CN108250676B - 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
CN108250676B
CN108250676B CN201611240101.1A CN201611240101A CN108250676B CN 108250676 B CN108250676 B CN 108250676B CN 201611240101 A CN201611240101 A CN 201611240101A CN 108250676 B CN108250676 B CN 108250676B
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halogen
resin composition
resin
free
free resin
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CN108250676A (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
    • 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
    • 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
    • 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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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 made of this halogen-free resin composition and laminate, there is low dielectric loss factor and be able to achieve 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 technical field of copper clad laminate, 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 technique
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 the dielectric constant of electronic material and dielectric loss are relatively low, these and material Structure it is related, and low-k, low dielectric loss tangent resin generally included 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 " about electric/electronic device instruction is scrapped " and " Restriction on the Use of Certain Hazardous Substances in Electrical and Electronic Equipment " is 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. The phosphorus flame retardant being widely used on copper-clad plate field at present is broadly divided into response type and two kinds of addition type.Response type is mainly DOPO class compound, based on phosphorous epoxy resin, phosphorus containing phenolic resin, phosphorus content is between 2~10%.However, actually answering With middle discovery, DOPO class compound has biggish water absorption rate and poor dielectric properties and plate humidity resistance poor.Addition type The flame retarding efficiency of predominantly phosphonitrile and phosphonate ester compound, additive flame retardant is lower, and needing to add more amounts could reach To flame-retardancy requirements.It is easy to migrate to plate in laminate process simultaneously because of its lower fusing point (generally below 150 DEG C) Surface influences plate property.
Summary of the invention
Aiming at the problem that prior art, the purpose of the present invention is to provide a kind of novel phosphorous active esters, and are drawn Enter in thermosetting resin, is prepared into halogen-free resin composition and prepreg and laminate using it, is had using it anti- Answering property group and specific thermosetting resin etc., which react, does not generate secondary hydroxyl, has both been able to satisfy high speed baseplate material low-dielectric loss The requirement of the factor is able to satisfy halogen-free flameproof requirement again, makes it possible that high-frequency high-speed baseplate material is non-halogen.
To achieve the goals above, the present invention adopts the following technical scheme:
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 indicate average degree of polymerization, m, n be 0~3.5 between arbitrary number, such as 0.25,0.5,1,1.2,1.8, 2.05,2.8,3 or 3.5, and m ≠ 0, n ≠ 0.
Specifically, phosphorous active ester of the present invention can be using such as flowering 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 indicate average degree of polymerization, m, n be 0~3.5 between arbitrary number, such as 0.25,0.5,1,1.2,1.8, 2.05,2.8,3 or 3.5, and m ≠ 0, n ≠ 0.
The phosphorous active ester resin can be using the concrete structure formula as described in one of the object of the invention.
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；Not only it had been able to satisfy halogen-free flameproof requirement, but also system electrical property (reducing dielectric loss factor) can be improved, has made it Realize the non-halogen of high-frequency high-speed baseplate material.
According to the present invention, the thermosetting resin be epoxy resin, it is benzoxazine resin, cyanate ester resin, unsaturated poly- Ester resin, vinylite, bimaleimide resin, BT resin, 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 Close object are as follows: epoxy resin and benzoxazine resin, 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- Restrictive mixture are as follows: 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 resin, 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 be 1:(0.9~ 1.1) the specific point value, such as between 1:0.9,1:0.95,1:1,1:1.05 or 1:1.1 and above-mentioned numerical value, as space is limited and For concise consideration, the specific point value that range described in the present invention no longer 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, in terms of by the sum of component (A) and component (B) additive amount for 100 parts by weight, the addition of the curing accelerator Amount be 0.05~1 parts by weight, such as 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 concise consideration, model described in the present invention no longer exclusive list Enclose including specific point value.
Preferably, the curing accelerator is 4-dimethylaminopyridine, 2-methylimidazole, 2- methyl 4- ethyl imidazol(e) or 2- In phenylimidazole any one or at least two mixture, wherein typical but non-limiting mixture are as follows: 4- diformazan Aminopyridine and 2-methylimidazole, 2-methylimidazole and 2- methyl 4- ethyl imidazol(e), 2- methyl 4- ethyl imidazol(e) and 2- phenyl miaow 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, in terms of by the sum of additive amount of component (A), component (B) and component (C) for 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 concise consideration, the specific point value that range described in the present invention no longer 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 are as follows: 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 also includes component (E) filler, and the filler is organic or/and inorganic fills out Material is mainly used to adjust some physical property effects of composition, such as reduces thermal expansion coefficient (CTE), reduces water absorption rate, improves heat Conductance etc..
Preferably, in terms of by the sum of additive amount of component (A), component (B), component (C) and component (D) for 100 parts by weight, institute The additive amount for stating filler is 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 Concise consideration, the specific point value that range described in the present invention no longer exclusive list includes.
Preferably, the inorganic filler is fused silica, crystalline sillica, 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 crystalline sillica, 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 crystalline sillica 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 powder and polytetrafluorethylepowder powder, the mixture of 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 partial size of filler, in the partial 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 especially except described group 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, ultraviolet absorbing agent, pigment, colorant or lubricant etc..These various additives can be single It solely uses, two or more can also be used in mixed way.
The preparation method of halogen-free resin composition of the invention is ordinary skill in the art means, method particularly includes: First solid content is put into, liquid solvent is then added and adds liquid resin and promotion after stirring is completely dissolved to solid content 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 Equal 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.The above solvent can be used alone, can also 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 comprising reinforcing material and by infiltration it is dry after adhere to 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 Prepreg can be obtained within heat drying 5~10 minutes in 155 DEG C of baking oven.
The fourth object of the present invention is to provide a kind of laminate comprising an at least prepreg as described above.
Laminate of the invention includes and being heated and pressurizeed, making the prepreg of a piece of or two panels or more to be bonded together Manufactured laminate, and it is bonded in the metal foil of laminate one or both sides or more.The laminate is in hot press Solidification is made, and solidification temperature is 150~250 DEG C, and solidifying pressure is 10~60kg/cm2.The metal foil be copper foil, nickel foil, Aluminium foil and SUS foil etc., material is unlimited.
The fifth object of the present invention is to provide a kind of printed circuit board comprising at least one preimpregnation as described above Material.
Compared with prior art, the invention has the following beneficial effects:
(1) it by introducing the active ester of novel phosphorus-containing structure in thermosetting resin, is reacted using it with epoxy resin etc. Secondary hydroxyl is not generated, has both been able to satisfy 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, Df value are realized halogen-free flameproof between 0.0077~0.0099, reached UL94V-0。
Specific embodiment
The technical scheme of the invention is further explained by means of specific implementation.
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, without departing from the principles of the embodiments of the present invention, several improvements and modifications can also be made, these improvement Also it is considered as the protection scope of the embodiment of the present invention 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, appropriate can 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 phenyl) -10- hydrogen -9- oxa- -10- phospho hetero phenanthrene -10- oxide (ODOPB) and 360g hydroxyl phenoxy group Three phosphonitrile of ring (wherein dihydroxy content is greater than 60%) and 816g methyl iso-butyl ketone (MIBK) (MIBK), set nitrogen is depressurized in system It changes, makes it dissolve.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 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 phase of object dissolution, is stirred, static liquid separation, water layer is removed.Aforesaid operations are repeated until the pH of water layer reaches To 7.0 or so.Then moisture is sloughed by decanter, then MIBK is sloughed in vacuum distillation, obtains phosphorous active ester Resin A 1.
Synthesis example 2
185g10- (2,5- is 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- oxide and 360g hydroxyl phenoxy cyclotriphosphazene (wherein two 60%) hydroxy radical content is greater than with 816g methyl iso-butyl ketone (MIBK) (MIBK), nitrogen displacement will be depressurized in system, is made it dissolve.Then 182.7g (0.9mol) paraphthaloyl chloride is put into, 2h is reacted, temperature control is at 60 DEG C or less in system；Then, into system 114g (1.2mol) phenol, the reaction was continued 1h is added；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 phase of reactant dissolution Water is put into, is stirred, static liquid separation, water layer is removed.Aforesaid operations are repeated until the pH of water layer reaches 7.0 or so.Then lead to It crosses decanter and sloughs moisture, then MIBK is sloughed in 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- oxide.
190g10- (2,5- is 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- oxide, 360g hydroxyl phenoxy cyclotriphosphazene (its 60%) middle dihydroxy content is greater than with 816g methyl iso-butyl ketone (MIBK) (MIBK), nitrogen displacement will be depressurized in system, is made it dissolve. Then, 182.7g (0.9mol) paraphthaloyl chloride is put into, 2h is reacted, temperature control is at 60 DEG C or less 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 phase of reactant dissolution Middle investment 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, then MIBK is sloughed in 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 name)
7200-3H: dicyclopentadiene type novolac epoxy resin (Japanese DIC trade name)
NC-3000H: biphenyl type novolac epoxy resin (the Japanization pharmacist name of an article)
HP8000: dicyclopentadiene type active ester (Japanese DIC trade name)
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- dimethylamino naphthyridine, promotor (wide honor commodity chemical name)
Embodiment 1
A container is taken, the 627 of 60 parts by weight are added, equivalent A1 active ester is added and continues to stir, suitable solidification is added Promotor 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 with glass fabric, and is controlled to appropriate Thickness, then drying removes solvent and obtains prepreg.It is superimposed with each other using prepreg obtained by several, in its two sides point A copper foil is not covered, is put into and is solidified the epoxy resin copper-clad plate lamination plate described in being made in hot press.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 the above characteristic is as follows:
(1) glass transition temperature (Tg): according to differential scanning calorimetry (DSC), according to IPC-TM-6502.4.25 institute Defined DSC method is measured.
(2) dielectric constant and dielectric loss factor: being tested according to the method for IPC-TM-650 2.5.5.9 defined, Test frequency is 10GHz.
(3) it anti-flammability: is carried out according to 94 standard method 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 biggish chemical structure of free volume, P element therein and N element meet UL94V-0 grades of flame-retardancy requirements by synergistic effect, And bigger free volume makes system all have lower dielectric loss factor and can satisfy 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, system is damaged with lower dielectric The factor is consumed, but is not able to satisfy the flame-retardancy requirements of UL94, 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 P and N in structure make it meet UL94V-0 grades of flame-retardancy requirements While due to introducing the big chemical structure of space free volume, so that system is there is lower dielectric loss factor and with higher Glass transition temperature.
By embodiment 8 in table 1 it is found that after introducing silica filler, 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 introducing cyanate and filler, the dielectric loss factor of system It further decreases, 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 it is unable to satisfy 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 by introducing fire retardant, but dielectric is damaged The consumption factor increased, and embodiment 9 is still higher than reducing the dielectric loss factor of system after through addition filler and is implemented The dielectric loss factor of 10 system of example.
As described above, the circuit base material of halogen-free composition of the invention has low Jie compared with general laminate Matter fissipation factor and it can be realized halogen-free flameproof.
The above, only presently preferred embodiments of the present invention for those of ordinary skill in the art can bases Technical solution of the present invention and technical concept make other various corresponding changes and modifications, and all these change and modification are all It should belong to the range of the claims in the present invention.
The Applicant declares that the present invention is explained by the above embodiments method detailed of the invention, but the present invention not office Be limited to above-mentioned method detailed, that is, do not mean that the invention must rely on the above detailed methods to 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 of which fall within the scope of protection and disclosure of the present invention.

Claims (24)

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 indicate that average degree of polymerization, 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 indicate that average degree of polymerization, 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 And oxazines resin, cyanate ester resin, unsaturated polyester resin, vinylite, bimaleimide resin, BT resin, phenolic aldehyde Any one in resin, polyurethane resin, Thermocurable polyimide, aryl ethane resin or furane resins or at least two Mixture.
4. halogen-free resin composition as claimed in claim 3, which is characterized in that the epoxy resin is bisphenol type epoxy tree Any one in rouge, bisphenol f type epoxy resin, DCPD-containing epoxy resin, biphenyl epoxy resin or naphthols epoxy resin Or at least two mixture.
5. halogen-free resin composition as claimed in claim 4, which is characterized in that the epoxy resin is biphenyl phenolic aldehyde asphalt mixtures modified by epoxy resin Rouge or/and dicyclopentadiene novolac epoxy resin.
6. halogen-free resin composition as claimed in claim 3, which is characterized in that the epoxide equivalent of the epoxy resin with it is phosphorous The ester group equivalent proportion of active ester resin is 1:(0.9~1.1).
7. halogen-free resin composition as claimed in claim 6, which is characterized in that the epoxide equivalent of the epoxy resin with it is phosphorous The ester group equivalent proportion of active ester resin is 1:(0.95~1.05).
8. halogen-free resin composition as claimed in claim 3, which is characterized in that the halogen-free resin composition also includes component (C) curing accelerator.
9. halogen-free resin composition as claimed in claim 8, which is characterized in that with the sum of component (A) and component (B) additive amount For 100 parts by weight meters, the additive amount of the curing accelerator is 0.05~1 parts by weight.
10. halogen-free resin composition as claimed in claim 8, which is characterized in that the curing accelerator is 4- dimethylamino In pyridine, 2-methylimidazole, 2- methyl 4- ethyl imidazol(e) or 2- phenylimidazole any one or at least two mixture.
11. the halogen-free resin composition as described in one of claim 2-10, which is characterized in that the halogen-free resin composition is also Include component (D) fire-retardant compound.
12. halogen-free resin composition as claimed in claim 11, which is characterized in that with component (A), component (B) and component (C) The sum of additive amount be 100 parts by weight meters, the additive amount of the fire-retardant compound is 0~50 parts by weight.
13. halogen-free resin composition as claimed in claim 11, which is characterized in that the fire-retardant compound is phosphorus-containing phenolic aldehyde Resin, phosphorous bismaleimide, phosphinic acids salt, aryl phosphoric acids ester type compound, nitrogen phosphorus expanding fire retardant, phosphonitrile type In fire retardant or organic polymer fire retardant any one or at least two mixture.
14. the halogen-free resin composition as described in one of claim 2-10, which is characterized in that the halogen-free resin composition is also Include component (E) filler.
15. halogen-free resin composition as claimed in claim 14, which is characterized in that the filler is organic or/and inorganic fills out Material.
16. halogen-free resin composition as claimed in claim 14, which is characterized in that with component (A), component (B), component (C) It is 100 parts by weight meters with the sum of the additive amount of component (D), the additive amount of the filler is 0~100 parts by weight.
17. halogen-free resin composition as claimed in claim 16, which is characterized in that the additive amount of the filler is 0~50 weight Measure part.
18. halogen-free resin composition as claimed in claim 15, which is characterized in that the inorganic filler is melting titanium dioxide Silicon, crystalline sillica, spherical silica, hollow silicon dioxide, aluminium hydroxide, aluminium oxide, talcum powder, aluminium nitride, nitrogen Change boron, silicon carbide, barium sulfate, barium titanate, strontium titanates, calcium carbonate, calcium silicates, in mica or glass fiber powder any one or The mixture of person at least two.
19. halogen-free resin composition as claimed in claim 15, which is characterized in that the organic filler is polytetrafluoroethylene powder In end, polyphenylene sulfide or polyether sulfone powder any one or at least two mixture.
20. halogen-free resin composition as claimed in claim 14, which is characterized in that the filler is silica, filler Angle value is 1~15 μm in partial size.
21. halogen-free resin composition as claimed in claim 20, which is characterized in that in the partial size of the filler angle value be 1~ 10μm。
22. a kind of prepreg comprising reinforcing material and by impregnation adhere to after dry thereon such as one of claim 2-10 The halogen-free resin composition.
23. a kind of laminate comprising an at least prepreg as claimed in claim 22.
24. a kind of printed circuit board comprising an at least prepreg as claimed in claim 22.
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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
CN113717493A (en) * 2021-09-09 2021-11-30 明光瑞智电子科技有限公司 Halogen-free low-expansion-coefficient resin composition for copper-clad plate
KR102574707B1 (en) * 2022-12-06 2023-09-06 주식회사 신아티앤씨 Epoxy resin containg Phosphorus

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