CN104774476A - Phosphorus-containing flame retardant composition, and phosphorus-containing polyphenyl ether resin composition, prepreg and laminated board using the same - Google Patents

Phosphorus-containing flame retardant composition, and phosphorus-containing polyphenyl ether resin composition, prepreg and laminated board using the same Download PDF

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CN104774476A
CN104774476A CN201510104950.3A CN201510104950A CN104774476A CN 104774476 A CN104774476 A CN 104774476A CN 201510104950 A CN201510104950 A CN 201510104950A CN 104774476 A CN104774476 A CN 104774476A
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alkyl
different
phenyl
carbonatoms
halogen atom
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CN104774476B (en
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曾宪平
陈广兵
关迟记
杨文华
何烈相
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Shengyi Technology Co Ltd
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    • BPERFORMING OPERATIONS; TRANSPORTING
    • B32LAYERED PRODUCTS
    • B32BLAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B15/00Layered products comprising a layer of metal
    • B32B15/04Layered products comprising a layer of metal comprising metal as the main or only constituent of a layer, which is next to another layer of the same or of a different material
    • B32B15/08Layered products comprising a layer of metal comprising metal as the main or only constituent of a layer, which is next to another layer of the same or of a different material of synthetic resin
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B32LAYERED PRODUCTS
    • B32BLAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B15/00Layered products comprising a layer of metal
    • B32B15/20Layered products comprising a layer of metal comprising aluminium or copper
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B32LAYERED PRODUCTS
    • B32BLAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B27/00Layered products comprising a layer of synthetic resin
    • B32B27/04Layered products comprising a layer of synthetic resin as impregnant, bonding, or embedding substance
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B32LAYERED PRODUCTS
    • B32BLAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B27/00Layered products comprising a layer of synthetic resin
    • B32B27/18Layered products comprising a layer of synthetic resin characterised by the use of special additives
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B32LAYERED PRODUCTS
    • B32BLAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B27/00Layered products comprising a layer of synthetic resin
    • B32B27/28Layered products comprising a layer of synthetic resin comprising synthetic resins not wholly covered by any one of the sub-groups B32B27/30 - B32B27/42
    • CCHEMISTRY; METALLURGY
    • C08ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08KUse of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K3/00Use of inorganic substances as compounding ingredients
    • C08K3/34Silicon-containing compounds
    • C08K3/36Silica
    • CCHEMISTRY; METALLURGY
    • C08ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08KUse of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K5/00Use of organic ingredients
    • C08K5/49Phosphorus-containing compounds
    • C08K5/51Phosphorus bound to oxygen
    • C08K5/53Phosphorus bound to oxygen bound to oxygen and to carbon only
    • C08K5/5313Phosphinic compounds, e.g. R2=P(:O)OR'
    • CCHEMISTRY; METALLURGY
    • C08ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08LCOMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L71/00Compositions of polyethers obtained by reactions forming an ether link in the main chain; Compositions of derivatives of such polymers
    • C08L71/08Polyethers derived from hydroxy compounds or from their metallic derivatives
    • C08L71/10Polyethers derived from hydroxy compounds or from their metallic derivatives from phenols
    • C08L71/12Polyphenylene oxides
    • CCHEMISTRY; METALLURGY
    • C08ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08LCOMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L85/00Compositions of macromolecular compounds obtained by reactions forming a linkage in the main chain of the macromolecule containing atoms other than silicon, sulfur, nitrogen, oxygen and carbon; Compositions of derivatives of such polymers
    • C08L85/02Compositions of macromolecular compounds obtained by reactions forming a linkage in the main chain of the macromolecule containing atoms other than silicon, sulfur, nitrogen, oxygen and carbon; Compositions of derivatives of such polymers containing phosphorus
    • HELECTRICITY
    • H05ELECTRIC TECHNIQUES NOT OTHERWISE PROVIDED FOR
    • H05KPRINTED CIRCUITS; CASINGS OR CONSTRUCTIONAL DETAILS OF ELECTRIC APPARATUS; MANUFACTURE OF ASSEMBLAGES OF ELECTRICAL COMPONENTS
    • H05K1/00Printed circuits
    • H05K1/02Details
    • H05K1/03Use of materials for the substrate

Abstract

The invention provides a phosphorus-containing flame retardant composition, including: a hypophosphite compound, a DOPO derivative and a polyphosphazene compound. The composition as a flame retardant can play a synergistic effect of several phosphorus-containing compounds, realizes halogen-free flame retardance under small addition amount and reaches level V-0. The invention also provides a contains a polyphenyl ether resin composition containing the above phosphorus-containing flame retardant compositions and a prepreg and a copper clad laminated board prepared from the same. After curing, the polyphenyl ether resin composition achieves flame retardance of V-0 grade under the condition to which the halogen flame retardant does not apply and keeps good dielectric property and heat resistance of polyphenyl ether resin; the prepreg and copper clad laminated board made from the composition have good dielectric property and heat resistance, and realize halogen-free flame retardance to UL 94-V0 grade while ensuring excellent heat resistance and dielectric property; and the composition is applicable to the field of high speed and high frequency printed circuit board, and is in line with the future requirements of green and environmental protection.

Description

Phosphor-containing flame-proof composition and use its phosphorous polyphenyl ether resin composition, prepreg and veneer sheet
Technical field
The invention belongs to copper-clad plate technical field, relate to a kind of phosphorus-containing composition and use its phosphorous polyphenyl ether resin composition, prepreg and veneer sheet.
Background technology
In recent years, along with the development of computer and information communication device high performance, multifunction and networking, in order to high-speed transfer and process Large Copacity information, operation signal trends towards high frequency, thus requirement is proposed to the material of circuit substrate, especially use the electronics in broadband to develop rapidly as mobile communications device has at those.
Existing in the material of tellite, widely use the epoxy resin of adhesion properties excellence.But the general specific inductivity of epoxy resin circuit substrate and dielectric loss angle tangent higher (specific inductivity is greater than 4, and dielectric loss angle tangent is about 0.02), high frequency characteristics is insufficient, can not the requirement of adaptation signal high frequency.Therefore the resin of dielectric characteristics excellence must be developed, i.e. specific inductivity and the low resin of dielectric loss angle tangent.Those skilled in the art is studied the good heat cured cyanate of dielectric properties, bimaleimide resin, hydrocarbon resin etc. for a long time; In addition, polyphenylene oxide resin is owing to having good dielectric properties, thermotolerance, also large quantifier elimination has been carried out by numerous technician as high-frequency high-speed material, but because its fusing point is high, poor fluidity and be subject to a lot of restriction in application, the melt viscosity of prepreg is large, and the technique that cannot meet multilayer printed wiring board makes requirement.By reducing the molecular weight of polyphenylene oxide resin, its melt temperature can be effectively reduced, improve liquidity, but this also sacrificing the thermotolerance of polyphenylene oxide resin.
CN1745142A employs a kind of end group and contains the polyphenylene oxide resin of vinyl phenyl and a vinyl phenyl as matrix resin, utilize isocyanuric acid triolefin ester as crosslinking and curing agent, mineral filler can also be added if desired, fire retardant obtains a kind of polyphenyl ether resin composition, then NE type glasscloth is flooded, obtain that there is excellent dielectric properties, there is prepreg and the veneer sheet of higher glass transition temperature, but owing to using isocyanuric acid triolefin ester as crosslinking and curing agent in said composition, its molecular weight is lower, as easy as rolling off a log volatilization in prepreg making processes, thus be unfavorable for stable making prepreg and laminated plate material.Although mention in this patent as improving thermotolerance, cohesiveness and dimensional stability, except PPE, if needed, olefin resin can being used as compatilizer, not studying carrying its properties to cured article.
US2009/0247032 have employed a kind of polyphenylene oxide resin of vinyl difunctionality as main body, and with the cyanate of naphthalene ring, bisphenol A cyanate ester, brominated flame retardant and mineral filler, obtain a kind of there is fine mobility and can ensure good dielectric properties prerequisite under obtain fine stripping strength, humidity resistance and flame retardant resistance.
WO2006/023371A1 provides the composition of a kind of Bifunctionalized polyphenylene oxide resin and ethylenic unsaturation hydrocarbon monomer, mobility and the rear performance of solidification of polyphenylene oxide resin can be improved, but do not point out that Bifunctionalized polyphenylene oxide resin is for performance advantage during veneer sheet field, and what use be ethylenic unsaturation hydrocarbon monomer is low-molecular weight compound, at high temperature also easily volatilize, manufacturability is poor.
Known from the above mentioned, by to low-molecular-weight functionalized be solve the problem that polyphenylene oxide molecular weight reduces the thermotolerance decline brought, but for when the embody rule in veneer sheet field, how to select the performance advantage of suitable curing cross-linked and embodiment functionalized polyphenylene ether resins, also need for further study.
In addition, along with society is to the reinforcement of environmental consciousness, the environmental issue of electronic product also becomes increasingly conspicuous, so how to realize the non-halogen of baseplate material, also be the emphasis of the art personnel research in this year, the technique means realizing halogen-free flameproof at present is mainly introduced phosphoric and is carried out fire-retardant, common material has phosphorous epoxy resin, phosphorus containing phenolic resin, phosphate compounds and polyphosphate compound, phosphazene compound, hypophosphite compounds, but due to the restriction of these material self characters, be used alone and all cannot meet the requirement of high-speed material field to thermotolerance and dielectric properties, as phosphorous epoxy resin, although phosphorus containing phenolic resin portion of material can reach good flame retardant effect, but owing to performing poor in dielectric properties, phosphorus introduces the deterioration bringing wet-hot aging performance too much simultaneously, the reliability requirement of high multi-layer PCB cannot be met, the flame retardant effect that the phosphinates of addition type is used alone is not good, is particularly becoming the resin system that charcoal is lower, polyphosphonitrile compound due to the fusing point of this province lower, plasticity is strong, and a large amount of interpolations brings thermotolerance to decline to a great extent as second-order transition temperature reduces, and when being used alone, even if a large amount of interpolations simultaneously, is also difficult to the rank of accomplishing fire-retardant V-0.There is Similar Problems too in other phosphate compounds.
In general, how to realize the superior dielectric performance simultaneously meeting the requirement of high speed baseplate material, as low specific inductivity and Dielectric loss tangent value, the new technology that can realize again halogen-free flameproof is one of emphasis direction for following this area research.
Summary of the invention
For the problem of prior art, the object of the invention is to a kind of phosphor-containing flame-proof composition, it can be issued to halogen-free flameproof at lower addition, reaches UL 94V-0.The present invention also aims to provide a kind of phosphorous polyphenyl ether resin composition, it can keep dielectric characteristics that polyphenylene oxide resin is good and thermotolerance, and realizes halogen-free flameproof, and fire retardant reaches UL 94V-0.Another object of the present invention is also to provide a kind of prepreg and the copper-clad laminate that use above-mentioned phosphorous polyphenyl ether resin composition making, and have good dielectric characteristics and thermotolerance, and realize halogen-free flameproof, fire retardant reaches UL 94V-0.
To achieve these goals, present invention employs following technical scheme:
A kind of phosphor-containing flame-proof composition, described fire-retardant combination comprises:
(A) the DOPO derivative shown in formula (1), 100 weight parts;
(B) hypophosphite compound, 5 ~ 50 weight parts;
(C) polyphosphonitrile compound, 10 ~ 50 weight parts
R 1for the one in the alkylene hydrocarbon of C2 ~ C20 or sub-aromatic hydrocarbon.
The content of described hypophosphite compound is such as 10 weight parts, 15 weight parts, 20 weight parts, 25 weight parts, 30 weight parts, 35 weight parts, 40 weight parts or 45 weight parts.
The content of described polyphosphonitrile compound is such as 10 weight parts, 15 weight parts, 20 weight parts, 25 weight parts, 30 weight parts, 35 weight parts, 40 weight parts or 45 weight parts.
In the present invention, use above-mentioned phosphorus-containing composition as fire retardant, the synergy between three kinds of P contained compounds can be played, under less addition, realize halogen-free flameproof, reach V-0 rank.
In the present invention, described component (A) DOPO derivative can be synthesized into by the following method, is specially: by Compound D OPO and dibasic alcohol under the effect of catalyzer, temperature of reaction is 50 ~ 300 DEG C, reaction times is 0.5 ~ 48 hour, is obtained by reacting, and concrete reaction formula is as follows:
In formula, n is the integer of 2 ~ 20.
Reaction described above by the reactive hydrogen atom of DOPO, with the obtaining of diatomic alcohol compounds generation dehydration condensation under catalyst action; Wherein the molar feed ratio of DOPO and dibasic alcohol controls 0.5 ~ 100, and preferably 0.5 ~ 10, be further preferably 0.5 ~ 5, if mol ratio is too low, DOPO low conversion rate will be caused, if mol ratio is too high, the recovery difficulty that dibasic alcohol can be brought again follow-up.
Described catalyzer is not particularly limited, any catalyzer that can promote that dehydration reaction and Arbuzov react can use, optional catalyzer has alkyl halide, basic metal, alkaline earth metal halide, transition metal and halides thereof, acid, Arbuzov catalyzer, is wherein preferably Arbuzov catalyzer.
For example, the derivative of described DOPO can be following structural formula:
Preferably, described component (B) hypophosphite compound has following structure:
Wherein m is 2 or 3; R 3and R 4be alkyl or aryl that carbonatoms is 1 ~ 6 independently, M is atoms metal, this atoms metal be selected from sodium, calcium, magnesium, aluminium, arsenic, zinc or iron any one.Consider from the angle reducing its water-intake rate and its phosphorus content of raising, M is preferably aluminium or sodium, if but further consider the impact reducing phosphorus-containing composition as far as possible and add the dielectric properties after on resin composition, M is more preferably aluminium.
More specifically, hypophosphite compound described in the present invention is
Component (C) described in the present invention is polyphosphonitrile compound.Polyphosphonitrile compound is a kind of complete non-conjugated compound of phosphorus nitrogen heterocyclic, has excellent light stability and thermostability, high limit oxygen index, low exhaust smoke level and have good chemical-resistant characteristic, water tolerance and solvent resistance.
Polyphosphonitrile compound in the present invention has following structural formula:
Wherein n is the integer of 3 ~ 100, such as 5,10,20,30,40,50,60,70,80 or 90.
Wherein R be phenoxy group, carbonatoms be 1 ~ 10 alkyl, any one in vinyl phenoxy group or allyl group phenoxy group;
Or,
Wherein q is the integer of 3 ~ 25, such as 4,6,7,10,13,16,19 or 22; Any one in R is phenoxy group, carbonatoms is 1 ~ 10 alkyl, vinyl phenoxy group or allyl group phenoxy group.
Present invention also offers a kind of phosphorous polyphenyl ether resin composition, it comprises phosphorus-containing composition as above and terminal group functional polyphenylene oxide resin.
In the present invention, described terminal group functional polyphenylene oxide resin is the mixture of any one or at least two kinds in terminal hydroxy group polyphenylene oxide resin, epoxidation polyphenylene oxide resin, vinylated polyphenylene oxide resin or cyanalation polyphenylene oxide resin, be preferably vinylated polyphenylene oxide resin or/and cyanalation polyphenylene oxide resin, more preferably vinylated polyphenylene oxide resin.
In the present invention, described terminal group functional polyphenylene oxide resin structural formula is such as formula shown in (2):
In formula (2), a and b is the integer of 1 ~ 30 independently, such as 2,5,8,11,14,17,20,23,26 or 29, Z is the structure shown in formula (3) or (4),-(-O-Y-)-be the structure shown in formula (5) ,-(-O-X-O-)-be the structure shown in formula (6):
In formula (4), the alkylidene group of A to be arylene, carbonyl or carbonatoms be 1 ~ 10 (such as 2,3,4,5,6,7,8 or 9), m is the integer of 0 ~ 10 (such as 1,2,3,4,5,6,7,8 or 9), R 1, R 2and R 3identical or different, be the alkyl of hydrogen or carbonatoms less than 10 independently;
In formula (5), R 4with R 6identical or different, be hydrogen atom, halogen atom, the alkyl of carbonatoms less than 8 or the phenyl of carbonatoms less than 8 independently, R 5with R 7identical or different, be halogen atom, the alkyl of carbonatoms less than 8 or the phenyl of carbonatoms less than 8 independently;
In formula (6), R 8, R 9, R 10, R 11, R 12, R 13, R 14and R 15between identical or different, be hydrogen atom, halogen atom, the alkyl of carbonatoms less than 8 or the phenyl of carbonatoms less than 8 independently, B be carbonatoms less than 20 alkylene, n is 0 or 1; R 16for the alkyl that hydrogen atom or carbonatoms are 1 ~ 10 (such as 2,3,4,5,6,7,8 or 9).
More specifically, described terminal group functional polyphenylene oxide resin is the structure shown in formula (7) or (8):
In formula (7), R 1~ R 3identical or different, be the alkyl of hydrogen or carbonatoms less than 10 independently; R 4with R 6identical or different, be the alkyl or phenyl of hydrogen atom, halogen atom, carbonatoms less than 8 independently; R 5with R 7identical or different, be halogen atom, the alkyl of carbonatoms less than 8 or the phenyl of carbonatoms less than 8 independently; R 8, R 9, R 10, R 11, R 12, R 13, R 14and R 15between identical or different, be hydrogen atom, halogen atom, the alkyl of carbonatoms less than 8 or the phenyl of carbonatoms less than 8 independently; A and b is the integer of 1 ~ 30 independently, such as 2,5,8,11,14,17,20,23,26 or 29, B be carbonatoms less than 20 alkylene, n is 0 or 1, R 16for hydrogen atom or carbonatoms are the alkyl of 1 ~ 10;
In formula (8), R 4with R 6identical or different, be the alkyl or phenyl of hydrogen atom, halogen atom, carbonatoms less than 8 independently; R 5with R 7identical or different, be the alkyl or phenyl of halogen atom, carbonatoms less than 8; R 8, R 9, R 10, R 11, R 12, R 13, R 14and R 15between identical or different, be the alkyl or phenyl of hydrogen atom, halogen atom, carbonatoms less than 8; A and b is the integer of 1 ~ 30 independently; B is the alkylene of carbonatoms less than 20, and n is 0 or 1.
Further, described terminal group functional polyphenylene oxide resin can also be the structure shown in formula (9) to (13):
In formula (9), R 1~ R 3identical or different, be the alkyl of hydrogen or carbonatoms less than 10; R 4with R 6identical or different, be the alkyl or phenyl of hydrogen atom, halogen atom, carbonatoms less than 8; R 5with R 7identical or different, be the alkyl or phenyl of halogen atom, carbonatoms less than 8; R 8, R 9, R 10, R 11, R 12, R 13, R 14and R 15between identical or different, be the alkyl or phenyl of hydrogen atom, halogen atom, carbonatoms less than 8; A and b is the integer of 1 ~ 30 independently.
In formula (10), R 1~ R 3identical or different, be the alkyl of hydrogen or carbonatoms less than 10; R 4with R 6identical or different, be the alkyl or phenyl of hydrogen atom, halogen atom, carbonatoms less than 8; R 5with R 7identical or different, be the alkyl or phenyl of halogen atom, carbonatoms less than 8; R 8, R 9, R 10, R 11, R 12, R 13, R 14and R 15between identical or different, be the alkyl or phenyl of hydrogen atom, halogen atom, carbonatoms less than 8; A and b is the integer of 1 ~ 30 independently.
In formula (11), R 1~ R 3identical or different, be the alkyl of hydrogen or carbonatoms less than 10; R 4with R 6identical or different, be the alkyl or phenyl of hydrogen atom, halogen atom, carbonatoms less than 8; R 5with R 7identical or different, be the alkyl or phenyl of halogen atom, carbonatoms less than 8; R 8, R 9, R 10, R 11, R 12, R 13, R 14and R 15between identical or different, be the alkyl or phenyl of hydrogen atom, halogen atom, carbonatoms less than 8; A and b is the integer of 1 ~ 30 independently.
In formula (12), R 4with R 6identical or different, be the alkyl or phenyl of hydrogen atom, halogen atom, carbonatoms less than 8; R 5with R 7identical or different, be the alkyl or phenyl of halogen atom, carbonatoms less than 8; R 8, R 9, R 10, R 11, R 12, R 13, R 14and R 15between identical or different, be the alkyl or phenyl of hydrogen atom, halogen atom, carbonatoms less than 8; A and b is the integer of 1 ~ 30 independently.
In formula (13), R 4with R 6identical or different, be the alkyl or phenyl of hydrogen atom, halogen atom, carbonatoms less than 8; R 5with R 7identical or different, be the alkyl or phenyl of halogen atom, carbonatoms less than 8; R 8, R 9, R 10, R 11, R 12, R 13, R 14and R 15between identical or different, be the alkyl or phenyl of hydrogen atom, halogen atom, carbonatoms less than 8; A and b is the integer of 1 ~ 30 independently.
Preferably, in phosphorous polyphenyl ether resin composition, be 100 parts by weight with described terminal group functional polyphenylene oxide resin, the addition of phosphor-containing flame-proof composition is 15 ~ 60 weight parts, such as 25 weight parts, 30 weight parts, 35 weight parts, 40 weight parts, 45 weight parts, 50 weight parts or 55 weight parts, be preferably 20 ~ 50 weight parts, more preferably 25 ~ 40 weight parts.By adding phosphor-containing flame-proof composition, playing the synergy between phosphorus-containing composition, making the polyphenyl ether resin composition after solidification can reach good fire-retardant.But when the addition of content fire-retardant combination is less than 15 weight part, the fire-retardant of system does not reach V-0 rank, to addition more than 60 parts time, although can ensure that the polyphenyl ether resin composition after solidifying reaches good fire-retardant fully, but because phosphor-containing flame-proof composition water suction itself is bigger than normal, cause the thermotolerance of system, dielectric properties significantly to worsen.
In the present invention, described phosphorous polyphenyl ether resin composition also comprises linking agent, described linking agent is the polyolefin resin with unsaturated double-bond, and the described polyolefin resin with unsaturated double-bond is polyhutadiene and graft-modified polymers thereof as the mixture of any one in maleic anhydride graft this property polybutadiene polymers, acrylic acid modified butadiene polymer, butadiene-styrene copolymer, butadiene-styrene-divinyl benzene copolymer or cyclic olefine copolymer or at least two kinds.
Be 100 parts by weight with terminal group functional polyphenylene oxide resin, the addition of the described polyolefin resin with unsaturated double-bond is 10 ~ 100 weight parts, such as 15 weight parts, 20 weight parts, 25 weight parts, 30 weight parts, 35 weight parts, 40 weight parts, 45 weight parts, 50 weight parts, 55 weight parts, 60 weight parts, 65 weight parts, 70 weight parts, 75 weight parts, 80 weight parts, 85 weight parts, 90 weight parts or 95 weight parts.Because the dielectric properties of olefin resin are excellent, so the olefin resin adding proper ratio can improve the dielectric properties of fixed line system further as Dk/Df, simultaneously due in olefin resin with unsaturated double-bond can crosslinking curing further with polyphenylene oxide resin, thermotolerance can be improved further.When addition is less than 10 parts, the unsaturated double-bond amount introduced in olefin resin very little, cannot play effectively crosslinked effect, does not reach the object improving thermotolerance and dielectric properties; If olefin resin amount is more than 100 parts, then the rigidity due to olefin resin itself is too poor, and the reason that the coefficient of expansion is large also can cause the huge decline of the thermotolerance of cured article.
Preferably, the number-average molecular weight of described terminal group functional polyphenylene oxide resin is 500 ~ 5000, and preferred number average molecular weight is 500 ~ 3000, and more preferably number-average molecular weight is 800 ~ 2500.When the terminal group functional polyphenylene oxide resin using number-average molecular weight more than 5000, in the course of processing, solvability is deteriorated, conventional veneer sheet technique cannot be used to carry out gluing, needs are heated, make difficulty in process in the copper-clad plate course of processing, operational hazards, and mobility also can decline thereupon, makes multi-ply wood processing difficulties; And when number-average molecular weight is less than 500 time, its thermotolerance, dielectric properties can decline, be unfavorable for resin combination and the laminate sheet material of obtained high heat resistance, dielectric characteristics also can reduce simultaneously.When described terminal group functional polyphenylene oxide resin mixes with linking agent further, the functionalized polyphenylene ether resins with less number-average molecular weight can improve the consistency between linking agent better, namely molecular weight is less, and the consistency between blending ingredients is better, and stability in storage is better.In addition, lower molecular weight can provide better mobility, and be conducive to provides better filler in the multi-ply wood course of processing.
In the present invention, described phosphorous polyphenyl ether resin composition also comprises co-crosslinker, described co-crosslinker be bimaleimide resin or/and multi-group methacrylates compound, be preferably maleimide resin.
Be 100 parts by weight with terminal group functional polyphenylene oxide resin, the addition of described co-crosslinker is 5 ~ 50 weight parts, such as 7 weight parts, 10 weight parts, 13 weight parts, 16 weight parts, 19 weight parts, 22 weight parts, 25 weight parts, 28 weight parts, 31 weight parts, 35 weight parts, 38 weight parts, 41 weight parts, 44 weight parts or 47 weight parts.The introducing of described co-crosslinker, main purpose is set out for the thermotolerance angle improving polyphenylene oxide cured product further, due to maleimide resin can with the unsaturated double-bond generation curing cross-linking reaction of terminal group functional polyphenylene oxide resin and olefin resin, form a cross-linked structure be jointly made up of three, system has better heat-resistant stability; Maleimide resin addition does not have very little and improves cross-linking density, improve the object of thermotolerance, if although amount effectively can improve the cross-linking density of system too much, because the polarity of this body structure of maleimide is comparatively large, the obvious decline of dielectric properties can be brought.
In the present invention, described phosphorous polyphenyl ether resin composition also comprises initiator.The half life temperature t of described initiator 1/2be not less than 100 DEG C, be peroxide radical initiator, be selected from dicumyl peroxide, peroxidized t-butyl perbenzoate, 2,5-bis-(2-ethyihexanoylperoxy)-2,5-dimethylhexanes, two-(tert-butylperoxyiso-propyl) benzene, peroxidation (2,4 dichloro benzene formyl), two (t-butyl peroxy) hexane of 2,5-dimethyl-2,5-, peroxidation-2-ethylhexyl carbonate the tert-butyl ester, two (the t-butyl peroxy)-3-alkynes of 2,5-dimethyl-2,5-, 4,4-bis-(tert-butyl hydroperoxide) butyl valerate, 1,1-two (tert-butyl hydroperoxide)-3,3,5-trimethylammonium cyclohexane, 3,3,5,7,7-pentamethyl--1,2,4-trioxepan, the mixture of any one or at least two kinds in ditertiary butyl peroxide or t-tutyl cumyl peroxide, preferred dicumyl peroxide, because this compound has higher half life temperature and reacting initial temperature, therefore when not needing solidification, in semicure process, exceedingly can not cause curing reaction, also can not reduce the stability in storage of polyphenylene oxide resin.
Initiator in polyphenyl ether resin composition of the present invention, object is to improve crosslinking curing effect.Although terminal group functional polyphenylene oxide resin and linking agent also can be cured under heating hot conditions, but during veneer sheet application, processing condition are difficult to meet high temperature requirement, its difficulty of processing is increased, also process efficiency is unfavorable on the one hand in addition, increase production cost, therefore add initiator advantageously.Be 100 parts by weight with terminal group functional polyphenylene oxide resin, the addition of described initiator is 0.5 ~ 7 weight part, such as 1.3 weight parts, 1.6 weight parts, 1.9 weight parts, 2.2 weight parts, 2.5 weight parts, 3.1 weight parts, 3.5 weight parts, 3.9 weight parts, 4.3 weight parts, 4.7 weight parts, 5 weight parts, 5.4 weight parts, 5.8 weight parts, 6.2 weight parts or 6.6 weight parts.
In the present invention, described phosphorous polyphenyl ether resin composition also comprises silane coupling agent, be 100 parts by weight with terminal group functional polyphenylene oxide resin, the addition of described silane coupling agent is 0.1 ~ 10 weight part, such as 0.5 weight part, 1 weight part, 1.5 weight parts, 2 weight parts, 2.5 weight parts, 3 weight parts, 3.5 weight parts, 4 weight parts, 4.5 weight parts, 5 weight parts, 5.5 weight parts, 6 weight parts, 6.5 weight parts, 7 weight parts, 7.5 weight parts, 8 weight parts, 8.5 weight parts, 9 weight parts or 9.5 weight parts.
To the kind of coupling agent, there is no particular limitation.Coupling agent can reduce the surface tension of resin cured matter further, and its viscosity is further reduced, and improves the mobility of resin combination.Especially under the occasion of adding filler, coupling agent add the bonding force that can effectively improve between resin and filler, the interface between both eliminations, reduce the water-intake rate of cured article further.Described coupling agent can be silicane, silane pre-polymer, titanate ester, and silane coupling agent can be epoxy silane coupling, amino silicane coupling agent, phenylamino silane coupling agent, vinyl silicane coupling agent, isocyanato silanes coupling agent, acrylsilanes coupling agent, isobutenyl silane coupling agent, styryl silane coupling agent, ureido silane coupling agent, chloropropyl silane coupling agent, sulfenyl silane coupling agent or sulfuration base silane coupling agent etc.
In the present invention, described phosphorous polyphenyl ether resin composition also comprises filler, described filler is organic or inorganic filler, and mineral filler is selected from the mixture of any one or at least two kinds in powdered quartz, fused silica, preparing spherical SiO 2, hollow silicon dioxide, glass powder, aluminium nitride, boron nitride, silicon carbide, aluminium hydroxide, titanium dioxide, strontium titanate, barium titanate, aluminum oxide, barium sulfate, talcum powder, Calucium Silicate powder, calcium carbonate or mica; Organic filler is selected from the mixture of any one or at least two kinds in polytetrafluorethylepowder powder, polyphenylene sulfide or polyethersulfone powder.
In addition, the shape, particle diameter etc. of mineral filler are also not particularly limited, and usual particle diameter is 0.01-50 μm, and be preferably 0.01-20 μm, be more preferably 0.01-10 μm, the mineral filler of this particle size range more easily disperses in resin liquid.
Be 100 parts by weight with terminal group functional polyphenylene oxide resin, the addition of described filler is 10 ~ 300 weight parts, such as 30 weight parts, 60 weight parts, 90 weight parts, 120 weight parts, 150 weight parts, 180 weight parts, 210 weight parts, 240 weight parts or 270 weight parts.
" comprising " of the present invention, mean it except described component, can also comprise other components, these other components give described phosphorous polyphenyl ether resin composition different characteristics.In addition, " comprising " of the present invention, can also replace with enclosed " being " or " by ... composition ".
Such as, described phosphorous polyphenyl ether resin composition can also contain various additive, as concrete example, can enumerate oxidation inhibitor, thermo-stabilizer, static inhibitor, UV light absorber, pigment, tinting material or lubricant etc.These various additives can be used alone, also can two kinds or two or more used in combination.
Further, the invention provides a kind of prepreg using above-mentioned phosphorous polyphenyl ether resin composition to make, comprise base material and by the as above phosphorous polyphenyl ether resin composition of the dry postadhesion of impregnation on base material.
During making, first by terminal group functional polyphenylene oxide resin, phosphorus-containing composition, optional linking agent, optionally co-crosslinker, optional initiator, optional coupling agent and optionally filler be dissolved in one or more organic solvents, obtained homogeneous glue.To organic solvent, there is no particular limitation, as long as can dissolve above component, and can not affect its reactivity; The solvent be applicable to comprises: ketone is as methylethylketone, acetone etc., and ethers is as propylene glycol monomethyl ether, dibutyl ether etc., and ester class is as ethyl acetate, and aromatics is as toluene, dimethylbenzene etc., and halogenated hydrocarbon is as trichloroethane etc.Often kind of solvent may be used alone, can also be used in combination.In glue, the concentration of resin solid matter can be impregnated into the kind of base material and technique according to glue and makes and suitably change, and such as its suitable concentration is 30 ~ 80%.Be impregnated into base material by above-mentioned obtained glue, then heating, drying carried out to remove organic solvent and resin combination in partially cured base material to it, just obtain prepreg.
Described base material is the obtained yarn fabric of organic fibre, carbon fiber or glass fibre or nonwoven fabric; The yarn fabric obtained for glass fibre or nonwoven fabric, include the SiO of weight ratio 50 ~ 80% in its main component 2, the CaO of weight ratio 0 ~ 30%, the Al of weight ratio 0 ~ 20% 2o 3, weight ratio 5 ~ 25% B 2o 3, and the MgO of weight ratio 0 ~ 5%.Described strongthener preferably works out cloth, is chosen as E-Glass, T-Glass, NE-Glass, L-Glass, Q-Glass.
Be used for flooding the resin content of above-mentioned base material, preferably make the resin content in prepreg be 30 quality % or higher.Because the specific inductivity of base material is often higher than resin combination, in order to reduce the specific inductivity of the veneer sheet obtained by these prepregs, the content of resin combination composition in prepreg is preferably higher than above-mentioned content.As use resin Composition content be 40% the obtained veneer sheet of prepreg, its specific inductivity is 3.5, and use resin content be 50% or higher the obtained veneer sheet of prepreg, its specific inductivity is 3.2 or lower.In addition, above-described prepreg toasts 2 ~ 15 minutes at condition is 80 ~ 170 DEG C, but be not limited thereto.
In addition, the present invention also provides a kind of veneer sheet, and it comprises at least one superimposed prepreg as above.
In addition, the present invention also provides a kind of copper-clad laminate using above-mentioned phosphorous polyphenyl ether resin composition to make, and comprises several superimposed prepregs and is overlaid on the Copper Foil of one or both sides of superimposed rear prepreg.
Specifically by stacking one or more prepreg of the present invention, enclose Copper Foil etc. at its one or both sides, then carry out hot pressing and obtain, the Copper Foil of laminate surface carries out etching and forms the wiring diagram of needs and obtain printed circuit board.In addition, multilayer printed wiring board can also be prepared by the following method: use printed circuit board as internal layer printed circuit board with step, surface treatment is carried out to the Copper Foil above it, according to demand in certain sequence by prepreg of the present invention with above-mentionedly carry out that surface-treated printed circuit board is stacking carries out hot pressing, hot pressing condition can be determined according to the proportion of composing of polyphenyl ether resin composition of the present invention, and to this, there is no particular limitation.Hot pressing condition is preferably hot pressing for some time under the pressure range of the temperature range of 150 ~ 250 DEG C and 1.0MPa ~ 10.0MPa.The veneer sheet obtained with step in this way and printed circuit board have good high frequency characteristics such as dielectric properties etc. and also have good processes, thermotolerance and wet fastness simultaneously.
In addition, in order to improve the application of material in high-frequency high-speed field further, during copper-clad laminate is in the present invention produced, the Copper Foil used, electrolytic copper foil or rolled copper foil can be selected, its surfaceness is less than 5 microns, can improve and improve the loss of signal that laminate sheet material uses at high-frequency high-speed printed circuit board.Simultaneously, in order to improve the bonding force of Copper Foil contact prepreg one side, above-mentioned Copper Foil used can also use silane coupling agent to carry out chemical treatment, coupling agent used is one or more the mixture in epoxy silane coupling, vinyl silicane coupling agent or acrylate-based silane coupling agent, object improves the bonding force of Copper Foil and base material, prevents from falling in printed circuit board use procedure newly, falls pad equivalent risk.
Present invention also offers a kind of printed circuit board, it comprises at least one superimposed prepreg as above.
Compared with the prior art, the present invention has following beneficial effect:
Polyphenyl ether resin composition of the present invention, for low-molecular-weight functionalized polyphenylene ether resins composition, there is good processes, maintain the good dielectric characteristics of polyphenylene oxide resin and thermotolerance, add ad hoc structure phosphonium flame retardant composition again, both maintain thermotolerance, dielectric properties, the low water absorbable of original polyphenylene oxide resin system, realized halogen-free flameproof simultaneously, fire-retardantly reach UL 94V-0 rank.
Embodiment
Technical scheme of the present invention is further illustrated below by embodiment.
The preparation of synthesis example 1:DOPO derivative
Potassium tert.-butoxide 230g is added, the anhydrous DMSO1.5L of solvent in the four neck reactors being furnished with feed hopper, thermopair, mechanical stirrer and nitrogen stream.At room temperature stir this mixture, until it becomes homogeneous solution.Solution is cooled to 10 DEG C, adds DOPO 42.3g with 10 aliquots, to keep temperature of reaction lower than 30 DEG C.In 1 hour, the ethylene dichloride 92g in feed hopper is slowly joined in above-mentioned solution.Be heated to 50 degree and react 1 hour.Be cooled to 10 DEG C react and 3L water will be added.Filter slurry, and close ethyl acetate washing wet cake with water, acetone, obtain the thick wet mass matter of 532g, this material is refluxed in MeCN/ ethanol/water 5320ml, and progressively cools to 5 DEG C.White solid is filtered by funnel, and in 80 DEG C of vacuum drying ovens dry 8 ~ 10 hours, obtain dry white powder 260g, be the DOPO derivative 1 of formula (1), wherein R 1for-CH2-CH2-.
Synthesis example 2
Methylene dichloride wherein, with reference to synthesis example 1, is replaced to dichloro-p-xylene, obtains the DOPO derivative 2 of formula (1), wherein R by synthetic method 1for phenyl.
Mixing example 1: the preparation (P15.4%) of phosphor-containing flame-proof composition
By the DOPO derivative of the synthesis example 1 of the hypophosphite compound of 35 weight parts, 100 weight parts and the polyphosphonitrile compound of 18 weight parts, obtain phosphorus-containing composition;
Described hypophosphite compound is:
Described polyphosphonitrile compound has following structure:
wherein R is methyl, and wherein n is the integer of 3 ~ 100.
Mixing example 2: the preparation (P16%) of phosphorus-containing composition
By the DOPO derivative of the synthesis example 1 of the hypophosphite compound of 50 weight parts, 100 weight parts and the polyphosphonitrile compound of 25 weight parts, obtain phosphorus-containing composition;
Described hypophosphite compound is:
Described polyphosphonitrile compound has following structure:
wherein R is ethyl, wherein n be 3 ~ 100 integer.
Mixing example 3: the preparation (P13.8%) of phosphorus-containing composition
By the DOPO derivative of the synthesis example 1 of the hypophosphite compound of 10 weight parts, 100 weight parts and the polyphosphonitrile compound of 25 weight parts, obtain phosphorus-containing composition;
Described hypophosphite compound is:
Described polyphosphonitrile compound has following structure:
Wherein q is 3; Wherein R is phenoxy group.
The preparation (P15%) of mixing example 4 phosphorus-containing composition
By the DOPO derivative of the synthesis example 2 of the hypophosphite compound of 30 weight parts, 100 weight parts and the polyphosphonitrile compound of 40 weight parts, obtain phosphorus-containing composition;
Described hypophosphite compound is:
Described polyphosphonitrile compound has the mixture of following both structures:
wherein R is methyl, and wherein n is the integer of 80;
Wherein q is 3; Wherein R is phenoxy group.
Embodiment 1
Using the polyphenylene oxide SA9000 of 100g methacryloxyethyl acid methyl esters modification with mix as the toluene of solvent, dissolve and obtain terminal group functional polyphenylene oxide resin solution completely, then 45g styrene-butadiene copolymer R100 is added as linking agent, add 2g dicumyl peroxide as initiator, 45g mixes the phosphorus-containing composition of example 1 as fire retardant, 0.8g epoxy silane coupling and 80g silicon-dioxide (SC-2050SQ) are as filler, said mixture is mixed in toluene, and stirring and dissolving obtains homogeneous resin combination, i.e. glue.
The above-mentioned glue prepared is infiltrated up to E-glass-fiber-fabric, heat drying 3 ~ 10min at 155 DEG C, solvent evaporates is complete, obtain prepreg.The Copper Foil that thickness is 35 μm is respectively enclosed on prepare more than overlap 8 prepreg two sides of rising, and under the pressure of the temperature of 200 DEG C and 3.0MPa, hot pressing 90 minutes, obtains the veneer sheet of double-sided copper-clad.
Embodiment 2
Using the polyphenylene oxide SA9000 of 100g methacryloxyethyl acid methoxycarbonyl modification with mix as the toluene of solvent, dissolve and obtain terminal group functional polyphenylene oxide resin solution completely, then 20g polyhutadiene polymers B-1000 is added as linking agent, add 2.0g dicumyl peroxide as initiator, 30g mixes the phosphorus-containing composition of example 2 as fire retardant, 0.8g vinyl silicane coupling agent and 80g silicon-dioxide (SC-2050SQ) are as filler, said mixture is mixed in toluene, and stirring and dissolving obtains homogeneous resin combination, i.e. glue.
The above-mentioned glue prepared is infiltrated up to E-glass-fiber-fabric, heat drying 3 ~ 10min at 155 DEG C, solvent evaporates is complete, obtain prepreg.The Copper Foil that thickness is 35 μm is respectively enclosed on 8 the prepreg two sides prepared more than overlap, and under the pressure of the temperature of 200 DEG C and 3.0MPa, hot pressing 90 minutes, obtains the veneer sheet of double-sided copper-clad.
Embodiment 3
Mix using the polyphenylene oxide SA9000 of 100g methacryloxyethyl acid methoxycarbonyl modification with as the toluene 100g of solvent, dissolve and obtain terminal group functional polyphenylene oxide resin solution completely, then 30g styrene-butadiene copolymer R100 is added as linking agent, 15g bimaleimide resin is as co-curing agent, add 3.0g dicumyl peroxide again as initiator, 35g mixes the phosphorus-containing composition of example 2 as fire retardant, 2g vinyl base silane coupling agent and 150g silicon-dioxide are as filler, said mixture is mixed in toluene, and stirring and dissolving obtains homogeneous resin combination, i.e. glue.
The above-mentioned glue prepared is infiltrated up to E-glass-fiber-fabric, heat drying 3 ~ 10min at 155 DEG C, solvent evaporates is complete, obtain prepreg.The Copper Foil that thickness is 35 μm is respectively enclosed on prepare more than overlap 8 prepreg two sides of rising, and under the pressure of the temperature of 200 DEG C and 3.0MPa, hot pressing 90 minutes, obtains the veneer sheet of double-sided copper-clad.
Embodiment 4
Mix using 100g styryl polyphenylene oxide OPE-2000 with as the toluene 100g of solvent, dissolve and obtain terminal group functional polyphenylene oxide resin solution completely, then 35g polybutadiene polymers B-2000 is added as linking agent, add 2.5g dicumyl peroxide as initiator, 50g mixes the phosphorus-containing composition of example 3 as fire retardant, and said mixture, as filler, mixes by the silicon-dioxide of 150g vinyl process in toluene, and stirring and dissolving obtains homogeneous resin combination, i.e. glue.
The above-mentioned glue prepared is infiltrated up to E-glass-fiber-fabric, heat drying 3 ~ 10min at 155 DEG C, solvent evaporates is complete, obtain prepreg.The Copper Foil that thickness is 35 μm is respectively enclosed on prepare more than overlap 8 prepreg two sides of rising, and under the pressure of the temperature of 200 DEG C and 3.0MPa, hot pressing 90 minutes, obtains the veneer sheet of double-sided copper-clad.
Embodiment 5
Terminal group functional polyphenylene oxide resin solution is obtained completely using polyphenylene oxide resin OPE-2000 styrene end-capped for 100g with as the toluene 100g mixed dissolution of solvent, then 20g styrene-butadiene copolymer R100 is added as linking agent, 10g bimaleimide resin is as co-curing agent, add 3.0g dicumyl peroxide again as initiator, 45g mixes the phosphorus-containing composition of example 2 as fire retardant, 200g vinyl base silane coupling agent and 150g silicon-dioxide are as filler, said mixture is mixed in toluene, and stirring and dissolving obtains homogeneous resin combination, i.e. glue.
The above-mentioned glue prepared is infiltrated up to E-glass-fiber-fabric, heat drying 3 ~ 10min at 155 DEG C, solvent evaporates is complete, obtain prepreg.The Copper Foil that thickness is 35 μm is respectively enclosed on prepare more than overlap 8 prepreg two sides of rising, and under the pressure of the temperature of 200 DEG C and 3.0MPa, hot pressing 90 minutes, obtains the veneer sheet of double-sided copper-clad.
Embodiment 6
Terminal group functional polyphenylene oxide resin solution is obtained completely using the polyphenylene oxide SA9000 of 100g methacryloxyethyl acid methoxycarbonyl modification with as the toluene 100g mixed dissolution of solvent, then 75g styrene-butadiene copolymer R100 is added as linking agent, 45g bimaleimide resin is as co-curing agent, add 3.0g dicumyl peroxide again as initiator, 35g mixes the phosphorus-containing composition of example 4 as fire retardant, the silicon-dioxide SC-2300SVJ of 200g vinyl base silane process is as filler, said mixture is mixed in toluene, and stirring and dissolving obtains homogeneous resin combination, i.e. glue.The above-mentioned glue prepared is infiltrated up to E-glass-fiber-fabric, heat drying 3 ~ 10min at 155 DEG C, solvent evaporates is complete, obtain prepreg.The Copper Foil that thickness is 35 μm is respectively enclosed on prepare more than overlap 8 prepreg two sides of rising, and under the pressure of the temperature of 200 DEG C and 3.0MPa, hot pressing 90 minutes, obtains the veneer sheet of double-sided copper-clad.
Embodiment 7
Just the modification of 100g methacryloxyethyl acid methoxycarbonyl polyphenylene oxide SA9000 and mix as the toluene 100g of solvent, dissolve and obtain terminal group functional polyphenylene oxide resin solution completely, then 30 modified by maleic acid anhydride graft polybutadiene polymers Ricon156MA17 are added as linking agent, 25g maleimide resin is as co-crosslinker, add 2.5g dicumyl peroxide as initiator, 35g mixes the phosphorus-containing composition of example 3 as fire retardant, the silicon-dioxide SC-2300SVJ of 300g vinyl base silane process is as filler, said mixture is mixed in toluene, and stirring and dissolving obtains homogeneous resin combination, i.e. glue.
The above-mentioned glue prepared is infiltrated up to E-glass-fiber-fabric, heat drying 3 ~ 10min at 155 DEG C, solvent evaporates is complete, obtain prepreg.The Copper Foil that thickness is 35 μm is respectively enclosed on prepare more than overlap 8 prepreg two sides of rising, and under the pressure of the temperature of 200 DEG C and 3.0MPa, hot pressing 90 minutes, obtains the veneer sheet of double-sided copper-clad.
Comparative example 1
Using the polyphenylene oxide SA9000 of 100g methacryloxyethyl acid methoxycarbonyl modification with mix as the toluene of solvent, dissolve and obtain terminal group functional polyphenylene oxide resin solution completely, then 45g styrene-butadiene copolymer R100 is added as linking agent, add 2g dicumyl peroxide as initiator, 54gDOPO derivative XP-7866 is as fire retardant, 0.8g epoxy silane coupling and 80g silicon-dioxide are as filler, said mixture is mixed in toluene, and stirring and dissolving obtains homogeneous resin combination, i.e. glue.
The above-mentioned glue prepared is infiltrated up to E-glass-fiber-fabric, heat drying 3 ~ 10min at 155 DEG C, solvent evaporates is complete, obtain prepreg.The Copper Foil that thickness is 35 μm is respectively enclosed on prepare more than overlap 8 prepreg two sides of rising, and under the pressure of the temperature of 200 DEG C and 3.0MPa, hot pressing 90 minutes, obtains the veneer sheet of double-sided copper-clad.
Comparative example 2
Using the polyphenylene oxide SA9000 of 100g methacryloxyethyl acid methoxycarbonyl modification with mix as the toluene of solvent, dissolve and obtain terminal group functional polyphenylene oxide resin solution completely, then 45g styrene-butadiene copolymer R100 is added as linking agent, add 2g dicumyl peroxide as initiator, 100g polyphosphonitrile SPB-100 is as fire retardant, 0.8g epoxy silane coupling and 80g silicon-dioxide are as filler, said mixture is mixed in toluene, and stirring and dissolving obtains homogeneous resin combination, i.e. glue.
The above-mentioned glue prepared is infiltrated up to E-glass-fiber-fabric, heat drying 3 ~ 10min at 155 DEG C, solvent evaporates is complete, obtain prepreg.The Copper Foil that thickness is 35 μm is respectively enclosed on prepare more than overlap 8 prepreg two sides of rising, and under the pressure of the temperature of 200 DEG C and 3.0MPa, hot pressing 90 minutes, obtains the veneer sheet of double-sided copper-clad.
Comparative example 3
Using the polyphenylene oxide SA9000 of 100g methacryloxyethyl acid methoxycarbonyl modification with mix as the toluene of solvent, dissolve and obtain terminal group functional polyphenylene oxide resin solution completely, then 45g styrene-butadiene copolymer R100 is added as linking agent, add 2g dicumyl peroxide as initiator, 45g ethyl-bis-(tetrabromo phthalimide) BT-93W, 0.8g epoxy silane coupling and 80g silicon-dioxide are as filler, said mixture is mixed in toluene, and stirring and dissolving obtains homogeneous resin combination, i.e. glue.
The above-mentioned glue prepared is infiltrated up to E-glass-fiber-fabric, heat drying 3 ~ 10min at 155 DEG C, solvent evaporates is complete, obtain prepreg.The Copper Foil that thickness is 35 μm is respectively enclosed on prepare more than overlap 8 prepreg two sides of rising, and under the pressure of the temperature of 200 DEG C and 3.0MPa, hot pressing 90 minutes, obtains the veneer sheet of double-sided copper-clad.
Comparative example 4
Mix using the polyphenylene oxide SA9000 of 100g methacryloxyethyl acid methoxycarbonyl modification with as the toluene 100g of solvent, dissolve and obtain terminal group functional polyphenylene oxide resin solution completely, 10g bimaleimide resin is as co-curing agent, add 3.0g dicumyl peroxide again as initiator, 25g mixes the phosphorus-containing composition of example 2 as fire retardant, 2g vinyl base silane coupling agent and 150g silicon-dioxide are as filler, said mixture is mixed in toluene, and stirring and dissolving obtains homogeneous resin combination, i.e. glue.
The above-mentioned glue prepared is infiltrated up to E-glass-fiber-fabric, heat drying 3 ~ 10min at 155 DEG C, solvent evaporates is complete, obtain prepreg.The Copper Foil that thickness is 35 μm is respectively enclosed on prepare more than overlap 8 prepreg two sides of rising, and under the pressure of the temperature of 200 DEG C and 3.0MPa, hot pressing 90 minutes, obtains the veneer sheet of double-sided copper-clad.
Performance test is carried out to embodiment and comparative example, result as shown in Table 1 and Table 2:
Table 1
Table 2
As can be seen from above test result, the phosphonium flame retardant composition that embodiment 1 ~ 7 kind adopts, can under less addition, reach good V-0 fire retardant rank, can to the flame-retardancy requirements meeting again UL 94V-0 while that there are excellent heat resistance, dielectric properties after the thermoset composition solidification of its functionalized polyphenylene oxide resin, olefin resin and bimaleimide resin composition of arranging in pairs or groups.
In comparative example 1, when being used alone DOPO derivative as fire retardant, even if addition increases, its flame retardant effect is also insufficient; And be used alone polyphosphonitrile compound as fire retardant, even if the very large flame-retardancy requirements that cannot meet UL 94V-0 of addition, and the second-order transition temperature bringing cured product due to plasticity sharply declines, thermotolerance extreme difference; When comparative example 4 kinds uses single bismaleimides as linking agent, the thermotolerance of cured product and flame retardant resistance better, but can cause the deterioration of dielectric properties; Comparative example 3 employs brominated fire retardant, can reach good thermotolerance and flame retardant properties, but cannot meet halogen-free environmental technical need.
Applicant states, the present invention illustrates method detailed of the present invention by above-described embodiment, but the present invention is not limited to above-mentioned method detailed, does not namely mean that the present invention must rely on above-mentioned method detailed and could implement.Person of ordinary skill in the field should understand, any improvement in the present invention, to equivalence replacement and the interpolation of ancillary component, the concrete way choice etc. of each raw material of product of the present invention, all drops within protection scope of the present invention and open scope.

Claims (10)

1. a phosphor-containing flame-proof composition, is characterized in that, described fire-retardant combination comprises:
(A) the DOPO derivative shown in formula (1), 100 weight parts;
(B) hypophosphite compound, 5 ~ 50 weight parts;
(C) polyphosphonitrile compound, 10 ~ 50 weight parts;
R 1be selected from the one in the alkylene hydrocarbon of C2 ~ C20 or sub-aromatic hydrocarbon.
2. fire-retardant combination as claimed in claim 1, it is characterized in that, described component (B) hypophosphite compound has following structure:
Wherein m is 2 or 3; R 3and R 4 independentground for carbonatoms be alkyl or the aryl of 1 ~ 6, M is atoms metal, this atoms metal be selected from sodium, calcium, magnesium, aluminium, arsenic, zinc or iron any one, preferably aluminium or sodium, be more preferably aluminium;
Preferably, described component (C) polyphosphonitrile compound has following structural formula:
Wherein R be phenoxy group, carbonatoms be 1 ~ 10 alkyl, any one in vinyl phenoxy group or allyl group phenoxy group;
N is the integer of 3 ~ 100;
Or,
Any one in R is phenoxy group, carbonatoms is 1 ~ 10 alkyl, vinyl phenoxy group or allyl group phenoxy group;
Q is the integer of 3 ~ 25.
3. a phosphorous polyphenyl ether resin composition, is characterized in that, it comprises phosphor-containing flame-proof composition as claimed in claim 1 or 2 and terminal group functional polyphenylene oxide resin.
4. resin combination as claimed in claim 3, it is characterized in that, be 100 parts by weight with described terminal group functional polyphenylene oxide resin, and the addition of phosphor-containing flame-proof composition is 15 ~ 60 weight parts, be preferably 20 ~ 50 weight parts, more preferably 25 ~ 40 weight parts;
Preferably, described terminal group functional polyphenylene oxide resin is the mixture of any one or at least two kinds in terminal hydroxy group polyphenylene oxide resin, epoxidation polyphenylene oxide resin, vinylated polyphenylene oxide resin or cyanalation polyphenylene oxide resin, be preferably vinylated polyphenylene oxide resin or/and cyanalation polyphenylene oxide resin, more preferably vinylated polyphenylene oxide resin;
Preferably, described terminal group functional polyphenylene oxide resin structural formula is such as formula shown in (2):
In formula (2), a and b independentground is the integer of 1 ~ 30, and Z is the structure shown in formula (3) or (4) ,-(-O-Y-)-and be the structure shown in formula (5) ,-(-O-X-O-)-be the structure shown in formula (6):
In formula (4), A to be arylene, carbonyl or carbonatoms be 1 ~ 10 alkylidene group, m is the integer of 0 ~ 10, R 1, R 2and R 3it is identical or different, independentground is the alkyl of hydrogen or carbonatoms less than 10;
In formula (5), R 4with R 6it is identical or different, independentground is hydrogen atom, halogen atom, the alkyl of carbonatoms less than 8 or the phenyl of carbonatoms less than 8, R 5with R 7it is identical or different, independentground is halogen atom, the alkyl of carbonatoms less than 8 or the phenyl of carbonatoms less than 8;
In formula (6), R 8, R 9, R 10, R 11, R 12, R 13, R 14and R 15between identical or different, independentground be hydrogen atom, halogen atom, the alkyl of carbonatoms less than 8 or the phenyl of carbonatoms less than 8, B be carbonatoms less than 20 alkylene, n is 0 or 1; R 16for hydrogen atom or carbonatoms are the alkyl of 1 ~ 10;
Preferably, described terminal group functional polyphenylene oxide resin is the structure shown in formula (7) or (8):
In formula (7), R 1~ R 3it is identical or different, independentground is the alkyl of hydrogen or carbonatoms less than 10; R 4with R 6it is identical or different, independentground is the alkyl or phenyl of hydrogen atom, halogen atom, carbonatoms less than 8; R 5with R 7it is identical or different, independentground is halogen atom, the alkyl of carbonatoms less than 8 or the phenyl of carbonatoms less than 8; R 8, R 9, R 10, R 11, R 12, R 13, R 14and R 15between identical or different, independentground is hydrogen atom, halogen atom, the alkyl of carbonatoms less than 8 or the phenyl of carbonatoms less than 8; A and b independentground be 1 ~ 30 integer, B be carbonatoms less than 20 alkylene, n is 0 or 1, R 16for hydrogen atom or carbonatoms are the alkyl of 1 ~ 10;
In formula (8), R 4with R 6it is identical or different, independentground is the alkyl or phenyl of hydrogen atom, halogen atom, carbonatoms less than 8; R 5with R 7identical or different, be the alkyl or phenyl of halogen atom, carbonatoms less than 8; R 8, R 9, R 10, R 11, R 12, R 13, R 14and R 15between identical or different, be the alkyl or phenyl of hydrogen atom, halogen atom, carbonatoms less than 8; A and b independentground is the integer of 1 ~ 30; B is the alkylene of carbonatoms less than 20, and n is 0 or 1;
Preferably, described terminal group functional polyphenylene oxide resin is the structure shown in formula (9) to (13):
In formula (9), R 1~ R 3identical or different, be the alkyl of hydrogen or carbonatoms less than 10; R 4with R 6identical or different, be the alkyl or phenyl of hydrogen atom, halogen atom, carbonatoms less than 8; R 5with R 7identical or different, be the alkyl or phenyl of halogen atom, carbonatoms less than 8; R 8, R 9, R 10, R 11, R 12, R 13, R 14and R 15between identical or different, be the alkyl or phenyl of hydrogen atom, halogen atom, carbonatoms less than 8; A and b independentground is the integer of 1 ~ 30; Or,
In formula (10), R 1~ R 3identical or different, be the alkyl of hydrogen or carbonatoms less than 10; R 4with R 6identical or different, be the alkyl or phenyl of hydrogen atom, halogen atom, carbonatoms less than 8; R 5with R 7identical or different, be the alkyl or phenyl of halogen atom, carbonatoms less than 8; R 8, R 9, R 10, R 11, R 12, R 13, R 14and R 15between identical or different, be the alkyl or phenyl of hydrogen atom, halogen atom, carbonatoms less than 8; A and b independentground is the integer of 1 ~ 30; Or,
In formula (11), R 1~ R 3identical or different, be the alkyl of hydrogen or carbonatoms less than 10; R 4with R 6identical or different, be the alkyl or phenyl of hydrogen atom, halogen atom, carbonatoms less than 8; R 5with R 7identical or different, be the alkyl or phenyl of halogen atom, carbonatoms less than 8; R 8, R 9, R 10, R 11, R 12, R 13, R 14and R 15between identical or different, be the alkyl or phenyl of hydrogen atom, halogen atom, carbonatoms less than 8; A and b independentground is the integer of 1 ~ 30; Or,
In formula (12), R 4with R 6identical or different, be the alkyl or phenyl of hydrogen atom, halogen atom, carbonatoms less than 8; R 5with R 7identical or different, be the alkyl or phenyl of halogen atom, carbonatoms less than 8; R 8, R 9, R 10, R 11, R 12, R 13, R 14and R 15between identical or different, be the alkyl or phenyl of hydrogen atom, halogen atom, carbonatoms less than 8; A and b independentground is the integer of 1 ~ 30; Or,
In formula (13), R 4with R 6identical or different, be the alkyl or phenyl of hydrogen atom, halogen atom, carbonatoms less than 8; R 5with R 7identical or different, be the alkyl or phenyl of halogen atom, carbonatoms less than 8; R 8, R 9, R 10, R 11, R 12, R 13, R 14and R 15between identical or different, be the alkyl or phenyl of hydrogen atom, halogen atom, carbonatoms less than 8; A and b independentground is the integer of 1 ~ 30.
5. the resin combination as described in one of claim 3-4, is characterized in that, described phosphorous polyphenyl ether resin composition also comprises linking agent;
Preferably, described linking agent is the polyolefin resin with unsaturated double-bond, and the described polyolefin resin with unsaturated double-bond is the mixture of any one or at least two kinds in polyhutadiene, maleic anhydride modified polybutadiene polymers, acrylic acid modified polybutadiene polymers, butadiene-styrene copolymer, butadiene-styrene-divinyl benzene copolymer or cyclic olefine copolymer;
Preferably, be 100 parts by weight with terminal group functional polyphenylene oxide resin, the addition of the described polyolefin resin with unsaturated double-bond is 10 ~ 100 weight parts;
Preferably, the number-average molecular weight of described terminal group functional polyphenylene oxide resin is 500 ~ 5000, and preferred number average molecular weight is 500 ~ 3000, and more preferably number-average molecular weight is 800 ~ 2500;
Preferably, described phosphorous polyphenyl ether resin composition also comprises co-crosslinker;
Preferably, described co-crosslinker be bimaleimide resin or/and multi-group methacrylates compound, be preferably maleimide resin;
Preferably, be 100 parts by weight with terminal group functional polyphenylene oxide resin, the addition of described co-crosslinker is 5 ~ 50 weight parts.
6. the resin combination as described in one of claim 3-5, is characterized in that, described phosphorous polyphenyl ether resin composition also comprises initiator;
Preferably, the half life temperature t of described initiator 1/2be not less than 100 DEG C, for peroxide radical initiator, be selected from dicumyl peroxide, peroxidized t-butyl perbenzoate, 2, 5-bis-(2-ethyihexanoylperoxy)-2, 5-dimethylhexane, two-(tert-butylperoxyiso-propyl) benzene, peroxidation (2, 4-dichloro-benzoyl), 2, 5-dimethyl-2, two (t-butyl peroxy) hexane of 5-, peroxidation-2-ethylhexyl carbonate the tert-butyl ester, 2, 5-dimethyl-2, two (the t-butyl peroxy)-3-alkynes of 5-, 4, 4-bis-(tert-butyl hydroperoxide) butyl valerate, 1, two (tert-butyl hydroperoxide)-3 of 1-, 3, 5-trimethylammonium cyclohexane, 3, 3, 5, 7, 7-pentamethyl--1, 2, 4-trioxepan, the mixture of any one or at least two kinds in ditertiary butyl peroxide or t-tutyl cumyl peroxide, preferred dicumyl peroxide,
Preferably, be 100 parts by weight with terminal group functional polyphenylene oxide resin, the addition of described initiator is 0.5 ~ 7 weight part;
Preferably, described phosphorous polyphenyl ether resin composition also comprises silane coupling agent, is 100 parts by weight with terminal group functional polyphenylene oxide resin, and the addition of described silane coupling agent is 0.1 ~ 10 weight part;
Preferably, described phosphorous polyphenyl ether resin composition also comprises filler, and described filler is organic or inorganic filler;
Preferably, described mineral filler is selected from the mixture of any one or at least two kinds in powdered quartz, fused silica, preparing spherical SiO 2, hollow silicon dioxide, glass powder, aluminium nitride, boron nitride, silicon carbide, aluminium hydroxide, titanium dioxide, strontium titanate, barium titanate, aluminum oxide, barium sulfate, talcum powder, Calucium Silicate powder, calcium carbonate or mica;
Preferably, described organic filler is selected from the mixture of any one or at least two kinds in polytetrafluorethylepowder powder, polyphenylene sulfide or polyethersulfone powder;
Preferably, be 100 parts by weight with terminal group functional polyphenylene oxide resin, the addition of described filler is 10 ~ 300 weight parts.
7. a prepreg, comprises base material and by the phosphorous polyphenyl ether resin composition as described in claim 3-6 one of of the dry postadhesion of impregnation on base material.
8. a veneer sheet, comprises at least one superimposed prepreg as claimed in claim 7.
9. a copper-clad laminate, comprises at least one superimposed prepreg as claimed in claim 7 and is overlaid on the Copper Foil of one or both sides of superimposed rear prepreg;
Preferably, described Copper Foil is electrolytic copper foil or rolled copper foil, described Copper Foil carries out chemical treatment for using silane coupling agent, coupling agent used is the mixture of a kind of in epoxy silane coupling, vinyl silicane coupling agent or acrylate-based silane coupling agent or at least two kinds, and its surfaceness is less than 5 microns.
10. a printed circuit board, comprises at least one superimposed prepreg as claimed in claim 7.
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