CN109504087A - A kind of resin combination and prepreg and laminate using its preparation - Google Patents
A kind of resin combination and prepreg and laminate using its preparation Download PDFInfo
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- CN109504087A CN109504087A CN201811435227.3A CN201811435227A CN109504087A CN 109504087 A CN109504087 A CN 109504087A CN 201811435227 A CN201811435227 A CN 201811435227A CN 109504087 A CN109504087 A CN 109504087A
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L79/00—Compositions of macromolecular compounds obtained by reactions forming in the main chain of the macromolecule a linkage containing nitrogen with or without oxygen or carbon only, not provided for in groups C08L61/00 - C08L77/00
- C08L79/04—Polycondensates having nitrogen-containing heterocyclic rings in the main chain; Polyhydrazides; Polyamide acids or similar polyimide precursors
- C08L79/08—Polyimides; Polyester-imides; Polyamide-imides; Polyamide acids or similar polyimide precursors
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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
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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
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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
- B32B27/00—Layered products comprising a layer of synthetic resin
- B32B27/06—Layered products comprising a layer of synthetic resin as the main or only constituent of a layer, which is next to another layer of the same or of a different material
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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
- 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
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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
- B32B7/00—Layered products characterised by the relation between layers; Layered products characterised by the relative orientation of features between layers, or by the relative values of a measurable parameter between layers, i.e. products comprising layers having different physical, chemical or physicochemical properties; Layered products characterised by the interconnection of layers
- B32B7/04—Interconnection of layers
- B32B7/06—Interconnection of layers permitting easy separation
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L2203/00—Applications
- C08L2203/20—Applications use in electrical or conductive gadgets
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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)
- Reinforced Plastic Materials (AREA)
Abstract
Present invention discloses a kind of resin combinations, with solid weight meter, comprising: modified bismaleimide prepolymer: 100 parts；Epoxy resin: 5-30 parts；Curing agent: 0-20 parts；Filler: 0-150 parts；Curing accelerator: 0.001-5 parts；The modified bismaleimide prepolymer is at least formed by bimaleimide resin and allylic compound pre-polymerization.Compared with prior art, resin combination in the present invention has excellent peel strength, halogen-free flame-retardance, high-fire resistance, high-temperature modulus conservation rate, excellent toughness, thermal expansion coefficient and high modulus conservation rate simultaneously, especially meet halogen-free flameproof UL94V-0 while there is excellent high-temperature modulus conservation rate and low thermal expansivity coefficient, therefore is applicable in the high performance line pipeline materials such as HDI high multilager base plate well.
Description
Technical field
The present invention relates to technical field of electronic materials, in particular to a kind of high heat resistance resin combination and using its preparation
Prepreg and laminate.
Background technique
In recent years, with the continuous development of development of Mobile Internet technology, multifunction, lightening constantly becomes electricity at portability
Sub- product pursues target, it is meant that the component that electronic product loads is more, printed circuit more uses high density to interconnect
Technology (HDI) and printed circuit whole plate is thinner, therefore, to production printed circuit board substrate --- copper-clad plate proposes more
High requirement, it is desirable that it has the performance of similar package substrate, the class wrapper material risen in the industry at once, it is desirable that copper-clad plate has
High heat resistance, high glass transition temperature, excellent cohesive force, good processability, it is often more important that plate is in high temperature
There is down preferable modulus conservation rate.
Bimaleimide resin has excellent heat resistance and higher high temperature as a kind of high performance resin material
Modulus conservation rate, but bimaleimide resin dissolubility is poor, can only be dissolved in some high boiling solvents such as N, N- dimethyl
Formamide, N-Methyl pyrrolidone etc., process conditions are harsh, while the solidfied material crosslink density of bismaleimide is high, brittleness
Greatly, other service performances are seriously affected.Therefore, generally use in the prior art aromatic diamine or diallyl compound into
Row is modified, and modified bimaleimide resin has good processability and excellent performance, no matter but diamines or two
Allyl compound modified maleimide resin, can not by it is intrinsic it is fire-retardant reach V-0 grades of UL94, need to add Halogen
Fire retardant meets the halogen-free flameproof of european union directive requirement.
The method for realizing laminate halogen-free flameproof used for printed circuit is usually that nitrogenous, phosphorus, silicon etc. are added in resin matrix
Anti-flammability element resin and inorganic filler (such as inorganic compound of aluminium hydroxide, magnesium hydroxide containing the crystallization water).And siliceous, nitrogen
Resin or inorganic filler fire retardant compare phosphorous resin fire retardant, there is a problem that flame retarding efficiency is low, are unable to satisfy UL94V-0
Requirement.Therefore, phosphorous resin occupies leading position in current Halogen baseplate material as main flame retardant.These phosphorous resistances
Firing agent is mainly reactive resin and additive flame retardant, such as phosphorous epoxy resin, phosphazene compound, phosphate or phosphorus-containing phenolic aldehyde
Resin etc..After introducing said components, the flame retardant property of plate is improved, but these are using epoxy resin or phenolic resin as base
The flame-retarded resin of body significantly reduces heat resistance, glass transition temperature and the height of modified bismaleimide resin system
Warm calculating modulus conservation rate etc., it is difficult to meet its answering in the high performances areas such as high density interconnection or integrated antenna package/class wrapper
With requiring.
Therefore, it in order to obtain non-halogen flame-retarding high performance bimaleimide resin, discloses come in span in the prior art
The scheme of phosphonium flame retardant is added in imide resin system.
The skill of phosphorus-containing compound (phosphonitrile class) is added in bismaleimide resin system as disclosed in patent CN102276837A
Art scheme, although can be halogen-free, and with preferable flame retardant property solidfied material, these fire retardants not with
Bismaleimide resin system forms preferable cross-linked network structure, bimaleimide resin high temperature curing conditions (often higher than
200 DEG C) under, having neither part nor lot in the phosphorus nitrile compounds of reaction, emersion is in substrate surface in a manner of being similar to " perspiration ", not only shadow
The heat resistance of castanets material more affects the binding force between plate and copper foil.
As disclosed allyl modified bismaleimide resin in patent CN103665864, and separately it is added in glue
Machine phosphorus fire retardant or organonitrogen compound etc., although the dissolubility that can solve bimaleimide resin in the technical solution is asked
Topic, and the flame retardant compositions that halogen-free high flame-retardant plate can be obtained, but in addition added influence final solidfied material heat resistance,
Humidity resistance and water absorption rate etc., therefore, it is difficult to obtain the high-performance plate of excellent combination property.
The technical side of phosphorous epoxy resin is added in bismaleimide resin system as disclosed in patent JP2012153896
Case, the technical solution also can satisfy halogen-free flameproof requirement, but because of the presence of epoxy resin, greatly reduce the vitrifying of resin
Modulus conservation rate under transition temperature, heat resistance and high temperature.
In summary, it is necessary to develop a kind of suitable for class support plate, encapsulating carrier plate and high density interconnection technique field
High-performance printed wiring board baseplate material has excellent halogen-free flame-retardance, height resistance to using the laminate of its preparation or copper-clad plate
High modulus conservation rate under hot, low thermal coefficient of expansion and high temperature.
Summary of the invention
The purpose of the present invention is to provide a kind of resin combination for solving above-mentioned technical problem and use the half of its preparation
Cured sheets and laminate, the resin combination have excellent peel strength, halogen-free flame-retardance, high-fire resistance, high temperature simultaneously
Modulus conservation rate, excellent toughness, thermal expansion coefficient and high modulus conservation rate, it is same especially to meet halogen-free flameproof UL94 V-0
When with excellent high-temperature modulus conservation rate and low thermal expansivity coefficient, therefore well be applicable in HDI high multilager base plate it is contour
Performance line material.
Wherein, resin combination, with solid weight meter, comprising:
Modified bismaleimide prepolymer: 100 parts；
Epoxy resin: 5-30 parts；
Curing agent: 0-20 parts；
Filler: 0-150 parts；
Curing accelerator: 0.001-5 parts；
Wherein, the modified bismaleimide prepolymer is at least by bimaleimide resin and allylic compound
Pre-polymerization forms, and phosphorous allylic shown in following structural formula (1) or structural formula (2) is contained in the allylic compound
Close object:
Wherein, R1For the straight-chain alkyl-sub or substituted alkylene of C1-C10 or the aromatic series base of C6-C20.
As a further improvement of the present invention, the weight ratio of the bimaleimide resin and allylic compound
For 100:10-100.
As a further improvement of the present invention, the bimaleimide resin has following structure formula:
Wherein, R base is selected from least one of following structural:
As a further improvement of the present invention, without phosphorus allyl compound, institute are also contained in the allylic compound
It states without phosphorus allyl compound and is selected from diallyl bisphenol, diallyl bisphenol S, allyl phenoxy resin, allyl phenolic aldehyde tree
One of rouge or diallyl diphenyl ether or any two or more mixture, content are with total allylic compound
100 mass point meter, contains 10-90 parts.
As a further improvement of the present invention, the epoxy resin be bisphenol A epoxide resin, it is bisphenol F epoxy resin, phosphorous
Epoxy resin, nitrogen-containing epoxy thermoset, o-cresol formaldehyde epoxy resin, bisphenol-A phenolic epoxy resin, phenol novolac epoxy resins, first
Phenol novolak epoxy, triphenyl methane epoxy resin, tetraphenyl ethane epoxy resin, biphenyl type epoxy resin, naphthalene nucleus type ring
Oxygen resin, dicyclopentadiene type epoxy resin, isocyanate-based epoxy resin, aralkyl novolac epoxy resin, polyphenylene oxide
It is modified epoxy, alicyclic based epoxy resin, glycidyl amine type epoxy resin, a kind of in glycidyl ester type epoxy resin
Or any several mixture.
As a further improvement of the present invention, the curing agent is amine compound, amide based compound, acid anhydrides system chemical combination
Object or phenol system compound.
As a further improvement of the present invention, the filler is inorganic filler or organic filler, and the inorganic filler is selected from
In nonmetal oxide, metal nitride, non-metal nitride, inorganic hydrate, inorganic salts, metal hydrate or Phos
A kind of or at least any two kinds of mixture；The organic filler is selected from polytetrafluorethylepowder powder, polyphenylene sulfide or polyether sulfone
One of powder or at least any two kinds of mixture.
Correspondingly, the present invention also provides a kind of prepregs, add in using described in any item resin combinations as above
Enter solvent dissolution and glue is made, reinforcing material is immersed in the glue, by the reinforcing material heat drying after dipping
Afterwards, the prepreg can be obtained.
Correspondingly, the present invention also provides a kind of laminates, are covered at least one the two-sided of prepreg as described above
The laminate can be obtained in release film, hot forming.
Correspondingly, the present invention also provides a kind of laminate, in the single side of at least one prepreg as described above or double
Face is covered with metal foil, and the laminate can be obtained in hot forming.
Due to the above technical solutions, the present invention has the following advantages over the prior art:
(1) modified as bimaleimide resin using the allyl compound of the structure containing DOPO or DPPO in the present invention
Phosphorus-containing groups are directed into bismaleimide tree well on the basis of not influencing bimaleimide resin performance by agent
In the cross-linked network structure of rouge, therefore nitrogen and P elements cooperative flame retardant in a cross-linked network structure, it can be reduced solidification
Object anti-flammability reaches phosphorus content needed for UL94V-0, does not need to be further added by other fire retardants, obtains while having excellent Halogen resistance
Combustion property, high-fire resistance, high-adhesion, excellent toughness and thermal expansion coefficient solidfied material；
(2) it in allyl compound structure, when straight chained alkyl is arranged in the middle position of DOPO or DPPO, can adjust
The crosslink density for saving whole bismaleimide polymer cross-linked network structure, is effectively reduced the crisp of bimaleimide resin
Property, alleviate the generation of stress during curing reaction, reduce the thermal expansion coefficient of plate, while keeping more excellent high temperature mould
Amount.
(3) when preparing modified bismaleimide prepolymer, being properly added without phosphorus allyl compound can effectively be controlled
The preparation process of prepolymer processed, the allyl compound play slow poly- in the addition reaction of dimaleoyl imino and allyl
Effect, while the dissolubility of bimaleimide resin is improved, bulk polymerization reaction rate can be controlled well, integrated
More excellent performance of final solidfied material.
(4) allyl compound of the structure of the invention containing DOPO or DPPO not only reacts with bismaleimide,
And the reactive hydrogen of-NH- in structure reacts with epoxy group, thus can also be obtained in the case where adding a small amount of epoxy resin compared with
The final solidfied material of high-fire resistance, low thermal expansion coefficient and high-modulus, and there is excellent caking property, so that it is more to meet HDI
The high performance printed wiring board requirement such as laminar substrate, ultra-thin packed substrate.
Specific embodiment
Below with reference to specific embodiment, the present invention will be described in detail.But these embodiments are not intended to limit this hair
Bright, structure that those skilled in the art are made according to these embodiments, method or transformation functionally include
Within the scope of the present invention.Reaction condition that those skilled in the art are done according to these embodiments, reaction
Transformation on object or raw material dosage is included within the scope of protection of the present invention.
In the embodiment of the invention, a kind of flame-retardant resin prepolymer, specially modified bismaleimide
Prepolymer is at least formed by bimaleimide resin and allylic compound pre-polymerization, is contained in allylic compound
Phosphorous allylic compound shown in structural formula (1) or structural formula (2):
Wherein, R1 is the straight-chain alkyl-sub of C1-C10 or the aromatic series base of substituted alkylene or C6-C20；
The weight ratio of bimaleimide resin and allylic compound is 100:10-100, preferably 100:20-
60, specifically can be 100:10,100:15,100:20,100:25,100:30,100:35,100:40,100:45,100:50,
100:55,100:60,100:65,100:70,100:75,100:80,100:85,100:90,100:95 or 100:100.
Further, in above-mentioned allylic structural formula of compound (1) and (2), R1 is the straight-chain alkyl-sub of C2-C6, when
R1 is straight-chain alkyl-sub, and middle position of the two sides containing DOPO or DPPO, adjustable entirety bismaleimide polymerization is arranged in
The brittleness of bimaleimide resin is effectively reduced in the crosslink density of object cross-linked network structure, alleviates curing reaction and answers in the process
The generation of power.But work as R1When the chain length of straight-chain alkyl-sub is too long, linear long-chain is easily broken off under the high temperature conditions, influences to solidify
The heat resistance of object, works as R1When the chain length of straight-chain alkyl-sub is too short, it is difficult to obtain said effect.
In above-mentioned allylic structural formula of compound (1) and (2), the aromatic series base in R1 is
Wherein it is preferablyStraight-chain alkyl-sub is
Or its substituted alkylene, wherein being preferably
Further, bimaleimide resin has following structure formula:
Wherein, R base is selected from least one of following structural:
Further, without phosphorus allyl compound is also contained in allylic compound, it is preferable that without phosphorus allyl chemical combination
Object is selected from diallyl bisphenol, diallyl bisphenol S, allyl phenoxy resin, allyl phenol urea formaldehyde or diallyl hexichol
The mixture of one or more of ether, the content of without phosphorus allyl compound are with total 100 matter of allylic compound
Amount point meter, containing 10-90 parts, preferably 30-50 parts, more preferably 30 parts, 31 parts, 32 parts, 33 parts, 34 parts, 35 parts, 36 parts,
37 parts, 38 parts, 39 parts, 40 parts, 41 parts, 42 parts, 43 parts, 44 parts, 45 parts, 46 parts, 47 parts, 48 parts, 49 parts, 50 parts.
When preparing prepolymer, the preparation process of prepolymer can effectively be controlled by being properly added without phosphorus allyl compound,
The without phosphorus allyl compound plays poly- effect of delaying in the addition reaction of dimaleoyl imino and allyl, while improving double
The dissolubility of maleimide resin, but when the content is higher, the reaction of phosphorous allyl and dimaleoyl imino is influenced,
DOPO or DPPO cannot be introduced into well in span system.
The present invention also provides a kind of resin combinations, with solid weight meter, comprising:
Above-mentioned flame-retardant resin prepolymer, i.e. modified bismaleimide prepolymer: 100 parts；
Epoxy resin: 5-30 parts；
Curing agent: 0-20 parts；
Filler: 0-150 parts；
Curing accelerator: 0.001-5 parts.
Further, epoxy resin is bisphenol A epoxide resin, bisphenol F epoxy resin, phosphorous epoxy resin, nitrogenous epoxy
Resin, o-cresol formaldehyde epoxy resin, bisphenol-A phenolic epoxy resin, phenol novolac epoxy resins, cresol novolak epoxy, three
Phenylmethane epoxy resin, tetraphenyl ethane epoxy resin, biphenyl type epoxy resin, naphthalene nucleus type epoxy resin, dicyclopentadiene
Type epoxy resin, isocyanate-based epoxy resin, aralkyl novolac epoxy resin, polyphenyl ether modified epoxy resin, alicyclic ring
Same clan's epoxy resin, glycidyl amine type epoxy resin, in glycidyl ester type epoxy resin one or any of several mixing
Object.The preferred bisphenol A epoxide resin of the present invention, bisphenol-A phenolic epoxy resin, biphenyl type epoxy resin, naphthalene nucleus type epoxy resin or
Dicyclopentadiene type epoxy resin.
Further, curing agent be amine compound, amide based compound, acid anhydrides based compound or phenol system compound,
Content contains 1-10 parts preferably in terms of 100 parts by weight of modified bismaleimide prepolymer.
Specifically, amine compound can be diaminodiphenyl-methane, diaminodiphenylsulfone, diethylenetriamines, double
Carboxyl phthalimide, imidazoles etc.；Amide based compound can be dicyandiamide, Versamid etc.；Acid anhydrides system chemical combination
Object can be phthalic anhydride, trimellitic anhydride, pyromellitic acid anhydride, maleic anhydride, hydrogenated phthalic anhydride, receive
Dick acid anhydrides etc., optimization styrene-maleic anhydride；Phenol system compound can be bisphenol A phenolic resin, phenol novolacs, naphthalene
Phenol phenolic resin, biphenyl phenol type phenolic resin, biphenyl phenol type naphthol resin, dicyclopentadiene phenol add-on type resin, benzene
Phenol aralkyl resin, naphthols aralkyl resin, Pehanorm resin, benzoxazine resin etc..
The preferred diaminodiphenylsulfone of curing agent of the present invention or biphenyl phenol type phenolic resin or benzoxazine resin.Work as solidification
When agent is diaminodiphenylsulfone, the component of resin combination and the content of each component are as follows:
Modified bismaleimide prepolymer: 100 parts；
Epoxy resin: 5-30 parts；
Diaminodiphenylsulfone: 0-10 parts
Filler: 20-150 parts；
Curing accelerator: 0.001-2 parts.
When curing agent is biphenyl phenol type phenolic resin, the component of resin combination and the content of each component are as follows:
Modified bismaleimide prepolymer: 100 parts；
Epoxy resin: 5-30 parts；
Biphenyl phenol type phenolic resin: 0-20 parts
Filler: 20-150 parts；
Curing accelerator: 0.001-2 parts.
When curing agent is benzoxazine resin, the component of resin combination and the content of each component are as follows:
Modified bismaleimide prepolymer: 100 parts；
Epoxy resin: 5-30 parts；
Benzoxazine resin: 0-20 parts
Filler: 20-150 parts；
Curing accelerator: 0.001-2 parts.
Further, filler is selected from organic filler or inorganic filler, wherein inorganic filler is selected from nonmetal oxide, gold
Belong to one of nitride, non-metal nitride, inorganic hydrate, inorganic salts, metal hydrate or Phos or at least appoints
The mixture of two kinds of meaning, preferred molten silica, crystalline sillica, spherical silica, hollow silicon dioxide, hydrogen-oxygen
Change aluminium, aluminium oxide, talcum powder, aluminium nitride, boron nitride, silicon carbide, barium sulfate, barium titanate, strontium titanates, calcium carbonate, calcium silicates, cloud
In female or glass fiber powder any one or at least two mixture；Organic filler is selected from polytetrafluorethylepowder powder, gathers
A kind of or at least any two kinds of mixture in diphenyl sulfide or polyether sulfone powder.
In the present invention, the preferred inorganic filler of filler, further preferred surface treated inorganic filler is most preferably passed through
The silica of surface treatment.It is low that the surface treating agent being surface-treated to inorganic filler is selected from silane coupling agent, organosilicon
In polymers or titanate coupling agent any one or at least two mixture, angle value is 0.2~20 μm in the partial size of filler,
Angle value is 0.5~5 μm in the partial size of preferred filler, has good dispersibility and preferable processing positioned at the filler of this partial size section
Property.
It is highly preferred that being in terms of 100% by inorganic filler quality, the dosage of surface treating agent is 0.1~5.0%, preferably 0.5
~3.0%, further preferred 0.75~2.0%.
Further, curing accelerator is selected from dimethyl aminopyridine, tertiary amine and its salt, imidazoles, organic metal salt, triphen
Base phosphine is Ji Qi phosphonium salt etc..Curing accelerator adds use according to the actual situation, can selected from dimethyl aminopyridine, tertiary amine and its
Salt, imidazoles, organic metal salt, triphenylphosphine are Ji Qi phosphonium salt etc., in terms of 100 parts of flame-retardant resin prepolymer, solidification promotes content
Agent is preferably 0.01-2.0 parts.
It further, further include elastomer in resin combination of the invention, elastomer is low modulus component, is selected from poly- fourth
At least one in dienes, phenylethylene, olefines, polyurethanes, polyesters, polyimides class, esters of acrylic acid or silicone
Kind, preferably the low modulus component containing reactive group, reactive group can be epoxy group, hydroxyl, amino, anhydride group, carboxyl or ethylene
Base etc. is more preferably selected as epoxy-modified polybutadiene, anhydride modified polybutadiene, styrene-butadiene-copolymer, styrene
Propylene copolymer or styrene acrylic copolymer, in terms of 100 parts of flame-retardant resin prepolymer, content is preferably elastomer content
5-20 parts.
When being properly added low modulus elastomer in flame resistance resin composite, stress can be reduced during curing reaction
Generation, be effectively improved the thermal expansion coefficient of plate, while further improving bimaleimide resin brittleness.
Further, it can also be added according to practical feelings in resin combination and use antioxidant, heat stabilizer, antistatic
Agent, ultraviolet absorbing agent, pigment, colorant or lubricant etc..These various additives can be used alone, can also two kinds or
Person is two or more to be used in mixed way.
The present invention also provides a kind of prepreg prepared using above-mentioned resin combination, preparation step is as follows:
Above-mentioned flame resistance resin composite is dissolved with solvent, solid content 60%-75% is stirred evenly, and is cured,
Resin combination composition glue liquid is made；
Reinforcing material is immersed in above-mentioned resin combination composition glue liquid, then by the reinforcing material after dipping at 50-170 DEG C
The prepreg in of the invention can be obtained after baking 1-10min is dry under environment.
Wherein, reinforcing material is natural fiber, organic synthetic fibers, organic fabric or inorganic fabric, and inorganic fabric is special
Glass fabric is not preferably used, and it is preferable to use fibrillation cloth or flat fabrics for glass fabric.In addition, in order to improve resin and glass
The interface cohesion of fiber cloth, glass fabric, which is typically necessary, to be chemically treated, and main method is coupling agent treatment, idol used
Join agent such as epoxy silane, amino silane etc..
Solvent be selected from acetone, butanone, toluene, methylisobutylketone, N, dinethylformamide, N, N- dimethyl acetamide,
One of ethylene glycol monomethyl ether, propylene glycol monomethyl ether, benzene, toluene, hexamethylene or any several combination.
The present invention also provides a kind of laminate prepared using above-mentioned prepreg, preparation step is as follows:
It is covered with release film at least the two-sided of above-mentioned prepreg, laminate can be obtained in hot forming, and half is solid
The quantity for changing piece can be as needed the thickness of laminate determine, can use one or more.Release film can be PET film or from
Type aluminium foil.
The present invention also provides another laminate using the preparation of above-mentioned prepreg, preparation step is as follows:
It is covered with metal foil in the single or double of an above-mentioned prepreg, or will at least be folded 2 above-mentioned prepregs
After adding, it is covered with metal foil in its single or double, metal foil laminate can be obtained in hot forming.
The quantity of prepreg can be as needed the thickness of laminate determine, can use one or more.The metal
Foil can be copper foil, be also possible to aluminium foil, their thickness is not particularly limited.
The pressing conditions of above-mentioned laminate is to suppress 2~4 hours at a temperature of 0.2~2MPa pressure and 180~250 DEG C.
Above-mentioned prepreg, laminate and metal foil laminate are used to prepare wiring board.
In order to preferably illustrate the present invention, some specific embodiments presented below are described further the present invention, below
Specific synthesis example is prepared for flame retardant type Bismaleimide prepolymer:
Synthesis example one
100 parts of solvent n,N-Dimethylformamide are added in 500mL three-necked flask, 4,4 '-diphenyl-methane spans are come
Allyl compound A-1 (straight chain fundamental mode), the diallyl bisphenol of acid imide and the base containing DOPO, according to mass parts 100:80:20
Successively in investment three-necked flask, is persistently stirred under the conditions of 110 DEG C of oil bath, start to count after solid in flask is completely dissolved
When, after persistently stirring 1hr, products therefrom is distilled, obtains the modified bismaleimide prepolymer that solid content is 75%
1。
Synthesis example two
100 parts of solvent n,N-Dimethylformamide are added in 500mL three-necked flask, 4,4 '-diphenyl-methane spans are come
Allyl compound A-2 (aromatic series fundamental mode), the diallyl bisphenol of acid imide and the base containing DOPO, according to mass parts 100:60:
20, successively in putting into three-necked flask, persistently stir under the conditions of 110 DEG C of oil bath, start after solid in flask is completely dissolved
Timing distills products therefrom after persistently stirring 1hr, obtains the modified bismaleimide pre-polymerization that solid content is 75%
Object 2.
Synthesis example three
100 parts of solvent n,N-Dimethylformamide are added in 500mL three-necked flask, 4,4 '-diphenyl-methane spans are come
Allyl compound A-3 (straight chain fundamental mode), the diallyl diphenyl ether of acid imide and the base containing DPPO, according to mass parts 100:40:
30, successively in putting into three-necked flask, persistently stir under the conditions of 110 DEG C of oil bath, start after solid in flask is completely dissolved
Timing distills products therefrom after persistently stirring 1hr, obtains the modified bismaleimide pre-polymerization that solid content is 75%
Object 3.
Synthesis example four
100 parts of solvent n,N-Dimethylformamide are added in 500mL three-necked flask, 4,4 '-diphenyl-methane spans are come
Allyl compound A-4 (aromatic series fundamental mode), the diallyl bisphenol of acid imide and the base containing DPPO, according to mass parts 100:30:
50, successively in putting into three-necked flask, persistently stir under the conditions of 110 DEG C of oil bath, start after solid in flask is completely dissolved
Timing distills products therefrom after persistently stirring 1hr, obtains the modified bismaleimide pre-polymerization that solid content is 75%
Object 4.
Synthesis example five (compares synthesis example 1, different content ratio)
100 parts of solvent n,N-Dimethylformamide are added in 500mL three-necked flask, 4,4 '-diphenyl-methane spans are come
Allyl compound A-1 (straight chain fundamental mode), the diallyl diphenyl ether of acid imide and the base containing DOPO, according to mass parts 100:20:
40, successively in putting into three-necked flask, persistently stir under the conditions of 110 DEG C of oil bath, start after solid in flask is completely dissolved
Timing distills products therefrom after persistently stirring 1hr, obtains the modified bismaleimide pre-polymerization that solid content is 75%
Object 5.
Synthesis example six
100 parts of solvent n,N-Dimethylformamide are added in 500mL three-necked flask, 4,4 '-diphenyl-methane spans are come
Allyl compound A-1 (straight chain fundamental mode), the diallyl bisphenol of acid imide and the base containing DOPO, according to mass parts 100:30:70
Successively in investment three-necked flask, is persistently stirred under the conditions of 110 DEG C of oil bath, start to count after solid in flask is completely dissolved
When, after persistently stirring 1hr, products therefrom is distilled, obtains the modified bismaleimide prepolymer that solid content is 75%
6。
Synthesis example seven
100 parts of solvent n,N-Dimethylformamide are added in 500mL three-necked flask, 4,4 '-diphenyl-methane spans are come
The allyl compound A-1 (straight chain fundamental mode) of acid imide and the base containing DOPO, diallyl diphenyl ether are according to mass parts 100:10:40
Successively in investment three-necked flask, is persistently stirred under the conditions of 110 DEG C of oil bath, start to count after solid in flask is completely dissolved
When, after persistently stirring 1hr, products therefrom is distilled, obtains the modified bismaleimide prepolymer that solid content is 75%
7。
Synthesis example eight (span and phosphorous allyl compound pre-polymerization)
100 parts of solvent n,N-Dimethylformamide are added in 500mL three-necked flask, 4,4 '-diphenyl-methane spans are come
The allyl compound A-1 (straight chain fundamental mode) of acid imide and the base containing DOPO, according to mass parts 100:50 successively in three mouthfuls of burnings of investment
In bottle, is persistently stirred under the conditions of 110 DEG C of oil bath, start timing after solid in flask is completely dissolved, persistently stir 1hr
Afterwards, products therefrom is distilled, obtains the modified bismaleimide resin prepolymer 8 that solid content is 75%.
Compare synthesis example nine (span+allyl compound copolymerization)
100 parts of solvent n,N-Dimethylformamide are added in 500mL three-necked flask, 4,4 '-diphenyl-methane spans are come
Acid imide and diallyl bisphenol, according to mass parts 100:60 successively in putting into three-necked flask, in 110 DEG C of oil bath condition
Lower lasting stirring, starts timing after solid in flask is completely dissolved, after persistently stirring 1hr, products therefrom is distilled, is obtained
The modified bismaleimide prepolymer 9 for being 75% to solid content.
Compare synthesis example ten (span+allyl+phosphorus-containing compound copolymerization)
100 parts of solvent n,N-Dimethylformamide are added in 500mL three-necked flask, 4,4 '-diphenyl-methane spans are come
Acid imide, diallyl bisphenol and phosphorus-containing compound (DOPO), according to mass parts 100:60:10 successively in investment three-necked flask
In, it is persistently stirred under the conditions of 110 DEG C of oil bath, starts timing after solid in flask is completely dissolved, persistently stir 0.2hr
Afterwards, products therefrom is distilled, obtains the modified bismaleimide prepolymer 10 that solid content is 75%.
Compare synthesis example 11 (span+allyl compound+phosphorous epoxy resin copolymerization)
100 parts of solvent n,N-Dimethylformamide are added in 500mL three-necked flask, 4,4 '-diphenyl-methane spans are come
Acid imide, allyl compound and phosphorous epoxy resin, according to mass parts 100:50:30 successively in investment three-necked flask in,
It is stirred to react 2hr under the conditions of 110 DEG C of oil bath, products therefrom is distilled, solid matter is obtained, then with organic solvent system
The modified bismaleimide prepolymer 11 that standby solid content is 75%.
It prepares prepreg: using the glue of component and obtained 62% solid content of proportion in following Tables 1 and 2, using
Glass fabric impregnates above-mentioned glue, and dries 5min in 160 DEG C of baking ovens and prepreg is made.
It prepares copper clad laminate: the above-mentioned semi-solid preparation that 8 are cut out burr removing being superimposed, 35 microns of copper foil is enclosed up and down, sets
Compacting obtains copper-clad plate in vacuum hotpressing machine.Specific process for pressing is that pressing 4 is small at a temperature of 1.5Mpa pressure, 220 DEG C
When.
The copper clad laminate performance of acquisition is as shown in Table 1 and Table 2:
Table 1 is specific embodiments of the present invention
The comparative example of the invention of table 2
* 1: glue reaction is too fast, and GT is shorter, the serious dried flower defect of plate substrate；
* 2: plate goes copper rear surface to have precipitate
Wherein, the preparation method of allyl compound A-1 to A-4 is following:
Step 1: 1mol allyamine compounds is taken to be uniformly mixed with suitable organic solvent, then temperature is in 50-100
The terephthalaldehyde for instilling 0.5mol at DEG C into reaction flask, reacts 1-5 hours under the protection of nitrogen；
Step 2: reaction mixture is cooling, and suction filtration obtains crude product, then uses deionized water dissolving to after reaction
And heat, it is then recrystallized, is repeated 2-5 times with same method is cooling, it is finally dry at 60-90 DEG C in a vacuum drying oven
24 hours, obtain intermediate product；
Step 3: taking 0.5mol intermediate product and the DOPO of 1mol, adds appropriate organic solvent, and gradually heating keeps its complete
Fully dissolved is reacted 5-7 hours under 90-120 DEG C, nitrogen protection, molten to be cooled to room temperature after reaction, then with deionized water
It solves and heats, then recrystallized with same method is cooling, repeat 2-5 times, finally done at 60-90 DEG C in a vacuum drying oven
Dry 24 hours, obtain the allyl compound.
Different aldehyde compound and phosphorus compound are selected in the above-mentioned methods, are obtained with flowering structure allyl compound:
Allyl compound A-1: structural formula (1), R1For
Allyl compound A-2: structural formula (1), R1For
Allyl compound A-3: structural formula (2), R1For
Allyl compound A-4: structural formula (2), R1For
Allyl compound A-5: structural formula (1), R1For
4,4 '-diphenyl methane dimaleimides: Xi'an span new material Co., Ltd；
Unmodified bismaleimide: 4,4 '-diphenyl methane dimaleimides, Xi'an span new material system；
4,4 '-diphenyl methane dimaleimides: Xi'an span new material Co., Ltd；
Biphenyl type epoxy resin: NC3000H, Japanese chemical drug；
Biphenyl phenol type phenolic resin: KAYAHARD GPH-103, Japanese chemical drug；
Phosphorus containing phenolic resin: LC950, SHIN-A；
Phosphorous epoxy resin: KEG-H5138, Kolon；
Phosphonitrile: SPB100, big tomb chemistry；
Filler: silica is surface-treated with silane coupling agent, and average grain diameter is 1.0 μm, and Jiangsu connection is auspicious；
Curing accelerator: 2-methylimidazole, four countries' chemical conversion；
Phosphorous epoxy resin: KEG-H5138, Kolon；
Phosphazene compound: SPB100, big tomb chemistry；
Elastomer: KMP-605, SHIN-ETSU HANTOTAI's chemistry.
Method of evaluating performance:
(1) glass transition temperature (DMA): being measured with DMA, and heating rate is 10 DEG C/min, and frequency is to measure under 10Hz
Tg,
Temperature range: 30-320 DEG C.
(2) modulus: being measured with DMA, and heating rate is 10 DEG C/min, and frequency is the mould of 50 DEG C and 260 DEG C of measurement under 10Hz
Magnitude, unit GPa.
(3) anti-flammability: UL94 vertical combustion (UL94V) is tested according to ASTM (D63-77) method.
(4) peel strength: according to " after thermal stress " experiment condition in IPC-TM-650 method, metallic cover layer is tested
Peel strength.
(5) thermal expansion coefficient (X/Y-CTE): being measured using TA instrument TMA, from 30 DEG C~350 DEG C, heating rate 10
DEG C/min, the linear expansion coefficient in the face direction of 50 DEG C to 130 DEG C of measurement, measurement direction is the transverse direction (X) of glass cloth cover, longitudinal
(Y), unit is X/Y ppm/ DEG C.
It should be appreciated that although this specification is described in terms of embodiments, but not each embodiment only includes one
A independent technical solution, this description of the specification is merely for the sake of clarity, and those skilled in the art should will say
As a whole, the technical solution in each embodiment may also be suitably combined to form those skilled in the art can for bright book
With the other embodiments of understanding.
The series of detailed descriptions listed above only for feasible embodiment of the invention specifically
Protection scope bright, that they are not intended to limit the invention, it is all without departing from equivalent implementations made by technical spirit of the present invention
Or change should all be included in the protection scope of the present invention.
Claims (10)
1. a kind of resin combination, which is characterized in that with solid weight meter, comprising:
Modified bismaleimide prepolymer: 100 parts；
Epoxy resin: 5-30 parts；
Curing agent: 0-20 parts；
Filler: 0-150 parts；
Curing accelerator: 0.001-5 parts；
Wherein, the modified bismaleimide prepolymer is at least by bimaleimide resin and allylic compound pre-polymerization
It forms, phosphorous allylic chemical combination shown in following structural formula (1) or structural formula (2) is contained in the allylic compound
Object:
Wherein, R1For the straight-chain alkyl-sub or substituted alkylene of C1-C10 or the aromatic series base of C6-C20.
2. resin combination according to claim 1, which is characterized in that the bimaleimide resin and allylic
The weight ratio of compound is 100:10-100.
3. resin combination according to claim 1, which is characterized in that the bimaleimide resin has following knot
Structure formula:
Wherein, R base is selected from least one of following structural:
4. resin combination according to claim 1, which is characterized in that also containing without phosphorus in the allylic compound
Allyl compound, the without phosphorus allyl compound are selected from diallyl bisphenol, diallyl bisphenol S, allyl phenol oxygen tree
One of rouge, allyl phenol urea formaldehyde or diallyl diphenyl ether or any two or more mixture, content are with total
100 mass of allylic compound point meter, contains 10-90 parts.
5. resin combination according to claim 1, which is characterized in that the epoxy resin is bisphenol A epoxide resin, double
Phenol F epoxy resin, phosphorous epoxy resin, nitrogen-containing epoxy thermoset, o-cresol formaldehyde epoxy resin, bisphenol-A phenolic epoxy resin, phenol
Novolac epoxy resin, cresol novolak epoxy, triphenyl methane epoxy resin, tetraphenyl ethane epoxy resin, biphenyl type ring
Oxygen resin, naphthalene nucleus type epoxy resin, dicyclopentadiene type epoxy resin, isocyanate-based epoxy resin, aralkyl line style phenolic aldehyde
Epoxy resin, polyphenyl ether modified epoxy resin, alicyclic based epoxy resin, glycidyl amine type epoxy resin, ethylene oxidic ester
The mixture of one or any of several in type epoxy resin.
6. resin combination according to claim 1, which is characterized in that the curing agent is amine compound, amide system
Compound, acid anhydrides based compound or phenol system compound.
7. resin combination according to claim 1, which is characterized in that the filler be inorganic filler or organic filler,
The inorganic filler is selected from nonmetal oxide, metal nitride, non-metal nitride, inorganic hydrate, inorganic salts, metal water
Close one of object or Phos or at least any two kinds of mixture；The organic filler be selected from polytetrafluorethylepowder powder,
One of polyphenylene sulfide or polyether sulfone powder or at least any two kinds of mixture.
8. a kind of prepreg, which is characterized in that add using in the described in any item resin combinations of claim 1-7 as above
Enter solvent dissolution and glue is made, reinforcing material is immersed in the glue, by the reinforcing material heat drying after dipping
Afterwards, the prepreg can be obtained.
9. a kind of laminate, which is characterized in that at least prepreg according to any one of claims 8 it is two-sided be covered with it is release
The laminate can be obtained in film, hot forming.
10. a kind of laminate, which is characterized in that covered in the single or double of at least one prepreg according to any one of claims 8
The laminate can be obtained in upper metal foil, hot forming.
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| CN114536923A (en) * | 2022-03-30 | 2022-05-27 | 常州中英科技股份有限公司 | Fluorine-containing resin-based high-thermal-conductivity high-frequency copper-clad plate with high dielectric constant |
| CN116004006A (en) * | 2022-12-27 | 2023-04-25 | 苏州生益科技有限公司 | Resin composition and use of the same |
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