WO2018120614A1 - Ester actif contenant du phosphore, composition exempte d'halogène et substrat de feuille revêtu de cuivre associé - Google Patents

Ester actif contenant du phosphore, composition exempte d'halogène et substrat de feuille revêtu de cuivre associé Download PDF

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Publication number
WO2018120614A1
WO2018120614A1 PCT/CN2017/085673 CN2017085673W WO2018120614A1 WO 2018120614 A1 WO2018120614 A1 WO 2018120614A1 CN 2017085673 W CN2017085673 W CN 2017085673W WO 2018120614 A1 WO2018120614 A1 WO 2018120614A1
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Prior art keywords
resin
halogen
phosphorus
weight
parts
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PCT/CN2017/085673
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English (en)
Chinese (zh)
Inventor
徐浩晟
曾宪平
何烈相
关迟记
陈广兵
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广东生益科技股份有限公司
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Priority to JP2019504744A priority Critical patent/JP2019531262A/ja
Publication of WO2018120614A1 publication Critical patent/WO2018120614A1/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
    • C08K5/5399—Phosphorus bound to nitrogen
    • 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
    • B32B15/00—Layered products comprising a layer of metal
    • B32B15/20—Layered products comprising a layer of metal comprising aluminium or copper
    • 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
    • B32B17/04—Layered products essentially comprising sheet glass, or glass, slag, or like fibres in the form of fibres or filaments bonded with or embedded in a plastic 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
    • 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
    • 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
    • B32B5/22—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 the presence of two or more layers which are next to each other and are fibrous, filamentary, formed of particles or foamed
    • B32B5/24—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 the presence of two or more layers which are next to each other and are fibrous, filamentary, formed of particles or foamed one layer being a fibrous or filamentary layer
    • B32B5/26—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 the presence of two or more layers which are next to each other and are fibrous, filamentary, formed of particles or foamed one layer being a fibrous or filamentary layer another layer next to it also being fibrous or filamentary
    • 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
    • C07F9/6581—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
    • C07F9/65815—Cyclic phosphazenes [P=N-]n, n>=3 n = 3
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G59/00—Polycondensates containing more than one epoxy group per molecule; Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups
    • C08G59/18—Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups ; e.g. general methods of curing
    • C08G59/40—Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups ; e.g. general methods of curing characterised by the curing agents used
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G63/00—Macromolecular compounds obtained by reactions forming a carboxylic ester link in the main chain of the macromolecule
    • C08G63/68—Polyesters containing atoms other than carbon, hydrogen and oxygen
    • C08G63/692—Polyesters containing atoms other than carbon, hydrogen and oxygen containing 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
    • 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
    • H05K1/0366—Organic insulating material consisting of two or more materials, e.g. two or more polymers, polymer + filler, + reinforcement reinforced, e.g. by fibres, fabrics
    • H—ELECTRICITY
    • H05—ELECTRIC TECHNIQUES NOT OTHERWISE PROVIDED FOR
    • H05K—PRINTED CIRCUITS; CASINGS OR CONSTRUCTIONAL DETAILS OF ELECTRIC APPARATUS; MANUFACTURE OF ASSEMBLAGES OF ELECTRICAL COMPONENTS
    • H05K1/00—Printed circuits
    • H05K1/02—Details
    • H05K1/03—Use of materials for the substrate
    • H05K1/0313—Organic insulating material
    • H05K1/0353—Organic insulating material consisting of two or more materials, e.g. two or more polymers, polymer + filler, + reinforcement
    • H05K1/0373—Organic insulating material consisting of two or more materials, e.g. two or more polymers, polymer + filler, + reinforcement containing additives, e.g. fillers
    • 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
    • B32B2260/023—Two or more layers
    • 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
    • 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
    • B32B2307/00—Properties of the layers or laminate
    • B32B2307/20—Properties of the layers or laminate having particular electrical or magnetic properties, e.g. piezoelectric
    • 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
    • B32B2307/00—Properties of the layers or laminate
    • B32B2307/30—Properties of the layers or laminate having particular thermal properties
    • B32B2307/306—Resistant to heat
    • B32B2307/3065—Flame resistant or retardant, fire resistant or retardant
    • 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
    • B32B2457/00—Electrical equipment
    • B32B2457/08—PCBs, i.e. printed circuit boards
    • 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

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 1 is R 3 is
  • n represents the average degree of polymerization
  • m and n are any numbers between 0 and 3.5, such as 0.25, 0.5, 1, 1.2, 1.8, 2.05, 2.8, 3 or 3.5, and m ⁇ 0, n ⁇ 0.
  • the phosphorus-containing active ester of the present invention may have the following structure:
  • 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 1 is R 3 is
  • n represents the average degree of polymerization
  • m and n are any numbers between 0 and 3.5, such as 0.25, 0.5, 1, 1.2, 1.8, 2.05, 2.8, 3 or 3.5, and m ⁇ 0, n ⁇ 0.
  • the phosphorus-containing active ester resin may employ a specific structural formula as described in one of the objects of the present invention.
  • 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 at least two Mixtures, typical but non-limiting mixtures of: bisphenol A type epoxy resin and bisphenol F type epoxy resin, bisphenol F type epoxy tree and dicyclopentadiene epoxy resin, biphenyl epoxy resin and Naphthol epoxy resin.
  • the epoxy resin is a biphenolic epoxy resin or/and a DCPD novolac epoxy resin, which has heat resistance, 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 specific values between the above values are limited 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 further comprises 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 a lower coefficient of thermal expansion (CTE), Reduce water absorption, improve thermal conductivity, and the like.
  • 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 a lower coefficient of thermal expansion (CTE), Reduce water absorption, improve thermal conductivity, and the like.
  • CTE coefficient of thermal expansion
  • 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 of barium sulfate, barium titanate, barium titanate, calcium carbonate, calcium silicate, mica or fiberglass powder or a mixture of at least two.
  • the mixture is, for example, a mixture of fused silica and crystalline silica, a mixture of spherical silica and hollow silica, a mixture of aluminum hydroxide and aluminum oxide, a mixture of talc and aluminum nitride, and nitrided.
  • the organic filler is selected from any one of a polytetrafluoroethylene powder, a polyphenylene sulfide or a polyethersulfone powder or a mixture of at least two.
  • the mixture is, for example, a mixture of polytetrafluoroethylene powder and polyphenylene sulfide, a mixture of polyethersulfone powder and polytetrafluoroethylene powder, a mixture of polyphenylene sulfide and polyethersulfone powder, polytetrafluoroethylene powder, polyphenylene a mixture of thioether 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 methanol.
  • Alcohols such as ethanol and butanol, ethers such as ethyl cellosolve, butyl cellosolve, ethylene glycol methyl ether, carbitol, butyl carbitol, acetone, methyl ethyl ketone, methyl ethyl ketone, ring Ketones such as ketone; aromatic hydrocarbons such as toluene and xylene; esters such as ethyl acetate and ethoxyethyl acetate; N,N-dimethylformamide, N,N-dimethylacetamide Such as nitrogen-containing solvents.
  • 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 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 the advantages of a low dielectric loss factor, and a Df value of between 0.0077 and 0.0099. And achieve halogen-free flame retardant, reaching UL94 V-0.
  • DOPO and phenylphenylhydrazine are recrystallized from ethoxyethanol by addition reaction or product to obtain 10-(2,5-dihydroxybiphenyl)-10-hydrogen-9-oxa-10-phosphine Phenanthrene-10-oxide.
  • 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)
  • 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
  • Example 8 627 60 7200-3H 60 NC-3000H 60 60 60 60 60 60 A1 1eq 1eq 1eq 0.9eq 1.1eq 1eq A2 1eq A3 1eq
  • CE-01PS filler 20
  • DMAP 0.05 0.06 0.07 0.08 0.08 0.08 0.07 0.07 Tg(DSC)/°C 180 177 167 168 165 168 168 170
  • Dk (10GHz) 3.97 3.86 3.96 3.96 3.95 3.95 3.96 4.03
  • Df (10GHz) 0.0099 0.0094 0.0090 0.0090 0.0089 0.0089 0.0089 0.0087 Flame retardant properties V-0 V-0 V-0 V-0 V-0 V-0 V-0 V-0 V-0 V-0 V-0 V-0 V-0 V-0 V-0 V-0 V-0 V-0 V-0 V-0 V-0 V-0 V-0 V-0 V-
  • Example 9 Example 10 Comparative example 1 Comparative example 2 Comparative example 3 Comparative example 4 Comparative example 5 Comparative example 6 NC-3000H 60 60 60 60 60 60 60 60 A1 20 20 A2 A3 HP8000 1eq 1eq 20 20 20 CE-01PS 20 20 20 20 20 filler 20 20 20 Flame retardant 15 15 15 15 DMAP 0.05 0.05 0.07 0.08 0.08 0.08 0.08 T g (DSC) / ° C 188 192 155 148 150 182 175 178 D k (10GHz) 3.96 4.03 3.95 3.96 4.02 4.02 4.08 4.06 D f (10GHz) 0.0079 0.0077 0.0095 0.0010 0.0098 0.0086 0.0089 0.0087 Flame retardant properties V-0 V-0 V-2 V-0 V-0 V-2 V-0 V-0 V-2 V-0 V-0 V-0 V-0 V-0 V-0 V-0 V-0
  • Tg Glass transition temperature: according to differential scanning calorimetry (DSC), according to The DSC method specified in IPC-TM-6502.4.25 was measured.
  • Comparative Example 1 of Table 2 It can be seen from Comparative Example 1 of Table 2 that after the introduction of the dicyclopentadiene type active curing agent, the system has a lower dielectric loss factor, but does not satisfy the flame retardancy requirement of UL94, and the dicyclopentadiene type is added to Comparative Example 2. Although the active ester curing agent and the phosphazene flame retardant can meet the UL94 flame retardant requirements, the dielectric loss factor is slightly increased. As can be seen from Examples 3 to 7, relative to Comparative Example 1 and Comparative Example 2, due to the synergistic flame retardant effect of P and N in the structure, the space free volume was introduced while meeting the UL94 V-0 flame retardant requirement. The large chemical structure gives the system a lower dielectric loss factor and a higher glass transition temperature.
  • Example 8 it can be seen from Example 8 in Table 1 that after the introduction of the silica filler, the system has a lower dielectric loss factor and meets the UL94 V-0 flame retardant requirements.
  • Example 9 It can be seen from Example 9 and Example 10 in Table 2 that after introducing cyanate ester and filler, the dielectric loss factor of the system is further reduced, as low as 0.0077, and meets UL94 V-0 flame retardant requirements.
  • the circuit substrate material 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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Abstract

La présente invention concerne un ester actif contenant du phosphore et une composition de résine exempte d'halogène à base de cet ester, ainsi qu'un préimprégné et un stratifié utilisant cette composition. La composition de résine exempte d'halogène comprend : (A) une résine thermodurcissable ; (B) une résine d'ester actif contenant du phosphore. Les préimprégnés et les stratifiés fabriqués à l'aide de ladite composition de résine exempte d'halogène ont un faible facteur de pertes diélectriques et peuvent présenter un caractère ignifugeant sans halogène.
PCT/CN2017/085673 2016-12-28 2017-05-24 Ester actif contenant du phosphore, composition exempte d'halogène et substrat de feuille revêtu de cuivre associé WO2018120614A1 (fr)

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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
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
JP6830586B1 (ja) * 2020-07-22 2021-02-17 株式会社伏見製薬所 オキサホスホリン環含有構造を有する環状ホスファゼン化合物
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
KR102574707B1 (ko) * 2022-12-06 2023-09-06 주식회사 신아티앤씨 인을 함유하는 에폭시 수지

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