WO2018120564A1 - 一种含磷活性酯及其无卤组合物与覆铜箔基板 - Google Patents

一种含磷活性酯及其无卤组合物与覆铜箔基板 Download PDF

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Publication number
WO2018120564A1
WO2018120564A1 PCT/CN2017/082802 CN2017082802W WO2018120564A1 WO 2018120564 A1 WO2018120564 A1 WO 2018120564A1 CN 2017082802 W CN2017082802 W CN 2017082802W WO 2018120564 A1 WO2018120564 A1 WO 2018120564A1
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resin
halogen
phosphorus
weight
parts
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PCT/CN2017/082802
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English (en)
French (fr)
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曾宪平
徐浩晟
何烈相
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广东生益科技股份有限公司
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Publication of WO2018120564A1 publication Critical patent/WO2018120564A1/zh

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    • 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
    • C08J5/241—Impregnating materials with prepolymers which can be polymerised in situ, e.g. manufacture of prepregs using inorganic fibres
    • C08J5/244—Impregnating materials with prepolymers which can be polymerised in situ, e.g. manufacture of prepregs using inorganic fibres using glass fibres
    • 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
    • C08K5/5313—Phosphinic compounds, e.g. R2=P(:O)OR'
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B15/00—Layered products comprising a layer of metal
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B15/00—Layered products comprising a layer of metal
    • B32B15/14—Layered products comprising a layer of metal next to a fibrous or filamentary layer
    • 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
    • B32B17/00—Layered products essentially comprising sheet glass, or glass, slag, or like fibres
    • B32B17/02—Layered products essentially comprising sheet glass, or glass, slag, or like fibres in the form of fibres or filaments
    • 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
    • B32B17/00—Layered products essentially comprising sheet glass, or glass, slag, or like fibres
    • B32B17/06—Layered products essentially comprising sheet glass, or glass, slag, or like fibres comprising glass as the main or only constituent of a layer, next to another layer of a specific 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
    • B32B27/04—Layered products comprising a layer of synthetic resin as impregnant, bonding, or embedding substance
    • 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
    • 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
    • B32B5/00—Layered products characterised by the non- homogeneity or physical structure, i.e. comprising a fibrous, filamentary, particulate or foam layer; Layered products characterised by having a layer differing constitutionally or physically in different parts
    • B32B5/02—Layered products characterised by the non- homogeneity or physical structure, i.e. comprising a fibrous, filamentary, particulate or foam layer; Layered products characterised by having a layer differing constitutionally or physically in different parts characterised by structural features of a fibrous or filamentary layer
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07F—ACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM
    • C07F9/00—Compounds containing elements of Groups 5 or 15 of the Periodic Table
    • 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
    • C07F9/6571—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 oxygen atoms as the only ring hetero atoms
    • C07F9/657163—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 oxygen atoms as the only ring hetero atoms the ring phosphorus atom being bound to at least one carbon atom
    • C07F9/657172—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 oxygen atoms as the only ring hetero atoms the ring phosphorus atom being bound to at least one carbon atom the ring phosphorus atom and one oxygen atom being part of a (thio)phosphinic acid ester: (X = O, S)
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07F—ACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM
    • C07F9/00—Compounds containing elements of Groups 5 or 15 of the Periodic Table
    • 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
    • C07F9/6571—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 oxygen atoms as the only ring hetero atoms
    • C07F9/6574—Esters of oxyacids of phosphorus
    • 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
    • C08J5/249—Impregnating materials with prepolymers which can be polymerised in situ, e.g. manufacture of prepregs characterised by the additives used in the prepolymer mixture
    • 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
    • C08K3/00—Use of inorganic substances as compounding ingredients
    • C08K3/34—Silicon-containing compounds
    • C08K3/36—Silica
    • 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
    • C08K7/00—Use of ingredients characterised by shape
    • C08K7/02—Fibres or whiskers
    • C08K7/04—Fibres or whiskers inorganic
    • C08K7/14—Glass
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L63/00—Compositions of epoxy resins; Compositions of derivatives of epoxy resins
    • H—ELECTRICITY
    • H05—ELECTRIC TECHNIQUES NOT OTHERWISE PROVIDED FOR
    • H05K—PRINTED CIRCUITS; CASINGS OR CONSTRUCTIONAL DETAILS OF ELECTRIC APPARATUS; MANUFACTURE OF ASSEMBLAGES OF ELECTRICAL COMPONENTS
    • H05K1/00—Printed circuits
    • H05K1/02—Details
    • H05K1/03—Use of materials for the substrate
    • H—ELECTRICITY
    • H05—ELECTRIC TECHNIQUES NOT OTHERWISE PROVIDED FOR
    • H05K—PRINTED CIRCUITS; CASINGS OR CONSTRUCTIONAL DETAILS OF ELECTRIC APPARATUS; MANUFACTURE OF ASSEMBLAGES OF ELECTRICAL COMPONENTS
    • H05K1/00—Printed circuits
    • H05K1/02—Details
    • H05K1/03—Use of materials for the substrate
    • H05K1/0313—Organic insulating material
    • H05K1/0353—Organic insulating material consisting of two or more materials, e.g. two or more polymers, polymer + filler, + reinforcement
    • 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
    • B32B2260/00—Layered product comprising an impregnated, embedded, or bonded layer wherein the layer comprises an impregnation, embedding, or binder material
    • B32B2260/02—Composition of the impregnated, bonded or embedded layer
    • B32B2260/021—Fibrous or filamentary layer
    • 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
    • B32B2260/00—Layered product comprising an impregnated, embedded, or bonded layer wherein the layer comprises an impregnation, embedding, or binder material
    • B32B2260/04—Impregnation, embedding, or binder material
    • B32B2260/046—Synthetic resin
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B2262/00—Composition or structural features of fibres which form a fibrous or filamentary layer or are present as additives
    • B32B2262/10—Inorganic fibres
    • B32B2262/101—Glass fibres
    • 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
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L2201/00—Properties
    • C08L2201/02—Flame or fire retardant/resistant

Definitions

  • the invention belongs to the technical field of copper clad laminates, and particularly relates to a phosphorus-containing active ester and a halogen-free resin composition thereof, and a prepreg, a laminate and a printed circuit board using the same.
  • phosphorus-based flame retardants widely used in the field of copper clad laminates are mainly classified into two types: reactive type and additive type.
  • the reaction type is mainly a DOPO compound, and the phosphorus-containing epoxy resin and the phosphorus-containing phenolic resin are mainly used, and the phosphorus content is between 2% and 10%.
  • DOPO-based compounds have a large water absorption rate and poor dielectric properties, and the sheet has poor heat and humidity resistance.
  • the addition type is mainly a phosphazene and a phosphonate compound, and the added flame retardant has a low flame retardancy efficiency, and it is necessary to add more amount to achieve the flame retardant requirement.
  • due to its lower melting point generally lower than 150 ° C, it is easy to migrate to the surface of the sheet during the processing of the laminate, which affects the performance of the sheet.
  • an object of the present invention is to provide a novel phosphorus-containing active ester which is incorporated into a thermosetting resin to prepare a halogen-free resin composition and a prepreg and a laminate using the same, using the same
  • the reactive group with the specific thermosetting resin does not produce secondary hydroxyl groups, which can meet the requirements of low dielectric loss factor of high-speed substrate materials and meet the requirements of halogen-free flame retardant, so that the high-frequency high-speed substrate material is halogen-free. become possible.
  • One of the objects of the present invention is to provide a phosphorus-containing active ester comprising a component of the structure shown in formula (I):
  • R is R 1 is m represents the average degree of polymerization
  • m is any number between 0.25 and 3, such as 0.25, 0.5, 1, 1.2, 1.8, 2.05, 2.8 or 3, and the specific point value between the above values, limited to length and for conciseness For the consideration of the present invention, the specific point values included in the scope are not exhaustive.
  • Another object of the present invention is to provide a halogen-free resin composition
  • a halogen-free resin composition comprising the following components:
  • thermosetting resin (A) a thermosetting resin
  • the phosphorus-containing active ester resin has a structure as shown in the formula (I):
  • R is R 1 is m represents the average degree of polymerization
  • m is any number between 0.25 and 3, such as 0.25, 0.5, 1, 1.2, 1.8, 2.05, 2.8 or 3, and the specific point value between the above values, limited to length and for conciseness For the consideration of the present invention, the specific point values included in the scope are not exhaustive.
  • the invention introduces a phosphorus-containing structural active ester into a thermosetting resin, and utilizes an active ester to react with an epoxy resin or the like without generating a secondary hydroxyl group; it can satisfy the halogen-free flame retardant requirement and can improve the electrical properties of the system (reducing the dielectric loss factor) ) to achieve halogen-free high-frequency high-speed substrate materials.
  • the thermosetting resin is an epoxy resin, a benzoxazine resin, a cyanate resin, an unsaturated polyester resin, a vinyl resin, a bismaleimide resin, a BT resin, a phenol resin, a polyurethane resin. Any one or a mixture of at least two of a thermosetting polyimide, an aryl acetylene resin or a furan resin, wherein a typical but non-limiting mixture is: an epoxy resin and a benzoxazine resin, a cyanate resin And unsaturated polyester resins, vinyl resins and bismaleimide resins.
  • the epoxy resin is any one of a bisphenol A type epoxy resin, a bisphenol F type epoxy resin, a dicyclopentadiene epoxy resin, a biphenyl epoxy resin or a naphthol epoxy resin. Or a mixture of at least two, wherein the typical but non-limiting mixture is: bisphenol A type epoxy resin and bisphenol F type epoxy resin, bisphenol F type epoxy tree and dicyclopentadiene epoxy resin, Benzene epoxy resin and naphthol epoxy resin.
  • the epoxy resin is a biphenolic epoxy resin or/and a DCPD novolac epoxy resin, which has both heat resistance and dielectric properties and low water absorption.
  • the epoxy equivalent of the epoxy resin and the ester group equivalent ratio of the phosphorus-containing active ester resin are 1: (0.9 to 1.1), for example, 1:0.9, 1:0.95, 1:1, 1:1.05 or 1 : 1.1, and the specific point values between the above values, limited to the length and for the sake of brevity, the present invention will not exhaustively enumerate the specific point values included in the range, preferably 1: (0.95 - 1.05).
  • the halogen-free resin composition may further contain a component (C) curing accelerator which cures the resin and accelerates the curing speed of the resin.
  • C component (C) curing accelerator which cures the resin and accelerates the curing speed of the resin.
  • the curing accelerator is added in an amount of 0.05 to 1 part by weight, such as 0.05 part by weight, 0.08 part by weight, or 0.1, based on 100 parts by weight of the sum of the components (A) and the component (B).
  • the curing accelerator is any one of a mixture of 4-dimethylaminopyridine, 2-methylimidazole, 2-methyl 4-ethylimidazole or 2-phenylimidazole or a mixture of at least two thereof, wherein Typical but non-limiting mixtures are: 4-dimethylaminopyridine and 2-methylimidazole, 2-methylimidazole and 2-methyl 4-ethylimidazole, 2-methyl 4-ethylimidazole and 2- Phenyl imidazole.
  • the halogen-free resin composition may further comprise a component (D) flame-retardant compound which is a halogen-free flame retardant.
  • the flame retardant compound is added in an amount of from 0 to 50 parts by weight, such as 1 based on 100 parts by weight of the sum of the addition amounts of the component (A), the component (B) and the component (C).
  • Parts by weight, 5 parts by weight, 10 Parts by weight, 15 parts by weight, 25 parts by weight, 30 parts by weight, 35 parts by weight, 40 parts by weight, 45 parts by weight or 50 parts by weight, and the specific values between the above values, are limited in length and for the sake of brevity.
  • the present invention is no longer exhaustive of the specific point values included in the scope.
  • the flame retardant compound is a phosphorus-containing phenolic resin, a phosphorus-containing bismaleimide, a phosphinate, an aryl phosphate type compound, a nitrogen-phosphorus-based intumescent flame retardant, and a phosphazene type resist.
  • a typical but non-limiting mixture is: a phosphorus-containing phenolic resin and a phosphorus-containing bismaleimide, a phosphorus-containing double horse Imide and phosphinates, nitrogen-phosphorus-based intumescent flame retardants and phosphazene-type flame retardants.
  • the halogen-free resin composition may further comprise a component (E) filler, which is an organic or/and inorganic filler, which is mainly used to adjust some physical properties of the composition, such as lowering the coefficient of thermal expansion (CTE). , reduce water absorption, improve thermal conductivity, and so on.
  • a component (E) filler which is an organic or/and inorganic filler, which is mainly used to adjust some physical properties of the composition, such as lowering the coefficient of thermal expansion (CTE). , reduce water absorption, improve thermal conductivity, and so on.
  • the filler is added in an amount of from 0 to 100 parts by weight based on 100 parts by weight of the sum of the components (A), the component (B), the component (C) and the component (D). It is preferably 0 to 50 parts by weight.
  • the filler is added in an amount of, for example, 0.5 parts by weight, 1 part by weight, 5 parts by weight, 10 parts by weight, 15 parts by weight, 20 parts by weight, 25 parts by weight, 30 parts by weight, 35 parts by weight, 40 parts by weight, and 45 parts by weight.
  • the inorganic filler is fused silica, crystalline silica, spherical silica, hollow silica, aluminum hydroxide, alumina, talc, aluminum nitride, boron nitride, silicon carbide Any one or a mixture of at least two of barium sulfate, barium titanate, barium titanate, calcium carbonate, calcium silicate, mica or fiberglass powder, wherein a typical but non-limiting mixture is: fused silica a mixture with crystalline silica, a mixture of spherical silica and hollow silica, aluminum hydroxide and oxidation a mixture of aluminum, a mixture of talc and aluminum nitride, a mixture of boron nitride and silicon carbide, a mixture of barium sulfate and barium titanate, a mixture of barium titanate and calcium carbonate, calcium silicate, mica and glass fiber powder Mixture, fused silica, a mixture of
  • the organic filler is any one of a polytetrafluoroethylene powder, a polyphenylene sulfide or a polyethersulfone powder or a mixture of at least two, wherein a typical but non-limiting mixture is: polytetrafluoroethylene powder a mixture with polyphenylene sulfide, a mixture of polyethersulfone powder and polytetrafluoroethylene powder, a mixture of polyphenylene sulfide and polyethersulfone powder, a mixture of polytetrafluoroethylene powder, polyphenylene sulfide and polyethersulfone powder .
  • the filler is silica, and the filler has a median particle diameter of 1 to 15 ⁇ m, and preferably the filler has a median particle diameter of 1 to 10 ⁇ m.
  • composition means that it may contain, in addition to the components, other components which impart different characteristics to the halogen-free resin composition.
  • the "comprising” described in the present invention may also 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.
  • the preparation method of the halogen-free resin composition of the present invention is a conventional technical means in the art, which is: firstly, the solid matter is put in, then the liquid solvent is added, and the mixture is stirred until the solid matter is completely dissolved, and then the liquid resin is added and promoted. Continue to stir evenly.
  • 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.
  • Kika An ether such as an alcohol, a ketone such as acetone, methyl ethyl ketone, methyl ethyl ketone or cyclohexanone; an aromatic hydrocarbon such as toluene or xylene; an ester such as ethyl acetate or 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.
  • a third object of the present invention is to provide a prepreg comprising a reinforcing material and a halogen-free resin composition as described above adhered thereto by dampening and drying.
  • Exemplary reinforcing materials are nonwoven fabrics and/or other fabrics such as natural fibers, organic synthetic fibers, and inorganic fibers.
  • the prepreg is obtained by using the glue-impregnated reinforcing material such as a fabric or an organic fabric such as glass cloth, and drying the infiltrated reinforcing material in an oven at 155 ° C for 5 to 10 minutes.
  • the glue-impregnated reinforcing material such as a fabric or an organic fabric such as glass cloth
  • a fourth object of the present invention is to provide a laminate comprising at least one prepreg as described above.
  • the laminate of the present invention comprises a laminate produced by bonding together one or two or more prepregs by heat and pressure, and a metal foil bonded to one or both sides of the laminate.
  • the laminate is obtained by curing in a hot press at a curing temperature of 150 to 250 ° C and a curing pressure of 10 to 60 kg/cm 2 .
  • the metal foil is copper foil, nickel foil, aluminum foil, SUS foil, etc., and the material thereof is not limited.
  • a fifth object of the present invention is to provide a printed circuit board comprising at least one prepreg as described above.
  • the present invention has the following beneficial effects:
  • thermosetting resin By introducing a novel phosphorus-containing active ester into a thermosetting resin, it can react with an epoxy resin or the like without generating a secondary hydroxyl group, thereby satisfying the halogen-free flame retardant requirement and improving the electrical properties of the system (reducing dielectric properties) Loss factor), making high-frequency high-speed substrate materials halogen-free possible;
  • a prepreg, a laminate, and a metal foil-clad laminate produced by using the halogen-free resin composition of the present invention have a low dielectric loss factor and a Df value of between 0.0076 and 0.0097, and Halogen-free flame retardant, reaching UL94V-0.
  • MIBK methyl isobutyl ketone
  • MIBK methyl isobutyl ketone
  • NC-3000H Biphenyl type phenolic epoxy resin (Japanese chemical product trade name)
  • HP8000 Dicyclopentadiene type active ester (Japan DIC trade name)
  • CE-01PS Bisphenol A type cyanate (Yangzhou Tianqi trade name)
  • DOPO structure flame retardant XP-7866 (Albemarle product name)
  • Example 2 The production process was the same as in Example 1, and the formulation composition and physical property index are shown in Tables 1-2.
  • the manufacturing process was the same as that of Example 1, and the formulation composition and physical property index are shown in Table 2.
  • Example 1 Example 2
  • Example 3 Example 4
  • Example 6 Example 7 627 60 7200-3H 60 NC-3000H 60 60 60 60 60 A1 1eq 1eq 1eq 0.9eq 1.1eq 1eq A2 1eq CE-01PS filler 20 DMAP 0.05 0.06 0.07 0.08 0.08 0.08 0.07 Tg(DSC)/°C 178 175 165 162 164 168 170 Dk (10GHz) 3.96 3.85 3.95 3.95 3.93 3.93 4.03 Df (10GHz) 0.0097 0.0092 0.0089 0.0089 0.0088 0.0088 0.0086
  • Tg Glass transition temperature
  • Comparative Example 1 and Comparative Example 2 of Table 2 that after the introduction of the dicyclopentadiene type active curing agent, the body Has a lower dielectric loss factor, but can not meet the flame retardant requirements of UL94, and even after adding flame retardant, although the UL94 flame retardant requirements can be met, the dielectric loss factor is slightly increased; and from Examples 3-6 It can be seen that, compared with Comparative Example 1 and Comparative Example 2, while satisfying the UL94V-0 flame retardant requirement, the system has a lower dielectric loss factor and has a lower dielectric loss factor due to the introduction of a free-volume and symmetrical annular DOPO structure. High glass transition temperature.
  • the circuit substrate material made of the halogen-free composition of the present invention has a low dielectric loss factor and can realize halogen-free flame retardancy as compared with a general laminate.

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  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Health & Medical Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Polymers & Plastics (AREA)
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Abstract

本发明提供了一种含磷活性酯及其无卤树脂组合物以及使用它的预浸料和层压板。该无卤树脂组合物包括：(A)热固性树脂；(B)含磷活性酯树脂。使用这种无卤树脂组合物制成的预浸料和层压板，具有低介电损耗因子并且能实现无卤阻燃。

Description

一种含磷活性酯及其无卤组合物与覆铜箔基板 技术领域
本发明属于覆铜板技术领域，具体涉及一种含磷活性酯及其无卤树脂组合物以及使用它的预浸料、层压板和印制电路板。
背景技术
随着电子元器件朝着小型轻量薄型化、高性能化、多功能化的方向发展，随之带来的是高频、高速的信号传输。这就要求电子材料的介电常数和介电损耗比较低，这些与材料的结构有关，而低介电常数、低介电损耗树脂在结构上一般具有：大的自由体积、低的可极化、低吸水率、低介电常数的结构存在等特点。此外，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。
在覆铜板的树脂基体中引入含磷化合物，成为覆铜板无卤阻燃的主要技术路线。目前覆铜板领域上广泛采用的磷系阻燃剂主要分为反应型与添加型两种。反应型主要为DOPO类化合物，以含磷环氧树脂、含磷酚醛树脂为主，磷含量在2～10％之间。然而，实际应用中发现，DOPO类化合物具有较大的吸水率和较差的介电性能及板材耐湿热性差。添加型主要为磷腈和膦酸酯类化合物，添加型阻燃剂的阻燃效率较低，需要添加更多的量才能达到阻燃要求。同时因其较低的熔点(一般低于150℃)，在层压板加工过程中，易迁移至板材表面，影响板材性能。
发明内容
针对已有技术的问题，本发明的目的在于提供一种新型的含磷活性酯，并将其引入热固性树脂中，制备成无卤树脂组合物以及使用它的预浸料和层压板，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二次羟基，既能满足高速基板材料低介电损耗因子的要求又能满足无卤阻燃要求，使高频高速基板材料无卤化成为可能。
为了实现上述目的，本发明采用如下技术方案：
本发明的目的之一在于提供一种含磷活性酯，其包含如式(I)所示结构的组分：
Figure PCTCN2017082802-appb-000001
其中，R为
Figure PCTCN2017082802-appb-000002
R1为
Figure PCTCN2017082802-appb-000003
m表示平均聚合度，m为0.25～3之间的任意数，例如0.25、0.5、1、1.2、1.8、2.05、2.8或3，以及上述数值之间的具体点值，限于篇幅及出于简明的考虑，本发明不再穷尽列举所述范围包括的具体点值。
本发明的目的之二在于提供一种无卤树脂组合物，其包含如下组分：
(A)热固性树脂；
(B)含磷活性酯树脂；
所述含磷活性酯树脂具有如式(I)所示结构：
Figure PCTCN2017082802-appb-000004
其中，R为
Figure PCTCN2017082802-appb-000005
R1为
Figure PCTCN2017082802-appb-000006
m表示平均聚合度，m为0.25～3之间的任意数，例如0.25、0.5、1、1.2、1.8、2.05、2.8或3，以及上述数值之间的具体点值，限于篇幅及出于简明的考虑，本发明不再穷尽列举所述范围包括的具体点值。
本发明通过在热固性树脂中引入含磷结构活性酯，利用活性酯与环氧树脂等反应不产生二次羟基；既能满足无卤阻燃要求，又能改良体系电性能(降低介电损耗因子)，使其实现高频高速基板材料的无卤化。
根据本发明，所述热固性树脂为环氧树脂、苯并噁嗪树脂、氰酸酯树脂、不饱和聚酯树脂、乙烯基树脂、双马来酰亚胺树脂、BT树脂、酚醛树脂、聚氨酯树脂、热固性聚酰亚胺、芳基乙炔树脂或呋喃树脂中的任意一种或者至少两种的混合物，其中典型但非限制性的混合物为：环氧树脂和苯并噁嗪树脂，氰酸酯树脂和不饱和聚酯树脂，乙烯基树脂和双马来酰亚胺树脂。
本发明中，所述环氧树脂为双酚A型环氧树脂、双酚F型环氧树脂、双环戊二烯环氧树脂、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，其中典型但非限制性的混合物为：双酚A型环氧树脂和双酚F型环氧树脂，双酚F型环氧树和双环戊二烯环氧树脂，联苯环氧树脂和萘酚环氧树脂。
优选地，所述环氧树脂为联苯酚醛环氧树脂或/和DCPD酚醛环氧树脂，其兼具耐热性和介电性能及低的吸水性。
本发明中，所述环氧树脂的环氧当量与含磷活性酯树脂的酯基当量比为1∶(0.9～1.1)，例如1∶0.9、1∶0.95、1∶1、1∶1.05或1∶1.1，以及上述数值之间的具体点值，限于篇幅及出于简明的考虑，本发明不再穷尽列举所述范围包括的具体点值，优选1∶(0.95～1.05)。
本发明中，所述无卤树脂组合物还可以包含组分(C)固化促进剂，其使树脂固化并加快树脂固化速度。
优选地，以组分(A)和组分(B)添加量之和为100重量份计，所述固化促进剂的添加量为0.05～1重量份，例如0.05重量份、0.08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1重量份，以及上述数值之间的具体点值，限于篇幅及出于简明的考虑，本发明不再穷尽列举所述范围包括的具体点值。
优选地，所述固化促进剂为4-二甲氨基吡啶、2-甲基咪唑、2-甲基4-乙基咪唑或2-苯基咪唑中的任意一种或者至少两种的混合物，其中典型但非限制性的混合物为：4-二甲氨基吡啶和2-甲基咪唑、2-甲基咪唑和2-甲基4-乙基咪唑、2-甲基4-乙基咪唑和2-苯基咪唑。
本发明中，所述无卤树脂组合物还可以包含组分(D)阻燃性化合物，该阻燃性化合物为无卤阻燃剂。
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，所述阻燃性化合物的添加量为0～50重量份，例如1重量份、5重量份、10 重量份、15重量份、25重量份、30重量份、35重量份、40重量份、45重量份或50重量份，以及上述数值之间的具体点值，限于篇幅及出于简明的考虑，本发明不再穷尽列举所述范围包括的具体点值。
优选地，所述阻燃性化合物为含磷酚醛树脂、含磷双马来酰亚胺、次膦酸盐类、芳基磷酸酯型化合物、氮磷系膨胀型阻燃剂、磷腈型阻燃剂或有机聚合物阻燃剂中的任意一种或者至少两种的混合物，其中典型但非限制性的混合物为：含磷酚醛树脂和含磷双马来酰亚胺，含磷双马来酰亚胺和次膦酸盐类，氮磷系膨胀型阻燃剂和磷腈型阻燃剂。
优选地，所述无卤树脂组合物还可以包含组分(E)填料，所述填料为有机或/和无机填料，其主要用来调整组合物的一些物性效果，如降低热膨胀系数(CTE)、降低吸水率、提高热导率等。
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，所述填料的添加量为0～100重量份，优选0～50重量份。所述填料的添加量例如为0.5重量份、1重量份、5重量份、10重量份、15重量份、20重量份、25重量份、30重量份、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、70重量份、75重量份、80重量份、85重量份、90重量份、95重量份或100重量份，以及上述数值之间的具体点值，限于篇幅及出于简明的考虑，本发明不再穷尽列举所述范围包括的具体点值。
优选地，所述无机填料为熔融二氧化硅、结晶型二氧化硅、球型二氧化硅、空心二氧化硅、氢氧化铝、氧化铝、滑石粉、氮化铝、氮化硼、碳化硅、硫酸钡、钛酸钡、钛酸锶、碳酸钙、硅酸钙、云母或玻璃纤维粉中的任意一种或者至少两种的混合物，其中典型但非限制性的混合物为：熔融二氧化硅和结晶型二氧化硅的混合物，球型二氧化硅和空心二氧化硅的混合物，氢氧化铝和氧化 铝的混合物，滑石粉和氮化铝的混合物，氮化硼和碳化硅的混合物，硫酸钡和钛酸钡的混合物，钛酸锶和碳酸钙的混合物，硅酸钙、云母和玻璃纤维粉的混合物，熔融二氧化硅、结晶型二氧化硅和球型二氧化硅的混合物，空心二氧化硅、氢氧化铝和氧化铝的混合物，滑石粉、氮化铝和氮化硼的混合物，碳化硅、硫酸钡和钛酸钡的混合物，钛酸锶、碳酸钙、硅酸钙、云母和玻璃纤维粉的混合物。
优选地，所述有机填料为聚四氟乙烯粉末、聚苯硫醚或聚醚砜粉末中的任意一种或者至少两种的混合物，其中典型但非限制性的混合物为：聚四氟乙烯粉末和聚苯硫醚的混合物，聚醚砜粉末和聚四氟乙烯粉末的混合物，聚苯硫醚和聚醚砜粉末的混合物，聚四氟乙烯粉末、聚苯硫醚和聚醚砜粉末的混合物。
优选地，所述填料为二氧化硅，填料的粒径中度值为1～15μm，优选填料的粒径中度值为1～10μm。
本发明所述的“包含”，意指其除所述组份外，还可以包含其他组份，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“包含”，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。
本发明的无卤树脂组合物的制备方法为本领域的常规技术手段，其具体方法为：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。
本发明的目的之三在于提供一种预浸料，其包括增强材料及通过浸润干燥后附着其上的如上所述的无卤树脂组合物。
示例性的增强材料如无纺织物或/和其他织物，例如天然纤维、有机合成纤维以及无机纤维。
使用该胶液浸润增强材料如玻璃布等织物或有机织物，将浸润好的增强材料在155℃的烘箱中加热干燥5～10分钟即可得到预浸料。
本发明的目的之四在于提供一种层压板，其包括至少一张如上所述的预浸料。
本发明的层压板包括通过加热和加压、使一片或两片以上的预浸料粘合在一起而制成的层压板，以及粘合在层压板一面或两面以上的金属箔。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/cm2。所述的金属箔为铜箔、镍箔、铝箔及SUS箔等，其材质不限。
本发明的目的之五在于提供一种印制电路板，其包括至少一张如上所述的预浸料。
与现有技术相比，本发明具有如下有益效果：
(1)通过在热固性树脂中引入新型含磷结构的活性酯，利用其与环氧树脂等反应不产生二次羟基，既能满足无卤阻燃要求，也能改良体系电性能(降低介电损耗因子)，使高频高速基板材料无卤化成为可能；
(2)使用本发明中该无卤树脂组合物制作而成的预浸料、层压板和覆金属箔层压板，具有低介电损耗因子，其Df值介于0.0076～0.0097之间，并实现无卤阻燃，达到UL94V-0。
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。
以下所述是本发明实施例的具体实施方式，应当指出，对于本技术领域的普通技术人员来说，在不脱离本发明实施例原理的前提下，还可以做出若干改进和润饰，这些改进和润饰也视为本发明实施例的保护范围。
下面分多个实施例对本发明实施例进行进一步的说明。本发明实施例不限定于以下的具体实施例。在不改变权利要求的范围内，可以适当的进行变更实施。
合成例1
将0.3mol DOPO升温至160℃融化，将0.1mol 4，4’-二羟基二苯甲酮加入熔融的DOPO中，反应过程中有水生成，减压蒸除生成的水，促进反应正向移动。反应4h后，降温至100℃，加入100ml甲苯，过量的DOPO溶于甲苯，产物呈白色粉末沉淀析出，过滤得产物，经四氢呋喃洗涤提纯，得到2DOPO-2PhOH。
在安装有温度计、滴液漏斗、冷凝管、分馏管、搅拌器的烧瓶中加入628.5g(1mol)2DOPO-2PhOH和816g甲基异丁基酮(MIBK)，将体系内减压氮气置换，使其溶解。接着，投入182.7g(0.9mol)对苯二甲酰氯，反应2h，体系内温度控制在60℃以下；然后，向体系中加入114g(1.2mol)苯酚，继续反应1h；通氮气条件下，缓慢滴加189g的20％氢氧化钠水溶液；在该条件下继续搅拌1h。反应结束后，静止分液除去水层。在反应物溶解的MIBK相中投入水，搅拌混合，静止分液，除去水层。重复上述操作直至水层的PH达到7.0左右。然后通 过倾析器脱去水分，接着减压蒸馏脱去MIBK，得到含磷活性酯树脂A1。
合成例2
将0.3mol DOPO升温至160℃融化，将0.1mol 4，4’-二羟基二苯甲酮加入熔融的DOPO中，反应过程中有水生成，减压蒸除生成的水，促进反应正向移动。反应4h后，降温至100℃，加入100ml甲苯，过量的DOPO溶于甲苯，产物呈白色粉末沉淀析出，过滤得产物，经四氢呋喃洗涤提纯，得到2DOPO-2PhOH。
在安装有温度计、滴液漏斗、冷凝管、分馏管、搅拌器的烧瓶中加入628.5g(1mol)2DOPO-2PhOH和816g甲基异丁基酮(MIBK)，将体系内减压氮气置换，使其溶解。接着，投入182.7g(0.9mol)对苯二甲酰氯，反应2h，体系内温度控制在60℃以下；然后，向体系中加入172.8g(1.2mol)萘酚，继续反应1h；通氮气条件下，缓慢滴加189g的20％氢氧化钠水溶液；在该条件下继续搅拌1小时。反应结束后，静止分液除去水层。在反应物溶解的MIBK相中投入水，搅拌混合，静止分液，除去水层。重复上述操作直至水层的PH达到7.0左右。然后通过倾析器脱去水分，接着减压蒸馏脱去MIBK，得到含磷活性酯树脂A2。
表中皆以固体组分重量份计，其中表1～2列举的材料具体如下：
627：双酚A型酚醛环氧树脂(美国Hexion商品名)
7200-3H：双环戊二烯型酚醛环氧树脂(日本DIC商品名)
NC-3000H：联苯型酚醛环氧树脂(日本化药商品名)
HP8000：双环戊二烯型活性酯(日本DIC商品名)
CE-01PS：双酚A型氰酸酯(扬州天启商品名)
填料：球形硅微粉DQ1040(江苏联瑞商品名)
阻燃剂：DOPO结构阻燃剂XP-7866(雅宝商品名)
A1：合成例1所述的含磷结构活性酯
A2：合成例2所述的含磷结构活性酯
DMAP：4-二甲氨基吡啶，促进剂(广荣化学商品名)
实施例1
取一容器，加入60重量份的627，加入等当量A1活性酯继续搅拌，加入适量的固化促进剂4-二甲氨基吡啶，继续搅拌均匀，最后用溶剂调整液体固含量至60％～80％而制成胶液。用玻璃纤维布浸渍上述胶液，即成胶液。用玻璃纤维布浸渍上述胶液，并控制至适当厚度，然后烘干除去溶剂得到半固化片。使用数张所制得的半固化片相互叠合，在其两侧分别压覆一张铜箔，放进热压机中固化制成所述的环氧树脂覆铜板层压板。物性数据如表1所示。
实施例2～9
制作工艺和实施例1相同，配方组成及其物性指标如表1～2所示。
对比例1～6
制作工艺与实施例1相同，配方组成及其物性指标如表2所示。
表1
物质 实施例1 实施例2 实施例3 实施例4 实施例5 实施例6 实施例7
627 60            
7200-3H   60          
NC-3000H     60 60 60 60 60
A1 1eq 1eq 1eq 0.9eq 1.1eq   1eq
A2           1eq  
CE-01PS              
填料             20
DMAP 0.05 0.06 0.07 0.08 0.08 0.08 0.07
Tg(DSC)/℃ 178 175 165 162 164 168 170
Dk(10GHz) 3.96 3.85 3.95 3.95 3.93 3.93 4.03
Df(10GHz) 0.0097 0.0092 0.0089 0.0089 0.0088 0.0088 0.0086
阻燃特性 94V-0 94V-0 94V-0 94V-0 94V-0 94V-0 94V-0
表2
物质 实施例8 实施例9 对比例1 对比例2 对比例3 对比例4 对比例5 对比例6
NC-3000H 60 60 60 60 60 60 60 60
A1 20 20            
A2                
HP8000     1eq 1eq 1eq 20 20 20
CE-01PS 20 20       20 20 20
填料   20     20     20
阻燃剂       15 15   15 15
DMAP 0.05 0.05 0.07 0.08 0.07 0.08 0.05 0.08
Tg(DSC)/℃ 187 190 155 148 150 182 175 178
Dk(10GHz) 3.98 4.05 3.95 3.96 4.02 4.02 4.08 4.06
Df(10GHz) 0.078 0.076 0.0095 0.0010 0.0098 0.0086 0.0089 0.0087
阻燃特性 94V-0 94V-0 94V-2 94V-0 94V-0 94V-2 94V-0 94V-0
以上特性的测试方法如下：
(1)玻璃化转变温度(Tg)：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)介电常数和介电损耗因子：按照IPC-TM-650 2.5.5.9所规定的方法进行测试，测试频率为10GHz。
(3)阻燃性：按照UL 94标准方法进行。
物性分析：
由表1～2中实施例1～9可知，引入含磷活性酯固化剂后，体系均具有较低的介电损耗因子并且能够满足UL94V-0级阻燃要求；由实施例7可知，在引入二氧化硅填料后，体系具有更低的介电损耗因子；由实施例8和实施例9可以看出，由于引入自由体积大且对称的环状DOPO结构，使三元体系具有更低的介电损耗因子及更高的玻璃化转变温度。
由表2的对比例1和对比例2可知，引入双环戊二烯型活性固化剂后，体 系具有较低的介电损耗因子，但不能满足UL94的阻燃要求，而且即使加入阻燃剂后虽然可满足UL94阻燃要求，但介电损耗因子略有增加；而从实施例3～6可知，相对于对比例1和对比例2，其在满足UL94V-0级阻燃要求的同时，由于引入自由体积大且对称的环状DOPO结构，体系具有更低的介电损耗因子及具有更高的玻璃化转变温度。
由表2的对比例3与实施例7相比，以及对比例5与实施例8相比可知，由DOPO结构阻燃剂和双环戊二烯型活性酯混合替代本发明的含磷活性酯固化剂，体系耐热性及介电性能差；由对比例4可知，引入氰酸酯可以降低体系的介电损耗因子，但仍无法满足UL94V-0级阻燃要求；由对比例5和对比例6可知，引入阻燃剂可以改善阻燃性能，但介电损耗因子有所增加，即使通过添加填料后降低体系的介电损耗因子但仍高于实施例8和实施例9体系的介电损耗因子。
如上所述，与一般的层压板相比，本发明的无卤组合物制成的电路基板材料具有低介电损耗因子并且能够实现无卤阻燃。
以上所述，仅为本发明的较佳实施例，对于本领域的普通技术人员来说，可以根据本发明的技术方案和技术构思做出其他各种相应的改变和变形，而所有这些改变和变形都应属于本发明权利要求的范围。
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 (9)

  1. 一种含磷活性酯，其特征在于，其包含如式(I)所示结构的组分：
    Figure PCTCN2017082802-appb-100001
    其中，R为
    Figure PCTCN2017082802-appb-100002
    R1为
    Figure PCTCN2017082802-appb-100003
    m表示平均聚合度，m为0.25～3之间的任意数。
  2. 一种无卤树脂组合物，其特征在于，所述无卤树脂组合物包含如下组分：
    (A)热固性树脂；
    (B)含磷活性酯树脂；
    所述含磷活性酯树脂具有如式(I)所示结构：
    Figure PCTCN2017082802-appb-100004
    其中，R为
    Figure PCTCN2017082802-appb-100005
    R1为
    Figure PCTCN2017082802-appb-100006
    m表示平均聚合度，m为0.25～3之间的任意数。
  3. 如权利要求2所述的无卤树脂组合物，其特征在于，所述热固性树脂为环氧树脂、苯并噁嗪树脂、氰酸酯树脂、不饱和聚酯树脂、乙烯基树脂、双马来酰亚胺树脂、BT树脂、酚醛树脂、聚氨酯树脂、热固性聚酰亚胺、芳基乙炔树脂或呋喃树脂中的任意一种或者至少两种的混合物；
    优选地，所述环氧树脂为双酚A型环氧树脂、双酚F型环氧树脂、双环戊二烯环氧树脂、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，优选为联苯酚醛环氧树脂或/和双环戊二烯酚醛环氧树脂；
    优选地，所述环氧树脂的环氧当量与含磷活性酯树脂的酯基当量比为1∶(0.9～1.1)，优选1∶(0.95～1.05)。
  4. 如权利要求2或3所述的无卤树脂组合物，其特征在于，所述无卤树脂组合物还包含组分(C)固化促进剂；
    优选地，以组分(A)和组分(B)添加量之和为100重量份计，所述固化促进剂的添加量为0.05～1重量份；
    优选地，所述固化促进剂为4-二甲氨基吡啶、2-甲基咪唑、2-甲基4-乙基咪唑或2-苯基咪唑中的任意一种或者至少两种的混合物。
  5. 如权利要求2-4之一所述的无卤树脂组合物，其特征在于，所述无卤树脂组合物还包含组分(D)阻燃性化合物；
    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，所述阻燃性化合物的添加量为0～50重量份；
    优选地，所述阻燃性化合物为含磷酚醛树脂、含磷双马来酰亚胺、次膦酸盐类、芳基磷酸酯型化合物、氮磷系膨胀型阻燃剂、磷腈型阻燃剂或有机聚合物阻燃剂中的任意一种或者至少两种的混合物。
  6. 如权利要求2-5之一所述的无卤树脂组合物，其特征在于，所述无卤树 脂组合物还包含组分(E)填料；
    优选地，所述填料为有机或/和无机填料；
    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，所述填料的添加量为0～100重量份，优选0～50重量份；
    优选地，所述无机填料为熔融二氧化硅、结晶型二氧化硅、球型二氧化硅、空心二氧化硅、氢氧化铝、氧化铝、滑石粉、氮化铝、氮化硼、碳化硅、硫酸钡、钛酸钡、钛酸锶、碳酸钙、硅酸钙、云母或玻璃纤维粉中的任意一种或者至少两种的混合物；
    优选地，所述有机填料为聚四氟乙烯粉末、聚苯硫醚或聚醚砜粉末中的任意一种或者至少两种的混合物；
    优选地，所述填料为二氧化硅，填料的粒径中度值为1～15μm，优选1～10μm。
  7. 一种预浸料，其包括增强材料及通过含浸干燥后附着其上的如权利要求2-6之一所述的无卤树脂组合物。
  8. 一种层压板，其包括至少一张如权利要求7所述的预浸料。
  9. 一种印制电路板，其包括至少一张如权利要求7所述的预浸料。
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Cited By (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN112442212A (zh) * 2019-08-28 2021-03-05 广东广山新材料股份有限公司 一种含磷的反应型阻燃剂及其制备方法和应用
CN113844129A (zh) * 2021-09-13 2021-12-28 山东金宝电子股份有限公司 一种无卤、低介电损耗、高耐热覆铜板的制备方法
CN113912981A (zh) * 2021-11-04 2022-01-11 江苏耀鸿电子有限公司 一种高耐热性中Tg覆铜板及其制备方法

Families Citing this family (8)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
TWI745627B (zh) * 2018-10-23 2021-11-11 台燿科技股份有限公司 熱固性樹脂組合物，使用彼所製得之預浸漬片、金屬箔積層板及印刷電路板
CN111363339A (zh) * 2018-12-26 2020-07-03 广东生益科技股份有限公司 含磷硅阻燃剂、其制备方法、阻燃树脂组合物、预浸料和覆金属箔层压板
CN111960956B (zh) * 2019-05-20 2022-12-30 广东生益科技股份有限公司 双端胺基活性酯、其制备方法、热固性树脂组合物及其应用
CN110181903B (zh) * 2019-06-06 2021-04-13 江门建滔电子发展有限公司 一种高频高速覆铜板及其制备方法
CN110746725B (zh) * 2019-11-13 2021-04-30 珠海国能新材料股份有限公司 一种高性能聚四氟乙烯薄膜及其微波基板的制造方法
CN113214461B (zh) * 2020-01-15 2023-04-28 苏州生益科技有限公司 一种活性酯树脂及其树脂组合物
CN113717493A (zh) * 2021-09-09 2021-11-30 明光瑞智电子科技有限公司 一种用于覆铜板的无卤低膨胀系数树脂组合物
CN114989395A (zh) * 2022-07-12 2022-09-02 广东福佑电子科技有限公司 一种含dopo阻燃剂的阻燃环氧树脂及其制备方法

Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2010037443A (ja) * 2008-08-06 2010-02-18 Toyo Ink Mfg Co Ltd 難燃剤および難燃性樹脂組成物
JP2012052008A (ja) * 2010-08-31 2012-03-15 Fujifilm Corp 環状リンエステル化合物、難燃剤、樹脂組成物、及び電気電子機器用筐体
CN103965249A (zh) * 2014-05-28 2014-08-06 苏州生益科技有限公司 一种活性酯化合物、其制备方法和用途
CN103965588A (zh) * 2014-05-28 2014-08-06 苏州生益科技有限公司 无卤热固性树脂组合物、半固化片及层压板

Patent Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2010037443A (ja) * 2008-08-06 2010-02-18 Toyo Ink Mfg Co Ltd 難燃剤および難燃性樹脂組成物
JP2012052008A (ja) * 2010-08-31 2012-03-15 Fujifilm Corp 環状リンエステル化合物、難燃剤、樹脂組成物、及び電気電子機器用筐体
CN103965249A (zh) * 2014-05-28 2014-08-06 苏州生益科技有限公司 一种活性酯化合物、其制备方法和用途
CN103965588A (zh) * 2014-05-28 2014-08-06 苏州生益科技有限公司 无卤热固性树脂组合物、半固化片及层压板

Cited By (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN112442212A (zh) * 2019-08-28 2021-03-05 广东广山新材料股份有限公司 一种含磷的反应型阻燃剂及其制备方法和应用
CN113844129A (zh) * 2021-09-13 2021-12-28 山东金宝电子股份有限公司 一种无卤、低介电损耗、高耐热覆铜板的制备方法
CN113912981A (zh) * 2021-11-04 2022-01-11 江苏耀鸿电子有限公司 一种高耐热性中Tg覆铜板及其制备方法

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