CN106336662A - Thermosetting resin composition and prepreg and laminated board manufactured from same - Google Patents
Thermosetting resin composition and prepreg and laminated board manufactured from same Download PDFInfo
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- CN106336662A CN106336662A CN201610749043.9A CN201610749043A CN106336662A CN 106336662 A CN106336662 A CN 106336662A CN 201610749043 A CN201610749043 A CN 201610749043A CN 106336662 A CN106336662 A CN 106336662A
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- C—CHEMISTRY; METALLURGY
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- 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
- C08L79/085—Unsaturated 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
- 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
- B32B27/08—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 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
- B32B27/18—Layered products comprising a layer of synthetic resin characterised by the use of special additives
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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
- B32B33/00—Layered products characterised by particular properties or particular surface features, e.g. particular surface coatings; Layered products designed for particular purposes not covered by another single class
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- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L47/00—Compositions of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, at least one having two or more carbon-to-carbon double bonds; Compositions of derivatives of such polymers
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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
- 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
- C08L71/126—Polyphenylene oxides modified by chemical after-treatment
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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
- B32B2250/00—Layers arrangement
- B32B2250/40—Symmetrical or sandwich layers, e.g. ABA, ABCBA, ABCCBA
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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
- B32B2260/00—Layered product comprising an impregnated, embedded, or bonded layer wherein the layer comprises an impregnation, embedding, or binder material
- B32B2260/02—Composition of the impregnated, bonded or embedded layer
- B32B2260/021—Fibrous or filamentary layer
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- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B2260/00—Layered product comprising an impregnated, embedded, or bonded layer wherein the layer comprises an impregnation, embedding, or binder material
- B32B2260/04—Impregnation, embedding, or binder material
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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
- B32B2262/00—Composition or structural features of fibres which form a fibrous or filamentary layer or are present as additives
- B32B2262/10—Inorganic fibres
- B32B2262/101—Glass fibres
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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
- B32B2270/00—Resin or rubber layer containing a blend of at least two different polymers
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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
- B32B2307/00—Properties of the layers or laminate
- B32B2307/30—Properties of the layers or laminate having particular thermal properties
- B32B2307/306—Resistant to heat
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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
- B32B2307/00—Properties of the layers or laminate
- B32B2307/30—Properties of the layers or laminate having particular thermal properties
- B32B2307/306—Resistant to heat
- B32B2307/3065—Flame resistant or retardant, fire resistant or retardant
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- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B2307/00—Properties of the layers or laminate
- B32B2307/50—Properties of the layers or laminate having particular mechanical properties
- B32B2307/546—Flexural strength; Flexion stiffness
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- B32—LAYERED PRODUCTS
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- B32B2307/00—Properties of the layers or laminate
- B32B2307/50—Properties of the layers or laminate having particular mechanical properties
- B32B2307/558—Impact strength, toughness
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- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B2307/00—Properties of the layers or laminate
- B32B2307/70—Other properties
- B32B2307/726—Permeability to liquids, absorption
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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
- B32B2457/00—Electrical equipment
- B32B2457/08—PCBs, i.e. printed circuit boards
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- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L2201/00—Properties
- C08L2201/02—Flame or fire retardant/resistant
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- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
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- C08L2201/00—Properties
- C08L2201/08—Stabilised against heat, light or radiation or oxydation
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- C08L2203/00—Applications
- C08L2203/20—Applications use in electrical or conductive gadgets
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Abstract
The invention discloses a thermosetting resin composition. The thermosetting resin composition is prepared from a, 10-100 parts of hydrocarbon resin, b, 20-100 parts of maleimide ester, c, 0.1-8 parts of initiator, and d, 10-100 parts of allyl modified polyphenyl ether resin according to the solid weight. Maleimide ester with a multifunctional long chain structure and rigid imide rings is adopted and matched with the flexible hydrocarbon resin to form the thermosetting resin composition, maleimide ester and the hydrocarbon resin mutually act, and finally the thermosetting resin composition and a prepreg and laminated board manufactured from the same and used for a printed circuit have the advantages of excellent dielectric performance, heat resistance, adhesion, flame retardance, bending strength and toughness, high peel strength, low water absorption rate, excellent processing process performance and the like.
Description
Technical field
The present invention relates to a kind of compositions of thermosetting resin and the prepreg making using it and laminate, belong to electronics
Field of material technology.
Background technology
In recent years, with the continuous propulsion of information processing and information transfer high-speed high frequency technology, to tellite
Material proposes higher and higher requirement in terms of dielectric properties.In simple terms, that is, tellite material need to have relatively low
Dielectric constant and dielectric loss tangent, to reduce during high-speed transfer between the delay of signal, distortion and loss, and signal
Interference.Accordingly, it is desired to provide a kind of compositions of thermosetting resin, the printed circuit being made using this compositions of thermosetting resin
Plate material just can show substantially low low-k and low-dielectric loss in the signals transmission of high speed, high frequency
Cut.
The resin excellent in order to obtain dielectric properties, to dielectric properties, good hydrocarbon resin enters those skilled in the art
Go substantial amounts of research, such as polybutadiene, butadiene and the resins such as cinnamic copolymer.Substantial amounts of research show although
Hydrocarbon resin can provide good dielectric properties, but the flexibility due to hydrocarbon resin, non-polar carbon chains structure, lead to hydrocarbon
Rigidity deficiency, low intensity, poor heat resistance after resin solidification, the problems such as glass transition temperature is low, cementability is poor, in practical application
Yet suffering from a lot of problems needs to solve.For example, changed using hydrocarbon resin and pi-allyl in Chinese invention patent cn10544841b
Property the composition of phenolic resin make printed circuit board although improving the adhesive property of resin so that sheet material peel strength
It is improved, but still low, and the heat resistance of system is low.Hydrocarbon resin, alkene is adopted in Chinese patent cn104845363a
The bimaleimide resin composition of modified benzoxazine resins and pi-allyl modification makes printed circuit board, improves
Heat resistance and peel strength, but it is because the modified benzoxazine resins of pi-allyl and the modified bismaleimide of pi-allyl
Polyimide resin can introduce substantial amounts of hydroxyl, the dielectric properties of infringement system.
Therefore, a kind of compositions of thermosetting resin and the prepreg making using it and laminate are developed so as to have concurrently
Excellent heat resistance, intensity, hard and soft and dielectric properties are it is clear that have positive realistic meaning.
Content of the invention
The goal of the invention of the present invention is to provide a kind of compositions of thermosetting resin and the prepreg making using it and layer
Pressing plate.
To achieve the above object of the invention, the technical solution used in the present invention is: a kind of compositions of thermosetting resin, with solid
Weight meter, comprising:
(a) hydrocarbon resin: 10 ~ 100 parts；
(b) maleimide ester: 20 ~ 100 parts；
(c) initiator: 0.1 ~ 8 part；
(d) pi-allyl modified polyphenylene ether resin: 10 ~ 100 parts；
The structure of described maleimide ester is as follows:, wherein:
N is 1 ~ 10, x is 1 ~ 10 for 2 ~ 20, y；
Ar is selected from one of following structural:
、、、、、、；
R for carbon number be less than or equal to 5 alkyl, or phenyl, aminomethyl phenyl, xenyl, n-propyl phenyl, isopropyl phenyl,
Tert-butyl-phenyl, ethenylphenyl, 4- maleimidophenyl, p-nitrophenyl.
Above, 2 and more than 2 dimaleoyl iminos and 2 and 2 are contained in a molecule of described maleimide ester
Above ester group.
Component (a) hydrocarbon resin, component (b) maleimide ester, the ratio of component (d) pi-allyl Noryl, all
Can be adjusted according to specific practical application, when applying in the tool that mechanical performance, plate heat resistance and peel strength are had high demands
During body field, can suitably increase the ratio of component (b) maleimide ester；When applying high to dielectric properties and toughness reguirements
Specific field when, can suitably increase the ratio of component (a) hydrocarbon resin；When being especially situated between to heat resistance, dielectric properties
When electrical loss tangent value requires higher, can suitably increase the ratio of component (d) pi-allyl Noryl.
The value of ratio x:y of x and y in the structure of described maleimide ester can also be according to specific practical application
Adjustment, can be 0.1,0.3,0.5,1,5,10,15,20 equivalences.When applying in the mechanical performance to laminate, heat resistance and stripping
From intensity requirement high specific field when, can by increase x construction unit ratio.Increase the ratio of x, molecule can be increased
The amount of imide ring in structure, thus be conducive to heat resistance and the raising of adhesive property.
In described maleimide ester structure, r base is vinyl or ethenylphenyl or 4- maleimidophenyl etc. contain
There is the structure of unsaturated double-bond.When r base is vinyl, in the molecular structure of maleimide ester in such scheme further
Introduce flexible vinyl reactive functionality, while increasing the crosslink density of resin system, improve heat resistance, do not affect resin
The toughness of system.When r base is ethenylphenyl or 4- maleimidophenyl, the maleimide ester in such scheme
In molecular structure, the further phenyl ring introducing rigidity or maleimide ring, can improve the rigidity of resin system further
And heat resistance.
Described initiator is the compound referring to be resolved into free radical by heat energy, can be used for causing alkenes, double vinyl monomer
Radical polymerization and copolymerization it can also be used to the crosslinking curing of unsaturated polyester (UP) and high molecular crosslink reaction.Described
Initiator can be azo-initiator, peroxide initiator, and redox type initiators are preferably as follows one of initiator
Or several: cumyl peroxide, di-t-butyl peroxide, peroxidized t-butyl perbenzoate, di-cyclohexylperoxy di-carbonate,
Isopropyl benzene hydroperoxide, azodiisobutyronitrile.
Preferably, in described maleimide ester structure, r base is vinyl, ethenylphenyl or 4- dimaleoyl imino benzene
Base.Contain unsaturated double-bond group in maleimide ester structure.
Preferably, in described maleimide ester structure, the ratio of x and y is 5:1 ~ 10:1.When the ratio of x and y is less than 5:1
When, the maleimide structure in Malaysia elder generation imines ester is less, and heat resistance and peel strength all can be affected；Ratio as x and y
When value is more than 10:1, the maleimide structure in Malaysia elder generation imines ester is more, and toughness can be under some influence；Ratio as x and y
Being worth is 5:1 ~ 10:1 heat resistance and toughness is attained by optimum.
Preferably, described pi-allyl modified polyphenylene ether resin is 20 ~ 60 parts.Preferably, described component (d) pi-allyl is modified
The molecular weight of polyphenylene oxide is less than 5000.Component (d) pi-allyl Noryl can optimize heat resistance and dielectric properties further,
Especially there is positive effect to the dielectric loss tangent value reducing resin system, but add and excessively can limit resin system bonding
The raising of performance.
In order to obtain more excellent heat resistance, peel strength and mechanical performance, preferably a kind of thermosetting resin combination
Thing, with solid weight meter, comprising:
(a) hydrocarbon resin: 10 ~ 25 parts；
(b) maleimide ester: 50 ~ 100 parts；
(c) initiator: 0.1 ~ 8 part；
(d) pi-allyl modified polyphenylene ether resin: 10 ~ 40 parts.
In order to obtain more excellent dielectric properties, heat resistance, moisture pick-up properties, preferably a kind of compositions of thermosetting resin,
With solid weight meter, comprising:
(a) hydrocarbon resin: 10 ~ 25 parts；
(b) maleimide ester: 20 ~ 60 parts；
(c) initiator: 0.1 ~ 8 part；
(d) pi-allyl modified polyphenylene ether resin: 60 ~ 90 parts.
Preferably, described hydrocarbon resin be selected from butadiene styrene resin, polybutadiene, polyisobutene resin, polyprene,
Polystyrene, 2- methylated polystyrene, 3- methylated polystyrene, 4- methylated polystyrene, 2,4- diisopropyl polystyrene, 2,
One or more of 4- diformazan base polystyrene, SB, styrene-isobutene copolymer；Described
The number-average molecular weight of hydrocarbon resin is less than 11000 and its contents of ethylene is more than 60%.Preferably, hydrocarbon in technique scheme
The number-average molecular weight of resin is less than 7000, and is liquid at room temperature.Preferably, in technique scheme, hydrocarbon resin is butylbenzene
One or more of resin, polybutadiene, polyisobutene resin.
In technique scheme, with solid weight meter, also include 1 ~ 100 part of component (e), described component (e) is selected from alkene
Modified benzoxazine resins, pi-allyl modified bismaleimide, cyanate ester resin, vinyl modified phenolic resin, alkene
One of hydrocarbon copolymer, Petropols, epoxy resin, unsaturated polyester resin, mono-component polyurethane resin or arbitrarily several
Mixture.
Described pi-allyl modified benzoxazine resins can be pi-allyl modified bisphenol a type Benzoxazine, pi-allyl modification
Bis-phenol g type Benzoxazine, pi-allyl modified bisphenol s type Benzoxazine, bis-phenol two amine type Benzoxazine, pi-allyl modified bicyclic penta
One of diene phenolic Benzoxazine or arbitrarily several mixtures.Preferably, described pi-allyl modified benzoxazine resins
Adding proportion be 1 ~ 20 weight portion.Add appropriate pi-allyl modified benzoxazine resins and can optimize heat resistance further
And adhesive property, but add and excessively the dielectric properties of resin system and toughness can be had undesirable effect.
Described pi-allyl modified bismaleimide can be by allyl compound and maleimide resin prepolymerization
The prepolymer producing, described allyl compound is selected from allyl ether compound, allyl phenoxy resin, pi-allyl phenolic aldehyde tree
One or more of fat, diallyl bis-phenol a, diallyl bis-phenol s；Described maleimide resin is selected from 4,4 '-hexichol
Methane bimaleimide resin, 4,4 '-Diphenyl Ether Bismaleimide resin, 4,4 '-hexichol isopropyl BMI
One or more of resin, 4,4 '-diphenyl sulphone (DPS) bimaleimide resin.Preferably, described pi-allyl modification span carrys out acyl
The number-average molecular weight of imines is 2000 ~ 5000g/mol.Add appropriate pi-allyl modified bismaleimide resin and can enter one
Step optimizes heat resistance and adhesive property, but adds and excessively the dielectric properties of resin system can be had undesirable effect.
Described cyanate ester resin refers to the compound containing cyanic acid ester group in structure, can be Bisphenol A Dicyanate Resin, double
Phenol g cyanate ester resin, bis-phenol m cyanate ester resin, dicyclopentadiene type ethylene rhodanate resin, o-cresol aldehyde type epoxy resin, benzene
One or more of phenolic cyanate ester resin, Cyanate Ester Resin Modified with Polyphenylene Oxide.Preferably, the interpolation of described cyanate ester resin
Ratio is 10 ~ 30 weight portions.Add appropriate cyanate ester resin can optimize further the heat resistance of resin system, cementability and
Dielectric properties, but add the decline that excessively can lead to the wet-hot aging performance of resin system.
Described vinyl modified phenolic resin can be pi-allyl modified maleimide base phenolic resin, pi-allyl modification
Phenolic resin, dicyclopentadiene-second dilute benzyl phenylate etc..Described pi-allyl modified maleimide base phenolic resin be have as
The resin of lower structure:
Or
；Wherein, x be 2 ~ 20, y be 1 ~ 10, s be 1 ~ 10.
Described Petropols can be alicyclic petroleum resin (ecpe), aromatic petroleum resin (c9), aliphatic/fragrance
One of race's copolymerized petroleum resin (c5/c9) or arbitrarily several mixtures.Preferably, the molecular weight of described Petropols
For 1000 ~ 3000g/mol.Preferably, the adding proportion of described Petropols is 5 ~ 25 weight portions.Add appropriate Petropols
Can optimize further resin system dielectric properties and adhesive property while moreover it is possible to improve resin system mobile performance change
Kind processing performance.
Described epoxy resin refers to the compound containing epoxy radicals, can be Epoxy Resin of Bisphenol A, bis-phenol g epoxy resin,
Phosphorous epoxy resin, nitrogen-containing epoxy thermoset, o-cresol formaldehyde epoxy resin, bis-phenol a novolac epoxy resin, phenol novolac epoxy tree
Fat, cresol novolak epoxy, triphenyl methane 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, poly-
In phenylate modified epoxy, alicyclic based epoxy resin, glycidyl amine type epoxy resin, glycidyl ester type epoxy resin
A kind of or arbitrarily several mixtures.Epoxy resin is added in compositions of thermosetting resin of the present invention, mainly ring
Ester group reaction in epoxy radicals in oxygen tree fat and component (b) maleimide ester.After adding epoxy resin, component (b) horse
Come effect, the ester group in component (b) maleimide ester molecular structure and epoxy resin that imide ester serves a bridge formation
Reaction, the double bond reaction in the dimaleoyl imino in structure and component (a) hydrocarbon resin, thus by epoxy resin and hydrocarbon tree
The advantage of fat concentrates in a kind of resin combination.In the resin combination adding epoxy resin, can further add
Curing accelerator, described curing accelerator can selected from dimethyl aminopyridine, tertiary amine and its salt, imidazoles, organic metal salt, three
Phenylphosphine and its salt etc..Preferably, epoxy resin is polyphenyl ether modified epoxy resin, polyphenyl ether modified epoxy mentioned here
Resin refers to the resin after the terminal epoxy of polyphenylene oxide.Preferably, the adding proportion of epoxy resin is 10 ~ 50 weight portions.
Add processing characteristics and the mechanical performance that appropriate epoxy resin can optimize resin system further.
Described unsaturated polyester resin or mono-component polyurethane resin, preferred adding proportion is 5 ~ 25 weight portions.Add
Appropriate unsaturated polyester resin or mono-component polyurethane resin can optimize adhesive property and the toughness of resin system, but add
Dosage excessively can have undesirable effect to the heat resistance of resin system and dielectric properties.
On the basis of technique scheme, described compositions of thermosetting resin also includes the component (f) of 1 ~ 80 weight portion
Fire retardant.Described fire retardant can be bromide fire retardant, phosphorus flame retardant, nitrogenated flame retardant, organic silicon fibre retardant, organic metal
Salt fire retardant, inorganic flame retardant etc..Wherein, bromide fire retardant can be deca-BDE, TDE, bromination benzene second
Alkene or tetrabromo-phthalic diformamide.Phosphorus flame retardant can be Phos, phosphate compound, phosphinic acid compounds, phosphinic acids
Compound, phosphine oxide compound and 9,10- dihydro -9 oxa- -10- phosphine miscellaneous phenanthrene -10- oxide, 10-(2,5 dihydroxy benzenes
Base) -9,10- dihydro -9 oxa- -10- phosphine miscellaneous phenanthrene -10- oxide, 10- phenyl -9,10- dihydro-9-oxy miscellaneous -10- phosphine phenanthrene -10-
The organophosphorus compounds such as oxide, three (2,6 3,5-dimethylphenyl) phosphine, phosphine nitrile.Nitrogenated flame retardant can be triaizine compounds, cyanogen
Uric acid compound, isocyanide acid compound, phenthazine etc..Organic silicon fibre retardant can be organic silicone oil, organic silicon rubber, organosilicon
Resin etc..Organic metal fire retardant can be ferrocene, acetylacetone metal complex, organic metal carbonyls etc..No
Machine fire retardant can be aluminium hydroxide, magnesium hydroxide, aluminum oxide, barium monoxide etc..The fire retardant being added can be according to laminate
Concrete application field and select, the application that halogen is required, preferably non-halogen fire retardant, such as phosphorous or nitrogenous resistance
Combustion agent.Preferably, when selecting phosphonium flame retardant, nitrogen can be formed with the nitrogen of maleimide ester in technique scheme
Phosphorus cooperative flame retardant, improves flame retarding efficiency.Preferably, the fire retardant addition in above-mentioned compositions of thermosetting resin is 5 ~ 50 weight
Part.
On the basis of technique scheme, described compositions of thermosetting resin also includes the component (g) of 1 ~ 100 weight portion
Filler.Described inorganic filler is selected from powdered quartz, fused silica, preparing spherical SiO 2, aluminum oxide, hydroxide
Aluminium, aluminium nitride, boron nitride, titanium dioxide, strontium titanates, barium titanate, barium sulfate, talcum powder, calcium silicates, calcium carbonate, mica, poly- four
One or more of PVF, Graphene filler, the particle diameter of above-mentioned inorganic filler is 0.3～20 micron, preferentially select 0.5～
5 microns.In resin combination inorganic filler can direct plunge into previously prepared filler dispersion liquid or make lotion put into tree
In oil/fat composition.Preferably, the inorganic filler addition in above-mentioned compositions of thermosetting resin is 10 ~ 50 weight portions.
In above-mentioned compositions of thermosetting resin, can also be added according to actual feelings and use silane coupler, pigment, emulsification
In the additives such as agent, dispersant, antioxidant, antistatic additive, heat stabilizer, ultra-violet absorber, colouring agent, lubricant one
Plant or several.
Above-mentioned compositions of thermosetting resin, can be used for manufacturing prepreg, laminate, printed circuit board, semiconductor close
Closure material, lamination adhering film, binding agent, resin cast material, conductive paste etc..
The present invention is claimed the prepreg making using above-mentioned resin combination simultaneously, and above-mentioned resin combination is used
Glue is made in solvent dissolving, then reinforcing material is immersed in above-mentioned glue；After reinforcing material heat drying after impregnating, that is,
Can get described prepreg.
Described solvent selected from acetone, butanone, toluene, methylisobutylketone, n, n- dimethylformamide, n, n- dimethyl second
One or more of acid amides, EGME, propylene glycol monomethyl ether.Described reinforcing material can adopt natural fiber, You Jihe
Become fiber, organic fabric or inorganic fabric.
The present invention is claimed the laminate making using above-mentioned resin combination simultaneously, at one by above-mentioned semi-solid preparation
The single or double of piece is covered with metal forming, or will at least 2 by above-mentioned prepreg be superimposed after, be covered with its single or double
Metal forming, hot forming, you can obtain described laminate.
The quantity of described prepreg be laminate thickness according to customer requirement to determine, can use one or more.Institute
State metal forming, can be Copper Foil or aluminium foil, their thickness is not particularly limited.
Because technique scheme is used, the present invention compared with prior art has the advantage that
1. present invention employs the maleimide ester with multifunctional backbone and rigid imide ring, cooperation has flexibility
Hydrocarbon resin form thermoset composition, both interact, and maleimide ester improves the heat resistance, just of hydrocarbon resin
Property, problem that intensity is not enough, hydrocarbon resin improves the not enough problem of maleimide ester toughness, so that composition has concurrently
Excellent heat resistance, intensity, hard and soft；Meanwhile, using pi-allyl modified polyphenylene ether resin, further improve Jie of solidfied material
Electrical property, finally makes the compositions of thermosetting resin of the present invention and its printed circuit prepreg of preparation and laminate simultaneous
Have excellent dielectric properties, heat resistance, cementability, anti-flammability, bending strength, toughness, peel strength is high, water absorption rate is low, plus
The features such as work processing performance is excellent, obtains unexpected technique effect；
2. the present invention adopt component (b) maleimide ester molecular structure in dimaleoyl imino and ester group improve hydrocarbon
The adhesive property of the system of resin, improves the peel strength between laminate copper foil layer and resin bed, has no effect on resin simultaneously
The dielectric properties of system；Additionally, the imide ring of the multifunctional backbone of component (b) maleimide ester and rigidity, carry
The resistance to heat energy of high resin system, rigidity and mechanical strength；The maleimide ester of backbone is conducive to improving component (a) carbon
Tacky characteristic after prepreg made by hydrogen resin, can also reduce the shrinkage factor after the solidification of component (a) hydrocarbon resin simultaneously；
3. the non-polar conformations of component (a) hydrocarbon resin that the present invention adopts contribute to excellent dielectric properties for resin system,
Its flexible carbon-chain structure can improve the toughness of maleimide ester solidfied material；
4. component (d) the pi-allyl modified polyphenylene ether resin that the present invention adopts can optimize heat resistance and dielectric properties further,
Especially there is positive effect to the dielectric loss tangent value reducing resin system.
Specific embodiment
With reference to embodiment, the invention will be further described:
Synthesis example 1～7 is the synthesis of maleimide ester of the present invention, and embodiment 1～12 and comparative example 1～6 are offers of the present invention
The preparation of compositions of thermosetting resin and evaluation of physical property.
Synthesis example 1
In the flask being provided with thermometer, condenser pipe, agitator put into n- (4- hydroxy phenyl) maleimide (190g,
1mol), phenol (94g, 1mol, m94) and oxalic acid (10g), after mixing and stirring, are placed in 70 DEG C of water bath with thermostatic control；Then,
Under agitation, with the 0.5 hour dropping formalin in flask (150ml, the ratio of phenol/aldehyde is 1/0.8)；After adding formaldehyde,
70 DEG C of temperature and stirring condition is maintained to react 15 hours；Then, with 400ml acetone by product dissolved dilution, Ran Houzai
The aqueous solution precipitation reaction product of the methyl alcohol with 40%；Dissolving-precipitation operation 3～5 times more than repeating, is filtered, is separated, being done
Dry obtain pure maleimide phenolic aldehyde (p-1).
Prepared maleimide phenolic aldehyde (p-1) 100g of said method and methyl isobutyl ketone solvent 500g is taken to be placed in flask
In be sufficiently mixed dissolving, by the logical nitrogen that reduces pressure in reaction system, and system temperature is controlled at 65 DEG C；Then, put into 140g benzene
Formyl chloride (1mol, m140.5), then, dripped 20% sodium hydroxide solution 210g toward in system with 3 hours, after completion of dropping,
Reaction 3 hours is maintained at 65 DEG C；After the completion of reaction, it is separated off water layer；Then again toward in system add water, stirring and washing,
It is separated off water layer；Repeat above cleaning operation 3～5 times；Then vacuumize decompression to remove methyl iso-butyl ketone (MIBK), obtain as follows
The maleimide ester (b-1) of structure:；Wherein, ar is:, r is phenyl；
Wherein, the ratio for 1 ~ 10, x and y for the n is 1:1.
Synthesis example 2
The method of the real synthesis example 1 of reference, the maleimide ester (b-2) of prepared following structure:
；Wherein, ar is
, r is phenyl；
Wherein, the ratio for 1 ~ 10, x and y for the n is 0.5:1.
Synthesis example 3
The method of reference synthesis example 1, the maleimide ester (b-3) of prepared following structure:
；Wherein, ar is:, r is dimaleoyl imino benzene
Base；
Wherein, the ratio for 1 ~ 10, x and y for the n is 0.1:1.
Synthesis example 4
The method of reference synthesis example 1, the maleimide ester (b-4) of prepared following structure:
；Wherein, ar is, r is ethenylphenyl；
Wherein, the ratio for 1 ~ 10, x and y for the n is 5:1.
Synthesis example 5
The method of reference synthesis example 1, the maleimide ester (b-5) of prepared following structure:
；Wherein, ar is, r is ethyl；
Wherein, the ratio for 1 ~ 10, x and y for the n is 10:1.
Synthesis example 6
The method of reference synthesis example 1, the maleimide ester (b-6) of prepared following structure:
；Wherein, ar is, r is methyl；
Wherein, the ratio for 1 ~ 10, x and y for the n is 20:1.
Synthesis example 7
The method of reference synthesis example 1, the maleimide ester (b-7) of prepared following structure:
；Wherein, ar is, r is maleimidophenyl；
Wherein, the ratio for 1 ~ 10, x and y for the n is 1:1.
Embodiment 1～12 and comparative example 1～7
Formula according to Tables 1 and 2, each component is mixed the resin solution making 65%, glass-fiber-fabric is used as increasing
Then the glass-fiber-fabric being impregnated with is heated 3 ~ 10 minutes in 175 DEG C of baking oven and makes by strong material impregnation above above-mentioned resin solution
Printed circuit pre-preg material, then makes laminate under the following conditions, and evaluates its dielectric properties, resistance to by following methods
The performances such as hot property, adhesive property, toughness, intensity, result is shown in Tables 1 and 2.
<laminate manufacturing conditions>
Base material: ordinary electronic level 2116 glass-fiber-fabric；
The number of plies: 8；
Sheet metal thickness after shaping: 1.0mm；
Pre-preg semi-solid preparation condition: 175 DEG C/5min；
Condition of cure: 150 DEG C/60min+220 DEG C/120min.
<mensure of dielectric constant and dielectric loss tangent>dielectric constant uses flat board according to ipc-tm-650 2.5.5.9
Method, measures the dielectric constant under 10ghz, dielectric loss tangent: uses flat band method according to ipc-tm-650 2.5.5.9, measures
Dielectric loss factor under 10ghz.
<peel strength>uses the peel strength of laminate to characterize the adhesive property of compositions of thermosetting resin, according to
" after thermal stress " experiment condition in ipc-tm-6502.8 method, test metal cladding peel strength.
<water absorption rate>is measured according to the method for ipc-tm-6502.6.2.1.
<thermally stratified layer time t-288>measures according to ipc-tm-6502.4.24.1 method.
<glass transition temperature>shows differential scanning calorimetry (dsc), according to ipc-tm-650 2.4.25 defined
Dsc method is measured.
<bending strength>using universal testing machine test material bend loading effect under rupture or reach regulation curved
The maximum stress that can bear during square, this stress is maximum (normal) stress during bending, with mpa(MPa) as unit.
<drop impact toughness>characterizes the toughness of laminate with this, using Apparatus for Impacting at low-temp, Apparatus for Impacting at low-temp height of the fall 45cm, under
Fall weight weight 1kg.Good and bad according to following Standard Judgement toughness: cross shape on laminate for the drop hammer is more clear
Clear, illustrate that the toughness of product is better；Cross shape is clear, good toughness is described, is designated as character ◎；Cross shape obscures, and illustrates tough
Property is poor, is designated as character δ；Cross, between clear and fuzzy, is designated as character.
<anti-flammability>measures according to ul94 vertical combustion.
Table 1
Table 2
The footnote of Tables 1 and 2:
A-1: butadiene styrene resin (sartomer, ricon 100)
A-2: polybutadiene (sartomer, ricon 153h)
The maleimide ester (b-1) being obtained in b-1: synthesis example 1
The maleimide ester (b-2) being obtained in b-2: synthesis example 2
The maleimide ester (b-3) being obtained in b-3: synthesis example 3
The maleimide ester (b-4) being obtained in b-4: synthesis example 4
The maleimide ester (b-5) being obtained in b-5: synthesis example 5
The maleimide ester (b-6) being obtained in b-6: synthesis example 6
C: initiator, cumyl peroxide
D: pi-allyl Noryl
E-1: pi-allyl modified bismaleimide (is made by oneself)
E-2: Petropols (eastman, c9resin)
E-3: pi-allyl modification Malaysia pn(self-control)
F: fire retardant, phenoxyphosphazene compound (Japan's big tomb chemistry, spb-100)
G: filler, ball-type silicon powder (NEC chemistry, sfp-30m)
P-1: maleimide phenolic aldehyde (the intermediate resin being obtained in embodiment 1)
Knowable to the result of Tables 1 and 2:
Embodiment 1, compared to the comparative example 1 simply using hydrocarbon resin, has more preferable heat resistance, bending strength, peels off by force
Degree, process industrial art performance, maintain relatively low dielectric properties.
Embodiment 1 is compared to the comparative example 2 of the Benzoxazine (boz) modified using pi-allyl and hydrocarbon resin combination, tool
There are more preferable heat resistance, dielectric properties and bending strength.
Embodiment 1 is compared to the comparative example of the BMI (bmi) modified using pi-allyl and hydrocarbon resin combination
3, there are more preferable dielectric properties.
Embodiment 1, compared to the comparative example 4 of the phenolic resin modified using pi-allyl and hydrocarbon resin combination, has more preferably
Heat resistance, dielectric properties and bending strength.
Embodiment 1, compared to the comparative example 5 using maleimide phenolic aldehyde and hydrocarbon resin combination, has more preferable dielectric
Performance.
Embodiment 1, compared to the comparative example 6 using pure maleimide ester, has more preferable dielectric properties, toughness.
Embodiment 1 employs the maleimide ester of greater proportion compared to embodiment 8, have more preferable heat resistance,
Bending strength, peel strength, but, embodiment 8 there are more preferable dielectric properties.
Embodiment 1 is compared with embodiment 2, has the x construction unit of greater proportion in molecular structure, has more excellent resistance to
Hot heat resistance, bending strength, peel strength, but, embodiment 2 there are more preferable dielectric properties.Embodiment 6 and embodiment
5 compare, in molecular structure x construction unit more although the performance such as heat resistance, peel strength, bending strength more preferably, but its
Toughness relative deficiency.
Embodiment 1 is compared with embodiment 7, and the r substituent in molecular structure is the group containing double bond structure, has more preferably
Heat resistance, bending strength, peel strength.
Embodiment 9 is compared with embodiment 1, with the addition of more pi-allyl Noryls in composition, has preferably
Dielectric properties, but peel strength is low.
Embodiment 10 is compared with embodiment 1, with the addition of pi-allyl modified maleimide resin in composition, has more preferably
Bending strength, heat resistance, but do not affect dielectric properties.
Embodiment 11 is compared with embodiment 1, with the addition of the Petropols of part in composition, has more preferable dielectricity
Energy.
Embodiment 12 is compared with embodiment 1, with the addition of pi-allyl modification Malaysia phenolic resin, have preferably in composition
Bending strength, heat resistance, but do not affect dielectric properties.
Embodiment 1～12, compared to the comparative example 1～6 simply using hydrocarbon resin, has excellent heat resistance, bending concurrently
Intensity, peel strength, process industrial art performance, maintain relatively low dielectric properties, especially have excellent dielectric loss
Tangent value.
In sum, using the compositions of thermosetting resin of the present invention and its printed circuit prepreg of preparation and layer
Pressing plate, has excellent dielectric properties, heat resistance, anti-flammability, bending strength, toughness concurrently, and peel strength is high, water absorption rate is low, plus
The features such as work processing performance is excellent.
Claims (10)
1. a kind of compositions of thermosetting resin is it is characterised in that with solid weight meter, comprising:
(a) hydrocarbon resin: 10 ~ 100 parts；
(b) maleimide ester: 20 ~ 100 parts；
(c) initiator: 0.1 ~ 8 part；
(d) pi-allyl modified polyphenylene ether resin: 10 ~ 100 parts；
The structural formula of described maleimide ester is:, wherein:
N is 1 ~ 10, x is 1 ~ 10 for 2 ~ 20, y；
Ar is selected from one of following structural:
、、、、、、；
R for carbon number be less than or equal to 5 alkyl, or phenyl, aminomethyl phenyl, xenyl, n-propyl phenyl, isopropyl phenyl,
Tert-butyl-phenyl, ethenylphenyl, 4- maleimidophenyl, p-nitrophenyl.
2. compositions of thermosetting resin according to claim 1 it is characterised in that: r in described maleimide ester structure
Base is vinyl, ethenylphenyl or 4- maleimidophenyl.
3. compositions of thermosetting resin according to claim 1 it is characterised in that: x in described maleimide ester structure
Ratio with y is 5:1 ~ 10:1.
4. compositions of thermosetting resin according to claim 1 it is characterised in that: described pi-allyl modified polyphenylene ether resin
For 20 ~ 60 parts.
5. compositions of thermosetting resin according to claim 1 it is characterised in that: with solid weight meter, comprising:
(a) hydrocarbon resin: 10 ~ 25 parts；
(b) maleimide ester: 50 ~ 100 parts；
(c) initiator: 0.1 ~ 8 part；
(d) pi-allyl modified polyphenylene ether resin: 10 ~ 40 parts.
6. compositions of thermosetting resin according to claim 1 it is characterised in that: with solid weight meter, comprising:
(a) hydrocarbon resin: 10 ~ 25 parts；
(b) maleimide ester: 20 ~ 60 parts；
(c) initiator: 0.1 ~ 8 part；
(d) pi-allyl modified polyphenylene ether resin: 60 ~ 90 parts.
7. compositions of thermosetting resin according to claim 1 it is characterised in that: described hydrocarbon resin be selected from butylbenzene tree
Fat, polybutadiene, polyisobutene resin, polyprene, polystyrene, 2- methylated polystyrene, 3- methyl polyphenyl second
Alkene, 4- methylated polystyrene, 2,4- diisopropyl polystyrene, 2,4- diformazan base polystyrene, styrene butadiene copolymers
One or more of thing, styrene-isobutene copolymer；The number-average molecular weight of described hydrocarbon resin be less than 11000 and its
Contents of ethylene is more than 60%.
8. compositions of thermosetting resin according to claim 1 it is characterised in that: with solid weight meter, also include 1 ~ 100
The component (e) of part, described component (e) is selected from pi-allyl modified benzoxazine resins, pi-allyl modified bismaleimide, cyanic acid
Ester resin, vinyl modified phenolic resin, olefin copolymer, Petropols, epoxy resin, unsaturated polyester resin, one pack system
One of polyurethane resin or arbitrarily several mixtures.
9. a kind of prepreg being made using any one compositions of thermosetting resin as described in claim 1 ~ 8, it is special
Levy and be: glue is made in any one the compositions of thermosetting resin solvent dissolving described in claim 1 ~ 8, then will increase
Strong material is immersed in above-mentioned glue；After reinforcing material heat drying after impregnating, you can obtain described prepreg.
10. a kind of using compositions of thermosetting resin as claimed in claim 1 make laminate it is characterised in that: one
Metal forming is covered with by the single or double of the prepreg described in claim 9, or will at least 2 by claim 9 institute
After the prepreg superposition stated, it is covered with metal forming, hot forming in its single or double, you can obtain described laminate.
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