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CN108250675A - 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
CN108250675A
CN108250675A CN201611238071.0A CN201611238071A CN108250675A CN 108250675 A CN108250675 A CN 108250675A CN 201611238071 A CN201611238071 A CN 201611238071A CN 108250675 A CN108250675 A CN 108250675A
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Prior art keywords
resin
halogen
weight
parts
component
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CN201611238071.0A
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CN108250675B (en
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曾宪平
徐浩晟
何烈相
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Shengyi Technology Co Ltd
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Shengyi Technology Co Ltd
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Priority to CN201611238071.0A priority Critical patent/CN108250675B/en
Priority to PCT/CN2017/082802 priority patent/WO2018120564A1/en
Publication of CN108250675A publication Critical patent/CN108250675A/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
    • C08K5/51—Phosphorus bound to oxygen
    • C08K5/53—Phosphorus bound to oxygen bound to oxygen and to carbon only
    • C08K5/5313—Phosphinic compounds, e.g. R2=P(:O)OR'
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B15/00—Layered products comprising a layer of metal
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B15/00—Layered products comprising a layer of metal
    • B32B15/14—Layered products comprising a layer of metal next to a fibrous or filamentary layer
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B17/00—Layered products essentially comprising sheet glass, or glass, slag, or like fibres
    • B32B17/02—Layered products essentially comprising sheet glass, or glass, slag, or like fibres in the form of fibres or filaments
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B17/00—Layered products essentially comprising sheet glass, or glass, slag, or like fibres
    • B32B17/06—Layered products essentially comprising sheet glass, or glass, slag, or like fibres comprising glass as the main or only constituent of a layer, next to another layer of a specific material
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B27/00—Layered products comprising a layer of synthetic resin
    • B32B27/04—Layered products comprising a layer of synthetic resin as impregnant, bonding, or embedding substance
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B27/00—Layered products comprising a layer of synthetic resin
    • B32B27/38—Layered products comprising a layer of synthetic resin comprising epoxy resins
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B5/00—Layered products characterised by the non- homogeneity or physical structure, i.e. comprising a fibrous, filamentary, particulate or foam layer; Layered products characterised by having a layer differing constitutionally or physically in different parts
    • B32B5/02—Layered products characterised by the non- homogeneity or physical structure, i.e. comprising a fibrous, filamentary, particulate or foam layer; Layered products characterised by having a layer differing constitutionally or physically in different parts characterised by structural features of a fibrous or filamentary layer
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07F—ACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM
    • C07F9/00—Compounds containing elements of Groups 5 or 15 of the Periodic Table
    • C07F9/02—Phosphorus compounds
    • C07F9/547—Heterocyclic compounds, e.g. containing phosphorus as a ring hetero atom
    • C07F9/6564—Heterocyclic compounds, e.g. containing phosphorus as a ring hetero atom having phosphorus atoms, with or without nitrogen, oxygen, sulfur, selenium or tellurium atoms, as ring hetero atoms
    • C07F9/6571—Heterocyclic compounds, e.g. containing phosphorus as a ring hetero atom having phosphorus atoms, with or without nitrogen, oxygen, sulfur, selenium or tellurium atoms, as ring hetero atoms having phosphorus and oxygen atoms as the only ring hetero atoms
    • C07F9/657163—Heterocyclic compounds, e.g. containing phosphorus as a ring hetero atom having phosphorus atoms, with or without nitrogen, oxygen, sulfur, selenium or tellurium atoms, as ring hetero atoms having phosphorus and oxygen atoms as the only ring hetero atoms the ring phosphorus atom being bound to at least one carbon atom
    • C07F9/657172—Heterocyclic compounds, e.g. containing phosphorus as a ring hetero atom having phosphorus atoms, with or without nitrogen, oxygen, sulfur, selenium or tellurium atoms, as ring hetero atoms having phosphorus and oxygen atoms as the only ring hetero atoms the ring phosphorus atom being bound to at least one carbon atom the ring phosphorus atom and one oxygen atom being part of a (thio)phosphinic acid ester: (X = O, S)
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07F—ACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM
    • C07F9/00—Compounds containing elements of Groups 5 or 15 of the Periodic Table
    • C07F9/02—Phosphorus compounds
    • C07F9/547—Heterocyclic compounds, e.g. containing phosphorus as a ring hetero atom
    • C07F9/6564—Heterocyclic compounds, e.g. containing phosphorus as a ring hetero atom having phosphorus atoms, with or without nitrogen, oxygen, sulfur, selenium or tellurium atoms, as ring hetero atoms
    • C07F9/6571—Heterocyclic compounds, e.g. containing phosphorus as a ring hetero atom having phosphorus atoms, with or without nitrogen, oxygen, sulfur, selenium or tellurium atoms, as ring hetero atoms having phosphorus and oxygen atoms as the only ring hetero atoms
    • C07F9/6574—Esters of oxyacids of phosphorus
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J5/00—Manufacture of articles or shaped materials containing macromolecular substances
    • C08J5/24—Impregnating materials with prepolymers which can be polymerised in situ, e.g. manufacture of prepregs
    • C08J5/249—Impregnating materials with prepolymers which can be polymerised in situ, e.g. manufacture of prepregs characterised by the additives used in the prepolymer mixture
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K3/00—Use of inorganic substances as compounding ingredients
    • C08K3/34—Silicon-containing compounds
    • C08K3/36—Silica
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K7/00—Use of ingredients characterised by shape
    • C08K7/02—Fibres or whiskers
    • C08K7/04—Fibres or whiskers inorganic
    • C08K7/14—Glass
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L63/00—Compositions of epoxy resins; Compositions of derivatives of epoxy resins
    • H—ELECTRICITY
    • H05—ELECTRIC TECHNIQUES NOT OTHERWISE PROVIDED FOR
    • H05K—PRINTED CIRCUITS; CASINGS OR CONSTRUCTIONAL DETAILS OF ELECTRIC APPARATUS; MANUFACTURE OF ASSEMBLAGES OF ELECTRICAL COMPONENTS
    • H05K1/00—Printed circuits
    • H05K1/02—Details
    • H05K1/03—Use of materials for the substrate
    • H—ELECTRICITY
    • H05—ELECTRIC TECHNIQUES NOT OTHERWISE PROVIDED FOR
    • H05K—PRINTED CIRCUITS; CASINGS OR CONSTRUCTIONAL DETAILS OF ELECTRIC APPARATUS; MANUFACTURE OF ASSEMBLAGES OF ELECTRICAL COMPONENTS
    • H05K1/00—Printed circuits
    • H05K1/02—Details
    • H05K1/03—Use of materials for the substrate
    • H05K1/0313—Organic insulating material
    • H05K1/0353—Organic insulating material consisting of two or more materials, e.g. two or more polymers, polymer + filler, + reinforcement
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B2260/00—Layered product comprising an impregnated, embedded, or bonded layer wherein the layer comprises an impregnation, embedding, or binder material
    • B32B2260/02—Composition of the impregnated, bonded or embedded layer
    • B32B2260/021—Fibrous or filamentary layer
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B2260/00—Layered product comprising an impregnated, embedded, or bonded layer wherein the layer comprises an impregnation, embedding, or binder material
    • B32B2260/04—Impregnation, embedding, or binder material
    • B32B2260/046—Synthetic resin
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B2262/00—Composition or structural features of fibres which form a fibrous or filamentary layer or are present as additives
    • B32B2262/10—Inorganic fibres
    • B32B2262/101—Glass fibres
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J2363/00—Characterised by the use of epoxy resins; Derivatives of epoxy resins
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L2201/00—Properties
    • C08L2201/02—Flame or fire retardant/resistant

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  • General Health & Medical Sciences (AREA)
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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 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 isOrR1ForM represents flat Homopolymerization is right, and m is the arbitrary number between 0.25~3, such as 0.25,0.5,1,1.2,1.8,2.05,2.8 or 3 and above-mentioned number Specific point value between value, as space is limited and for it is concise the considerations of, present invention tool that no longer range described in exclusive list includes Body point value.
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 isOrR1ForM represents flat Homopolymerization is right, and m is the arbitrary number between 0.25~3, such as 0.25,0.5,1,1.2,1.8,2.05,2.8 or 3 and above-mentioned number Specific point value between value, as space is limited and for it is concise the considerations of, present invention tool that no longer range described in exclusive list includes Body point value.
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 and 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 fire-retardant 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 can also include component (E) filler, and the filler is organic or/and nothing Machine filler, is mainly used to adjust some physical property effects of composition, such as reduces coefficient of thermal expansion (CTE), reduces water absorption rate, carries High 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, wherein typical but nonrestrictive Mixture be：The mixture of fused silica and powdered quartz, spherical silica and hollow silicon dioxide The mixing of the mixture of the mixture of mixture, aluminium hydroxide and aluminium oxide, talcum powder and aluminium nitride, boron nitride and silicon carbide The mixture of the mixture of object, barium sulfate and barium titanate, strontium titanates and calcium carbonate, calcium silicates, mica and glass fiber powder it is mixed Close object, the mixture of fused silica, powdered quartz and spherical silica, hollow silicon dioxide, aluminium hydroxide With the mixture of aluminium oxide, the mixture of talcum powder, aluminium nitride and boron nitride, the mixture of silicon carbide, barium sulfate and barium titanate, Strontium titanates, calcium carbonate, calcium silicates, mica and glass fiber powder mixture.
Preferably, the organic filler is any one in polytetrafluorethylepowder powder, polyphenylene sulfide or polyether sulfone powder Or at least two mixture, wherein typical but non-limiting mixture is：Polytetrafluorethylepowder powder and polyphenylene sulfide The mixture of the mixture of mixture, polyether sulfone powder and polytetrafluorethylepowder powder, polyphenylene sulfide and polyether sulfone powder, polytetrafluoro The mixture of ethylene powder, polyphenylene sulfide 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 low dielectric loss factor, and Df values realize halogen-free flameproof between 0.0076~0.0097, reach 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
0.3mol DOPO are warming up to 160 DEG C of thawings, 0.1mol 4,4'-Dihydroxybenzophenones are added in into melting There is water generation in DOPO, in reaction process, remove the water of generation under reduced pressure, promote reaction forward movement.After reacting 4h, it is cooled to 100 DEG C, 100ml toluene is added in, excessive DOPO is dissolved in toluene, and the white powder precipitation of product is precipitated, and product is filtered to obtain, through four The washing purification of hydrogen furans, obtains 2DOPO-2PhOH.
628.5g (1mol) is added in the flask for being equipped with thermometer, dropping funel, condenser pipe, fractionating column, blender 2DOPO-2PhOH and 816g methyl iso-butyl ketone (MIBK)s (MIBK) will depressurize nitrogen displacement, make its dissolving in system.Then, it puts into 182.7g (0.9mol) paraphthaloyl chloride reacts 2h, and temperature control is below 60 DEG C in system；Then, it is added in into system 114g (1.2mol) phenol, the reaction was continued 1h；Under logical condition of nitrogen gas, 20% sodium hydrate aqueous solution of 189g is slowly added dropwise； Continue to stir 1h under this condition.After reaction, static liquid separation removes water layer.Water is put into the MIBK phases of reactant dissolving, It is stirred, static liquid separation, removes water layer.Aforesaid operations are repeated until the PH of water layer reaches 7.0 or so.Then pass through decanter Moisture is sloughed, MIBK is sloughed in then vacuum distillation, obtains phosphorous active ester Resin A 1.
Synthesis example 2
0.3mol DOPO are warming up to 160 DEG C of thawings, 0.1mol 4,4'-Dihydroxybenzophenones are added in into melting There is water generation in DOPO, in reaction process, remove the water of generation under reduced pressure, promote reaction forward movement.After reacting 4h, it is cooled to 100 DEG C, 100ml toluene is added in, excessive DOPO is dissolved in toluene, and the white powder precipitation of product is precipitated, and product is filtered to obtain, through four The washing purification of hydrogen furans, obtains 2DOPO-2PhOH.
628.5g (1mol) is added in the flask for being equipped with thermometer, dropping funel, condenser pipe, fractionating column, blender 2DOPO-2PhOH and 816g methyl iso-butyl ketone (MIBK)s (MIBK) will depressurize nitrogen displacement, make its dissolving in system.Then, it puts into 182.7g (0.9mol) paraphthaloyl chloride reacts 2h, and temperature control is below 60 DEG C in system；Then, it is added in into system 172.8g (1.2mol) naphthols, the reaction was continued 1h；Under logical condition of nitrogen gas, 20% sodium hydrate aqueous solution of 189g is slowly added dropwise； Continue stirring 1 hour under this condition.After reaction, static liquid separation removes water layer.It is thrown in the MIBK phases of reactant dissolving Enter water, be stirred, static liquid separation removes water layer.Aforesaid operations are repeated until the PH of water layer reaches 7.0 or so.Then pass through Decanter sloughs moisture, and MIBK is sloughed in then vacuum distillation, obtains phosphorous active ester Resin A 2.
In table all in terms of solid component parts by weight, the material that wherein table 1~2 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：DOPO structure fire retardants XP-7866 (refined treasured trade name)
A1：Phosphor-containing structure active ester described in synthesis example 1
A2：Phosphor-containing structure active ester described in synthesis example 2
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.
Embodiment 2~9
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
Table 2
Substance Embodiment 8 Embodiment 9 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
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 0.07 0.08 0.05 0.08
Tg(DSC)/℃ 187 190 155 148 150 182 175 178
Dk(10GHz) 3.98 4.05 3.95 3.96 4.02 4.02 4.08 4.06
Df(10GHz) 0.078 0.076 0.0095 0.0010 0.0098 0.0086 0.0089 0.0087
Flame-retarding characteristic 94 V-0 94 V-0 94 V-2 94 V-0 94 V-0 94 V-2 94 V-0 94 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 9 in table 1~2 it is found that introducing phosphorous active ester curing agent after, system is respectively provided with relatively low dielectric Fissipation factor and it disclosure satisfy that V-0 grades of flame-retardancy requirements of UL94；By embodiment 7 it is found that after silica filler is introduced, body System has lower dielectric loss factor；It is big and symmetrical due to introducing free volume it can be seen from embodiment 8 and embodiment 9 Cyclic annular DOPO structures, make ternary system have lower dielectric loss factor and higher glass transition temperature.
By comparative example 1 and the comparative example 2 of table 2 it is found that after introducing dicyclopentadiene type active curing agent, system has relatively low Dielectric loss factor, the flame-retardancy requirements of UL94 cannot be met, although and even if adding in fire retardant after can meet UL94 resistances Combustion requirement, but dielectric loss factor is increased slightly；And from embodiment 3~6 it is found that relative to comparative example 1 and comparative example 2, While meeting UL94V-0 grades of flame-retardancy requirements, due to introducing the big and symmetrical ring-type DOPO structures of free volume, system has more Low dielectric loss factor and with higher glass transition temperature.
By table 2 comparative example 3 compared with Example 7 and comparative example 5 as known from compared to Example 8, hindered by DOPO structures It fires agent and the mixing of dicyclopentadiene type active ester substitutes the phosphorous active ester curing agent of the present invention, system heat resistance and dielectric properties Difference；By comparative example 4 it is found that the dielectric loss factor of system can be reduced by introducing cyanate, but still UL94V-0 grades of resistances can not be met Combustion requirement；By comparative example 5 and comparative example 6 it is found that flame retardant property can be improved, but dielectric loss factor is increased by introducing fire retardant Add, even if by reducing the dielectric loss factor of system after adding filler but remaining above the dielectric of 9 system of embodiment 8 and embodiment Fissipation factor.
As described above, compared with general laminate, circuit base material made of halogen-free composition of the invention has Low dielectric loss 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 isR1ForM represents average poly- Right, m is the arbitrary number between 0.25~3.
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 isR1ForM represents average poly- Right, m is the arbitrary number between 0.25~3.
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.
CN201611238071.0A 2016-12-28 2016-12-28 Phosphorus-containing active ester, halogen-free composition thereof and copper-clad substrate Expired - Fee Related CN108250675B (en)

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CN113214461A (en) * 2020-01-15 2021-08-06 苏州生益科技有限公司 Active ester resin and resin composition 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
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