基或 /和双键。
优选地， 所述碳氢树脂选自数均分子量在 11000以下的乙烯基丁苯树脂、 带极性基团的乙烯基聚丁二烯树脂或马来酸酐接枝丁二烯与苯乙烯树脂中的任 意一种或者至少两种的共聚物。
优选地， 所述固化剂选自双氰胺、 芳香胺、 酸酐、 酚类化合物、 异氰尿酸 三烯酯或含磷酚醛中的任意一种或者至少两种的混合物。 所述混合物例如双氰 胺和芳香胺的混合物， 酸酐和酚类化合物的混合物， 异氰尿酸三烯酯和含磷酚 醛的混合物， 双氰胺、 芳香胺和酸酐的混合物， 酚类化合物、 异氰尿酸三烯酯 和含磷酚醛的混合物。
优选地， 所述固化促进剂选自 2-甲基咪唑、 2-乙基 -4 甲基咪唑、 2-苯基咪 唑、 吡啶、 DMP-30、 六次甲基四胺、 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、 乙酰丙酮酸盐或锌酸盐中的任意 一种或者至少两种的混合物。 所述混合物例如 2-甲基咪唑和 2-乙基 -4甲基咪唑 的混合物， 2-苯基咪唑和吡啶的混合物， DMP-30 和六次甲基四胺的混合物， 过氧化二异丙苯和过氧化苯甲酸叔丁酯的混合物， 2,5-二 (2-乙基己酰过氧 )-2,5- 二甲基己烷、 乙酰丙酮酸盐和锌酸盐的混合物， 2-甲基咪唑、 2-乙基 -4 甲基咪 唑和 2-苯基咪唑的混合物， 吡啶、 DMP-30和六次甲基四胺的混合物， 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、 乙 酰丙酮酸盐和锌酸盐的混合物。
优选地， 所述无机填料选自氢氧化铝、 氢氧化镁、 沸石、 硅灰石、 二氧化 硅、 氧化镁、 硅酸钙、 碳酸钙、 粘土、 滑石或云母中的任意一种或者至少两种 的混合物。 所述混合物例如氢氧化铝和氢氧化镁的混合物， 沸石和硅灰石的混 合物， 二氧化硅和氧化镁的混合物， 硅酸钙和碳酸钙的混合物， 粘土、 滑石和 云母的混合物， 氢氧化铝、 氢氧化镁和沸石的混合物， 硅灰石、 二氧化硅、 氧 化镁和硅酸钙的混合物， 碳酸钙、 粘土、 滑石和云母的混合物。
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。 本发明的目的之三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 ^树脂组合物。
本发明的目的之四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。
本发明的目的之五在于提供一种印制线路板， 所述印制线路板含有至少一 张如上所述的预浸料。
示例性的层压板的制备方法包括如下步骤：
( 1 )将配方量的苯氧基环三磷腈活性酯溶于苯类或酮类等溶剂中， 在常温 或中温条件下完全溶解；
(2 )将配方量的热固性树脂、 固化剂、 任选地固化促进剂以及任选地无机 填料加入步骤 （1 ) 所得溶液中， 搅拌均匀得到胶液， 选取表面平整的增强材 料， 均匀涂覆上述胶液， 然后烘制成预浸料；
(3 )根据压机大小， 将预浸料切成合适的尺寸， 整齐叠加， 并上下各放一 张铜箔置于真空热压机中进行压制， 得到覆铜箔层压板。
步骤（2)所述烘制温度根据胶液所用溶剂的沸点来设置， 温度范围一般为 85〜175 °C， 烘制时间一般在 5〜20min。
步骤（3 ) 中， 压制工艺采用阶梯式压制（分步升温及升压）法， 具体步骤 为： 15分钟从室温升至 150°C保持 30min， 然后 5min升至 180°C保持 2hr， 最后 30min 降温室温； 压力 Imin从零升至 0.6MPa保压 20min， 然后 Imin升至 l .OMPa保压 2.5hr; 后处理条件为 200〜245 °C保持 l〜5hr。
与已有技术相比， 本发明具有如下有益效果：
本发明通过在热固性树脂中引入苯氧基环三磷腈活性酯， 利用活性酯与环 氧树脂等反应不产生羟基， 既能满足无卤阻燃要求， 又能改良体系电性能 （降 低、 稳定 Dk和 Df) ， 使高频高速基板材料无卤化成为可能。
此外， 在本发明中， 苯氧基环三磷腈活性酯与环氧树脂、 苯并噁嗪树脂、 氰酸酯树脂、 双马来酰亚胺树脂、 小分子聚苯醚树脂、 碳氢树脂等热固性树脂 复配， 用复合固化剂加以固化， 配合一些有机、 无机填料进行混胶、 上胶、 层 压得到覆铜板， 所得覆铜板满足无卤要求， 耐热、 耐湿优异， 且介电损耗低等 优点。
具体实舫式
下面通过具体实施方式来进一步说明本发明的技术方案。
实施例 1
将溶剂、 含有羟基的苯氧基环三磷腈 (其中含 2个羟基的比例大于 65%)、 缚酸剂和催化剂加入反应装置内， 搅拌， 通入氮气保护， 低温下逐步滴加一定 量对苯甲酰氯， 反应 1〜8小时后， 加入适量苯酚， 继续反应 1〜8小时冷却至室 温， 抽滤， 对滤液进行加压蒸馏， 蒸发溶剂， 得到粘稠状产物。
取上述产物 30g溶于有机溶剂后， 加入 DCPD环氧树脂 70g (所选 DCPD 环氧树脂为 HP-7200H (DIC) ， 当量 275-280) 、 适量的咪唑和吡啶， 搅拌混 合均匀得到胶液。
选取 300 X 300cm、 表面光洁、 平整的 E-玻纤布， 均匀涂覆上述胶液， 在 烘箱中 155°C下烘烤 7min制得粘结片。
将 5张裁去毛边的粘结片叠加， 上下附上 35μη 的铜箔， 置于真空热压机 中压制得到覆铜板。 采用阶梯式 （分步升温及升压） 程序压制， 其中， 15分钟 从室温升至 150°C保持 30min， 然后 5min升至 180°C保持 2hr， 最后 30min降温 室温； 压力 Imin从零升至 0.6MPa保压 20min， 然后 Imin升至 l.OMPa保压 2.5hr。 基本性能如表 1。 实施例 2
将溶剂、 含有羟基的苯氧基环三磷腈 (其中含 2个羟基的比例大于 65%)、 缚酸剂和催化剂加入反应装置内， 搅拌， 通入氮气保护， 低温下逐步滴加一定 量对苯甲酰氯， 反应 1〜8小时后， 加入适量苯酚， 继续反应 1〜8小时冷却至室 温， 抽滤， 对滤液进行加压蒸馏， 蒸发溶剂， 得到粘稠状产物。
取上述产物 30g溶于有机溶剂后， 加入 DCPD苯并噁嗪 40g (所选 DCPD 苯并噁嗪为 LZ8260 (Huntsman) ) 、 DCPD环氧树脂 20g (所选 DCPD环氧树 脂为 HP-7200H (DIC) ， 当量 275-280) 、 苯乙烯 /顺丁烯二酸酐 10g (所选酸 酐为 EF-30, Sartomer) 、 适量的咪唑和吡啶， 搅拌混合均匀得到胶液。
选取 300 X 300cm、 表面光洁、 平整的 E-玻纤布， 均匀涂覆上述胶液， 在 烘箱中 155°C下烘烤 7min制得粘结片。
将 5张裁去毛边的粘结片叠加， 上下附上 35μη 的铜箔， 置于真空热压机 中压制得到覆铜板。 采用阶梯式 （分步升温及升压） 程序压制， 其中， 15分钟 从室温升至 150°C保持 30min， 然后 5min升至 190°C保持 2hr， 最后 30min降温 室温； 压力 Imin从零升至 0.6MPa保压 20min， 然后 Imin升至 l.OMPa保压 2.5hr。 基本性能如表 1。
实施例 3
将溶剂、 含有羟基的苯氧基环三磷腈 (其中含 2个羟基的比例大于 65%)、 缚酸剂和催化剂加入反应装置内， 搅拌， 通入氮气保护， 低温下逐步滴加一定 量对苯甲酰氯， 反应 1〜8小时后， 加入适量苯酚， 继续反应 1〜8小时冷却至室 温， 抽滤， 对滤液进行加压蒸馏， 蒸发溶剂， 得到粘稠状产物。
取上述产物 30g溶于有机溶剂后， 加入 DCPD氰酸酯 30g (所选 DCPD氰 酸酯为 LONZA-Primaset DT-4000) 、 4,4 ' -二苯甲烷双马来酰亚胺 20g、 DCPD 环氧树脂 20g (所选 DCPD环氧树脂为 HP-7200H (DIC) ， 当量 275-280) 、 适量的乙酰丙酮酸铝和吡啶， 搅拌混合均匀得到胶液。
选取 300 X 300cm、 表面光洁、 平整的 E-玻纤布， 均匀涂覆上述胶液， 在 烘箱中 155°C下烘烤 7min制得粘结片。
将 5张裁去毛边的粘结片叠加， 上下附上 35μη 的铜箔， 置于真空热压机 中压制得到覆铜板。 采用阶梯式 （分步升温及升压） 程序压制， 其中， 15分钟 从室温升至 150°C保持 30min， 然后 5min升至 210°C保持 2hr， 最后 30min降温 室温； 压力 Imin从零升至 0.6MPa保压 20min， 然后 Imin升至 l.OMPa保压 2.5hr。 基本性能如表 1。
实施例 4
将溶剂、 含有羟基的苯氧基环三磷腈 (其中含 2个羟基的比例大于 65%)、 缚酸剂和催化剂加入反应装置内， 搅拌， 通入氮气保护， 低温下逐步滴加一定 量对苯甲酰氯， 反应 1〜8小时后， 加入适量苯酚， 继续反应 1〜8小时冷却至室 温， 抽滤， 对滤液进行加压蒸馏， 蒸发溶剂， 得到粘稠状产物。
取上述产物 30g溶于有机溶剂后， 加入反应性聚苯醚树脂 50g (所选反应 性聚苯醚树脂 MX9000, SABIC) 、 DCPD环氧树脂 20g (所选 DCPD环氧树 脂为 HP-7200H (DIC) ， 当量 275-280) 、 适量的 2,5-二（2-乙基己酰过氧）和 吡啶， 搅拌混合均匀得到胶液。
选取 300 X 300cm、 表面光洁、 平整的 E-玻纤布， 均匀涂覆上述胶液， 在 烘箱中 155°C下烘烤 7min制得粘结片。
将 5张裁去毛边的粘结片叠加， 上下附上 35μη 的铜箔， 置于真空热压机 中压制得到覆铜板。 采用阶梯式 （分步升温及升压） 程序压制， 其中， 15分钟 从室温升至 150°C保持 30min， 然后 5min升至 190°C保持 2hr， 最后 30min降温 室温； 压力 Imin从零升至 0.6MPa保压 20min， 然后 Imin升至 l.OMPa保压 2.5hr。 基本性能如表 1。 用双酚 A酚醛型环氧树脂 （BNE200, 台湾长春人造树脂厂） 替换 DCPD 环氧树脂， 其余与实施例 1相同。
实施例 6
将溶剂、 含有羟基的苯氧基环三磷腈 (其中含 2个羟基的比例大于 65%)、 缚酸剂和催化剂加入反应装置内， 搅拌， 通入氮气保护， 低温下逐步滴加一定 量对苯甲酰氯， 反应 1〜8小时后， 加入适量苯酚， 继续反应 1〜8小时冷却至室 温， 抽滤， 对滤液进行加压蒸馏， 蒸发溶剂， 得到粘稠状产物。
取上述产物 10g 溶于有机溶剂后， 加入氰酸酯 15g (所选氰酸酯为 LONZA-Primaset BA-230s ) 、 萘酚环氧树脂 5g (HPC-9500 (DIC) 、 适量的 乙酰丙酮酸铝和吡啶， 搅拌混合均匀得到胶液。
选取 300 X 300cm、 表面光洁、 平整的 E-玻纤布， 均匀涂覆上述胶液， 在 烘箱中 155°C下烘烤 7min制得粘结片。
将 2张裁去毛边的粘结片叠加， 上下附上 35μη 的铜箔， 置于真空热压机 中压制得到覆铜板。 采用阶梯式 （分步升温及升压） 程序压制， 其中， 15分钟 从室温升至 150°C保持 30min， 然后 5min升至 210°C保持 2hr， 最后 30min降温 室温； 压力 Imin从零升至 0.6MPa保压 20min， 然后 Imin升至 l.OMPa保压 2.5hr。 基本性能如表 1。
实施例 7
将溶剂、 含有羟基的苯氧基环三磷腈 (其中含 2个羟基的比例大于 65%)、 缚酸剂和催化剂加入反应装置内， 搅拌， 通入氮气保护， 低温下逐步滴加一定 量对苯甲酰氯， 反应 1〜8小时后， 加入适量苯酚， 继续反应 1〜8小时冷却至室 温， 抽滤， 对滤液进行加压蒸馏， 蒸发溶剂， 得到粘稠状产物。
取上述产物 50g溶于有机溶剂后， 加入 DCPD环氧树脂 85g (所选 DCPD 环氧树脂为 HP-7200H (DIC) ， 当量 275-280) 、 适量的咪唑和吡啶， 搅拌混 合均匀得到胶液。
选取 300 X 300cm、 表面光洁、 平整的 E-玻纤布， 均匀涂覆上述胶液， 在 烘箱中 155°C下烘烤 7min制得粘结片。
将 1张裁去毛边的粘结片叠加， 上下附上 18μη 的铜箔， 置于真空热压机 中压制得到覆铜板。 采用阶梯式 （分步升温及升压） 程序压制， 其中， 15分钟 从室温升至 150°C保持 30min， 然后 5min升至 180°C保持 2hr， 最后 30min降温 室温； 压力 Imin从零升至 0.6MPa保压 20min， 然后 Imin升至 l.OMPa保压 2.5hr。 基本性能如表 1。
比较例 1
将实施例 3中的 30g苯氧基环三磷腈活性酯替换为 30g含磷酚醛 （所选含 磷酚醛为 Dow Chemical XZ92741 ) ， 其余不变。
比较例 2
将实施例 4中的 30g苯氧基环三磷腈活性酯替换为 30g含磷酚醛 （所选含 磷酚醛为 Dow Chemical XZ92741 ) ， 其余不变。
比较例 3
将实施例 1 中 30g苯氧基环三磷腈活性酯替换为 30g活性酯 （DIC公司 HP8000) ， 其余不变。
比较例 4
将实施例 2 中 30g苯氧基环三磷腈活性酯替换为 30g其它偶磷氮类活性
S
， 结构式如下:
Figure imgf000014_0001
R为苯基， R1为偶磷氮骨架， R2为苯基。
其余不变。
基本性能如表 1。
1特性评估
实 实 实 实 实施 实施 实施 比 比 比较 比较 施 施 施 施 例 5 例 6 例 7 较 较 例 3 例 4 例 1 例 2 例 3 例 4 例 1 例 2
玻璃化转 195-2 195-2 160-1 180-1 190-2
170 180 195 185 200 190
变温度 25 30 70 90 00
(Tg，。c，
180 195 225 215 230 220
DMA)
剥离强度 >1.2 >1.0 >1.2 >1.0 >1.0
>1. >1. >0. >0. >1. >1.
( 1/20Z,
2 2 8 8 0 0
N/mm)
耐 燃 烧 V-1 V-0 V-0 燃烧 V-1 ( 1.60m V-1 V-0 V-0 V-0 V-0 V-0
m)
耐浸焊性 〇 〇 〇 〇 X
〇 Δ 〇 〇 〇 〇
(分层）
吸水性 0.010 0.006 0.008 0.06 0.15
0.07 0.06 0.08 0.07 0.12 0.12
(%)
介 电 4.3 3.9 4.1 3.9 4.0 常数
4.0 4.2 3.8 3.6 3.7 3.5
(RC50,
1GHZ)
0.018 0.004 0.011 0.009 0.010
0.01 0.00 0.00 0.00 0.00 0.00
0 9 5 3 5 3
T-30 >12 >12 >60 >120 >60 >12 >12 >120 >30
>60 >60
0/min 0 0 0 0 冲孔 〇 〇 〇 〇 〇
〇 Δ 〇 〇 Δ 〇
性
以上特性的测试方法如下：
耐燃烧性 （难燃性） ： 依据 UL 94法测定。 耐浸焊性：
将在 121 °C和 105KPa的加压蒸煮处理装置内保持 2小时后的试样 （100 X 100mm的基材）浸在加热至 260 °C的焊锡槽中 20秒钟， 以肉眼观察（hi )有无 分层， （h2) 有无发生白斑或起皱。 表中的符号〇示无变化， Δ示发生白斑， X示发生分层。
吸水性：
按照 IPC-TM-650 2.6.2.1方法进行测定。 介电损耗因数：
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 损耗因数。
冲孔性：
将 1.60mm厚的基材放于一定图形的冲模上进行冲孔， 以肉眼观察 （hi ) 孔边无白圈， （h2) 孔边有白圈， （h3 ) 孔边裂开， 表中分别以符号〇、 Δ、
上述结果可知， 依据本发明采用苯氧基环三磷腈活性酯， 与 DIC 公司 ΗΡ8000活性酯相比， 含有 Ν与 Ρ原子， 阻燃效果更佳； 与比较例 4含磷酸酯 的活性酯相比， 吸水率低， 本发明采用苯氧基环三磷腈活性酯， 可达到不降低 介电性能的基础上达到无卤阻燃 （卤素含量在 JPCA无卤标准要求范围内） ， 且具有优异的耐热性， 同时也具有较好的可加工性。 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

权 利 要 求 书
1、 一种苯氧基环三磷腈活性酯， 其特征在于， 其含有至少 65%摩尔比的 ：
Figure imgf000017_0001
式中，
Figure imgf000017_0002
n 0.25-3的任意数。
2、 一种无^树脂组合物， 其特征在于， 所述无 ^树脂组合物按重量份数 包括:
50重量份的权利要求 1所述的苯氧基环三磷腈活性酯、 15〜85重量份的 热固性树脂、 1〜35重量份的固化剂、 0〜5重量份的固化促进剂以及 0〜100份的 无机填料；
其中， 所述热固性树脂选自环氧树脂、 苯并噁嗪树脂、 氰酸酯树脂、 双马 来酰亚胺树脂、 反应性聚苯醚树脂或碳氢树脂中的任意一种或者至少两种的混 合物。
3、 如权利要求 2所述的无卤树脂组合物， 其特征在于， 所述热固性树脂具 有双环戊二烯、 联苯或萘环基团。
4、 如权利要求 2或 3所述的无卤树脂组合物， 其特征在于， 所述环氧树脂 选自双酚 A型环氧树脂、 双酚 F型环氧树脂、 DCPD环氧树脂、 三酚环氧树 脂、 联苯环氧树脂或萘酚环氧树脂中的任意一种或者至少两种的混合物。
5、 如权利要求 2或 3所述的无卤树脂组合物， 其特征在于， 所述环氧树脂 为磷含量在 1.5-6.0wt%的含磷环氧树脂。
6、 如权利要求 2或 3所述的无卤树脂组合物， 其特征在于， 所述苯并噁嗪 树脂选自双酚 A型苯并噁嗪树脂、 双酚 F型苯并噁嗪树脂、 DCPD型苯并噁嗪 树脂或酚酞型苯并噁嗪树脂中的任意一种或者至少两种的混合物。
7、 如权利要求 2或 3所述的无卤树脂组合物， 其特征在于， 所述氰酸酯树 脂选自双酚 A型氰酸酯树脂、 DCPD型氰酸酯树脂或酚醛型氰酸酯树脂中的任 意一种或者至少两种的混合物。
8、 如权利要求 2或 3所述的无卤树脂组合物， 其特征在于， 所述双马来酰 亚胺树脂包括 4,4'-二苯甲烷双马来酰亚胺或 /和烯丙基改性二苯甲烷双马来酰 亚胺。
9、 如权利要求 2或 3所述的无卤树脂组合物， 其特征在于， 所述反应性聚 苯醚树脂的数均分子量在 1000〜7000， 其反应基团为羟基或 /和双键。
10、 如权利要求 2或 3所述的无卤树脂组合物， 其特征在于， 所述碳氢树 脂选自数均分子量在 11000 以下的乙烯基丁苯树脂、 带极性基团的乙烯基聚丁 二烯树脂或马来酸酐接枝丁二烯与苯乙烯树脂中的任意一种或至少两种的共聚 物。
11、 如权利要求 2所述的无卤树脂组合物， 其特征在于， 所述固化剂选自 双氰胺、 芳香胺、 酸酐、 酚类化合物、 异氰尿酸三烯酯或含磷酚醛中的任意一 种或者至少两种的混合物。
12、 如权利要求 2所述的无卤树脂组合物， 其特征在于， 所述固化促进剂 选自 2-甲基咪唑、 2-乙基 -4甲基咪唑、 2-苯基咪唑、 B比啶、 DMP-30、 六次甲基 四胺、 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、 乙酰丙酮酸盐或锌酸盐中的任意一种或者至少两种的混合物。
13、 如权利要求 2所述的无卤树脂组合物， 其特征在于， 所述无机填料选 自氢氧化铝、 氢氧化镁、 沸石、 硅灰石、 二氧化硅、 氧化镁、 硅酸钙、 碳酸 钙、 粘土、 滑石或云母中的任意一种或者至少两种的混合物。
14、 如权利要求 2所述的无卤树脂组合物， 其特征在于， 所述无机填料的 重量份数为 25〜100重量份。
15、 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 后附着在其上的如权利要求 2-14之一所述的无卤树脂组合物。
16、 一种层压板， 其特征在于， 所述层压板含有至少一张如权利要求 15 所述的预浸料。
17、 一种印制线路板， 其特征在于， 所述印制线路板含有至少一张如权利 要求 15所述的预浸料。
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CN108164685A (zh) * 2016-12-07 2018-06-15 广东生益科技股份有限公司 一种热固性树脂组合物
WO2018103199A1 (zh) * 2016-12-07 2018-06-14 广东生益科技股份有限公司 一种热固性树脂组合物
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CN109439246A (zh) * 2018-09-11 2019-03-08 法施达(大连)工程材料有限公司 一种双组份环氧结构胶黏剂及其制备方法
CN109439246B (zh) * 2018-09-11 2021-04-23 法施达(大连)实业集团有限公司 一种双组份环氧结构胶黏剂及其制备方法
TWI728781B (zh) * 2020-04-21 2021-05-21 穗曄實業股份有限公司 熱固型樹脂組成物

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