CN103992641B - Compositions of thermosetting resin and use prepreg and the laminate of its making - Google Patents
Compositions of thermosetting resin and use prepreg and the laminate of its making Download PDFInfo
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G59/00—Polycondensates containing more than one epoxy group per molecule; Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups
- C08G59/18—Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups ; e.g. general methods of curing
- C08G59/40—Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups ; e.g. general methods of curing characterised by the curing agents used
- C08G59/4007—Curing agents not provided for by the groups C08G59/42 - C08G59/66
- C08G59/4014—Nitrogen containing compounds
- C08G59/4042—Imines; Imides
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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
- B32B15/14—Layered products comprising a layer of metal next to a fibrous or filamentary layer
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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
- C08L63/00—Compositions of epoxy resins; Compositions of derivatives of epoxy resins
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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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- 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
- B32B2260/046—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
- 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
- B32B2457/00—Electrical equipment
- B32B2457/08—PCBs, i.e. printed circuit boards
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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
- C08L2201/00—Properties
- C08L2201/02—Flame or fire retardant/resistant
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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
- C08L2201/00—Properties
- C08L2201/08—Stabilised against heat, light or radiation or oxydation
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L2203/00—Applications
- C08L2203/20—Applications use in electrical or conductive gadgets
Abstract
The invention discloses a kind of compositions of thermosetting resin, with solid weight meter, including: (a) active ester resin: 20 ~ 50 parts；(b) epoxy resin: 10 ~ 60 parts；(c) pi-allyl modified bismaleimide resin: 20 ~ 60 parts.The laminate prepared by the compositions of thermosetting resin of the present invention has thermostability and the toughness of excellence, significantly improve the glass transition temperature after epoxy resin composition, also have the low-k of excellence, low-dielectric loss tangent concurrently simultaneously, achieve significant effect, there is positive realistic meaning.
Description
Technical field
The present invention relates to a kind of compositions of thermosetting resin, and use prepreg and laminate that this resin combination makes, belong to technical field of electronic materials.
Background technology
In recent years, along with information processing and information transmit the continuous propelling of high-speed high frequency technology, increasingly higher requirement is proposed in dielectric properties tellite material.In simple terms, namely tellite material needs possess relatively low dielectric constant and dielectric loss tangent, the delay of signal, distortion and loss during to reduce high-speed transfer, and the interference between signal.Accordingly, it is desired to provide a kind of compositions of thermosetting resin, use the printed circuit board material that this compositions of thermosetting resin makes can show substantially low low-k and low-dielectric loss tangent at the signals transmission of high speed, high frequency.
In prior art, with epoxy resin and firming agent thereof for having good thermostability, insulating properties, processability and the advantage such as with low cost by the material prepared of the compositions of thermosetting resin of composition, therefore it is widely used in the electronic material such as quasiconductor, printed circuit board.The firming agent that epoxy resin is conventional has polyamines, anhydride, phenolic resin etc..Containing the firming agent of reactive hydrogen in amine, this kind of molecular structure of phenolic resin, there is substantial amounts of hydroxyl in the epoxy resin of its solidification, this can cause that the water absorption rate of solidfied material rises, and wet-hot aging performance and dielectric properties decline.The epoxy resin of anhydride-cured, although be absent from hydroxyl, but anhydride is reactive poor, it is desirable to condition of cure harshness.
For the problems referred to above occurred when solving Common Curing Agents cured epoxy resin, it has been found that active ester is the very promising epoxy curing agent of one.Active ester just can react with epoxy resin under relatively mild condition；Meanwhile, the epoxy resin that active ester solidifies, does not contain hydroxyl, the substitute is ester group, it is possible to obtain wet-hot aging performance and the excellent epoxy resin-cured product of dielectric properties.Japanese Patent Laid-Open JP2002012650A, a series of active ester resins disclosed in JP2003082063A, JP2004155990A, JP2009235165A and JP2012246367A, used as epoxy curing agent, it is possible to substantially reduce dielectric constant and the dielectric loss of epoxy resin cured product.But, all there is the problem that heat resistance is not enough in the epoxy resin that these active ester resins solidify, it is difficult to takes into account heat resistance and low-k, low-dielectric loss tangent, thus can not meet the requirement in material practical application.
Accordingly, it would be desirable to research and develop a kind of new active ester resin so that it is under the premise improving resin combination dielectric properties, compositions is kept to have higher thermostability, relatively low hydroscopicity and good humidity resistance.
Summary of the invention
The goal of the invention of the present invention is to provide a kind of compositions of thermosetting resin and uses prepreg and the laminate of its making.
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, including:
(a) active ester resin: 20～50 parts；
(b) epoxy resin: 10～60 parts；
(c) pi-allyl modified bismaleimide resin: 20～60 parts；
The structural formula of described active ester resin is as follows:
Wherein, n is the integer of 1～10, and x is the integer of 1～5, and y is the integer of 1～10；Ar one in following structural:
R is the carbon number alkyl less than or equal to 5, or phenyl, aminomethyl phenyl, xenyl, n-pro-pyl phenyl, isopropyl phenyl, tert-butyl-phenyl, 4-maleimidophenyl, p-nitrophenyl；
Ester functional groups's equivalent of described active ester resin is 200～300g/eq；
Described pi-allyl modified bismaleimide resin is the prepolymer produced by allyl compound and maleimide resin prepolymerization, and its number-average molecular weight is 2000～5000g/mol；One or more in allyl ether compound, allyl phenoxy resin, allyl phenol urea formaldehyde, diallyl bisphenol, diallyl bisphenol S of described allyl compound；Described maleimide resin is selected from 4,4 '-diphenyl methane dimaleimide resin, 4, one or more in 4 '-Diphenyl Ether Bismaleimide resin, 4,4 '-hexichol isopropyl bimaleimide resin, 4,4 '-diphenyl sulphone (DPS) bimaleimide resin.
Above, described active ester resin can prepare by the following method: first, and the mixture of N-(4-hydroxy phenyl) maleimide and little molecule phenolic compounds in acid condition, generates the multifunctional phenolic compounds of line style with appropriate formaldehyde reaction；Then, aforementioned prepared multifunctional phenolic compounds, carboxylic acid or its acyl chlorides are prepared under certain catalytic condition the active ester resin in technique scheme.
Described epoxy resin is selected from bisphenol A epoxide resin, bisphenol F epoxy resin, phosphorous epoxy resin, nitrogen-containing epoxy thermoset, o-cresol formaldehyde epoxy resin, bisphenol-A phenolic epoxy resin, phenol novolac epoxy resins, 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, alicyclic based epoxy resin, glycidyl amine type epoxy resin, in glycidyl ester type epoxy resin one or more.
Preferably, one or more in biphenyl type epoxy resin, naphthalene nucleus type epoxy resin, dicyclopentadiene type epoxy resin, aralkyl novolac epoxy resin of described epoxy resin.
In technique scheme, also include fire retardant, inorganic filler and curing accelerator.
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, brominated styrene or tetrabromo-phthalic diformamide.Phosphorus flame retardant can be the general organophosphor based compounds and 9 such as Phos, phosphate compound, phosphinic acid compounds, phosphinic compounds, phosphine oxide compound, organic system Nitrogen-and Phosphorus-containing compound, 10-dihydro-9 oxa--10-phosphine assorted phenanthrene-10-oxide, 10-(2,5 dihydroxy phenyls)-9,10-dihydro-9 oxa--10-phosphine assorted phenanthrene-10-oxide, 10-phenyl-9, the organophosphorus compound of the DOPO structure such as 10-dihydro-9-oxy assorted-10-phosphine phenanthrene-10-oxide and use its derivant etc. reacted with the compound such as epoxy resin, phenolic resin.Nitrogenated flame retardant can be triaizine compounds, cyanuric acid compound, Carbimide. compound, phenothiazine etc..Organic silicon fibre retardant can be organic silicone oil, organic silicon rubber, organic siliconresin etc..Organic metal fire retardant can be ferrocene, acetylacetone metal complex, organic metal carbonyl compound etc..Inorganic flame retardant can be aluminium hydroxide, magnesium hydroxide, aluminium oxide, Barium monoxide etc..
The content of described inorganic filler amounts to 100 weight portions relative to compositions of thermosetting resin, is 5～300 weight portions.One or more in powdered quartz, fused silica, preparing spherical SiO 2, aluminium oxide, aluminium hydroxide, aluminium nitride, boron nitride, titanium dioxide, strontium titanates, Barium metatitanate., barium sulfate, Pulvis Talci, calcium silicates, calcium carbonate, Muscovitum, politef of described inorganic filler.
Described curing accelerator adds use according to practical situation, it is possible to selected from dimethyl aminopyridine, tertiary amine and salt, imidazoles, organic metal salt, triphenylphosphine and salt thereof etc..
Preferably, the one in following structural of the Ar in the structural formula of described active ester resin:
In above-mentioned compositions of thermosetting resin, it is also possible to add, according to actual feelings, additives such as using silane coupler, pigment, emulsifying agent, dispersant.
Above-mentioned compositions of thermosetting resin, it is possible to be used for manufacturing semiconductor-encapsulating material, lamination adhering film, binding agent, resin cast material, conductive paste etc..
The present invention is claimed the prepreg adopting above-mentioned resin combination to make simultaneously, is dissolved by above-mentioned resin combination solvent and makes glue, is then immersed in above-mentioned glue by reinforcing material；After impregnating after reinforcing material heat drying, described prepreg can be obtained.
One or more in described solvent selected from acetone, butanone, toluene, methylisobutylketone, N, dinethylformamide, N, N-dimethyl acetylamide, ethylene glycol monomethyl ether, propylene glycol monomethyl ether.Described reinforcing material can adopt natural fiber, organic synthetic fibers, organic fabric or inorganic fabric.
The present invention is claimed the laminate adopting above-mentioned resin combination to make simultaneously; it is covered with metal forming by the single or double of above-mentioned prepreg at one; or by least 2 by after above-mentioned prepreg superposition; it is covered with metal forming at its single or double; hot forming, can obtain described laminate.
The quantity of described prepreg is that laminate thickness as requested is determined, available one or more.Described metal forming, it is possible to be Copper Foil, it is also possible to be aluminium foil, their thickness is not particularly limited.
Owing to technique scheme is used, the present invention compared with prior art has the advantage that
1. practical application proves: the laminate prepared by the compositions of thermosetting resin of the present invention has thermostability and the toughness of excellence, significantly improve the glass transition temperature after epoxy resin composition, also have the low-k of excellence, low-dielectric loss tangent concurrently simultaneously, achieve significant effect, there is positive realistic meaning.
Detailed description of the invention
Below in conjunction with embodiment, the present invention is further described.
Embodiment and comparative example:
Embodiment 1～3 is the synthesis of active ester resin of the present invention, and comparative example 1 is the synthesis of common phenol aldehyde type active ester resin, and embodiment 4～6 and comparative example 2～5 are preparation and the evaluation of physical property of compositions of thermosetting resin.Hereinafter without special instruction, " part " representative " weight portion ", " % " representative " weight % ".
Embodiment 1
The flask being provided with thermometer, condensing tube, agitator puts into N-(4-hydroxy phenyl) maleimide (40g, 0.21mol), phenol (160g, 1.70mol) with oxalic acid (10g), after mixing and stirring, it is placed in the water bath with thermostatic control of 70 DEG C；Then, under agitation, in flask, formalin (125mL, the ratio of phenol/aldehyde is 1/0.8) was dripped with 0.5 hour.After adding formaldehyde, the temperature and the stirring condition that maintain 70 DEG C react 15 hours.Then, with 400mL acetone by product dissolved dilution, then again with the aqueous solution precipitation product of the methanol of 40%.Repeat above dissolvings-precipitation operation 3～5 times, filtered, separate, dry and obtain pure nitrogenous multifunctional phenolic compounds.
The multifunctional phenolic compounds 130g and methyl isobutyl ketone solvent 500g taking said method prepared is placed in flask and is sufficiently mixed dissolving, by logical for decompression in reaction system nitrogen, and is controlled by system temperature at 65 DEG C.Then, put into 155g Benzenecarbonyl chloride. (1.1mol), then, with 3 hours toward the sodium hydroxide solution 210g of dropping 20% in system, after dropwising, at 65 DEG C, maintain reaction 3 hours.After having reacted, it is separated off water layer.Then in system, add water, stirring and washing again, be separated off water layer.Repeat above cleaning operation 3～5 times.Then methyl iso-butyl ketone (MIBK) is removed by evacuation decompression, obtains active ester resin (A-1), and its structure is as follows:
Wherein, n is the integer of 1～10, and x is the integer of 1～5, and y is the integer of 1～10；
Wherein, Ar is:R is:
The functional equivalent of this active ester resin (A-1) is 233g/eq according to input ratio.
Embodiment 2
The flask being provided with thermometer, dephlegmator, condensing tube, agitator puts into N-(4-hydroxy phenyl) maleimide (80g, 0.42mol), phenol (120g, 1.28mol) with oxalic acid (10g), after mixing and stirring, it is placed in the water bath with thermostatic control of 70 DEG C.Then, under agitation, in flask, formalin (ratio of phenol/aldehyde is 1/0.8 for 110mL, 37% formalin) was dripped with 0.5 hour.After adding formaldehyde, the temperature and the stirring condition that maintain 60 DEG C react 15 hours.Then, with 500mL acetone by product dissolved dilution, then again with the aqueous solution precipitation product of the methanol of 40%.Repeat above dissolvings-precipitation operation 3～5 times, filtered, separate, dry and obtain pure nitrogenous multifunctional phenolic compounds.
The multifunctional phenolic compounds 142g and methyl isobutyl ketone solvent 600g taking said method prepared is placed in flask and is sufficiently mixed dissolving, by logical for decompression in reaction system nitrogen, and is controlled by system temperature at 60 DEG C.Then, put into 155g Benzenecarbonyl chloride. (1.1mol), then, with 3 hours toward the sodium hydroxide solution 210g of dropping 20% in system, after dropwising, at 65 DEG C, maintain reaction 3 hours.After having reacted, it is separated off water layer.Then in system, add water, stirring and washing again, be separated off water layer.Repeat above cleaning operation 3～5 times.Then methyl iso-butyl ketone (MIBK) is removed by evacuation decompression, obtains active ester resin (A-2), and its structure is with (A-1) of embodiment one.
The functional equivalent of this active ester resin (A-2) is 247g/eq according to input ratio.
Embodiment 3
The flask being provided with thermometer, dephlegmator, condensing tube, agitator puts into N-(4-hydroxy phenyl) maleimide (60g, 0.32mol), bisphenol-A (120g, 0.44mol) with oxalic acid (10g), after mixing and stirring, it is placed in the water bath with thermostatic control of 70 DEG C.Then, under agitation, in flask, formalin (ratio of phenol/aldehyde is 1/0.8 for 50mL, 37% formalin) was dripped with 0.5 hour.After adding formaldehyde, the temperature and the stirring condition that maintain 60 DEG C react 15 hours.Then, with 500mL acetone by product dissolved dilution, then again with the aqueous solution precipitation product of the methanol of 40%.Repeat above dissolvings-precipitation operation 3～5 times, filtered, separate, dry and obtain pure nitrogenous multifunctional phenolic compounds.
The multifunctional phenolic compounds 149g and methyl isobutyl ketone solvent 600g taking said method prepared is placed in flask and is sufficiently mixed dissolving, by logical for decompression in reaction system nitrogen, and is controlled by system temperature at 60 DEG C.Then, put into 155g Benzenecarbonyl chloride. (1.1mol), then, with 3 hours toward the sodium hydroxide solution 210g of dropping 20% in system, after dropwising, at 65 DEG C, maintain reaction 3 hours.After having reacted, it is separated off water layer.Then in system, add water, stirring and washing again, be separated off water layer.Repeat above cleaning operation 3～5 times.Then methyl iso-butyl ketone (MIBK) is removed by evacuation decompression, obtains active ester resin (A-3), and its structure is as follows:
Wherein, n is the integer of 1～10, and x is the integer of 1～5, and y is the integer of 1～10；
Wherein, Ar is:R is:
The functional equivalent of this active ester resin (A-3) is 254g/eq according to input ratio.
Comparative example 1
In the flask being provided with thermometer, dephlegmator, condensing tube, agitator, put into 106 phenolic resin (common linear phenol-aldehyde resin, hydroxyl equivalent 106g/eq) and methyl isobutyl ketone solvent 500g be placed in flask and be sufficiently mixed dissolving, by logical for decompression in reaction system nitrogen, and system temperature is controlled at 60 DEG C.Then, put into 155g Benzenecarbonyl chloride. (1.1mol), then, with 3 hours toward the sodium hydroxide solution 210g of dropping 20% in system, after dropwising, at 65 DEG C, maintain reaction 3 hours.After having reacted, it is separated off water layer.Then in system, add water, stirring and washing again, be separated off water layer.Repeat above cleaning operation 3～5 times.Then methyl iso-butyl ketone (MIBK) is removed by evacuation decompression, obtains active ester resin (B-1), and its structure is as follows:
Wherein n is the integer of 1～10.
The functional equivalent of this active ester resin (B-1) is 210g/eq according to input ratio.
Embodiment 4～6 and comparative example 2～5
According to the formula that table 1 is recorded, mixture dicyclopentadiene type epoxy resin (epoxide equivalent 265g/eq, softening point 80 DEG C), active ester resin, pi-allyl modified bismaleimide resin (self-control), and then addition curing accelerator, all components is completely dissolved in ethylene glycol monomethyl ether and is configured to the resin combination that solid content is 60%.
Wherein, the active ester resin of embodiment 4～6 is the active ester resin of (A-1)～(A-3), the active ester resin of comparative example 2～4 is the active ester resin of (A-1)～(A-2), and the active ester resin of comparative example 5 is the active ester resin of (B-1).
Then laminate is made under the following conditions, and by following method evaluation anti-flammability, wet-hot aging performance and dielectric property.Result is shown in table 1.
<laminate manufacturing conditions>
Base material: ordinary electronic level 2116 glass-fiber-fabric；
The number of plies: 5；
Sheet metal thickness after molding: 1.0mm；
Pre-preg semi-solid preparation condition: 160 DEG C/5min；
Condition of cure: 150 DEG C/60min+220 DEG C/120min；
<anti-flammability>measures according to UL94 method.
<thermostability>characterizes thermostability with glass transition temperature (Tg), according to differential scanning calorimetry, is measured according to the DSC method of IPC-TM-6502.4.25 defined.
<mensuration of dielectric constant and dielectric loss tangent>dielectric constant uses flat band method according to IPC-TM-6502.5.5.9, measures the dielectric constant under 1GHz；Dielectric loss tangent: use flat band method according to IPC-TM-6502.5.5.9, measures the dielectric loss factor under 1GHz.
<drop impact toughness>characterizes the toughness of laminate with this, uses Apparatus for Impacting at low-temp, Apparatus for Impacting at low-temp height of the fall 45cm, whereabouts weight weight 1Kg.Good and bad according to following Standard Judgement toughness: drop hammer cross shape on laminate is more clear, illustrates that the toughness of product is more good；Cross shape is clear, good toughness is described, is designated as character ◎；Cross shape obscures, and poor toughness is described, is designated as character Δ；Cross between clear and fuzzy, is designated as character.
Table 1
The footnote of table 1:
A-1: the active ester resin (A-1) prepared in embodiment 1；
A-2: the active ester resin (A-2) prepared in embodiment 2；
A-3: the active ester resin (A-3) prepared in embodiment 3；
B-1: the active ester resin (B-1) prepared in comparative example 1；
Fire retardant: phosphorus containing phenolic resin, phosphorus content 9.2%wt；
Curing accelerator: 2-methyl-4-ethyl imidazol(e)；
Filler: silicon dioxide.
The synthetic method of pi-allyl modified BMI resin prepolymer is: by 100 parts of bimaleimide resins and 50 parts of allyl compounds, reacting 85min at 130 degree of temperature, reaction is cooled to room temperature after terminating and namely obtains described pi-allyl modified bismaleimide resin prepolymer.
From upper table 1, what embodiment 4～6 adopted is the active ester resin and the pi-allyl modified bismaleimide resin co-curing epoxy resin that use the present invention in the present invention, compare and use the system (comparative example 5) of active ester resin cured epoxy resin, and compare the system of the active ester resin cured epoxy resin only using (A-1)～(A-3), all significantly improve the thermostability after epoxy resin composition and toughness, also have the low-k of excellence, low-dielectric loss tangent simultaneously concurrently.
Claims (6)
1. a compositions of thermosetting resin, it is characterised in that with solid weight meter, including:
(a) active ester resin: 20 ~ 50 parts；
(b) epoxy resin: 10 ~ 60 parts；
(c) pi-allyl modified bismaleimide resin: 20 ~ 60 parts；
The structural formula of described active ester resin is as follows:,
Wherein, n is the integer of 1 ~ 10, and x is the integer of 1 ~ 5, and y is the integer of 1 ~ 10；Ar one in following structural:、、、、、、；
R is the carbon number alkyl less than or equal to 5, or phenyl, aminomethyl phenyl, xenyl, n-pro-pyl phenyl, isopropyl phenyl, tert-butyl-phenyl, 4-maleimidophenyl, p-nitrophenyl；
Ester functional groups's equivalent of described active ester resin is 200 ~ 300g/eq；
Described pi-allyl modified bismaleimide resin is the prepolymer produced by allyl compound and maleimide resin prepolymerization, and its number-average molecular weight is 2000 ~ 5000；One or more in allyl ether compound, allyl phenoxy resin, allyl phenol urea formaldehyde, diallyl bisphenol, diallyl bisphenol S of described allyl compound；Described maleimide resin is selected from 4,4 '-diphenyl methane dimaleimide resin, 4, one or more in 4 '-Diphenyl Ether Bismaleimide resin, 4,4 '-hexichol isopropyl bimaleimide resin, 4,4 '-diphenyl sulphone (DPS) bimaleimide resin.
2. resin combination according to claim 1, it is characterised in that: one or more in biphenyl type epoxy resin, naphthalene nucleus type epoxy resin, dicyclopentadiene type epoxy resin, aralkyl novolac epoxy resin of described epoxy resin.
3. resin combination according to claim 1, it is characterised in that: also include fire retardant, inorganic filler and curing accelerator.
4. resin combination according to claim 1, it is characterised in that: the one in following structural of the Ar in the structural formula of described active ester resin:
、、、。
5. the prepreg that any one resin combination adopted as described in claim 1 ~ 4 makes, it is characterized in that: any one resin combination solvent described in claim 1 ~ 4 is dissolved and makes glue, then reinforcing material is immersed in above-mentioned glue；After the reinforcing material heat drying after dipping, described prepreg can be obtained.
6. the laminate that any one resin combination adopted as described in claim 1 ~ 4 makes, it is characterized in that: the single or double at a prepreg described in claim 5 is covered with metal forming, or after at least 2 prepreg superpositions described in claim 5, it is covered with metal forming at its single or double, hot forming, can obtain described laminate.
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| CN106349442B (en) * | 2016-08-29 | 2018-08-21 | 苏州生益科技有限公司 | A kind of compositions of thermosetting resin and prepreg and laminate using its making |
| CN106243626B (en) * | 2016-08-29 | 2018-08-21 | 苏州生益科技有限公司 | A kind of compositions of thermosetting resin and prepreg and laminate using its making |
| CN106336662B (en) * | 2016-08-29 | 2018-10-19 | 苏州生益科技有限公司 | A kind of compositions of thermosetting resin and prepreg and laminate using its making |
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