WO2018120564A1 - Ester actif contenant du phosphore, composition sans halogène et son substrat feuil plaqué de cuivre - Google Patents

Ester actif contenant du phosphore, composition sans halogène et son substrat feuil plaqué de cuivre 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)
Chinese (zh)
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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/fr

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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)
  • Chemical Kinetics & Catalysis (AREA)
  • Medicinal Chemistry (AREA)
  • Materials Engineering (AREA)
  • Manufacturing & Machinery (AREA)
  • Inorganic Chemistry (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Biochemistry (AREA)
  • General Health & Medical Sciences (AREA)
  • Molecular Biology (AREA)
  • Microelectronics & Electronic Packaging (AREA)
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Abstract

La présente invention concerne un ester actif contenant du phosphore, sa composition de résine sans halogène, et un préimprégné et un stratifié l'utilisant. La composition de résine sans halogène comprend : (A) une résine thermodurcissable ; (B) une résine d'ester actif contenant du phosphore. Les préimprégnés et les stratifiés qui sont fabriqués en utilisant ladite composition de résine sans halogène présentent un faible facteur de perte diélectrique et peuvent permettre d'atteindre une ignifugation sans halogène.
PCT/CN2017/082802 2016-12-28 2017-05-03 Ester actif contenant du phosphore, composition sans halogène et son substrat feuil plaqué de cuivre WO2018120564A1 (fr)

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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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