CN106336662B - A kind of compositions of thermosetting resin and prepreg and laminate using its making - Google Patents

A kind of compositions of thermosetting resin and prepreg and laminate using its making Download PDF

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CN106336662B
CN106336662B CN201610749043.9A CN201610749043A CN106336662B CN 106336662 B CN106336662 B CN 106336662B CN 201610749043 A CN201610749043 A CN 201610749043A CN 106336662 B CN106336662 B CN 106336662B
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resin
compositions
parts
thermosetting resin
allyl
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CN106336662A (en
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何继亮
崔春梅
马建
肖升高
陈诚
罗鹏辉
易强
储正振
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Suzhou Shengyi Technology Co Ltd
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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
    • C08L79/085—Unsaturated polyimide precursors
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B15/00—Layered products comprising a layer of metal
    • B32B15/04—Layered products comprising a layer of metal comprising metal as the main or only constituent of a layer, which is next to another layer of the same or of a different material
    • B32B15/08—Layered products comprising a layer of metal comprising metal as the main or only constituent of a layer, which is next to another layer of the same or of a different material of synthetic resin
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • 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
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B27/00—Layered products comprising a layer of synthetic resin
    • B32B27/18—Layered products comprising a layer of synthetic resin characterised by the use of special additives
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • 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
    • C—CHEMISTRY; METALLURGY
    • 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
    • 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
    • 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
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B2260/00—Layered product comprising an impregnated, embedded, or bonded layer wherein the layer comprises an impregnation, embedding, or binder material
    • B32B2260/02—Composition of the impregnated, bonded or embedded layer
    • B32B2260/021—Fibrous or filamentary layer
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B2260/00—Layered product comprising an impregnated, embedded, or bonded layer wherein the layer comprises an impregnation, embedding, or binder material
    • B32B2260/04—Impregnation, embedding, or binder material
    • 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
    • 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
    • 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
    • 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
    • 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
    • B32B2307/50—Properties of the layers or laminate having particular mechanical properties
    • B32B2307/546—Flexural strength; Flexion stiffness
    • 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
    • B32B2307/50—Properties of the layers or laminate having particular mechanical properties
    • B32B2307/558—Impact strength, toughness
    • 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
    • B32B2307/70—Other properties
    • B32B2307/726—Permeability to liquids, absorption
    • 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
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L2201/00—Properties
    • C08L2201/02—Flame or fire retardant/resistant
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L2201/00—Properties
    • C08L2201/08—Stabilised against heat, light or radiation or oxydation
    • 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
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L2205/00—Polymer mixtures characterised by other features
    • C08L2205/03—Polymer mixtures characterised by other features containing three or more polymers in a blend

Abstract

The invention discloses a kind of compositions of thermosetting resin, with solid weight meter, including：(a) hydrocarbon resin：10 ~ 100 parts；(b) maleimide ester：20 ~ 100 parts；(c) initiator：0.1 ~ 8 part；(d) allyl modified polyphenylene ether resin：10 ~ 100 parts.Present invention employs the maleimide esters with multifunctional backbone and rigid imide ring, there is hydrocarbon resin flexible to form thermoset composition for cooperation, the two interacts, it is final that the compositions of thermosetting resin of the present invention and its printed circuit prepreg and laminate of preparation is made to have both excellent dielectric properties, heat resistance, cementability, anti-flammability, bending strength, toughness, the features such as peel strength is high, water absorption rate is low, and process industrial art performance is excellent.

Description

A kind of compositions of thermosetting resin and prepreg and laminate using its making
Technical field
The present invention relates to a kind of compositions of thermosetting resin and using prepreg and laminate that it makes, belong to electronics Field of material technology.
Background technology
In recent years, as information processing and information transmit the continuous propulsion of high-speed high frequency technology, to tellite Material proposes increasingly higher demands in terms of dielectric properties.In simple terms, i.e., tellite material need to have it is relatively low Dielectric constant and dielectric loss tangent, when reducing high-speed transfer between the delay, distortion and loss and signal of signal Interference.Accordingly, it is desired to provide a kind of compositions of thermosetting resin, the printed circuit made using this compositions of thermosetting resin Plate material can show substantially low low-k and low-dielectric loss just in the signals transmission of high speed, high frequency It cuts.
The excellent resin of dielectric properties in order to obtain, those skilled in the art to the good hydrocarbon resin of dielectric properties into The resins such as a large amount of research, such as the copolymer of polybutadiene, butadiene and styrene are gone.Although it is a large amount of studies have shown that Hydrocarbon resin is capable of providing good dielectric properties, but due to the flexibility of hydrocarbon resin, non-polar carbon chains structure, causes hydrocarbon Rigidity is insufficient after resin solidification, intensity is low, poor heat resistance, the problems such as glass transition temperature is low, cementability is poor, in practical application There are still many problems to need to solve.For example, being changed using hydrocarbon resin and allyl in Chinese invention patent CN10544841B Property phenolic resin composition make printed circuit board, although improving the adhesive property of resin so that plank peel strength It is improved, but still relatively low, and the heat resistance of system is low.Using hydrocarbon resin, alkene in Chinese patent CN104845363A The bimaleimide resin composition that modified benzoxazine colophony and allyl are modified makes printed circuit board, improves Heat resistance and peel strength, but because the bismaleimide that benzoxazine colophony and allyl that allyl is modified are modified Polyimide resin can introduce a large amount of hydroxyl, damage the dielectric properties of system.
Therefore, a kind of compositions of thermosetting resin and prepreg and laminate using its making are developed, it is made to have both Excellent heat resistance, intensity, hard and soft and dielectric properties, it is clear that there is positive realistic meaning.
Invention content
The goal of the invention of the present invention is to provide a kind of compositions of thermosetting resin and prepreg and layer using its making Pressing plate.
To achieve the above object of the invention, the technical solution adopted by the present invention is：A kind of compositions of thermosetting resin, with solid Weight meter, including：
(a) hydrocarbon resin：10 ~ 100 parts；
(b) maleimide ester：20 ~ 100 parts；
(c) initiator：0.1 ~ 8 part；
(d) allyl modified polyphenylene ether resin：10 ~ 100 parts；
The structure of the maleimide ester is as follows：, wherein：
It is 2 ~ 20, y is 1 ~ 10 that n, which is 1 ~ 10, x,；
The one kind of Ar in following structural：
、、、、、、；
R is alkyl or phenyl, aminomethyl phenyl, xenyl, n-propyl phenyl, cumene of the carbon atom number less than or equal to 5 Base, tert-butyl-phenyl, ethenylphenyl, 4- maleimidophenyls, p-nitrophenyl.
Above, 2 and 2 or more dimaleoyl iminos and 2 and 2 are contained in a molecule of the maleimide ester The above ester group.
Component（a）Hydrocarbon resin, component（b）Maleimide ester, component（d）The ratio of allyl Noryl, It can be adjusted according to specific practical application, high tool is being required to mechanical performance, plate heat resistance and peel strength when applying When body field, it can suitably increase component（b）The ratio of maleimide ester；When applying high to dielectric properties and toughness reguirements Specific field when, can suitably increase component（a）The ratio of hydrocarbon resin；Especially it is situated between when to heat resistance, dielectric properties When electrical loss tangent value is more demanding, it can suitably increase component（d）The ratio of allyl Noryl.
The ratio x of x and y in the structure of the maleimide ester：The value of y can also according to specific practical application and Adjustment can be 0.1,0.3,0.5,1,5,10,15,20 equivalences.When applying in the mechanical performance, heat resistance and stripping to laminate When high from intensity requirement specific field, the ratio for increasing x structural units can be passed through.The ratio for increasing x, can increase molecule The amount of imide ring in structure, to be conducive to the raising of heat resistance and adhesive property.
R bases are that vinyl or ethenylphenyl or 4- maleimidophenyls etc. contain in the maleimide ester structure There is the structure of unsaturated double-bond.When R bases are vinyl, in the molecular structure of the maleimide ester in said program further Vinyl reactive functionality flexible is introduced, does not influence resin while increasing the crosslink density of resin system, improve heat resistance The toughness of system.When R bases are ethenylphenyl or 4- maleimidophenyls, maleimide ester in said program Rigid phenyl ring or maleimide ring are further introduced in molecular structure, can further increase the rigidity of resin system And heat resistance.
The initiator be refer to the compound that free radical is resolved by thermal energy, can be used for cause alkenes, double vinyl monomers Free radical polymerization and copolymerization, it can also be used to the crosslinking curing and high molecular crosslink of unsaturated polyester (UP) react.Described Initiator can be azo-initiator, peroxide initiator, redox type initiators, one kind in preferably following initiator Or it is several：Cumyl peroxide, di-t-butyl peroxide, peroxidized t-butyl perbenzoate, di-cyclohexylperoxy di-carbonate, Isopropyl benzene hydroperoxide, azodiisobutyronitrile.
Preferably, R bases are vinyl, ethenylphenyl or 4- dimaleoyl imino benzene in the maleimide ester structure Base.Contain unsaturated double-bond group i.e. in maleimide ester structure.
Preferably, the ratio of x and y is 5 in the maleimide ester structure：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 can all be affected；When the ratio of x and y Value is more than 10：When 1, the maleimide structure in Malaysia elder generation imines ester is more, and toughness can be affected；When the ratio of x and y Value is 5：1~10：1 heat resistance and toughness are attained by optimal.
Preferably, the allyl modified polyphenylene ether resin is 20 ~ 60 parts.Preferably, the component（d）Allyl is modified The molecular weight of polyphenylene oxide is less than 5000.Component（d）Allyl Noryl can advanced optimize heat resistance and dielectric properties, Especially there is positive effect to the dielectric loss tangent value for reducing resin system, but addition can excessively limit resin system bonding The raising of performance.
Superior heat resistance, peel strength and mechanical performance in order to obtain, preferably a kind of thermosetting resin combination Object, with solid weight meter, including：
(a) hydrocarbon resin：10 ~ 25 parts；
(b) maleimide ester：50 ~ 100 parts；
(c) initiator：0.1 ~ 8 part；
(d) allyl modified polyphenylene ether resin：10 ~ 40 parts.
Superior dielectric properties, heat resistance, moisture pick-up properties in order to obtain, preferably a kind of compositions of thermosetting resin, With solid weight meter, including：
(a) hydrocarbon resin：10 ~ 25 parts；
(b) maleimide ester：20 ~ 60 parts；
(c) initiator：0.1 ~ 8 part；
(d) allyl modified polyphenylene ether resin：60 ~ 90 parts.
Preferably, the hydrocarbon resin be selected from butadiene styrene resin, polybutadiene, polyisobutene resin, polyprene, Polystyrene, 2- methylated polystyrenes, 3- methylated polystyrenes, 4- methylated polystyrenes, 2,4- diisopropyls polystyrene, 2, One or more of 4- diformazans base polystyrene, styrene-butadiene copolymer, styrene-isobutene copolymer；It is 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 above-mentioned technical proposal The number-average molecular weight of resin is less than 7000, and is liquid at room temperature.Preferably, hydrocarbon resin is butylbenzene in above-mentioned technical proposal One or more of resin, polybutadiene, polyisobutene resin.
Further include 1 ~ 100 part of component (e) with solid weight meter, the component (e) is selected from alkene in above-mentioned technical proposal Modified benzoxazine colophony, allyl modified bismaleimide, cyanate ester resin, vinyl modified phenolic resin, alkene Hydrocarbon copolymer, Petropols, epoxy resin, unsaturated polyester resin, one kind in mono-component polyurethane resin or arbitrary several Mixture.
The allyl modifying benzoxazine resin can be allyl modified bisphenol A type benzoxazine, allyl modification Bis-phenol g types benzoxazine, allyl modified bisphenol S types benzoxazine, two amine type benzoxazine of bis-phenol, allyl are modified bicyclic penta One kind in diene phenolic benzoxazine or arbitrary several mixture.Preferably, the allyl modifying benzoxazine resin Adding proportion be 1 ~ 20 parts by weight.Heat resistance can be advanced optimized by adding suitable allyl modifying benzoxazine resin And adhesive property, but addition excessively can cause harmful effect to the dielectric properties and toughness of resin system.
The allyl modified bismaleimide can be by allyl compound and maleimide resin prepolymerization The prepolymer of generation, the allyl compound are selected from allyl ether compound, allyl phenoxy resin, allyl phenolic aldehyde tree One or more of fat, diallyl bisphenol, diallyl bisphenol S；The maleimide resin is selected from 4,4 '-hexichol Methane bimaleimide resin, 4,4 '-Diphenyl Ether Bismaleimide resins, 4,4 '-hexichol isopropyl bismaleimide One or more of resin, 4,4 '-diphenyl sulphone (DPS) bimaleimide resins.Preferably, the allyl modification span carrys out acyl The number-average molecular weight of imines is 2000 ~ 5000g/mol.Adding suitable allyl modified bismaleimide resin can be into one Step optimization heat resistance and adhesive property, but addition excessively can cause harmful effect to the dielectric properties of resin system.
The cyanate ester resin refers to the compound containing cyanic acid ester group in structure, can be bisphenol A cyanate ester resin, double Phenol g cyanate ester resins, bis-phenol M cyanate ester resins, 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 addition of the cyanate ester resin Ratio is 10 ~ 30 parts by weight.Add suitable cyanate ester resin can advanced optimize the heat resistance of resin system, cementability and Dielectric properties, but addition can excessively lead to the decline of the wet-hot aging performance of resin system.
The vinyl modified phenolic resin can be allyl modified maleimide base phenolic resin, allyl modification Dilute benzyl phenylate of phenolic resin, dicyclopentadiene-second etc..The allyl modified maleimide base phenolic resin is that have such as The resin of lower structure：
Or； Wherein, it be 1 ~ 10, s is 1 ~ 10 that x, which is 2 ~ 20, y,.
The Petropols can be alicyclic petroleum resin（eCPe）, aromatic petroleum resin（C9）, aliphatic/fragrance Race's copolymerized petroleum resin（C5/C9）In one or any several mixture.Preferably, the molecular weight of the Petropols For 1000 ~ 3000g/mol.Preferably, the adding proportion of the Petropols is 5 ~ 25 parts by weight.Add suitable Petropols While the dielectric properties and adhesive property of resin system can be advanced optimized, moreover it is possible to which the mobile performance for improving resin system changes Kind processing performance.
The epoxy resin refers to the compound containing epoxy group, can be bisphenol A epoxide resin, bis-phenol g epoxy resin, Phosphorous epoxy resin, nitrogen-containing epoxy thermoset, o-cresol formaldehyde epoxy resin, bisphenol-A phenolic 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, isocyanate-based epoxy resin, aralkyl novolac epoxy resin, gathers dicyclopentadiene type epoxy resin In phenylate modified epoxy, alicyclic based epoxy resin, glycidyl amine type epoxy resin, glycidyl ester type epoxy resin A kind of or arbitrary several mixture.Epoxy resin is added in compositions of thermosetting resin of the present invention, mainly ring Epoxy group in oxygen resin and component（b）Ester group reaction in maleimide ester.After adding epoxy resin, component（b）Horse Carry out imide ester and plays the role of a bridge formation, component（b）Ester group in maleimide ester molecular structure and epoxy resin It reacts, the dimaleoyl imino in structure and component（a）Double bond reaction in hydrocarbon resin, thus by epoxy resin and hydrocarbon tree The advantages of fat, concentrates in a kind of resin combination.In the resin combination of addition epoxy resin, can further it add Curing accelerator, the curing accelerator can be selected from dimethyl aminopyridine, tertiary amine and its salt, imidazoles, organic metal salt, three Phenylphosphine is Ji Qi phosphonium 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 by polyphenylene oxide.Preferably, the adding proportion of epoxy resin is 10 ~ 50 parts by weight. The processing performance and mechanical performance of resin system can be advanced optimized by adding suitable epoxy resin.
The unsaturated polyester resin or mono-component polyurethane resin, preferred adding proportion are 5 ~ 25 parts by weight.Addition Suitable unsaturated polyester resin or mono-component polyurethane resin can optimize the adhesive property and toughness of resin system, but add Dosage excessively can cause harmful effect to the heat resistance and dielectric properties of resin system.
Based on the above technical solution, the compositions of thermosetting resin further includes the component of 1 ~ 80 parts by weight（f） Fire retardant.The 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, decabromodiphenylethane, 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 the miscellaneous phenanthrene -10- oxides of -9 oxa- -10- phosphines of 9,10- dihydros, 10-（2,5 dihydroxy benzenes Base）Miscellaneous phenanthrene -10- the oxides of -9 oxa- -10- phosphines of -9,10- dihydros, the miscellaneous -10- phosphines phenanthrene -10- of 10- phenyl -9,10- dihydro-9-oxies Oxide, three（2,6 3,5-dimethylphenyls）The organophosphorus compounds such as 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..Nothing Machine fire retardant can be aluminium hydroxide, magnesium hydroxide, aluminium oxide, barium monoxide etc..The fire retardant added can be according to laminate Concrete application field and select, to the application field that halogen requires, preferably non-halogen fire retardant, such as phosphorous or nitrogenous resistance Fire agent.Preferably, when selecting phosphonium flame retardant, nitrogen can be formed with the nitrogen of maleimide ester in above-mentioned technical proposal Phosphorus cooperative flame retardant improves flame retarding efficiency.Preferably, the fire retardant additive amount in above-mentioned compositions of thermosetting resin is 5 ~ 50 weight Part.
Based on the above technical solution, the compositions of thermosetting resin further includes the component of 1 ~ 100 parts by weight（g） Filler.The inorganic filler is selected from powdered quartz, fused silica, preparing spherical SiO 2, aluminium 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 vinyl fluoride, graphene filler, the grain size of above-mentioned inorganic filler are 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 be made lotion input tree In oil/fat composition.Preferably, the inorganic filler additive amount in above-mentioned compositions of thermosetting resin is 10 ~ 50 parts by weight.
In above-mentioned compositions of thermosetting resin, it can also be added using silane coupling agent, pigment, emulsification according to practical feelings One in the additives such as agent, dispersant, antioxidant, antistatic agent, heat stabilizer, ultra-violet absorber, colorant, lubricant Kind is several.
Above-mentioned compositions of thermosetting resin can be used for manufacturing prepreg, laminate, printed circuit board, semiconductor close Closure material, lamination adhering film, binder, resin cast material, conductive paste etc..
The prepreg made of above-mentioned resin combination is claimed in the present invention simultaneously, and above-mentioned resin combination is used Glue is made in solvent dissolving, and then reinforcing material is immersed in above-mentioned glue；After impregnating after reinforcing material heat drying, i.e., The prepreg can be obtained.
The solvent is selected from acetone, butanone, toluene, methylisobutylketone, N, dinethylformamide, N, N- dimethyl second One or more of amide, ethylene glycol monomethyl ether, propylene glycol monomethyl ether.Natural fiber, You Jihe can be used in the reinforcing material At fiber, organic fabric or inorganic fabric.
The laminate made of above-mentioned resin combination is claimed in the present invention simultaneously, at one by above-mentioned semi-solid preparation The single or double of piece is covered with metal foil, or will at least 2 be superimposed by above-mentioned prepreg after, be covered in its single or double Metal foil, hot forming, you can obtain the laminate.
The quantity of the prepreg is determined according to the laminate thickness of customer requirement, can use one or more.Institute Metal foil is stated, can be copper foil, can also be aluminium foil, their thickness is not particularly limited.
Since above-mentioned technical proposal is used, the present invention has following advantages compared with prior art：
1. present invention employs the maleimide ester with multifunctional backbone and rigid imide ring, cooperation has Hydrocarbon resin flexible forms thermoset composition, and the two interacts, the heat resistance of maleimide ester improvement hydrocarbon resin, Rigidity, the problem of intensity deficiency, hydrocarbon resin improves the problem of maleimide ester toughness deficiency, so that composition is simultaneous Have excellent heat resistance, intensity, hard and soft；Meanwhile using allyl modified polyphenylene ether resin, further improving solidfied material Dielectric properties, it is final so that the compositions of thermosetting resin of the present invention and its printed circuit prepreg and laminate of preparation Excellent dielectric properties, heat resistance, cementability, anti-flammability, bending strength, toughness are had both, peel strength is high, water absorption rate is low, The features such as process industrial art performance is excellent obtains unexpected technique effect；
2. the component that the present invention uses（b）Dimaleoyl imino and ester group in maleimide ester molecular structure improve The adhesive property of the system of hydrocarbon resin improves the peel strength between laminate copper foil layer and resin layer, has no effect on simultaneously The dielectric properties of resin system；In addition, component（b）The multifunctional backbone of maleimide ester and the acid imide of rigidity Ring improves resistance to thermal energy, rigidity and the mechanical strength of resin system；The maleimide ester of backbone is conducive to improve component （a）Hydrocarbon resin makes tacky characteristic after prepreg, while can also reduce component（a）Contraction after hydrocarbon resin solidification Rate；
3. the component that the present invention uses（a）The non-polar conformations of hydrocarbon resin are that resin system contributes to excellent dielectricity Can, carbon-chain structure flexible can improve the toughness of maleimide ester solidfied material；
4. the component that the present invention uses（d）Allyl modified polyphenylene ether resin can advanced optimize heat resistance and dielectricity Can, especially there is positive effect to the dielectric loss tangent value for reducing resin system.
Specific implementation mode
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 the present invention The preparation of the compositions of thermosetting resin of offer and evaluation of physical property.
Synthesis example 1
N- (4- hydroxy phenyls) maleimide is put into the flask for being equipped with thermometer, condenser pipe, blender （190g, 1mol）, phenol（94g, 1mol, M94）And oxalic acid（10g）, after being mixed evenly, it is placed in 70 DEG C of water bath with thermostatic control In；Then, under stiring, formalin was added dropwise into flask with 0.5 hour（The ratio of 150mL, phenol/aldehyde are 1/0.8）；It adds After formaldehyde, the temperature and stirring condition that maintain 70 DEG C are reacted 15 hours；Then, with 400mL acetone by reaction product dissolved dilution, Then again with 40% methanol aqueous solution precipitation reaction product；It repeats above dissolving-precipitation operation 3~5 times, is filtered, divided From, be dried to obtain pure maleimide phenolic aldehyde（P-1）.
Take maleimide phenolic aldehyde made from the above method（P-1）100g and methyl isobutyl ketone solvent 500g are placed in flask In be sufficiently mixed dissolving, will in reaction system depressurize lead to nitrogen, and by system temperature control at 65 DEG C；Then, 140g benzene is put into Formyl chloride（1mol, M140.5）, then, with 3 hours into system be added dropwise 20% sodium hydroxide solution 210g, after being added dropwise, Reaction 3 hours is maintained at 65 DEG C；After the completion of reaction, it is separated off water layer；Then it is added water into system again, stirring and washing, It is separated off water layer；Repeat the above cleaning operation 3~5 times；Then it vacuumizes decompression to remove methyl iso-butyl ketone (MIBK), obtain as follows The maleimide ester of structure（B-1）：；Wherein, Ar is：, R is phenyl；
Wherein, the ratio that n is 1 ~ 10, x and y is 1：1.
Synthesis example 2
With reference to the method for real synthesis example 1, the maleimide ester such as lower structure is made（B-2)：
；Wherein, Ar is , R is phenyl；
Wherein, the ratio that n is 1 ~ 10, x and y is 0.5：1.
Synthesis example 3
With reference to the method for synthesis example 1, the maleimide ester such as lower structure is made（B-3)：
；Wherein, Ar is：, R is maleimide Base phenyl；
Wherein, the ratio that n is 1 ~ 10, x and y is 0.1：1.
Synthesis example 4
With reference to the method for synthesis example 1, the maleimide ester such as lower structure is made（B-4)：；Wherein, Ar is, R is ethenylphenyl；
Wherein, the ratio that n is 1 ~ 10, x and y is 5：1.
Synthesis example 5
With reference to the method for synthesis example 1, the maleimide ester such as lower structure is made（B-5)：
；Wherein, Ar is, R is ethyl；
Wherein, the ratio that n is 1 ~ 10, x and y is 10：1.
Synthesis example 6
With reference to the method for synthesis example 1, the maleimide ester such as lower structure is made（B-6)：
；Wherein, Ar is, R is methyl；
Wherein, the ratio that n is 1 ~ 10, x and y is 20：1.
Synthesis example 7
With reference to the method for synthesis example 1, the maleimide ester such as lower structure is made（B-7)：
；Wherein, Ar is, R is dimaleoyl imino Phenyl；
Wherein, the ratio that n is 1 ~ 10, x and y is 1：1.
Embodiment 1~12 and comparative example 1~7
Be formulated according to shown in Tables 1 and 2, by each component be uniformly mixed be made 65% resin solution, made using glass-fiber-fabric It is impregnated with upper above-mentioned resin solution for reinforcing material, then heats the glass-fiber-fabric being impregnated with 3 ~ 10 minutes in 175 DEG C of baking oven Printed circuit pre-preg material is made, laminate is then made under the following conditions, and its dielectricity is evaluated by following methods The performances such as energy, heat resistance, adhesive property, toughness, intensity, are as a result shown in Tables 1 and 2.
<Laminate manufacturing conditions>
Base material：2116 glass-fiber-fabric of ordinary electronic grade；
The number of plies：8；
Plate thickness after molding：1.0mm；
Pre-preg semi-solid preparation condition：175℃/5min；
Condition of cure：150℃/60min+220℃/120min.
<The measurement of dielectric constant and dielectric loss tangent>Dielectric constant uses tablet according to IPC-TM-650 2.5.5.9 Method measures the dielectric constant under 10GHz, dielectric loss tangent：Flat band method is used according to IPC-TM-650 2.5.5.9, is measured Dielectric loss factor under 10GHz.
<Peel strength>The adhesive property that compositions of thermosetting resin is characterized using the peel strength of laminate, according to " after thermal stress " experiment condition in IPC-TM-6502.8 methods, tests the peel strength of metal cladding.
<Water absorption rate>It is measured according to the method for IPC-TM-6502.6.2.1.
<Thermally stratified layer time T-288>It is measured according to IPC-TM-6502.4.24.1 methods.
<Glass transition temperature>Show differential scanning calorimetry（DSC）, according to IPC-TM-650 2.4.25 defineds DSC method is measured.
<Bending strength>Using universal testing machine test material bend loading effect under rupture or reach regulation it is curved The maximum stress that can be born when square, maximum (normal) stress when this stress is bending, with MPa（Megapascal）For unit.
<Drop impact toughness>The toughness that laminate is characterized 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.According to the good and bad of following Standard Judgement toughness：Cross shape of the drop hammer on laminate is more clear It is clear, illustrate that the toughness of product is better；Cross shape is clear, illustrates good toughness, is denoted as character ◎；Cross shape is fuzzy, illustrates tough Property is poor, is denoted as character Δ；Cross between it is clear with it is fuzzy between, be denoted as character.
<Anti-flammability>It is measured according to UL94 vertical combustions.
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）
B-1：Maleimide ester obtained in synthesis example 1（B-1）
B-2：Maleimide ester obtained in synthesis example 2（B-2）
B-3：Maleimide ester obtained in synthesis example 3（B-3）
B-4：Maleimide ester obtained in synthesis example 4（B-4）
B-5：Maleimide ester obtained in synthesis example 5（B-5）
B-6：Maleimide ester obtained in synthesis example 6（B-6）
C：Initiator, cumyl peroxide
D：Allyl Noryl
E-1：Allyl modified bismaleimide（Self-control）
E-2：Petropols (Eastman, C9Resin)
E-3：Allyl is modified Malaysia PN（Self-control）
F：Fire retardant, phenoxyphosphazene compound（Japanese big tomb chemistry, SPB-100）
G：Filler, ball-type silicon powder（Japan Electric chemistry, SFP-30M）
P-1：Maleimide phenolic aldehyde（Intermediate resin obtained in embodiment 1）
It was found from the result of Tables 1 and 2：
Embodiment 1 has better heat resistance, bending strength, stripping compared to the comparative example 1 that hydrocarbon resin is only used only From intensity, process industrial art performance, lower dielectric properties are maintained.
Embodiment 1 is compared to the benzoxazine for using allyl to be modified（BOZ）With the comparative example 2 of hydrocarbon resin combination, tool There are better heat resistance, dielectric properties and bending strength.
Embodiment 1 is compared to the bismaleimide for using allyl to be modified（BMI）With the comparative example of hydrocarbon resin combination 3, there are better dielectric properties.
Embodiment 1 has more preferable compared to the comparative example 4 of the phenolic resin and hydrocarbon resin combination that use allyl to be modified Heat resistance, dielectric properties and bending strength.
Embodiment 1 has better dielectric compared to the comparative example 5 for using maleimide phenolic aldehyde and hydrocarbon resin to combine Performance.
Embodiment 1 has better dielectric properties, toughness compared to the comparative example 6 for using pure maleimide ester.
Embodiment 1 has used the maleimide ester of greater proportion compared to embodiment 8, have better heat resistance, Bending strength, peel strength, still, embodiment 8 have better dielectric properties.
Embodiment 1 is compared with embodiment 2, and the x structural units with greater proportion in molecular structure have superior resistance to Hot heat resistance, bending strength, peel strength, still, embodiment 2 have better dielectric properties.Embodiment 6 and embodiment 5 compare, and x structural units are more in molecular structure, although the performances such as heat resistance, peel strength, bending strength are more preferable, 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, is had more preferable Heat resistance, bending strength, peel strength.
Embodiment 9 is compared with embodiment 1, and more allyl Noryls are added in composition, is had better Dielectric properties, but peel strength is relatively low.
Embodiment 10 is compared with embodiment 1, and allyl modified maleimide resin is added in composition, is had more preferable Bending strength, heat resistance, but do not influence dielectric properties.
Embodiment 11 is compared with embodiment 1, and the Petropols of part are added in composition, has better dielectricity Energy.
Embodiment 12 is compared with embodiment 1, and allyl is added in composition and is modified Malaysia phenolic resin, is had better Bending strength, heat resistance, but do not influence dielectric properties.
Embodiment 1~12 has both excellent heat resistance, bending compared to the comparative example 1~6 that hydrocarbon resin is only used only Intensity, peel strength, process industrial art performance maintain lower dielectric properties, especially have excellent dielectric loss Tangent value.
In conclusion compositions of thermosetting resin using the present invention and its printed circuit prepreg and layer of preparation Pressing plate has both excellent dielectric properties, heat resistance, anti-flammability, bending strength, toughness, and peel strength is high, water absorption rate is low, adds The features such as work processing performance is excellent.

Claims (10)

1. a kind of compositions of thermosetting resin, which is characterized in that with solid weight meter, including：
(a) hydrocarbon resin：10 ~ 100 parts；
(b) maleimide ester：20 ~ 100 parts；
(c) initiator：0.1 ~ 8 part；
(d) allyl modified polyphenylene ether resin：10 ~ 100 parts；
The structural formula of the maleimide ester is：, wherein：
It is 2 ~ 20, y is 1 ~ 10 that n, which is 1 ~ 10, x,；
The one kind of Ar in following structural：
、、、、、、；
R be carbon atom number less than or equal to 5 alkyl or phenyl, aminomethyl phenyl, xenyl, n-propyl phenyl, isopropyl phenyl, Tert-butyl-phenyl, ethenylphenyl, 4- maleimidophenyls, p-nitrophenyl.
2. compositions of thermosetting resin according to claim 1, it is characterised in that：R in the maleimide ester structure Base is vinyl, ethenylphenyl or 4- maleimidophenyls.
3. compositions of thermosetting resin according to claim 1, it is characterised in that：X in the 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：The allyl modified polyphenylene ether resin It is 20 ~ 60 parts.
5. compositions of thermosetting resin according to claim 1, it is characterised in that：With solid weight meter, including：
(a) hydrocarbon resin：10 ~ 25 parts；
(b) maleimide ester：50 ~ 100 parts；
(c) initiator：0.1 ~ 8 part；
(d) 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, including：
(a) hydrocarbon resin：10 ~ 25 parts；
(b) maleimide ester：20 ~ 60 parts；
(c) initiator：0.1 ~ 8 part；
(d) allyl modified polyphenylene ether resin：60 ~ 90 parts.
7. compositions of thermosetting resin according to claim 1, it is characterised in that：The hydrocarbon resin is selected from butylbenzene tree Fat, polybutadiene, polyprene, polystyrene, poly- 2-methyl styrene, poly- 3- methyl styrenes, poly- 4- methylbenzenes second One or more of alkene, poly- 2,4- diisopropyls styrene, poly- 2,4- dimethyl styrenes, styrene-butadiene copolymer； The number-average molecular weight of the hydrocarbon resin is 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：Further include 1 ~ 100 with solid weight meter The component (e) of part, the component (e) are selected from allyl modifying benzoxazine resin, allyl modified bismaleimide, cyanic acid Ester resin, vinyl modified phenolic resin, olefin copolymer, Petropols, epoxy resin, unsaturated polyester resin, one pack system One kind in polyurethane resin or arbitrary several mixture.
9. the prepreg that a kind of any one compositions of thermosetting resin using as described in claim 1 ~ 8 makes, special Sign is：Glue is made in any one compositions of thermosetting resin solvent dissolving described in claim 1 ~ 8, then will be increased Strong material is immersed in above-mentioned glue；After impregnating after reinforcing material heat drying, you can obtain the prepreg.
10. a kind of laminate made of compositions of thermosetting resin as described in claim 1, it is characterised in that：One Metal foil 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 foil, hot forming in its single or double, you can obtain the laminate.
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