CN104774476B - Phosphor-containing flame-proof composition and use its phosphorous polyphenyl ether resin composition, prepreg and laminate - Google Patents

Phosphor-containing flame-proof composition and use its phosphorous polyphenyl ether resin composition, prepreg and laminate Download PDF

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CN104774476B
CN104774476B CN201510104950.3A CN201510104950A CN104774476B CN 104774476 B CN104774476 B CN 104774476B CN 201510104950 A CN201510104950 A CN 201510104950A CN 104774476 B CN104774476 B CN 104774476B
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resin
polyphenylene oxide
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CN104774476A (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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Priority to PCT/CN2015/090079 priority patent/WO2016141707A1/en
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    • 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
    • B32B15/04—Layered 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
    • B32B15/08—Layered 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
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B15/00—Layered products comprising a layer of metal
    • B32B15/20—Layered products comprising a layer of metal comprising aluminium or copper
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • 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
    • B32B27/18—Layered products comprising a layer of synthetic resin characterised by the use of special additives
    • 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
    • B32B27/28—Layered products comprising a layer of synthetic resin comprising synthetic resins not wholly covered by any one of the sub-groups B32B27/30 - B32B27/42
    • 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
    • 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'
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L71/00—Compositions of polyethers obtained by reactions forming an ether link in the main chain; Compositions of derivatives of such polymers
    • C08L71/08—Polyethers derived from hydroxy compounds or from their metallic derivatives
    • C08L71/10—Polyethers derived from hydroxy compounds or from their metallic derivatives from phenols
    • C08L71/12—Polyphenylene oxides
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L85/00—Compositions 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
    • C08L85/02—Compositions 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
    • 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

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  • Chemical & Material Sciences (AREA)
  • Health & Medical Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Organic Chemistry (AREA)
  • Engineering & Computer Science (AREA)
  • Microelectronics & Electronic Packaging (AREA)
  • Compositions Of Macromolecular Compounds (AREA)
  • Laminated Bodies (AREA)
  • Reinforced Plastic Materials (AREA)

Abstract

The invention provides a kind of phosphor-containing flame-proof composition, including：Hypophosphite compound, DOPO derivatives and polyphosphazene compound, using said composition as fire-retardant, the synergy between several phosphorus-containing compounds can be played, under less addition, realizes halogen-free flameproof, reaches the ranks of V 0.Prepreg and copper-clad laminate present invention also offers a kind of polyphenyl ether resin composition comprising above-mentioned phosphor-containing flame-proof composition and using its making.After polyphenyl ether resin composition solidification, the fire-retardant ranks of V 0 are realized under conditions of inapplicable halogen flame, and maintain polyphenylene oxide resin good dielectric property and heat resistance, by the prepreg and copper-clad laminate of its making, with good dielectric property and heat resistance, halogen-free flameproof is realized while excellent heat resistance and dielectric properties are ensured, it is fire-retardant to reach the V0 ranks of UL 94；It is adapted to high-frequency high-speed printed wiring board field to use, meets the environment protection requirement in future.

Description

Phosphor-containing flame-proof composition and using it phosphorous polyphenyl ether resin composition, preimpregnation Material and laminate
Technical field
The invention belongs to copper-clad plate technical field, is related to a kind of phosphorus-containing composition and uses its phosphorous polyphenylene oxide resin Composition, prepreg and laminate.
Background technology
In recent years, with computer and information communication device high performance, the development of multifunction and networking, in order to High-speed transfer and processing Large Copacity information, operation signal is intended to high frequency, thus proposes requirement to the material of circuit substrate, Especially there is rapid development on those electronic equipments such as mobile communications device using broadband.
In the existing material for tellite, the excellent epoxy resin of adhesion properties is widely used.However, ring The general dielectric constant of oxygen tree fat circuit substrate and dielectric loss angle tangent it is higher (dielectric constant be more than 4, dielectric loss angle tangent exists 0.02 or so), high frequency characteristics is insufficient, it is impossible to adapts to the requirement of signal high frequency.Therefore it is excellent dielectric property must to be developed The low resin of resin, i.e. dielectric constant and dielectric loss angle tangent.For a long time those skilled in the art to dielectric properties very Heat cured cyanate well, bimaleimide resin, hydrocarbon resin etc. are studied；In addition, polyphenylene oxide resin due to With good dielectric properties, heat resistance, substantial amounts of research has also been carried out as high-frequency high-speed material by numerous technical staff, but Due to its fusing point is high, poor fluidity and much limited in application, the melt viscosity of prepreg is big, can not meet multilayer print The technique of wiring board processed, which makes, to be required.By reducing the molecular weight of polyphenylene oxide resin, its melting temperature can be effectively reduced, changed Kind mobility, but this also sacrifices the heat resistance of polyphenylene oxide resin.
CN1745142A has used a kind of end group to contain the polyphenylene oxide resin of vinyl phenyl and a vinyl phenyl as main body Resin, crosslinking and curing agent is used as by the use of isocyanuric acid triolefin ester, it may also be necessary to add inorganic filler, fire retardant obtains one kind Polyphenyl ether resin composition, NE type glass fabrics are then impregnated, are obtained with excellent dielectric properties, had compared with high-vitrification The prepreg and laminate of transition temperature, but due to using isocyanuric acid triolefin ester in said composition as crosslinking and curing agent, Its molecular weight is relatively low, and volatilization is easy in prepreg manufacturing process, so as to be unfavorable for stable making prepreg and laminate Material.Although mentioned in the patent to improve heat resistance, caking property and dimensional stability, in addition to PPE, if it is desired, can with Using olefin resin as compatilizer, but do not study carrying its properties to solidfied material.
US2009/0247032 employs a kind of polyphenylene oxide resin of vinyl bifunctionality as main body, and with naphthalene Cyanate, bisphenol A cyanate ester, brominated flame retardant and the inorganic filler of ring structure, obtain a kind of there is fine mobility and can To obtain fine peel strength, humidity resistance and anti-flammability on the premise of good dielectric properties are ensured.
WO2006/023371A1 provides a kind of combination of Bifunctionalized polyphenylene oxide resin and ethylenic unsaturation hydrocarbon monomer Thing, can improve polyphenylene oxide resin mobility and solidification after performance, but do not point out that Bifunctionalized polyphenylene oxide resin is used for layer Performance advantage during pressing plate field, and what is used is low molecular weight compound for ethylenic unsaturation hydrocarbon monomer, it is also easy at high temperature Volatilization, manufacturability are poor.
Understand from the above mentioned, by being to solve polyphenylene oxide molecular weight to reduce the heat resistance brought to the functionalization of low molecule amount The problem of decline, but in the concrete application in laminate field, how to select suitable solidification crosslinking and embody functionalization The performance advantage of polyphenylene oxide resin, also need for further study.
In addition, with reinforcement of the society to environmental consciousness, the environmental issue of electronic product also becomes increasingly conspicuous, then how real Now baseplate material is non-halogen, and carrys out the emphasis of those skilled in the art's research this year, realizes the technology of halogen-free flameproof at present Means be introduced primarily into P elements carry out it is fire-retardant, common material has phosphorous epoxy resin, phosphorus containing phenolic resin, phosphoric acid ester chemical combination Thing and polyphosphate compound, phosphazene compound, hypophosphorous acid salt compounds, but due to the limit of these material self characters System, exclusive use can not all meet requirement of the high-speed material field to heat resistance and dielectric properties, such as phosphorous epoxy resin, phosphorous Although phenolic resin moiety material can reach good flame retardant effect, due to being performed poor in terms of dielectric properties, together When too much phosphorus introduce and bring the deterioration of wet-hot aging performance, the reliability requirement of high multi-layer PCB can not be met；The secondary phosphine of addition type The flame retardant effect that hydrochlorate is used alone is bad, particularly into the relatively low resin system of charcoal；Polyphosphazene compound is due to this province For fusing point than relatively low, plasticity is strong, and substantial amounts of addition brings heat resistance to decline to a great extent as glass transition temperature reduces, while individually In use, even if substantial amounts of addition, it is also difficult to accomplish fire-retardant V-0 rank.Other phosphate compounds are similarly present Similar Problems.
In general, how to realize while meet the superior dielectric performance of high speed baseplate material requirement, such as low dielectric is normal Number and Dielectric loss tangent value, and can realize the new technology of halogen-free flameproof be the research of following this area an emphasis direction it One.
The content of the invention
The problem of for prior art, it is an object of the invention to a kind of phosphor-containing flame-proof composition, and it can be relatively low Addition is issued to halogen-free flameproof, reaches UL 94V-0.The present invention also aims to provide a kind of phosphorous polyphenylene oxide resin group Compound, it can keep the good dielectric property and heat resistance of polyphenylene oxide resin, and realize halogen-free flameproof, and fire retardant reaches UL 94V-0.Another object of the present invention, which also resides in, provides a kind of prepreg made using above-mentioned phosphorous polyphenyl ether resin composition And copper-clad laminate, there is good dielectric property and heat resistance, and halogen-free flameproof is realized, fire retardant reaches UL 94V-0.
To achieve these goals, present invention employs following technical scheme：
A kind of phosphor-containing flame-proof composition, the fire-retardant combination include：
(A) the DOPO derivatives shown in formula (1), 100 parts by weight；
(B) hypophosphite compound, 5~50 parts by weight；
(C) polyphosphazene compound, 10~50 parts by weight
R1One kind in alkylene hydrocarbon or sub- aromatic hydrocarbon for C2~C20.
The content of the hypophosphite compound is, for example, 10 parts by weight, 15 parts by weight, 20 parts by weight, 25 parts by weight, 30 Parts by weight, 35 parts by weight, 40 parts by weight or 45 parts by weight.
The content of the polyphosphazene compound is, for example, 10 parts by weight, 15 parts by weight, 20 parts by weight, 25 parts by weight, 30 weights Measure part, 35 parts by weight, 40 parts by weight or 45 parts by weight.
In the present invention, using above-mentioned phosphorus-containing composition as fire retardant, can play between three kinds of phosphorus-containing compounds Synergy, under less addition, halogen-free flameproof is realized, reach V-0 ranks.
In the present invention, component (A) the DOPO derivatives can be synthesized into by the following method, be specially：By chemical combination In the presence of catalyst, reaction temperature is 50~300 DEG C for thing DOPO and dihydric alcohol, and the reaction time is 0.5~48 hour, reaction Obtain, specific reaction equation is as follows：
N is 2~20 integer in formula.
Reaction described above occurs to take off under catalyst action by DOPO reactive hydrogen atom with diatomic alcohol compounds Water condensation reaction obtains；The molar feed ratio of wherein DOPO and dihydric alcohol is controlled in 0.5~100, preferably 0.5~10, is more entered One step is preferably 0.5~5, if mol ratio is too low, it will causes DOPO conversion ratios low, if mol ratio is too high, can bring again The follow-up recovery of dihydric alcohol is difficult.
Described catalyst is not particularly limited, any to promote dehydration and the catalyst of Arbuzov reactions all It can use, optional catalyst has alkyl halide, alkali metal, alkaline-earth halide, transition metal and its halides, Acid, Arbuzov catalyst, wherein preferably Arbuzov catalyst.
For example, described DOPO derivative can be following structural formula：
Preferably, component (B) hypophosphite compound has following structure：
Wherein m is 2 or 3；R3And R4The alkyl or aryl that carbon number is 1~6 independently are, M is metallic atom, Any one of the metallic atom in sodium, calcium, magnesium, aluminium, arsenic, zinc or iron.From its water absorption rate of reduction and improve its phosphorus content From the point of view of, M is preferably aluminium or sodium, but if further considering that reducing phosphorus-containing composition as far as possible adds to resin combination The influence of dielectric properties after solidification, M are more preferably aluminium.
For more specifically, heretofore described hypophosphite compound is
Heretofore described component (C) is polyphosphazene compound.Polyphosphazene compound is non-common for a kind of full phosphorus azacyclo- Compound conjugate, has excellent a photostability and heat endurance, high limit oxygen index (OI), low exhaust smoke level and has good chemically-resistant special Property, water resistance and solvent resistance.
Polyphosphazene compound in the present invention has following structural formula：
Wherein n is 3~100 integer, such as 5,10,20,30,40,50,60,70,80 or 90.
Appointing in wherein R is phenoxy group, carbon number is 1~10 alkyl, vinyl benzene epoxide or allyl benzene epoxide Meaning is a kind of；
Or,
Wherein q is 3~25 integer, such as 4,6,7,10,13,16,19 or 22；R is phenoxy group, carbon number be 1~ Any one in 10 alkyl, vinyl benzene epoxide or allyl benzene epoxide.
Present invention also offers a kind of phosphorous polyphenyl ether resin composition, and it includes phosphorus-containing composition as described above and end Base functionalized polyphenylene ether resins.
In the present invention, the terminal group functional polyphenylene oxide resin is terminal hydroxy group polyphenylene oxide resin, epoxidation polyphenylene oxide tree In fat, vinylated polyphenylene oxide resin or cyanalation polyphenylene oxide resin any one or at least two mixture, preferably For vinylated polyphenylene oxide resin or/and cyanalation polyphenylene oxide resin, more preferably vinylated polyphenylene oxide resin.
In the present invention, shown in the terminal group functional polyphenylene oxide resin structural formula such as formula (2)：
In formula (2), a and b independently are 1~30 integer, for example, 2,5,8,11,14,17,20,23,26 or 29, Z be formula (3) or the structure shown in (4) ,-(- O-Y-)-are the structure shown in formula (5), and-(- O-X-O-)-is the structure shown in formula (6)：
In formula (4), A is the alkylene that arylene, carbonyl or carbon number are 1~10 (such as 2,3,4,5,6,7,8 or 9) Base, m be 0~10 (such as 1,2,3,4,5,6,7,8 or 9) integer, R1、R2And R3It is identical or different, it independently is hydrogen or carbon is former Alkyl of the subnumber below 10；
In formula (5), R4With R6It is identical or different, independently be alkyl below 8 of hydrogen atom, halogen atom, carbon number or Phenyl of the carbon number below 8, R5With R7It is identical or different, it independently is the alkyl or carbon of halogen atom, carbon number below 8 Phenyl of the atomicity below 8；
In formula (6), R8、R9、R10、R11、R12、R13、R14And R15Between it is identical or different, it is former independently to be hydrogen atom, halogen Son, alkyl or carbon number phenyl less than 8 of the carbon number below 8, B be alkylene of the carbon number below 20 ,-O-, N is 0 or 1；R16It is 1 for hydrogen atom or carbon number The alkyl of~10 (such as 2,3,4,5,6,7,8 or 9).
More specifically, the terminal group functional polyphenylene oxide resin is the structure shown in formula (7) or (8)：
In formula (7), R1~R3It is identical or different, it independently is the alkyl of hydrogen or carbon number below 10；R4With R6It is identical or Difference, it independently is the alkyl or phenyl of hydrogen atom, halogen atom, carbon number below 8；R5With R7It is identical or different, independently The phenyl of alkyl or carbon number below 8 for being halogen atom, carbon number below 8；R8、R9、R10、R11、R12、R13、R14And R15 Between it is identical or different, independently be the benzene of alkyl or carbon number below 8 of hydrogen atom, halogen atom, carbon number below 8 Base；A and b independently is 1~30 integer, for example, 2,5,8,11,14,17,20,23,26 or 29, B be carbon number below 20 Alkylene ,-O- N is 0 or 1, R16It is former for hydrogen Son or the alkyl that carbon number is 1~10；
In formula (8), R4With R6It is identical or different, independently be alkyl below 8 of hydrogen atom, halogen atom, carbon number or Phenyl；R5With R7It is identical or different, it is the alkyl or phenyl of halogen atom, carbon number below 8；R8、R9、R10、R11、R12、R13、 R14And R15Between it is identical or different, be the alkyl or phenyl of hydrogen atom, halogen atom, carbon number below 8；A and b are independently For 1~30 integer；B is alkylene of the carbon number below 20, and n is 0 or 1.
Further, the terminal group functional polyphenylene oxide resin can also be the structure shown in formula (9) to (13)：
In formula (9), R1~R3It is identical or different, it is the alkyl of hydrogen or carbon number below 10；R4With R6It is identical or different, For the alkyl or phenyl of hydrogen atom, halogen atom, carbon number below 8；R5With R7It is identical or different, it is halogen atom, carbon atom Alkyl or phenyl of the number below 8；R8、R9、R10、R11、R12、R13、R14And R15Between it is identical or different, be that hydrogen atom, halogen are former Son, alkyl or phenyl of the carbon number below 8；A and b independently is 1~30 integer.
In formula (10), R1~R3It is identical or different, it is the alkyl of hydrogen or carbon number below 10；R4With R6It is identical or different, For the alkyl or phenyl of hydrogen atom, halogen atom, carbon number below 8；R5With R7It is identical or different, it is halogen atom, carbon atom Alkyl or phenyl of the number below 8；R8、R9、R10、R11、R12、R13、R14And R15Between it is identical or different, be that hydrogen atom, halogen are former Son, alkyl or phenyl of the carbon number below 8；A and b independently is 1~30 integer.
In formula (11), R1~R3It is identical or different, it is the alkyl of hydrogen or carbon number below 10；R4With R6It is identical or different, For the alkyl or phenyl of hydrogen atom, halogen atom, carbon number below 8；R5With R7It is identical or different, it is halogen atom, carbon atom Alkyl or phenyl of the number below 8；R8、R9、R10、R11、R12、R13、R14And R15Between it is identical or different, be that hydrogen atom, halogen are former Son, alkyl or phenyl of the carbon number below 8；A and b independently is 1~30 integer.
In formula (12), R4With R6It is identical or different, it is the alkyl or phenyl of hydrogen atom, halogen atom, carbon number below 8； R5With R7It is identical or different, it is the alkyl or phenyl of halogen atom, carbon number below 8；R8、R9、R10、R11、R12、R13、R14And R15Between it is identical or different, be the alkyl or phenyl of hydrogen atom, halogen atom, carbon number below 8；A and b independently is 1~ 30 integer.
In formula (13), R4With R6It is identical or different, it is the alkyl or phenyl of hydrogen atom, halogen atom, carbon number below 8； R5With R7It is identical or different, it is the alkyl or phenyl of halogen atom, carbon number below 8；R8、R9、R10、R11、R12、R13、R14And R15Between it is identical or different, be the alkyl or phenyl of hydrogen atom, halogen atom, carbon number below 8；A and b independently is 1~ 30 integer.
Preferably, in phosphorous polyphenyl ether resin composition, using the terminal group functional polyphenylene oxide resin as 100 parts by weight Meter, the addition of phosphor-containing flame-proof composition are 15~60 parts by weight, such as 25 parts by weight, 30 parts by weight, 35 parts by weight, 40 weight Part, 45 parts by weight, 50 parts by weight or 55 parts by weight, more preferably preferably 20~50 parts by weight, 25~40 parts by weight.It is logical Addition phosphor-containing flame-proof composition is crossed, the synergy between phosphorus-containing composition is played, makes the polyphenyl ether resin composition after solidification It can reach good fire-retardant.But when the addition of content fire-retardant combination is less than 15 parts by weight, the fire-retardant of system does not reach V-0 Rank, to addition more than 60 parts when, although can sufficiently ensure solidification after polyphenyl ether resin composition reach good It is fire-retardant, but because phosphor-containing flame-proof composition absorbs water bigger than normal in itself, cause the heat resistance of system, dielectric properties significantly to deteriorate.
In the present invention, the phosphorous polyphenyl ether resin composition also includes crosslinking agent, and the crosslinking agent is with unsaturation The vistanex of double bond, the vistanex with unsaturated double-bond be polybutadiene and its graft-modified polymers such as Maleic anhydride is grafted property polybutadiene polymers, acrylic acid modified butadiene polymer, BS, the fourth In styrene-divinyl benzene copolymer or cyclic olefine copolymer any one or at least two mixture.
Counted by 100 parts by weight of terminal group functional polyphenylene oxide resin, the vistanex with unsaturated double-bond Addition is 10~100 parts by weight, such as 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 Parts by weight, 90 parts by weight or 95 parts by weight.Because the dielectric properties of olefin resin are excellent, so the alkene tree of addition proper ratio Fat can further improve the dielectric properties such as Dk/Df of fixed line system, simultaneously because the unsaturated double-bond carried in olefin resin Heat resistance can be further improved with the further crosslinking curing of polyphenylene oxide resin.When addition is less than 10 parts, alkene tree The unsaturated double-bond amount introduced in fat very little, can not play the effect being effectively crosslinked, and do not reach and improve heat resistance and dielectric properties Purpose；If olefin resin amount is more than 100 parts, due to the reason for rigidity of olefin resin in itself is too poor, and the coefficient of expansion is big Also result in the huge decline of heat resistance of solidfied material.
Preferably, the number-average molecular weight of the terminal group functional polyphenylene oxide resin is 500~5000, preferred number average molecular weight For 500~3000, more preferably number-average molecular weight is 800~2500.When use terminal group functional of the number-average molecular weight more than 5000 During polyphenylene oxide resin, dissolubility is deteriorated in process, conventional laminate technique can not be used to be glued, it is necessary to plus Temperature so that the difficulty in process in copper-clad plate process, operational hazards, and mobility can also decline therewith so that multi-layer sheet adds Work is difficult；And when number-average molecular weight is less than 500, its heat resistance, dielectric properties can decline, and be unfavorable for that high-fire resistance is made Resin combination and laminate sheet material, while dielectric property can also reduce.When the terminal group functional polyphenylene oxide resin enters one Step and crosslinking agent mixing when, have smaller number-average molecular weight functionalized polyphenylene ether resins can preferably improve with crosslinking agent it Between compatibility, i.e. molecular weight is smaller, and the compatibility between blending ingredients is more preferable, and storage stability is more preferable.In addition, relatively low point Son amount can provide more preferable mobility, be advantageous to provide better filler in multi-layer sheet process.
In the present invention, the phosphorous polyphenyl ether resin composition also includes co-crosslinker, and the co-crosslinker comes for span Imide resin or/and multi-group methacrylates compound, preferably maleimide resin.
Counted by 100 parts by weight of terminal group functional polyphenylene oxide resin, the addition of the co-crosslinker is 5~50 weight Part, such as 7 parts by weight, 10 parts by weight, 13 parts by weight, 16 parts by weight, 19 parts by weight, 22 parts by weight, 25 parts by weight, 28 weight Part, 31 parts by weight, 35 parts by weight, 38 parts by weight, 41 parts by weight, 44 parts by weight or 47 parts by weight.The introducing of the co-crosslinker, Main purpose, which is in order at, further to be improved the heat resistance angle of polyphenylene oxide cured product and sets out, because maleimide resin can be with Curing cross-linking reaction occurs with the unsaturated double-bond of terminal group functional polyphenylene oxide resin and olefin resin, forms one and is total to by three With the cross-linked structure of composition, system has more preferable heat-resistant stability；Maleimide resin addition does not have very little Improve crosslink density, improve the purpose of heat resistance, if although the too many crosslink density that can effectively improve system of amount, by It is larger in the polarity of maleimide this body structure, being decreased obviously for dielectric properties can be brought.
In the present invention, the phosphorous polyphenyl ether resin composition also includes initiator.The half-life period temperature of the initiator Spend t1/2It is peroxide radical initiator not less than 100 DEG C, selected from cumyl peroxide, the tertiary fourth of perbenzoic acid Ester, 2,5- bis- (2- ethyihexanoylperoxies) -2,5- dimethylhexanes, two-(tert-butylperoxyiso-propyl) benzene, peroxidating (2,4- Dichloro-benzoyl), 2,5- dimethyl -2,5- double (t-butyl peroxy) hexane, the peroxidating -2- ethylhexyl carbonates tert-butyl ester, 2, Double (the t-butyl peroxy) -3- of 5- dimethyl -2,5- double (tert-butyl groups of alkynes, 4,4- bis- (tert-butyl hydroperoxide) butyl valerate, 1,1- Peroxidating) -3,3,5- trimethyls thiacyclohexane, 3,3,5,7,7- pentamethyl -1,2,4- trioxepans, di-tert-butyl peroxide In thing or cumyl t-butyl peroxide any one or at least two mixture, preferred cumyl peroxide, because There is higher half life temperature and reacting initial temperature for the compound, therefore when that need not solidify, in semi-solid preparation process In, it will not exceedingly trigger curing reaction, will not also reduce the storage stability of polyphenylene oxide resin.
Initiator in polyphenyl ether resin composition of the present invention, it is therefore intended that improve crosslinking curing effect.Although end group official Polyphenylene oxide resin and crosslinking agent, which can be changed, to be solidified in the case where heating hot conditions, but during laminate application, technique bar Part is difficult to meet high temperature requirement, makes the increase of its difficulty of processing, and still further aspect is also unfavorable for process efficiency, and increase is produced into This, therefore add initiator advantageously.Counted by 100 parts by weight of terminal group functional polyphenylene oxide resin, the initiator adds Dosage is 0.5~7 parts by weight, such as 1.3 parts by weight, 1.6 parts by weight, 1.9 parts by weight, 2.2 parts by weight, 2.5 parts by weight, 3.1 Parts by weight, 3.5 parts by weight, 3.9 parts by weight, 4.3 parts by weight, 4.7 parts by weight, 5 parts by weight, 5.4 parts by weight, 5.8 parts by weight, 6.2 parts by weight or 6.6 parts by weight.
In the present invention, the phosphorous polyphenyl ether resin composition also includes silane coupler, with terminal group functional polyphenylene oxide Resin is 100 parts by weight meters, and the addition of the silane coupler is 0.1~10 parts by weight, such as 0.5 parts by weight, 1 weight Part, 1.5 parts by weight, 2 parts by weight, 2.5 parts by weight, 3 parts by weight, 3.5 parts by weight, 4 parts by weight, 4.5 parts by weight, 5 parts by weight, 5.5 parts by weight, 6 parts by weight, 6.5 parts by weight, 7 parts by weight, 7.5 parts by weight, 8 parts by weight, 8.5 parts by weight, 9 parts by weight or 9.5 Parts by weight.
To the species of coupling agent, there is no particular limitation.Coupling agent can further reduce the surface of resin cured matter Power, its viscosity is further reduced, improve the mobility of resin combination.It is even especially under the occasion of addition filler The addition of connection agent can effectively improve the adhesion between resin and filler, eliminate the interface between both, further drop The water absorption rate of low solidfied material.Described coupling agent can be silanes, silane pre-polymer, titanate ester, and silane coupler can be with For epoxy silane coupling, amino silicane coupling agent, phenylamino silane coupler, vinyl silicane coupling agent, isocyanates Base silane coupling agent, acrylsilanes coupling agent, isobutenyl silane coupler, styryl silane coupler, ureido silane Coupling agent, chloropropyl silane coupler, sulfenyl silane coupler or vulcanization base silane coupling agent etc..
In the present invention, the phosphorous polyphenyl ether resin composition also includes filler, and the filler is organic or inorganic filler, Inorganic filler is selected from powdered quartz, fused silica, preparing spherical SiO 2, hollow silicon dioxide, glass dust, nitridation Aluminium, boron nitride, carborundum, aluminium hydroxide, titanium dioxide, strontium titanates, barium titanate, aluminum oxide, barium sulfate, talcum powder, calcium silicates, In calcium carbonate or mica any one or at least two mixture；Organic filler is selected from polytetrafluorethylepowder powder, polyphenyl In thioether or polyether sulfone powder any one or at least two mixture.
In addition, the shape of inorganic filler, particle diameter etc. are also not particularly limited, usual particle diameter is 0.01-50 μm, is preferably 0.01-20 μm, more preferably 0.01-10 μm, the inorganic filler of this particle size range are more easy to disperse in resin liquid.
To be counted by 100 parts by weight of terminal group functional polyphenylene oxide resin, the addition of the filler is 10~300 parts by weight, Such as 30 parts by weight, 60 parts by weight, 90 parts by weight, 120 parts by weight, 150 parts by weight, 180 parts by weight, 210 parts by weight, 240 weights Measure part or 270 parts by weight.
" 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 phosphorous polyphenyl ether resin composition different characteristics.In addition, " comprising " of the present invention, can also replace For enclosed " for " or " by ... form ".
For example, the phosphorous polyphenyl ether resin composition can also contain various additives, as concrete example, can enumerate Antioxidant, heat stabilizer, antistatic additive, ultra-violet absorber, pigment, colouring agent or lubricant etc..These various additives can To be used alone, two kinds or two or more can also be used in mixed way.
Further, the present invention provides a kind of prepreg made using above-mentioned phosphorous polyphenyl ether resin composition, including Base material and the phosphorous polyphenyl ether resin composition as described above being attached to by impregnation after dry on base material.
During making, first by terminal group functional polyphenylene oxide resin, phosphorus-containing composition, optionally optional crosslinking agent, co-crosslinking Agent, optional initiator, optional coupling agent and optionally filler is dissolved into one or more organic solvents, it is made homogeneous Glue.To organic solvent, there is no particular limitation, as long as above component can be dissolved, and does not interfere with its reactivity；Suitable Solvent includes：Ketone such as MEK, acetone etc., ethers such as propylene glycol monomethyl ether, butyl oxide etc., esters such as ethyl acetate, fragrance Class such as toluene, dimethylbenzene etc., halogenated hydrocarbon such as trichloroethanes etc..Every kind of solvent may be used alone, can also be used in combination.Glue The concentration of resin solid matter can be impregnated into the species of base material according to glue in liquid and technique is made and suitably changed, such as its conjunction Suitable concentration is 30~80%.Base material is impregnated into by glue obtained above, heating, drying then is carried out to it to have removed Resin combination in solvent and partially cured base material, just obtains prepreg.
The base material is organic fiber, carbon fiber or yarn fabric made from glass fibre or adhesive-bonded fabric；For glass fibers Yarn fabric made from dimension or adhesive-bonded fabric, include SiO of the weight than 50~80% in its main component2, weight is than 0~30% The Al of CaO, weight than 0~20%2O3, B of the weight than 5~25%2O3And MgO of the weight than 0~5%.The strengthening material Material is preferably establishment fiber cloth, is chosen as E-Glass, T-Glass, NE-Glass, L-Glass, Q-Glass.
For impregnating the resin content of above-mentioned base material, it is preferably such that resin content in prepreg for 30 mass % or more It is high.Because the dielectric constant of base material is often higher than resin combination, in order to reduce the laminate as made from these prepregs Dielectric constant, content of the resin combination composition in prepreg are preferably above above-mentioned content.Such as it is using resin Composition content Laminate made from 40% prepreg, its dielectric constant is 3.5, and uses the prepreg system that resin content is 50% or higher The laminate obtained, its dielectric constant are 3.2 or lower.In addition, above-described prepreg is dried in the case where condition is 80~170 DEG C It is roasting 2~15 minutes, but be not limited thereto.
In addition, the present invention also provides a kind of laminate, it includes the prepreg as described above of at least one overlapping.
In addition, the present invention also provides a kind of copper-clad laminate made using above-mentioned phosphorous polyphenyl ether resin composition, Including several overlapping prepregs and be overlaid on overlapping after prepreg one or both sides copper foil.
Specifically by the prepreg for stacking one or more present invention, copper foil etc. is enclosed in its one or both sides, then Carry out hot pressing and be made, the line map to form needs is etched on the copper foil of laminate surface and obtains printed wiring board. Further, it is also possible to prepare multilayer printed wiring board with step by the following method：Internal layer track is used as using printed wiring board Road plate, the copper foil above it is surface-treated, by the prepreg of the present invention and above-mentioned carried out in certain sequence as desired The printed wiring board of surface treatment, which stacks, carries out hot pressing, and hot pressing condition can be according to the composition of the polyphenyl ether resin composition of the present invention Depending on ratio, to this, there is no particular limitation.Hot pressing condition be preferably 150~250 DEG C temperature range and 1.0MPa~ Hot pressing is for a period of time under 10.0MPa pressure limit.The laminate and printed wiring board obtained in this way with step has Good high frequency characteristics such as dielectric properties etc. also have good technique processability, heat resistance and moisture-proof simultaneously.
In addition, in order to further improve application of the material in high-frequency high-speed field, copper-clad laminate in the present invention In production, the copper foil that uses can select electrolytic copper foil or rolled copper foil, and its surface roughness is less than 5 microns, can improve and Improve the loss of signal that laminate sheet material uses in high-frequency high-speed printed wiring board.Meanwhile in order to improve copper foil contact prepreg Adhesion simultaneously, above-mentioned copper foil used can also be chemically treated using silane coupler, and coupling agent used is ring One or more mixtures in TMOS coupling agent, vinyl silicane coupling agent or acrylate-based silane coupler, Purpose is to improve the adhesion of copper foil and base material, prevent from falling during printed wiring board use newly, fall pad equivalent risk.
Present invention also offers a kind of printed circuit board, and it includes the prepreg as described above of at least one overlapping.
Compared with the prior art, the present invention has the advantages that：
The polyphenyl ether resin composition of the present invention, it is the functionalized polyphenylene ether resins composition of low molecule amount, has good Technique processability, maintain polyphenylene oxide resin good dielectric property and heat resistance, then add specific structure phosphonium flame retardant Composition, had both maintained the heat resistance, dielectric properties, low water absorbable of original polyphenylene oxide resin system, while realized halogen-free flameproof, resistance Combustion reaches UL 94V-0 ranks.
Embodiment
Technical scheme is further illustrated below by embodiment.
Synthesis example 1：The preparation of DOPO derivatives
Potassium tert-butoxide 230g is added into the four neck reactors equipped with charging hopper, thermocouple, mechanical agitator and nitrogen stream, The anhydrous DMSO1.5L of solvent.The mixture is stirred at room temperature, until it becomes homogeneous solution.Solution is cooled to 10 DEG C, with 10 aliquots add DOPO 42.3g, to keep reaction temperature to be less than 30 DEG C.By the dichloroethanes in charging hopper in 1 hour 92g is slowly added into above-mentioned solution.50 degree are heated to react 1 hour.It is cooled to 10 DEG C of reactions and 3L water will be added.Cross filter pulp Material, and close ethyl acetate with water, acetone and wash wet cake, 532g slightly wet materials are obtained, by the material in MeCN/ ethanol/waters Flowed back in 5320ml, and progressively cool to 5 DEG C.White solid is filtered by funnel, and 8~10 are dried in 80 DEG C of vacuum drying ovens Hour, obtain dry white powder 260g, as formula (1) DOPO derivatives 1, wherein R1For-CH2-CH2-.
Synthesis example 2
Dichloromethane therein is substituted for dichloro-p-xylene, obtains formula (1) by synthetic method with reference to synthesis example 1 DOPO derivatives 2, wherein R1For phenyl.
Mix example 1：The preparation (P15.4%) of phosphor-containing flame-proof composition
By the hypophosphite compound of 35 parts by weight, the DOPO derivatives of the synthesis example 1 of 100 parts by weight and 18 parts by weight Polyphosphazene compound mixing, obtain phosphorus-containing composition；
The hypophosphite compound is：
The polyphosphazene compound has following structure：
Wherein R is methyl, and wherein n is 3~100 integer.
Mix example 2：The preparation (P16%) of phosphorus-containing composition
By the hypophosphite compound of 50 parts by weight, the DOPO derivatives of the synthesis example 1 of 100 parts by weight and 25 parts by weight Polyphosphazene compound mixing, obtain phosphorus-containing composition；
The hypophosphite compound is：
The polyphosphazene compound has following structure：
Wherein R is ethyl, 3~100 integer that wherein n is.
Mix example 3：The preparation (P13.8%) of phosphorus-containing composition
By the hypophosphite compound of 10 parts by weight, the DOPO derivatives of the synthesis example 1 of 100 parts by weight and 25 parts by weight Polyphosphazene compound mixing, obtain phosphorus-containing composition；
The hypophosphite compound is：
The polyphosphazene compound has following structure：
Wherein q is 3；Wherein R is phenoxy group.
Mix the preparation (P15%) of the phosphorus-containing composition of example 4
By the hypophosphite compound of 30 parts by weight, the DOPO derivatives of the synthesis example 2 of 100 parts by weight and 40 parts by weight Polyphosphazene compound mixing, obtain phosphorus-containing composition；
The hypophosphite compound is：
The polyphosphazene compound has the mixture of both following structures：
Wherein R is methyl, and wherein n is 80 integer；
Wherein q is 3；Wherein R is phenoxy group.
Embodiment 1
The polyphenylene oxide SA9000 that 100g methacryloxyethyl acids methyl esters is modified and the toluene mixing as solvent, dissolving are complete Terminal group functional polyphenylene oxide resin solution is obtained, 45g SBs R100 is then added as crosslinking agent, adds Enter 2g cumyl peroxides as initiator, the phosphorus-containing composition of 45g mixing examples 1 is as fire retardant, 0.8g epoxy radicals silicone hydrides Coupling agent and 80g silica (SC-2050SQ) are used as filler, said mixture are mixed in toluene, and stirring and dissolving obtains To homogeneous resin combination, i.e. glue.
The above-mentioned glue being prepared is infiltrated up to E- glass-fiber-fabrics, 3~10min of heat drying, solvent is waved at 155 DEG C Distribute entirely, obtain prepreg.It is overlapping it is made above obtain 8 rise that respectively to enclose thickness be 35 μm of copper foil on prepreg two sides, Hot pressing 90 minutes, obtains the laminate of double-sided copper-clad at 200 DEG C of temperature and 3.0MPa pressure.
Embodiment 2
The polyphenylene oxide SA9000 that 100g methacryloxyethyl acids carbomethoxy is modified and the toluene mixing as solvent, have dissolved Terminal group functional polyphenylene oxide resin solution is obtained entirely, 20g polybutadiene polymers B-1000 is then added as crosslinking agent, adds 2.0g cumyl peroxides are as initiator, and the phosphorus-containing composition of 30g mixing examples 2 is as fire retardant, 0.8g vinyl silanes Coupling agent and 80g silica (SC-2050SQ) are used as filler, said mixture are mixed in toluene, and stirring and dissolving obtains To homogeneous resin combination, i.e. glue.
The above-mentioned glue being prepared is infiltrated up to E- glass-fiber-fabrics, 3~10min of heat drying, solvent is waved at 155 DEG C Distribute entirely, obtain prepreg.The copper foil that thickness is 35 μm is respectively enclosed on overlapping 8 obtained prepreg two sides made above, Hot pressing 90 minutes, obtains the laminate of double-sided copper-clad at 200 DEG C of temperature and 3.0MPa pressure.
Embodiment 3
The polyphenylene oxide SA9000 that 100g methacryloxyethyl acids carbomethoxy is modified and the toluene 100g mixing as solvent, it is molten Solution obtains terminal group functional polyphenylene oxide resin solution completely, then adds 30g SBs R100 as crosslinking Agent, 15g bimaleimide resins add 3.0g cumyl peroxides as initiator, 35g mixing as co-curing agent The phosphorus-containing composition of example 2, as filler, above-mentioned will mix as fire retardant, 2g vinyl base silane coupling agents and 150g silica Compound mixes in toluene, and stirring and dissolving obtains homogeneous resin combination, i.e. glue.
The above-mentioned glue being prepared is infiltrated up to E- glass-fiber-fabrics, 3~10min of heat drying, solvent is waved at 155 DEG C Distribute entirely, obtain prepreg.It is overlapping it is made above obtain 8 rise that respectively to enclose thickness be 35 μm of copper foil on prepreg two sides, Hot pressing 90 minutes, obtains the laminate of double-sided copper-clad at 200 DEG C of temperature and 3.0MPa pressure.
Embodiment 4
Mixed using 100g styryl polyphenylene oxide OPE-2000 and as the toluene 100g of solvent, dissolving obtains end group completely Functionalized polyphenylene ether resins solution, 35g polybutadiene polymers B-2000 is then added as crosslinking agent, adds 2.5g peroxidating Diisopropylbenzene (DIPB) is as initiator, and the phosphorus-containing composition of 50g mixing examples 3 is as fire retardant, the silica of 150g vinyl processing As filler, said mixture is mixed in toluene, and stirring and dissolving obtains homogeneous resin combination, i.e. glue.
The above-mentioned glue being prepared is infiltrated up to E- glass-fiber-fabrics, 3~10min of heat drying, solvent is waved at 155 DEG C Distribute entirely, obtain prepreg.It is overlapping it is made above obtain 8 rise that respectively to enclose thickness be 35 μm of copper foil on prepreg two sides, Hot pressing 90 minutes, obtains the laminate of double-sided copper-clad at 200 DEG C of temperature and 3.0MPa pressure.
Embodiment 5
It is using polyphenylene oxide resin OPE-2000 styrene end-capped 100g and complete as the toluene 100g mixed dissolutions of solvent Terminal group functional polyphenylene oxide resin solution is obtained entirely, then adds 20g SBs R100 as crosslinking agent, 10g bimaleimide resins add 3.0g cumyl peroxides as initiator, 45g mixing examples 2 as co-curing agent Phosphorus-containing composition as fire retardant, 200g vinyl base silane coupling agents and 150g silica as filler, will be above-mentioned mixed Compound mixes in toluene, and stirring and dissolving obtains homogeneous resin combination, i.e. glue.
The above-mentioned glue being prepared is infiltrated up to E- glass-fiber-fabrics, 3~10min of heat drying, solvent is waved at 155 DEG C Distribute entirely, obtain prepreg.It is overlapping it is made above obtain 8 rise that respectively to enclose thickness be 35 μm of copper foil on prepreg two sides, Hot pressing 90 minutes, obtains the laminate of double-sided copper-clad at 200 DEG C of temperature and 3.0MPa pressure.
Embodiment 6
Mixed using the polyphenylene oxide SA9000 of 100g methacryloxyethyl acids carbomethoxy modification and as the toluene 100g of solvent molten Solution obtains terminal group functional polyphenylene oxide resin solution completely, then adds 75g SBs R100 as crosslinking Agent, 45g bimaleimide resins add 3.0g cumyl peroxides as initiator, 35g mixing as co-curing agent The phosphorus-containing composition of example 4, will as filler as fire retardant, the silica SC-2300SVJ of 200g vinyl base silane processing Said mixture mixes in toluene, and stirring and dissolving obtains homogeneous resin combination, i.e. glue.It is prepared above-mentioned Glue is infiltrated up to E- glass-fiber-fabrics, 3~10min of heat drying at 155 DEG C, solvent is volatilized complete, obtains prepreg.Overlapping It is made above obtain 8 rise that respectively to enclose thickness be 35 μm of copper foil on prepreg two sides, in 200 DEG C of temperature and 3.0MPa pressure Lower hot pressing 90 minutes, obtains the laminate of double-sided copper-clad.
Embodiment 7
Mixed by the polyphenylene oxide SA9000 for being modified 100g methacryloxyethyl acids carbomethoxy and as the toluene 100g of solvent, Dissolving obtains terminal group functional polyphenylene oxide resin solution completely, then adds 30 modified by maleic acid anhydride graft polybutadiene polymers Ricon156MA17 adds 2.5g cumyl peroxides and made as crosslinking agent, 25g maleimide resins as co-crosslinker For initiator, the phosphorus-containing composition of 35g mixing examples 3 is as fire retardant, the silica SC- of 300g vinyl base silane processing 2300SVJ mixes said mixture, and stirring and dissolving obtains homogeneous resin combination, i.e. glue as filler in toluene Liquid.
The above-mentioned glue being prepared is infiltrated up to E- glass-fiber-fabrics, 3~10min of heat drying, solvent is waved at 155 DEG C Distribute entirely, obtain prepreg.It is overlapping it is made above obtain 8 rise that respectively to enclose thickness be 35 μm of copper foil on prepreg two sides, Hot pressing 90 minutes, obtains the laminate of double-sided copper-clad at 200 DEG C of temperature and 3.0MPa pressure.
Comparative example 1
The polyphenylene oxide SA9000 that 100g methacryloxyethyl acids carbomethoxy is modified and the toluene mixing as solvent, have dissolved Terminal group functional polyphenylene oxide resin solution is obtained entirely, then adds 45g SBs R100 as crosslinking agent, 2g cumyl peroxides are added as initiator, 54gDOPO derivatives XP-7866 is as fire retardant, 0.8g epoxy radicals silicone hydrides Coupling agent and 80g silica mix said mixture, and stirring and dissolving obtains homogeneous resin as filler in toluene Composition, i.e. glue.
The above-mentioned glue being prepared is infiltrated up to E- glass-fiber-fabrics, 3~10min of heat drying, solvent is waved at 155 DEG C Distribute entirely, obtain prepreg.It is overlapping it is made above obtain 8 rise that respectively to enclose thickness be 35 μm of copper foil on prepreg two sides, Hot pressing 90 minutes, obtains the laminate of double-sided copper-clad at 200 DEG C of temperature and 3.0MPa pressure.
Comparative example 2
The polyphenylene oxide SA9000 that 100g methacryloxyethyl acids carbomethoxy is modified and the toluene mixing as solvent, have dissolved Terminal group functional polyphenylene oxide resin solution is obtained entirely, then adds 45g SBs R100 as crosslinking agent, 2g cumyl peroxides are added as initiator, 100g polyphosphazenes SPB-100 is as fire retardant, the coupling of 0.8g epoxy radicals silicone hydrides Agent and 80g silica mix said mixture, and stirring and dissolving obtains homogeneous resin combination as filler in toluene Thing, i.e. glue.
The above-mentioned glue being prepared is infiltrated up to E- glass-fiber-fabrics, 3~10min of heat drying, solvent is waved at 155 DEG C Distribute entirely, obtain prepreg.It is overlapping it is made above obtain 8 rise that respectively to enclose thickness be 35 μm of copper foil on prepreg two sides, Hot pressing 90 minutes, obtains the laminate of double-sided copper-clad at 200 DEG C of temperature and 3.0MPa pressure.
Comparative example 3
The polyphenylene oxide SA9000 that 100g methacryloxyethyl acids carbomethoxy is modified and the toluene mixing as solvent, have dissolved Terminal group functional polyphenylene oxide resin solution is obtained entirely, then adds 45g SBs R100 as crosslinking agent, 2g cumyl peroxides are added as initiator, 45g ethyls-bis- (tetrabromo phthalimide) BT-93W, 0.8g epoxies Base silane coupling agent and 80g silica mix said mixture as filler in toluene, and stirring and dissolving obtain it is homogeneous Resin combination, i.e. glue.
The above-mentioned glue being prepared is infiltrated up to E- glass-fiber-fabrics, 3~10min of heat drying, solvent is waved at 155 DEG C Distribute entirely, obtain prepreg.It is overlapping it is made above obtain 8 rise that respectively to enclose thickness be 35 μm of copper foil on prepreg two sides, Hot pressing 90 minutes, obtains the laminate of double-sided copper-clad at 200 DEG C of temperature and 3.0MPa pressure.
Comparative example 4
The polyphenylene oxide SA9000 that 100g methacryloxyethyl acids carbomethoxy is modified and the toluene 100g mixing as solvent, it is molten Solution obtains terminal group functional polyphenylene oxide resin solution completely, and 10g bimaleimide resins add 3.0g as co-curing agent Cumyl peroxide is as initiator, and the phosphorus-containing composition of 25g mixing examples 2 is as fire retardant, the coupling of 2g vinyl base silane Agent and 150g silica mix said mixture, and stirring and dissolving obtains homogeneous resin group as filler in toluene Compound, i.e. glue.
The above-mentioned glue being prepared is infiltrated up to E- glass-fiber-fabrics, 3~10min of heat drying, solvent is waved at 155 DEG C Distribute entirely, obtain prepreg.It is overlapping it is made above obtain 8 rise that respectively to enclose thickness be 35 μm of copper foil on prepreg two sides, Hot pressing 90 minutes, obtains the laminate of double-sided copper-clad at 200 DEG C of temperature and 3.0MPa pressure.
Performance test is carried out to embodiment and comparative example, as a result as shown in Table 1 and Table 2：
Table 1
Table 2
The phosphonium flame retardant composition of 1~7 kind of use of embodiment is can be seen that from above test result, can be less Addition under, reach good V-0 fire retardant ranks, when its polyphenylene oxide resin of functionalization of arranging in pairs or groups, olefin resin and double It can be arrived after the thermoset composition solidification of maleimide resin composition to simultaneously and full with excellent heat resistance, dielectric properties Sufficient UL 94V-0 flame-retardancy requirements.
In comparative example 1, when DOPO derivatives are used alone as fire retardant, even if addition increases, its flame retardant effect It is insufficient；And polyphosphazene compound is used alone as fire retardant, even if the very big resistance that can not meet UL 94V-0 of addition Combustion is required, and the glass transition temperature for being brought due to plasticity cured product is drastically declined, heat resistance extreme difference；Comparative example 4 When kind uses single BMI as crosslinking agent, the heat resistance and anti-flammability of cured product are preferable, but can cause The deterioration of dielectric properties；Comparative example 3 has used brominated fire retardant, can reach good heat resistance and fire resistance, but nothing Method meets halogen-free environmental technical need.
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 implemented.Art 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., within the scope of all falling within protection scope of the present invention and disclosing.

Claims (36)

1. a kind of phosphorous polyphenyl ether resin composition, it is characterised in that the phosphorous polyphenyl ether resin composition contains end group official Polyphenylene oxide resin and flame-retardant compound can be changed；
The fire-retardant combination includes：
(A) the DOPO derivatives shown in formula (1), 100 parts by weight；
(B) hypophosphite compound, 5~50 parts by weight；
(C) polyphosphazene compound, 10~50 parts by weight；
R1One kind in alkylene hydrocarbon or sub- aromatic hydrocarbon selected from C2~C20；
Component (B) hypophosphite compound has following structure：
Wherein m is 2 or 3；R3And R4The alkyl or aryl that carbon number is 1~6 independently are, M is metallic atom, the gold Belong to any one of atom in sodium, calcium, magnesium, aluminium, arsenic, zinc or iron；
Component (C) the polyphosphazene compound has following structural formula：
It is any one in wherein R is phenoxy group, carbon number is 1~10 alkyl, vinyl benzene epoxide or allyl benzene epoxide Kind；
N is 3~100 integer；
Or,
Any one in R is phenoxy group, carbon number is 1~10 alkyl, vinyl benzene epoxide or allyl benzene epoxide；
Q is 3~25 integer.
2. resin combination as claimed in claim 1, it is characterised in that M is aluminium or sodium.
3. resin combination as claimed in claim 1, it is characterised in that M is aluminium.
4. resin combination as claimed in claim 1, it is characterised in that using the terminal group functional polyphenylene oxide resin as 100 Parts by weight meter, the addition of phosphor-containing flame-proof composition is 15~60 parts by weight.
5. resin combination as claimed in claim 4, it is characterised in that the addition of phosphor-containing flame-proof composition is 20~50 weights Measure part.
6. resin combination as claimed in claim 4, it is characterised in that the addition of phosphor-containing flame-proof composition is 25~40 weights Measure part.
7. resin combination as claimed in claim 1, it is characterised in that the terminal group functional polyphenylene oxide resin is terminal hydroxy group Change any one in polyphenylene oxide resin, epoxidation polyphenylene oxide resin, vinylated polyphenylene oxide resin or cyanalation polyphenylene oxide resin Kind or at least two mixture.
8. resin combination as claimed in claim 7, it is characterised in that the terminal group functional polyphenylene oxide resin is vinyl Change polyphenylene oxide resin or/and cyanalation polyphenylene oxide resin.
9. resin combination as claimed in claim 7, it is characterised in that the terminal group functional polyphenylene oxide resin is vinyl Change polyphenylene oxide resin.
10. resin combination as claimed in claim 7, it is characterised in that the terminal group functional polyphenylene oxide resin structural formula As shown in formula (2)：
In formula (2), a and b independently are 1~30 integer, and Z is formula (3) or the structure shown in (4), and-(- O-Y-)-is formula (5) Shown structure ,-(- O-X-O-)-are the structure shown in formula (6)：
In formula (4), A is the alkylidene that arylene, carbonyl or carbon number are 1~10, and m is 0~10 integer, R1、R2And R3 It is identical or different, it independently is the alkyl of hydrogen or carbon number below 10；
In formula (5), R4With R6It is identical or different, it is former independently to be the alkyl or carbon of hydrogen atom, halogen atom, carbon number below 8 Phenyl of the subnumber below 8, R5With R7It is identical or different, it independently is the alkyl or carbon atom of halogen atom, carbon number below 8 Phenyl of the number below 8；
In formula (6), R8、R9、R10、R11、R12、R13、R14And R15Between it is identical or different, independently be hydrogen atom, halogen atom, Alkyl or carbon number phenyl less than 8 of the carbon number below 8, B be alkylene of the carbon number below 20 ,-O-, N is 0 or 1；R16It is 1 for hydrogen atom or carbon number ~10 alkyl.
11. resin combination as claimed in claim 7, it is characterised in that the terminal group functional polyphenylene oxide resin is formula (7) Or the structure shown in (8)：
In formula (7), R1~R3It is identical or different, it independently is the alkyl of hydrogen or carbon number below 10；R4With R6It is identical or different, It independently is the alkyl or phenyl of hydrogen atom, halogen atom, carbon number below 8；R5With R7It is identical or different, it independently is halogen The phenyl of alkyl or carbon number below 8 of plain atom, carbon number below 8；R8、R9、R10、R11、R12、R13、R14And R15Between It is identical or different, it independently is the phenyl of alkyl or carbon number below 8 of hydrogen atom, halogen atom, carbon number below 8；a 1~30 integer independently is with b, B is alkylene ,-O- of the carbon number below 20N is 0 or 1, R16It is for hydrogen atom or carbon number 1~10 alkyl；
In formula (8), R4With R6It is identical or different, it independently is the alkyl or benzene of hydrogen atom, halogen atom, carbon number below 8 Base；R5With R7It is identical or different, it is the alkyl or phenyl of halogen atom, carbon number below 8；R8、R9、R10、R11、R12、R13、R14 And R15Between it is identical or different, be the alkyl or phenyl of hydrogen atom, halogen atom, carbon number below 8；A and b independently are 1 ~30 integer；B is alkylene of the carbon number below 20, and n is 0 or 1.
12. resin combination as claimed in claim 7, it is characterised in that the terminal group functional polyphenylene oxide resin is formula (9) To the structure shown in (13)：
In formula (9), R1~R3It is identical or different, it is the alkyl of hydrogen or carbon number below 10；R4With R6It is identical or different, it is that hydrogen is former The alkyl or phenyl of son, halogen atom, carbon number below 8；R5With R7It is identical or different, be halogen atom, carbon number 8 with Under alkyl or phenyl；R8、R9、R10、R11、R12、R13、R14And R15Between it is identical or different, be that hydrogen atom, halogen atom, carbon are former Alkyl or phenyl of the subnumber below 8；A and b independently is 1~30 integer；Or,
In formula (10), R1~R3It is identical or different, it is the alkyl of hydrogen or carbon number below 10；R4With R6It is identical or different, it is hydrogen The alkyl or phenyl of atom, halogen atom, carbon number below 8；R5With R7It is identical or different, it is halogen atom, carbon number 8 Following alkyl or phenyl；R8、R9、R10、R11、R12、R13、R14And R15Between it is identical or different, be hydrogen atom, halogen atom, carbon Alkyl or phenyl of the atomicity below 8；A and b independently is 1~30 integer；Or,
In formula (11), R1~R3It is identical or different, it is the alkyl of hydrogen or carbon number below 10；R4With R6It is identical or different, it is hydrogen The alkyl or phenyl of atom, halogen atom, carbon number below 8；R5With R7It is identical or different, it is halogen atom, carbon number 8 Following alkyl or phenyl；R8、R9、R10、R11、R12、R13、R14And R15Between it is identical or different, be hydrogen atom, halogen atom, carbon Alkyl or phenyl of the atomicity below 8；A and b independently is 1~30 integer；Or,
In formula (12), R4With R6It is identical or different, it is the alkyl or phenyl of hydrogen atom, halogen atom, carbon number below 8；R5With R7It is identical or different, it is the alkyl or phenyl of halogen atom, carbon number below 8；R8、R9、R10、R11、R12、R13、R14And R15It Between it is identical or different, be the alkyl or phenyl of hydrogen atom, halogen atom, carbon number below 8；A and b independently are 1~30 Integer；Or,
In formula (13), R4With R6It is identical or different, it is the alkyl or phenyl of hydrogen atom, halogen atom, carbon number below 8；R5With R7It is identical or different, it is the alkyl or phenyl of halogen atom, carbon number below 8；R8、R9、R10、R11、R12、R13、R14And R15It Between it is identical or different, be the alkyl or phenyl of hydrogen atom, halogen atom, carbon number below 8；A and b independently are 1~30 Integer.
13. the resin combination as described in one of claim 1-12, it is characterised in that the phosphorous polyphenyl ether resin composition Also include crosslinking agent.
14. resin combination as claimed in claim 13, it is characterised in that the crosslinking agent is poly- with unsaturated double-bond Olefin resin, the vistanex with unsaturated double-bond be polybutadiene, maleic anhydride modified polybutadiene polymers, Acrylic acid modified polybutadiene polymers, BS, butadiene-styrene-divinyl benzene copolymer or In cyclic olefine copolymer any one or at least two mixture.
15. resin combination as claimed in claim 14, it is characterised in that using terminal group functional polyphenylene oxide resin as 100 weights Part meter is measured, the addition of the vistanex with unsaturated double-bond is 10~100 parts by weight.
16. resin combination as claimed in claim 7, it is characterised in that the number of the terminal group functional polyphenylene oxide resin is equal Molecular weight is 500~5000.
17. resin combination as claimed in claim 16, it is characterised in that the number of the terminal group functional polyphenylene oxide resin is equal Molecular weight is 500~3000.
18. resin combination as claimed in claim 17, it is characterised in that the number of the terminal group functional polyphenylene oxide resin is equal Molecular weight is 800~2500.
19. the resin combination as described in one of claim 1-12, it is characterised in that the phosphorous polyphenyl ether resin composition Also include co-crosslinker.
20. resin combination as claimed in claim 19, it is characterised in that the co-crosslinker is bimaleimide resin Or/and multi-group methacrylates compound.
21. resin combination as claimed in claim 20, it is characterised in that the co-crosslinker is maleimide resin.
22. resin combination as claimed in claim 19, it is characterised in that using terminal group functional polyphenylene oxide resin as 100 weights Part meter is measured, the addition of the co-crosslinker is 5~50 parts by weight.
23. the resin combination as described in one of claim 1-12, it is characterised in that the phosphorous polyphenyl ether resin composition Also include initiator.
24. resin combination as claimed in claim 23, it is characterised in that the half life temperature t of the initiator1/2It is not small It is peroxide radical initiator, selected from cumyl peroxide, peroxidized t-butyl perbenzoate, 2,5- bis- in 100 DEG C (2- ethyihexanoylperoxies) -2,5- dimethylhexanes, two-(tert-butylperoxyiso-propyl) benzene, peroxidating (2,4 dichloro benzene first Acyl), double (t-butyl peroxy) hexanes of 2,5- dimethyl -2,5-, the peroxidating -2- ethylhexyl carbonates tert-butyl ester, 2,5- dimethyl - Double (the t-butyl peroxy) -3- of 2,5- alkynes, 4,4- bis- (tert-butyl hydroperoxide) butyl valerate, 1,1- double (tert-butyl hydroperoxides) - 3,3,5- trimethyls thiacyclohexane, 3,3,5,7,7- pentamethyl -1,2,4- trioxepans, di-tert-butyl peroxide or tertiary fourth In base dicumyl peroxide any one or at least two mixture.
25. resin combination as claimed in claim 24, it is characterised in that the initiator is cumyl peroxide.
26. resin combination as claimed in claim 23, it is characterised in that using terminal group functional polyphenylene oxide resin as 100 weights Part meter is measured, the addition of the initiator is 0.5~7 parts by weight.
27. the resin combination as described in claim any one of 1-12, it is characterised in that the phosphorous polyphenylene oxide resin combination Thing also includes silane coupler, is counted by 100 parts by weight of terminal group functional polyphenylene oxide resin, the addition of the silane coupler For 0.1~10 parts by weight.
28. the resin combination as described in claim any one of 1-12, it is characterised in that the phosphorous polyphenylene oxide resin combination Thing also includes filler, and the filler is organic or inorganic filler.
29. resin combination as claimed in claim 28, it is characterised in that the inorganic filler is selected from crystal type titanium dioxide Silicon, fused silica, preparing spherical SiO 2, hollow silicon dioxide, glass dust, aluminium nitride, boron nitride, carborundum, hydroxide It is any one in aluminium, titanium dioxide, strontium titanates, barium titanate, aluminum oxide, barium sulfate, talcum powder, calcium silicates, calcium carbonate or mica Kind or at least two mixture.
30. resin combination as claimed in claim 28, it is characterised in that the organic filler is selected from polytetrafluoroethylene powder In end, polyphenylene sulfide or polyether sulfone powder any one or at least two mixture.
31. resin combination as claimed in claim 28, it is characterised in that using terminal group functional polyphenylene oxide resin as 100 weights Part meter is measured, the addition of the filler is 10~300 parts by weight.
32. a kind of prepreg, including base material and by be impregnated with dry after be attached on base material such as one of claim 1-31 institutes The phosphorous polyphenyl ether resin composition stated.
33. a kind of laminate, include the prepreg as claimed in claim 32 of at least one overlapping.
34. a kind of copper-clad laminate, including the prepreg as claimed in claim 32 of at least one overlapping and it is overlaid on folded The copper foil of the one or both sides of prepreg after conjunction.
35. copper-clad laminate as claimed in claim 34, it is characterised in that the copper foil is electrolytic copper foil or calendering copper Paper tinsel, for the copper foil to be chemically treated using silane coupler, coupling agent used is epoxy silane coupling, vinyl Silane coupler or one kind or at least two mixture in acrylate-based silane coupler, and its surface roughness is less than 5 microns.
36. a kind of printed circuit board, include the prepreg as claimed in claim 32 of at least one overlapping.
CN201510104950.3A 2015-03-10 2015-03-10 Phosphor-containing flame-proof composition and use its phosphorous polyphenyl ether resin composition, prepreg and laminate Active CN104774476B (en)

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