CN108250676A - A kind of phosphorous active ester and its halogen-free composition and copper clad foil substrate - Google Patents

A kind of phosphorous active ester and its halogen-free composition and copper clad foil substrate Download PDF

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Publication number
CN108250676A
CN108250676A CN201611240101.1A CN201611240101A CN108250676A CN 108250676 A CN108250676 A CN 108250676A CN 201611240101 A CN201611240101 A CN 201611240101A CN 108250676 A CN108250676 A CN 108250676A
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resin
halogen
weight
component
parts
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CN108250676B (en
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徐浩晟
曾宪平
何烈相
关迟记
陈广兵
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Shengyi Technology Co Ltd
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Shengyi Technology Co Ltd
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Priority to CN201611240101.1A priority Critical patent/CN108250676B/en
Priority to JP2019504744A priority patent/JP2019531262A/en
Priority to PCT/CN2017/085673 priority patent/WO2018120614A1/en
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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

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  • Chemical Kinetics & Catalysis (AREA)
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  • Life Sciences & Earth Sciences (AREA)
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  • Epoxy Resins (AREA)
  • Laminated Bodies (AREA)

Abstract

The present invention provides a kind of phosphorous active ester and its halogen-free resin composition and use its prepreg and laminate.The halogen-free resin composition includes：(A) thermosetting resin；(B) phosphorous active ester resin.Using prepreg and laminate made of this halogen-free resin composition, there is low dielectric loss factor and can realize halogen-free flameproof.

Description

A kind of phosphorous active ester and its halogen-free composition and copper clad foil substrate
Technical field
The invention belongs to copper-clad plate technical fields, and in particular to a kind of phosphorous active ester and its halogen-free resin composition and Use its prepreg, laminate and printed circuit board.
Background technology
Direction with electronic component towards small-size light-weight slimming, high performance, multifunction is developed, and brings therewith Be high frequency, high speed signal transmission.This requires dielectric constant and the dielectric loss ratio of electronic material are relatively low, these and material Structure it is related, and low-k, low dielectric loss tangent resin generally have in structure：Big free volume, it is low can pole Change, low water absorption, low-k structure there are the features such as.In addition, on July 1st, 2006, two parts of environmental protection instructions of European Union 《It is instructed about electric/electronic device is scrapped》With《Restriction on the Use of Certain Hazardous Substances in Electrical and Electronic Equipment》Just Formula is implemented, and the hot spot for being developed into industry of halogen-free flameproof copper-clad laminate, each copper-clad laminate producer all releases one after another The halogen-free flameproof copper-clad laminate of oneself.
Phosphorus-containing compound is introduced in the resin matrix of copper-clad plate, becomes the main technological route of copper-clad plate halogen-free flameproof. Phosphorus flame retardant widely used on copper-clad plate field is broadly divided into two kinds of response type and addition type at present.Response type is mainly DOPO class compounds, based on phosphorous epoxy resin, phosphorus containing phenolic resin, phosphorus content is between 2~10%.However, practical should With middle discovery, DOPO classes compound has larger water absorption rate and poor dielectric properties and the plank humidity resistance poor.Addition type Predominantly phosphonitrile and phosphonate ester compound, the flame retarding efficiency of additive flame retardant is relatively low, and needing to add more amount could reach To flame-retardancy requirements.It is easy to migrate to plank in laminate process simultaneously because of its relatively low fusing point (generally below 150 DEG C) Surface influences plate property.
Invention content
The problem of for prior art, the purpose of the present invention is to provide a kind of novel phosphorous active ester, and is drawn Enter in thermosetting resin, be prepared into halogen-free resin composition and use its prepreg and laminate, carried using it anti- Answering property group and specific thermosetting resin etc., which react, does not generate secondary hydroxyl, can meet high speed baseplate material low-dielectric loss The requirement of the factor can meet halogen-free flameproof requirement again, make it possible that high-frequency high-speed baseplate material is non-halogen.
To achieve these goals, the present invention adopts the following technical scheme that：
One of the objects of the present invention is to provide a kind of phosphorous active esters, and it includes the components of the structure as shown in formula (I)：
Wherein, R is
R1ForR3For
R2For
M, n represent average degree of polymerization, m, n be 0~3.5 between arbitrary number, such as 0.25,0.5,1,1.2,1.8, 2.05th, 2.8,3 or 3.5, and m ≠ 0, n ≠ 0.
Specifically, phosphorous active ester of the present invention may be used such as lower structure：
The second object of the present invention is to provide a kind of halogen-free resin composition, and it includes following components：
(A) thermosetting resin；
(B) phosphorous active ester resin；
The phosphorous active ester resin has the structure as shown in formula (I)：
Wherein, R is
R1ForR3For
R2For
M, n represent average degree of polymerization, m, n be 0~3.5 between arbitrary number, such as 0.25,0.5,1,1.2,1.8, 2.05th, 2.8,3 or 3.5, and m ≠ 0, n ≠ 0.
The concrete structure formula as described in one of the object of the invention may be used in the phosphorous active ester resin.
The present invention is reacted by introducing phosphor-containing structure active ester in thermosetting resin using active ester and epoxy resin etc. Secondary hydroxyl is not generated；Halogen-free flameproof requirement can be met and improve system electrical property (reducing dielectric loss factor), make it Realize the non-halogen of high-frequency high-speed baseplate material.
According to the present invention, the thermosetting resin is epoxy resin, benzoxazine colophony, cyanate ester resin, unsaturated poly- Ester resin, vinylite, bimaleimide resin, BT resins, phenolic resin, polyurethane resin, Thermocurable polyimide, In aryl ethane resin or furane resins any one or at least two mixture, wherein typical but non-limiting mixed Closing object is：Epoxy resin and benzoxazine colophony, cyanate ester resin and unsaturated polyester resin, vinylite and span carry out acyl Imide resin.
In the present invention, the epoxy resin is bisphenol A type epoxy resin, bisphenol f type epoxy resin, dicyclopentadiene epoxy In resin, biphenyl epoxy resin or naphthols epoxy resin any one or at least two mixture, wherein typical but non- Restricted mixture is：Bisphenol A type epoxy resin and bisphenol f type epoxy resin, bisphenol F type epoxy tree and dicyclopentadiene ring Oxygen resin, biphenyl epoxy resin and naphthols epoxy resin.
Preferably, the epoxy resin is biphenyl novolac epoxy resin or/and DCPD novolac epoxy resins, is had both heat-resisting Property, dielectric properties and low water imbibition.
In the present invention, the ester group equivalent proportion of the epoxide equivalent of the epoxy resin and phosphorous active ester resin is 1:(0.9~ , such as 1 1.1):0.9、1:0.95、1:1、1:1.05 or 1:Specific point value between 1.1 and above-mentioned numerical value, as space is limited and For it is concise the considerations of, the present invention specific point value that no longer range described in exclusive list includes, preferably 1:(0.95~1.05).
In the present invention, the halogen-free resin composition can also include component (C) curing accelerator, make resin solidification simultaneously Accelerate resin solidification speed.
Preferably, by the sum of component (A) and component (B) additive amount in terms of 100 parts by weight, the addition of the curing accelerator Measure as 0.05~1 parts by weight, for example, 0.05 parts by weight, 0.08 parts by weight, 0.1 parts by weight, 0.15 parts by weight, 0.2 parts by weight, 0.25 parts by weight, 0.3 parts by weight, 0.35 parts by weight, 0.4 parts by weight, 0.45 parts by weight, 0.5 parts by weight, 0.55 weight, 0.6 weight Part, 0.65 parts by weight, 0.7 parts by weight, 0.75 parts by weight, 0.8 parts by weight, 0.85 parts by weight, 0.9 parts by weight or 1 parts by weight are measured, And the specific point value between above-mentioned numerical value, as space is limited and for it is concise the considerations of, model no longer described in exclusive list of the invention Enclose including specific point value.
Preferably, the curing accelerator is 4-dimethylaminopyridine, 2-methylimidazole, 2- methyl 4- ethyl imidazol(e)s or 2- In phenylimidazole any one or at least two mixture, wherein typical but non-limiting mixture is：4- diformazans Aminopyridine and 2-methylimidazole, 2-methylimidazole and 2- methyl 4- ethyl imidazol(e)s, 2- methyl 4- ethyl imidazol(e)s and 2- phenyl miaows Azoles.
In the present invention, the halogen-free resin composition can also include component (D) fire-retardant compound, the anti-flammability chemical combination Object is halogen-free flame retardants.
Preferably, by the sum of additive amount of component (A), component (B) and component (C) in terms of 100 parts by weight, the anti-flammability The additive amount of compound is 0~50 parts by weight, such as 1 parts by weight, 5 parts by weight, 10 parts by weight, 15 parts by weight, 25 parts by weight, 30 Specific point value between parts by weight, 35 parts by weight, 40 parts by weight, 45 parts by weight or 50 parts by weight and above-mentioned numerical value, is limited to a piece Width and for it is concise the considerations of, the present invention specific point value that no longer range described in exclusive list includes.
Preferably, the flame retardant type compound is phosphorus containing phenolic resin, phosphorous bismaleimide, phosphinic acids salt, virtue It is any one in base phosphate type compound, nitrogen phosphorus expanding fire retardant, phosphonitrile type fire retardant or organic polymer fire retardant Kind or at least two mixture, wherein typical but non-limiting mixture is：Phosphorus containing phenolic resin and phosphorous span come Acid imide, phosphorous bismaleimide and phosphinic acids salt, nitrogen phosphorus expanding fire retardant and phosphonitrile type fire retardant.
Preferably, the halogen-free resin composition is also comprising component (E) filler, and the filler is organic or/and inorganic fill out Material, is mainly used to adjust some physical property effects of composition, such as reduces coefficient of thermal expansion (CTE), reduces water absorption rate, improves heat Conductance etc..
Preferably, by the sum of additive amount of component (A), component (B), component (C) and component (D) in terms of 100 parts by weight, institute The additive amount of filler is stated as 0~100 parts by weight, preferably 0~50 parts by weight.The additive amount of the filler be, for example, 0.5 parts by weight, 1 parts 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 weight Part, 45 parts by weight, 50 parts by weight, 55 parts by weight, 60 parts by weight, 65 parts by weight, 70 parts by weight, 75 parts by weight, 80 parts by weight, 85 Specific point value between parts by weight, 90 parts by weight, 95 parts by weight or 100 parts by weight and above-mentioned numerical value, as space is limited and for The considerations of concise, the present invention specific point value that no longer range described in exclusive list includes.
Preferably, the inorganic filler is fused silica, powdered quartz, spherical silica, hollow two Silica, aluminium hydroxide, aluminium oxide, talcum powder, aluminium nitride, boron nitride, silicon carbide, barium sulfate, barium titanate, strontium titanates, carbonic acid In calcium, calcium silicates, mica or glass fiber powder any one or at least two mixture.The mixture for example melts The mixture of the mixture of silica and powdered quartz, spherical silica and hollow silicon dioxide, aluminium hydroxide With the mixture of aluminium oxide, the mixture of talcum powder and aluminium nitride, the mixture of boron nitride and silicon carbide, barium sulfate and barium titanate Mixture, the mixture of strontium titanates and calcium carbonate, the mixture of calcium silicates, mica and glass fiber powder, fused silica, The mixture of powdered quartz and spherical silica, the mixture of hollow silicon dioxide, aluminium hydroxide and aluminium oxide are sliding The mixture of mountain flour, aluminium nitride and boron nitride, the mixture of silicon carbide, barium sulfate and barium titanate, strontium titanates, calcium carbonate, silicic acid The mixture of calcium, mica and glass fiber powder.
Preferably, the organic filler is any one in polytetrafluorethylepowder powder, polyphenylene sulfide or polyether sulfone powder Kind or at least two mixture.The mixture of the mixture such as polytetrafluorethylepowder powder and polyphenylene sulfide, polyether sulfone The mixture of the mixture of powder and polytetrafluorethylepowder powder, polyphenylene sulfide and polyether sulfone powder, polytetrafluorethylepowder powder, polyphenyl The mixture of thioether and polyether sulfone powder.
Preferably, the filler is silica, and angle value is 1~15 μm in the grain size of filler, in the grain size of preferred filler Angle value is 1~10 μm.
"comprising" of the present invention, it is intended that it can also include other components, these other components in addition to the component Assign the halogen-free resin composition different characteristics.In addition to this, "comprising" of the present invention may be replaced by closing " for " of formula or " by ... form ".
For example, the halogen-free resin composition can also contain various additives, as concrete example, antioxygen can be enumerated Agent, heat stabilizer, antistatic agent, ultra-violet absorber, pigment, colorant or lubricant etc..These various additives can be single It solely uses, two kinds or two or more can also be used in mixed way.
The preparation method of the halogen-free resin composition of the present invention is ordinary skill in the art means, and specific method is： First solid content is put into, then adds in liquid solvent, is stirred to solid content after being completely dissolved, adds liquid resin and promotion Agent continues to stir evenly.
As the solvent in the present invention, there is no particular limitation, as concrete example, can enumerate methanol, ethyl alcohol, butanol Wait alcohols, the ethers such as ethyl cellosolve, butyl cellosolve, ethylene glycol monomethyl ether, carbitol, butyl carbitol, acetone, butanone, first The ketones such as methyl ethyl ketone methyl ketone, cyclohexanone；The arenes such as toluene, dimethylbenzene；The esters such as ethyl acetate, ethoxyethyl acetate Class；The nitrogen-containing solvents such as N,N-dimethylformamide, DMAC N,N' dimethyl acetamide.More than solvent can be used alone, also can be two kinds Or it two or more is used in mixed way.It is preferred that the ketones such as acetone, butanone, methyl ethyl ketone, cyclohexanone.The additive amount of the solvent by Those skilled in the art select according to oneself experience so that resin adhesive liquid reaches the viscosity for being suitble to use.
The third object of the present invention is to provide a kind of prepreg, including reinforcing material and by adhering to after infiltrating drying Halogen-free resin composition as described above thereon.
Illustrative reinforcing material such as adhesive-bonded fabric or/and other fabrics, for example, natural fiber, organic synthetic fibers and Inorfil.
Using fabrics or organic fabrics such as glue infiltration reinforcing material such as glass cloth, the reinforcing material infiltrated is existed Heat drying can obtain prepreg in 5~10 minutes in 155 DEG C of baking oven.
The fourth object of the present invention is to provide a kind of laminate, including an at least prepreg as described above.
The present invention laminate include by be heated and pressurizeed, make prepreg more than a piece of or two panels to be bonded together and Manufactured laminate and the metal foil being bonded in more than laminate one or both sides.The laminate is in hot press Curing is made, and solidification temperature is 150~250 DEG C, and solidifying pressure is 10~60kg/cm2.The metal foil for copper foil, nickel foil, Aluminium foil and SUS foils etc., material is unlimited.
The fifth object of the present invention is to provide a kind of printed circuit board, including at least one preimpregnation as described above Material.
Compared with prior art, the present invention has the advantages that：
(1) it by introducing the active ester of novel phosphorus-containing structure in thermosetting resin, is reacted using itself and epoxy resin etc. Secondary hydroxyl is not generated, can meet halogen-free flameproof requirement, can be improved system electrical property (reducing dielectric loss factor) yet, be made height Frequency high speed baseplate material is non-halogen to be possibly realized；
(2) it is laminated using the prepreg, laminate and clad with metal foil that the halogen-free resin composition is made in the present invention Plate, has the advantages that low dielectric loss factor, and Df values are realized halogen-free flameproof between 0.0077~0.0099, reached UL94V-0。
Specific embodiment
The technical solution further illustrated the present invention below by specific embodiment.
As described below is the specific embodiment of the embodiment of the present invention, it is noted that for the common skill of the art For art personnel, under the premise of principle of the embodiment of the present invention is not departed from, several improvements and modifications can also be made, these improvement The protection domain of the embodiment of the present invention is also considered as with retouching.
Divide multiple embodiments that the embodiment of the present invention is further detailed below.The embodiment of the present invention be not limited to Under specific embodiment.Do not changing in the scope of the claims, can suitably change implementation.
Synthesis example 1
160g (0.5mol) is added in the flask for being equipped with thermometer, dropping funel, condenser pipe, fractionating column, blender 10- (2,5- dihydroxy phenyls) -10- hydrogen -9- oxa- -10- phospho hetero phenanthrene -10- oxides (ODOPB) and 360g hydroxyl phenoxy groups Three phosphonitrile of ring (wherein dihydroxy content is more than 60%) and 816g methyl iso-butyl ketone (MIBK)s (MIBK), put nitrogen is depressurized in system It changes, makes its dissolving.Then put into 182.7g (0.9mol) paraphthaloyl chloride, react 2h, in system temperature control 60 DEG C with Under；Then, 114g (1.2mol) phenol, the reaction was continued 1h are added in into system；Under logical condition of nitrogen gas, it is slowly added dropwise 189g's 20% sodium hydrate aqueous solution；Continue stirring 1 hour under this condition.After reaction, static liquid separation removes water layer.It is reacting Water is put into the MIBK phases of object dissolving, is stirred, static liquid separation, removes water layer.Aforesaid operations are repeated until the pH of water layer reaches To 7.0 or so.Then moisture is sloughed by decanter, MIBK is sloughed in then vacuum distillation, obtains phosphorous active ester Resin A 1.
Synthesis example 2
185g10- (2,5- are added in the flask for being equipped with thermometer, dropping funel, condenser pipe, fractionating column, blender Dihydroxy naphthalene) -10- hydrogen -9- oxa- -10- phospho hetero phenanthrene -10- oxides and 360g hydroxyls phenoxy cyclotriphosphazene (wherein two 60%) hydroxy radical content is more than with 816g methyl iso-butyl ketone (MIBK)s (MIBK), nitrogen displacement will be depressurized in system, makes its dissolving.Then 182.7g (0.9mol) paraphthaloyl chloride is put into, reacts 2h, temperature control is below 60 DEG C in system；Then, into system Add in 114g (1.2mol) phenol, the reaction was continued 1h；Under logical condition of nitrogen gas, 20% sodium hydroxide that 189g is slowly added dropwise is water-soluble Liquid；Continue stirring 1 hour under this condition.After reaction, static liquid separation removes water layer.In the MIBK phases of reactant dissolving Water is put into, is stirred, static liquid separation, removes water layer.Aforesaid operations are repeated until the pH of water layer reaches 7.0 or so.Then lead to It crosses decanter and sloughs moisture, MIBK is sloughed in then vacuum distillation, obtains phosphorous active ester Resin A 2.
Synthesis example 3
DOPO and Phenylbenzoquinone by addition reaction or product, recrystallized in ethoxy ethanol, obtain 10- (2,5- Dihydroxybiphenyl base) -10- hydrogen -9- oxa- -10- phospho hetero phenanthrene -10- oxides.
190g10- (2,5- are added in the flask for being equipped with thermometer, dropping funel, condenser pipe, fractionating column, blender Dihydroxybiphenyl base) -10- hydrogen -9- oxa- -10- phospho hetero phenanthrene -10- oxides, 360g hydroxyls phenoxy cyclotriphosphazene (its 60%) middle dihydroxy content is more than with 816g methyl iso-butyl ketone (MIBK)s (MIBK), nitrogen displacement will be depressurized in system, makes its dissolving. Then, 182.7g (0.9mol) paraphthaloyl chloride is put into, reacts 2h, temperature control is below 60 DEG C in system；Then, Xiang Ti 114g (1.2mol) phenol, the reaction was continued 1h are added in system；Under logical condition of nitrogen gas, the 20% sodium hydroxide water of 189g is slowly added dropwise Solution；Continue stirring 1 hour under this condition.After reaction, static liquid separation removes water layer.In the MIBK phases of reactant dissolving Middle input water, is stirred, static liquid separation, removes water layer.Aforesaid operations are repeated until the PH of water layer reaches 7.0 or so.Then Moisture is sloughed by decanter, MIBK is sloughed in then vacuum distillation, obtains phosphorous active ester Resin A 3.
In table all in terms of solid component parts by weight, the material that wherein table 1 is enumerated is specific as follows：
627：Bisphenol A-type novolac epoxy resin (U.S.'s Hexion trade names)
7200-3H：Dicyclopentadiene type novolac epoxy resin (Japanese DIC trade names)
NC-3000H：Biphenyl type novolac epoxy resin (the Japanization pharmacist name of an article)
HP8000：Dicyclopentadiene type active ester (Japanese DIC trade names)
CE-01PS：Bisphenol A cyanate ester (Yangzhou apocalypse trade name)
Filler：Ball-shaped silicon micro powder DQ1040 (Jiangsu joins auspicious trade name)
Fire retardant：Phosphonitrile fire retardant SPB100 (big tomb commodity chemical name)
A1：Phosphor-containing structure active ester described in synthesis example 1
A2：Phosphor-containing structure active ester described in synthesis example 2
A3：Phosphor-containing structure active ester described in synthesis example 3
DMAP：4-dimethylaminopyridine, accelerating agent (wide honor commodity chemical name)
Embodiment 1
A container is taken, adds in the 627 of 60 parts by weight, equivalent A1 active esters is added in and continues to stir, add in suitable curing Accelerating agent 4-dimethylaminopyridine continues to stir evenly, and is finally made of solvent adjustment liquid solid content to 60%~80% Glue.Impregnate above-mentioned glue with glass fabric, glue.Above-mentioned glue is impregnated, and control to appropriate with glass fabric Thickness, then drying remove solvent and obtain prepreg.It is superimposed with each other using the prepreg obtained by several, in its both sides point A copper foil is not covered, puts curing in hot press into and the epoxy resin copper-clad plate lamination plate is made.Physical data such as 1 institute of table Show.
Implementation column 2~10
Manufacture craft and embodiment 1 are identical, and formula composition and its physical index are as shown in table 1~2.
Comparative example 1~6
Manufacture craft is same as Example 1, and formula composition and its physical index are as shown in table 2.
Table 1
Substance Embodiment 1 Embodiment 2 Embodiment 3 Embodiment 4 Embodiment 5 Embodiment 6 Embodiment 7 Embodiment 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)/℃ 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-retarding characteristic V-0 V-0 V-0 V-0 V-0 V-0 V-0 V-0
Table 2
Substance Embodiment 9 Embodiment 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 1eq 20 20 20
CE-01PS 20 20 20 20 20
Filler 20 20 20
Fire retardant 15 15 15 15
DMAP 0.05 0.05 0.07 0.08 0.08 0.08 0.08 0.08
Tg(DSC)/℃ 188 192 155 148 150 182 175 178
Dk(10GHz) 3.96 4.03 3.95 3.96 4.02 4.02 4.08 4.06
Df(10GHz) 0.0079 0.0077 0.0095 0.0010 0.0098 0.0086 0.0089 0.0087
Flame-retarding characteristic V-0 V-0 V-2 V-0 V-0 V-2 V-0 V-0
The test method of more than characteristic is as follows：
(1) glass transition temperature (Tg)：According to differential scanning calorimetry (DSC), according to IPC-TM-6502.4.25 institutes Defined DSC method is measured.
(2) dielectric constant and dielectric loss factor：Method according to IPC-TM-650 2.5.5.9 defineds is tested, Test frequency is 10GHz.
(3) anti-flammability：It is carried out according to 94 standard methods of UL.
Physical Property Analysis：
By Examples 1 to 10 in table 1~2 it is found that introducing phosphorous active ester curing agent after, contain P element and N element and sky Between the larger chemical constitution of free volume, P element therein meets UL94V-0 grades of flame-retardancy requirements with N element by synergistic effect, And the free volume of bigger makes system be respectively provided with relatively low dielectric loss factor and disclosure satisfy that UL94V-0 grades of flame-retardancy requirements.
By the comparative example 1 of table 2 it is found that after introducing dicyclopentadiene type active curing agent, there is system relatively low dielectric to damage The factor is consumed, but the flame-retardancy requirements of UL94 cannot be met, and dicyclopentadiene type active ester curing agent and phosphonitrile are added in comparative example 2 Although can meet UL94 flame-retardancy requirements after fire retardant, dielectric loss factor is increased slightly.And from embodiment 3~7 it is found that opposite In comparative example 1 and comparative example 2, since the cooperative flame retardant effect of the P in structure and N makes it meet UL94V-0 grades of flame-retardancy requirements While due to introducing the big chemical constitution of space free volume, make system with lower dielectric loss factor and with higher Glass transition temperature.
By embodiment 8 in table 1 it is found that after silica filler is introduced, system has lower dielectric loss factor, and Meet UL94V-0 grades of flame-retardancy requirements.
By embodiment 9 in table 2 and embodiment 10 it is found that after cyanate and filler is introduced, the dielectric loss factor of system It further reduces, down to 0.0077, and meets UL94V-0 grades of flame-retardancy requirements.
By the comparative example 4 of table 2 it is found that the dielectric loss factor of system can be reduced by introducing cyanate, but still can not meet UL94V-0 grades of flame-retardancy requirements；By comparative example 5 and comparative example 6 it is found that flame retardant property can be improved, but dielectric is damaged by introducing fire retardant The consumption factor increased, even if by reducing the dielectric loss factor of system after adding filler but remaining above embodiment 9 and implementation The dielectric loss factor of 10 system of example.
As described above, compared with general laminate, the circuit base material of halogen-free composition of the invention has low Jie Matter fissipation factor and it can realize halogen-free flameproof.
The above, only presently preferred embodiments of the present invention, for those of ordinary skill in the art, can basis Technical scheme of the present invention and technical concept make other various corresponding changes and deformation, and all these changes and deformation are all The range of the claims in the present invention should be belonged to.
Applicant states that the present invention illustrates the method detailed of the present invention, but not office of the invention by above-described embodiment It is limited to above-mentioned method detailed, that is, does not mean that the present invention has to rely on above-mentioned method detailed and could implement.Technical field Technical staff it will be clearly understood that any improvement in the present invention, equivalence replacement and auxiliary element to each raw material of product of the present invention Addition, selection of concrete mode etc., all fall within protection scope of the present invention and the open scope.

Claims (9)

1. a kind of phosphorous active ester, which is characterized in that it includes the components of the structure as shown in formula (I)：
Wherein, R is
R1ForR3For
R2For
M, n represent average degree of polymerization, and m, n are the arbitrary number between 0~3.5, and m ≠ 0, n ≠ 0.
2. a kind of halogen-free resin composition, which is characterized in that the halogen-free resin composition includes following component：
(A) thermosetting resin；
(B) phosphorous active ester resin；
The phosphorous active ester resin has the structure as shown in formula (I)：
Wherein, R is
R1ForR3For
R2For
M, n represent average degree of polymerization, and m, n are the arbitrary number between 0~3.5, and m ≠ 0, n ≠ 0.
3. halogen-free resin composition as claimed in claim 2, which is characterized in that the thermosetting resin is epoxy resin, benzene Bing oxazines resin, cyanate ester resin, unsaturated polyester resin, vinylite, bimaleimide resin, BT resins, phenolic aldehyde Any one in resin, polyurethane resin, Thermocurable polyimide, aryl ethane resin or furane resins or at least two Mixture；
Preferably, the epoxy resin for bisphenol A type epoxy resin, bisphenol f type epoxy resin, DCPD-containing epoxy resin, In biphenyl epoxy resin or naphthols epoxy resin any one or at least two mixture, preferably biphenyl epoxy novolac Resin or/and dicyclopentadiene novolac epoxy resin；
Preferably, the ester group equivalent proportion of the epoxide equivalent of the epoxy resin and phosphorous active ester resin is 1:(0.9~1.1), It is preferred that 1:(0.95~1.05).
4. halogen-free resin composition as claimed in claim 2 or claim 3, which is characterized in that the halogen-free resin composition also includes Component (C) curing accelerator；
Preferably, by the sum of component (A) and component (B) additive amount in terms of 100 parts by weight, the additive amount of the curing accelerator is 0.05~1 parts by weight；
Preferably, the curing accelerator is 4-dimethylaminopyridine, 2-methylimidazole, 2- methyl 4- ethyl imidazol(e)s or 2- phenyl In imidazoles any one or at least two mixture.
5. the halogen-free resin composition as described in one of claim 2-4, which is characterized in that the halogen-free resin composition also wraps Containing component (D) fire-retardant compound；
Preferably, by the sum of additive amount of component (A), component (B) and component (C) in terms of 100 parts by weight, the anti-flammability chemical combination The additive amount of object is 0~50 parts by weight；
Preferably, the fire-retardant compound is phosphorus containing phenolic resin, phosphorous bismaleimide, phosphinic acids salt, aryl phosphorus In acid esters type compound, nitrogen phosphorus expanding fire retardant, phosphonitrile type fire retardant or organic polymer fire retardant any one or The mixture of person at least two.
6. the halogen-free resin composition as described in one of claim 2-5, which is characterized in that the halogen-free resin composition also wraps Containing component (E) filler；
Preferably, the filler is organic or/and inorganic filler；
Preferably, it is described to fill out by the sum of additive amount of component (A), component (B), component (C) and component (D) in terms of 100 parts by weight The additive amount of material be 0~100 parts by weight, preferably 0~50 parts by weight；
Preferably, the inorganic filler is fused silica, powdered quartz, spherical silica, hollow titanium dioxide Silicon, aluminium hydroxide, aluminium oxide, talcum powder, aluminium nitride, boron nitride, silicon carbide, barium sulfate, barium titanate, strontium titanates, calcium carbonate, silicon In sour calcium, mica or glass fiber powder any one or at least two mixture；
Preferably, the organic filler for any one in polytetrafluorethylepowder powder, polyphenylene sulfide or polyether sulfone powder or At least two mixture；
Preferably, the filler is silica, and angle value is 1~15 μm, preferably 1~10 μm in the grain size of filler.
7. a kind of prepreg, including reinforcing material and by be impregnated with it is dry after adhere to thereon such as one of claim 2-6 institutes The halogen-free resin composition stated.
8. a kind of laminate, including an at least prepreg as claimed in claim 7.
9. a kind of printed circuit board, including an at least prepreg as claimed in claim 7.
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JP6830586B1 (en) * 2020-07-22 2021-02-17 株式会社伏見製薬所 Cyclic phosphazene compound having an oxaphosphorin ring-containing structure
CN113234103B (en) * 2021-05-28 2023-07-25 青岛大学 Phosphazene flame retardant, preparation method and application thereof
KR102574707B1 (en) * 2022-12-06 2023-09-06 주식회사 신아티앤씨 Epoxy resin containg Phosphorus

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