CN104004323A - Resin composite and prepreg and laminated board made of same - Google Patents
Resin composite and prepreg and laminated board made of same Download PDFInfo
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- CN104004323A CN104004323A CN201410265974.2A CN201410265974A CN104004323A CN 104004323 A CN104004323 A CN 104004323A CN 201410265974 A CN201410265974 A CN 201410265974A CN 104004323 A CN104004323 A CN 104004323A
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Abstract
The invention discloses resin composite. The resin composite comprises, by solid weight, (a) 40-60 parts of active ester resin and (b) 30-60 parts of epoxy resin. Dyhydroxyl is not generated after the active ester resin cures the epoxy resin, and a low dielectric constant, low dielectric loss tangent and excellent humidity and heat resistance are given to condensate. Nitrogenous and phosphorus-contained perssads in the molecular structure of the active ester resin can play a role in nitrogen and phosphorus synergistic flame retardant, a maleinimide ring can play a role in body flame retardant, excellent fire resistance is achieved, and therefore the resin composite with the low dielectric constant, low dielectric loss tangent, excellent humidity and heat resistance and excellent fire resistance is obtained.
Description
Technical field
The present invention relates to a kind of resin combination, and the prepreg and the veneer sheet that use this resin combination to make, technical field of electronic materials belonged to.
Background technology
In recent years, along with the continuous propelling of information processing and information transmission high-speed high frequency technology, tellite material is being proposed to more and more higher requirement aspect dielectric properties.In simple terms, tellite material require possesses lower specific inductivity and dielectric loss tangent, delay, distortion and the loss of signal when reducing high-speed transfer, and the interference between signal.Therefore, expectation provides a kind of compositions of thermosetting resin, uses the printed circuit board material that this compositions of thermosetting resin is made can show fully low low-k and low-dielectric loss tangent at the signals transmission of high speed, high frequency.
In prior art, the material that epoxy resin and solidifying agent thereof prepared as compositions of thermosetting resin that must composition of take has good thermotolerance, insulativity, processibility and the advantage such as with low cost, is therefore widely used in the electronic materials such as semi-conductor, printed circuit board.The solidifying agent that epoxy resin is conventional has polyamines, acid anhydrides, resol etc., there is a large amount of hydroxyls in its curing epoxy resin in the solidifying agent as contained active hydrogen in amine, this quasi-molecule structure of resol, this can cause the water-intake rate of cured article to rise, and wet-hot aging performance and dielectric properties decline.The epoxy resin of anhydride-cured, although there is not hydroxyl, the reactivity of acid anhydrides is poor, the condition of cure of requirement is harsh.
The problems referred to above that occur when solving Common Curing Agents cured epoxy resin, it is found that active ester is a kind of very promising epoxy curing agent.Active ester just can react with epoxy resin under relatively mild condition; Meanwhile, the epoxy resin that active ester is curing, does not contain hydroxyl, the substitute is ester group, can obtain the epoxy resin-cured product that wet-hot aging performance and dielectric properties are good.Japanese Patent Laid-Open JP2002012650A, discloses a series of active ester resins in JP2003082063A, used as epoxy curing agent, can obviously reduce specific inductivity and the dielectric loss of epoxy resin cured product.A kind of active ester resin is disclosed in Chinese invention patent CN103221442A, by the partial cross-linked resistance toheat of improving its curing epoxy resin to active ester molecular resin main framing, with its curing epoxy resin, there is low-k, low-dielectric loss tangent, have excellent resistance toheat simultaneously concurrently.
On the other hand, when developing rapidly along with electronic technology, people are more and more higher to environmental protection requirement, and printed circuit board material is outside the pale of civilization except adapting to the high-speed high frequency of information transmission, also must tackle the challenge of environmental requirement.Traditional tellite material is mainly to reach fire-retardant object with halogenide, and during the circuit substrate ignition of halide, not only the amount of being fuming is large, the smell is awful, and can emit the hydrogen halide that toxicity is large, corrodibility is strong, not only contaminate environment, is also detrimental to health.Yet aforementioned disclosed active ester resin does not all relate to the research of halogen-free flameproof aspect.Therefore, develop a kind of active ester resin, by its curing epoxy resin cured product, can meet in high-speed high frequency Application Areas and there is fully low specific inductivity and the requirement of tangent of the dielectric loss angle, can meet again the requirement of halogen-free flameproof.
Summary of the invention
Goal of the invention of the present invention is to provide a kind of resin combination and uses prepreg and the veneer sheet of its making.
To achieve the above object of the invention, the technical solution used in the present invention is: a kind of resin combination, with solid weight meter, comprising:
(a) active ester resin: 40～60 parts;
(b) epoxy resin: 30～60 parts;
The structural formula of described active ester resin is as follows:
Wherein, the integer that n is 1～10, the integer that x is 1～5, the integer that y is 1～10;
R is
r wherein
1be selected from methyl, ethyl, propyl group, phenyl, aminomethyl phenyl, ethylphenyl, xenyl, n-propyl phenyl, isopropyl phenyl, tert-butyl-phenyl, dimaleoyl imino phenyl or nitrophenyl;
Ar is selected from a kind of in following structural:
in formula, R is
r
1be selected from methyl, ethyl, propyl group, phenyl, aminomethyl phenyl, ethylphenyl, xenyl, n-propyl phenyl, isopropyl phenyl, tert-butyl-phenyl, dimaleoyl imino phenyl or nitrophenyl;
The nitrogen content of described active ester resin is 0.1%～4.5%, and phosphorus content is 0.1%～5.0%.
Above, described active ester resin can make by the following method:
(1) first, small molecules phenolic compound, N-(4-hydroxy phenyl) maleimide, formaldehyde, acid catalyst are placed in to reaction vessel, are heated to 60～130 ℃ of reactions and within 1～15 hour, make nitrogenous multifunctional phenolic compound, structural formula is as follows:
in formula, n is repeating unit, the integer that mean value is 1～10; The value of x is 1～5 integer; The value of y is 1～10 integer; The structure of Ar is selected from one of lower array structure:
described small molecules phenolic compound can be selected from following phenolic compound: phenol, naphthols, xenol, '-biphenyl diphenol, Bisphenol F, dihydroxyphenyl propane, bisphenol S, bis-phenol ether;
Described acid catalyst can be selected from following acid compounds: hydrochloric acid, sulfuric acid, oxalic acid, phosphoric acid, Phenylsulfonic acid, mahogany acid, monochloroacetic acid;
(2) then, by above-mentioned nitrogenous multifunctional phenolic compound, 9, mix-10-phosphine phenanthrene-10-oxa-(DOPO) (phosphorous-containing monomers) of 10-dihydro-9-oxy, solvent are placed in reaction vessel, are heated to 70～150 ℃ of reactions and within 1～20 hour, make nitrogenous phosphorous multifunctional phenolic compound;
(3) finally by above-mentioned nitrogenous phosphorous multifunctional phenolic compound and carboxylic acid or the reaction of its carboxylic acid halides, can make described active ester resin.
Above, in the reaction of described nitrogenous phosphorous multifunctional phenolic compound and carboxylic acid or its carboxylic acid halides, adopt organic solvent and catalyzer, described organic solvent can be selected methyl iso-butyl ketone (MIBK), butanone, acetone, tetrahydrofuran (THF), toluene or their mixture, and described catalyzer can be selected one or more in sodium hydroxide, potassium hydroxide, DMAP, triethylamine, Lewis acid.
Preferably, the reaction of described nitrogenous phosphorous multifunctional phenolic compound and carboxylic acid or its carboxylic acid halides is preferably carried out 3～20 hours at room temperature to 80 ℃.
Described carboxylic acid can be selected from the alkylbenzoic acids such as phenylformic acid, Phenylbenzoic acid, tolyl acid, ethyl benzoate, n-propylbenzene formic acid, isopropyl acid, tert-butyl-phenyl acid, or the lipid acid such as formic acid, acetic acid, propionic acid, or the nitrogenous acid such as 4-maleimide yl benzoic acid, p-nitrobenzoic acid, and the carboxylic acid halides such as their acyl fluorides, acyl chlorides, acylbromide, acyl iodides, preferentially adopt acyl chlorides.Preferably, carboxylic acid is 4-maleimide yl benzoic acid.
In technique scheme, in the structural formula of described active ester resin, Ar is selected from a kind of in following structural:
in formula, R is
r
1be selected from methyl, ethyl, propyl group, phenyl, aminomethyl phenyl, ethylphenyl, xenyl, n-propyl phenyl, isopropyl phenyl, tert-butyl-phenyl, dimaleoyl imino phenyl or nitrophenyl.
Preferably, described R
1be selected from methyl, phenyl or dimaleoyl imino phenyl.
Preferably, the nitrogen content of described active ester resin is 1.5%～3.8%, and phosphorus content is 1.6%～3.0%.
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, described epoxy resin is selected from one or more in biphenyl type epoxy resin, naphthalene nucleus type epoxy resin, dicyclopentadiene type epoxy resin, aralkyl novolac epoxy resin.
In technique scheme, the ester group functional group equivalent of described active ester resin is 220～460g/eq.
In technique scheme, also comprise co-curing agent, mineral filler and curing catalyst.
Described co-curing agent can be the solidifying agent such as amine compound, acid amides based compound, acid anhydrides based compound, phenol system compound.Particularly, amine is that solidifying agent can be diaminodiphenyl-methane, diaminodiphenylsulfone(DDS), diethylenetriamine, bismaleimides, two carboxyl phthalic imidine, imidazoles etc.; Acid amides based compound can be Dyhard RU 100, Versamid etc.; Acid anhydrides based compound can be Tetra hydro Phthalic anhydride, trimellitic anhydride, pyromellitic acid anhydride, maleic anhydride, hydrogenation Tetra hydro Phthalic anhydride, carbic anhydride etc.; Phenol system compound can be phosphorus containing phenolic resin, Nitrogen-containing Phenolic Resins, bisphenol A phenolic resin, phenol resol, naphthol novolac resin, biphenyl modified phenolic resins, biphenyl modification naphthol resin, dicyclopentadiene type resol, phenol aralkyl resin, naphthols aralkyl resin, Pehanorm resin, benzoxazine colophony etc.Wherein, one or more in preferred bismaleimides, naphthol novolac resin, biphenyl modified phenolic resins, biphenyl modification naphthol resin, dicyclopentadiene type resol.
The content of described mineral filler amounts to 100 weight parts with respect to resin combination, is 5～200 weight parts.Described mineral filler is selected from one or more in powdered quartz, fused silica, preparing spherical SiO 2, aluminum oxide, aluminium hydroxide, aluminium nitride, boron nitride, titanium dioxide, strontium titanate, barium titanate, barium sulfate, talcum powder, Calucium Silicate powder, calcium carbonate, mica, tetrafluoroethylene.
Described curing catalyst adds and uses according to practical situation, can be selected from tertiary amine and salt thereof, pyridine, imidazoles, organic metal salt, triphenylphosphine Ji Qi phosphonium salt etc.
In above-mentioned resin combination, can also add additives such as using silane coupling agent, pigment, emulsifying agent, dispersion agent according to actual feelings.
Above-mentioned resin combination, can be for the manufacture of semiconductor-encapsulating material, adhering film, binding agent, resin cast material, conductive paste etc. for lamination.
The present invention asks for protection the prepreg that adopts above-mentioned resin combination to make simultaneously, and above-mentioned resin combination is made to glue by dissolution with solvents, then strongthener is immersed in above-mentioned glue; After flooding, after strongthener heat drying, can obtain described prepreg.
Described solvent is selected from one or more in acetone, butanone, toluene, mibk, N, dinethylformamide, N, N-N,N-DIMETHYLACETAMIDE, ethylene glycol monomethyl ether, propylene glycol monomethyl ether.Described strongthener can adopt natural fiber, organic synthetic fibers, organic fabric or without woven fabrics.
The present invention asks for protection the veneer sheet that adopts above-mentioned resin combination to make simultaneously; at a single or double by above-mentioned prepreg, be covered with tinsel; or after at least 2 are superposeed by above-mentioned prepreg; at its single or double, be covered with tinsel; hot compacting, can obtain described veneer sheet.
The quantity of described prepreg is that veneer sheet thickness is as requested determined, available one or more.Described tinsel, can be Copper Foil, can be also aluminium foil, and their thickness is not particularly limited.
Because technique scheme is used, the present invention compared with prior art has following advantages:
1. practical application proves, can not produce secondary hydroxyl after adopting active ester resin solidification epoxy resin of the present invention, gives cured article low-k, low-dielectric loss tangent and excellent wet-hot aging performance; Simultaneously, nitrogenous phosphorus-containing groups in active ester resinous molecular structure can be brought into play the effect of nitrogen-phosphorus cooperative flame retardant, body fire retardation is waved in maleimide environment-development, excellent flame retardant resistance is provided, thereby obtained thering is low-k, low-dielectric loss tangent, and had excellent humidity resistance and the resin combination of flame retardant resistance concurrently.
2. practical application proves: the veneer sheet being made by resin combination of the present invention can meet in high-speed high frequency Application Areas and has fully low specific inductivity and the requirement of tangent of the dielectric loss angle, can meet the requirement of halogen-free flameproof again, obtain significant effect, there is positive realistic meaning.
Embodiment
Below in conjunction with embodiment, the present invention is further described.
Embodiment and comparative example:
Embodiment 1～3rd, the nitrogenous phosphorous multifunctional phenolic compound of the present invention synthetic, and embodiment 4～8th, active ester resin synthetic, embodiment 9～14 and comparative example 1～2nd, the preparation of resin combination and evaluation of physical property.Hereinafter without special instruction, " part " representative " weight part ", " % " representative " % by weight ".
Embodiment 1
In the there-necked flask that thermometer, prolong, agitator are installed, drop into N-(4-hydroxy phenyl) maleimide (50g, 0.265mol), phenol (50g, 0.532mol) and oxalic acid (5g), after mixing and stirring, be placed in the water bath with thermostatic control of 70 ℃; Then, under agitation, with 0.5 hour, in flask, drip formaldehyde solution (ratio of phenol/aldehyde is 1/0.8 for 55mL, 37% formalin); Add after formaldehyde, the temperature and the agitation condition that maintain 70 ℃ react 15 hours; Then, with 200mL acetone by reaction product dissolved dilution, and then with the aqueous solution precipitin reaction product of 40% methyl alcohol; Repeat above dissolvings-precipitation operation 3～5 times, filtered, separation, be dried and obtain pure nitrogenous multifunctional phenolic compound; Then, get above-mentioned synthetic nitrogenous multifunctional phenolic compound (50g), with 9, mix-10-phosphine phenanthrene-10-oxa-(24g of 10-dihydro-9-oxy, 0.116mol) join in the there-necked flask that thermometer, prolong, agitator are installed, add in the mixing solutions (volume ratio 1/1) of 200mL toluene-tetrahydrofuran (THF), stirring and dissolving fully after, be heated to 85 ℃ and maintain isothermal reaction 20 hours; Separated removing after desolventizing, uses toluene wash product 3～5 times, obtains pure nitrogenous phosphorous multifunctional phenolic compound (P-1).The nitrogen content of resulting nitrogenous phosphorous multifunctional phenolic compound is 2.1%, and phosphorus content is 4.6%, and hydroxyl equivalent is 218g/eq.
Embodiment 2
In the there-necked flask that thermometer, prolong, agitator are installed, drop into N-(4-hydroxy phenyl) maleimide (50g, 0.265mol), dihydroxyphenyl propane (50g, 0.201mol) and oxalic acid (5g), after mixing and stirring, be placed in the water bath with thermostatic control of 70 ℃; Then, under agitation, with 0.5 hour, in flask, drip formaldehyde solution (ratio of phenol/aldehyde is 1/0.8 for 35mL, 37% formalin); Add after formaldehyde, the temperature and the agitation condition that maintain 70 ℃ react 15 hours; Then, with 200mL acetone by reaction product dissolved dilution, and then with the aqueous solution precipitin reaction product of 40% methyl alcohol; Repeat above dissolvings-precipitation operation 3～5 times, filtered, separation, be dried and obtain pure nitrogenous multifunctional phenolic compound; Then, get above-mentioned synthetic nitrogenous multifunctional phenolic compound (50g), with 9, mix-10-phosphine phenanthrene-10-oxa-(26g of 10-dihydro-9-oxy, 0.116mol) join in the there-necked flask that thermometer, prolong, agitator are installed, add in the mixing solutions (volume ratio 1/1) of 200mL toluene-tetrahydrofuran (THF), stirring and dissolving fully after, be heated to 85 ℃ and maintain isothermal reaction 20 hours; Separated removing after desolventizing, uses toluene wash product 3～5 times, obtains pure nitrogenous phosphorous multifunctional phenolic compound (P-2).The nitrogen content of resulting nitrogenous phosphorous multifunctional phenolic compound is 2.2%, and phosphorus content is 4.8%, and hydroxyl equivalent is 252g/eq.
Embodiment 3
In the there-necked flask that thermometer, prolong, agitator are installed, drop into N-(4-hydroxy phenyl) maleimide (20g, 0.106mol), phenol (90g, 0.978mol) and oxalic acid (5g), after mixing and stirring, be placed in the water bath with thermostatic control of 70 ℃; Then, under agitation, with 0.5 hour, in flask, drip formaldehyde solution (ratio of phenol/aldehyde is 1/0.8 for 55mL, 37% formalin); Add after formaldehyde, the temperature and the agitation condition that maintain 70 ℃ react 15 hours; Then, with 200mL acetone by reaction product dissolved dilution, and then with the aqueous solution precipitin reaction product of 40% methyl alcohol; Repeat above dissolvings-precipitation operation 3～5 times, filtered, separation, be dried and obtain pure nitrogenous multifunctional phenolic compound; Then, get above-mentioned synthetic nitrogenous multifunctional phenolic compound (50g), with 9, mix-10-phosphine phenanthrene-10-oxa-(9.5g of 10-dihydro-9-oxy, 0.044mol) join in the there-necked flask that thermometer, prolong, agitator are installed, add in the mixing solutions (volume ratio 1/1) of 200mL toluene-tetrahydrofuran (THF), stirring and dissolving fully after, be heated to 85 ℃ and maintain isothermal reaction 20 hours; Separated removing after desolventizing, uses toluene wash product 3～5 times, obtains pure nitrogenous phosphorous multifunctional phenolic compound (P-3).The nitrogen content of resulting nitrogenous phosphorous multifunctional phenolic compound is 1.0%, and phosphorus content is 2.2%, and hydroxyl equivalent is 149g/eq.
Embodiment 4
In the flask that thermometer, prolong, dropping funnel, fractionating tube, agitator are installed, drop into the nitrogenous phosphorous multifunctional phenolic compound of 218g (the synthetic product P-1 in embodiment 1: nitrogen content is 2.1%, phosphorus content is 4.6%, hydroxyl equivalent is 218g/eq) and 1200g methyl iso-butyl ketone (MIBK), abundant mixed dissolution, by the logical nitrogen of decompression in reaction system, and system temperature is controlled to 65 ℃; Then, with 1 hour, in reaction system, drip 20% sodium hydroxide solution 20g; Then, drop into 155g Benzoyl chloride (1.1mol), then, with 3 hours, in system, drip 20% sodium hydroxide solution 200g, after dropwising, at 65 ℃, maintain reaction 3 hours; After having reacted, water layer is removed in separation; Then in system, add water again, stirring and washing, water layer is removed in separation; Repeat above cleaning operation 3～5 times; Then vacuumize decompression and remove methyl iso-butyl ketone (MIBK), obtain active ester resin (A-1); Functional group's equivalent of this active ester resin (A-1) is 323g/eq according to input ratio, and N content is 1.4%, and phosphorus content is 3.2%; Its structural formula is as follows:
n is 1～10 integer, the integer that x is 1～5, the integer that y is 1～10.
Embodiment 5
In the flask that thermometer, prolong, agitator are installed, drop into the nitrogenous phosphorous multifunctional phenolic compound of 218g (the synthetic product P-1 in embodiment 1: nitrogen content is 2.1%, phosphorus content is 4.6%, hydroxyl equivalent is 218g/eq) and 1500g tetrahydrofuran solvent, abundant mixed dissolution, by the logical nitrogen of decompression in reaction system, and system temperature is controlled to 30 ℃; Then, drop into 235g4-maleimide yl benzoic acid (1mol), and add the AlCl3 of catalytic amount and the mixture of ZnCl2 as catalyzer, at 30 ℃, maintain reaction 8 hours; After having reacted, separating-purifying product, obtains active ester resin (A-2); Functional group's equivalent of this active ester resin (A-2) is 415g/eq according to input ratio, and N content is 4.4%, and phosphorus content is 2.4%; Its structural formula is as follows:
n is 1～10 integer, the integer that x is 1～5, the integer that y is 1～10.
Embodiment 6
In the flask that thermometer, prolong, dropping funnel, fractionating tube, agitator are installed, drop into the nitrogenous phosphorous multifunctional phenolic compound of 252g (the synthetic product P-2 in embodiment 2: nitrogen content is 2.2%, phosphorus content is 4.8%, hydroxyl equivalent is 252g/eq) and 1500g methyl iso-butyl ketone (MIBK), abundant mixed dissolution, by the logical nitrogen of decompression in reaction system, and system temperature is controlled to 65 ℃; Then, with 1 hour, in reaction system, drip 20% sodium hydroxide solution 20g; Then, drop into 140g Benzoyl chloride (1mol), then, with 3 hours, in system, drip 20% sodium hydroxide solution 200g, after dropwising, at 65 ℃, maintain reaction 3 hours; After having reacted, water layer is removed in separation; Then in system, add water again, stirring and washing, water layer is removed in separation; Repeat above cleaning operation 3～5 times; Then vacuumize decompression and remove methyl iso-butyl ketone (MIBK), obtain active ester resin (A-3).Functional group's equivalent of this active ester resin (A-3) is 356g/eq according to input ratio, and N content is 1.5%, and phosphorus content is 3.4%; Its structural formula is as follows:
n is 1～10 integer, the integer that x is 1～5, the integer that y is 1～10.
Embodiment 7
In the flask that thermometer, prolong, dropping funnel, fractionating tube, agitator are installed, drop into the nitrogenous phosphorous multifunctional phenolic compound of 252g (the synthetic product P-2 in embodiment 2: nitrogen content is 2.2%, phosphorus content is 4.8%, hydroxyl equivalent is 218g/eq) and 2000g methyl iso-butyl ketone (MIBK), abundant mixed dissolution, by the logical nitrogen of decompression in reaction system, and system temperature is controlled to 65 ℃; Then, with 1 hour, in reaction system, drip 20% sodium hydroxide solution 20g; Then, drop into 235g4-dimaleoyl imino Benzoyl chloride (1mol), with 3, in system, drip 20% sodium hydroxide solution 200g, after dropwising, at 65 ℃, maintain reaction 3 hours; After having reacted, water layer is removed in separation; Then in system, add water again, stirring and washing, water layer is removed in separation; Repeat above cleaning operation 3～5 times; Then vacuumize decompression methyl iso-butyl ketone (MIBK) is removed, obtain active ester resin (A-4).Functional group's equivalent of this active ester resin (A-4) is 451g/eq according to input ratio, and N content is 4.3%, and phosphorus content is 2.7%, and its structural formula is as follows:
n is 1～10 integer, the integer that x is 1～5, the integer that y is 1～10.
Embodiment 8
In the flask that thermometer, prolong, dropping funnel, fractionating tube, agitator are installed, drop into the nitrogenous phosphorous multifunctional phenolic compound of 149g (the synthetic product P-3 in embodiment 3: nitrogen content is 1.0%, phosphorus content is 2.2%, hydroxyl equivalent is 149g/eq) and 800g methyl iso-butyl ketone (MIBK), abundant mixed dissolution, by the logical nitrogen of decompression in reaction system, and system temperature is controlled to 65 ℃; Then, with 1 hour, in reaction system, drip 20% sodium hydroxide solution 20g; Then, drop into 160g Benzoyl chloride (1.15mol), then, with 3 hours, in system, drip 20% sodium hydroxide solution 200g, after dripping, at 65 ℃, maintain reaction 3 hours; After having reacted, water layer is removed in separation; Then in system, add water again, stirring and washing, water layer is removed in separation; Repeat above cleaning operation 3～5 times; Then vacuumize decompression and remove methyl iso-butyl ketone (MIBK), obtain active ester resin (A-5).Functional group's equivalent of this active ester resin (A-5) is 253g/eq according to input ratio, and N content is 0.6%, and phosphorus content is 1.3%, and its structure is with (A-1).
Embodiment 9～14 and comparative example 1～2
The formula of recording according to table 1, the biphenyl type epoxy resin that is mixed, epoxy curing agent, and then, add curing catalyst, all components is fully dissolved in in ethylene glycol monomethyl ether, to be mixed with solid content be 60% resin combination; Wherein the epoxy curing agent of embodiment 9～13 is the active ester resin of (A-1)～(A-5), and the epoxy curing agent of comparative example 1～2 is respectively common active ester resin, nitrogenous phosphorous multifunctional phenolic compound P-2 (resol).In addition, the phosphorous epoxy resin being used in conjunction with in formula regulates phosphorus content.Then make under the following conditions veneer sheet, and by following method evaluation flame retardant resistance, wet-hot aging performance and dielectric characteristics.The results are shown in table 1.
< veneer sheet manufacturing conditions > base material: ordinary electronic level 2116 glass-fiber-fabrics; The number of plies: 5; Preimpregnation semicure condition: 165 ℃/5min; Condition of cure: 150 ℃/60min+200 ℃/90min; Sheet metal thickness after moulding: 1.0mm.
< flame retardant resistance > measures according to UL94 method.
After < wet-hot aging performance > wet heat treatment, test wicking thermotolerance (PCT), getting 3 10cm * 10cm, thickness is the sample that tinsel is removed on 1.0mm, two sides, at 100 ℃, be dried 2 hours, then pressure-cook test (Pressure Cooker test) machine, under 121 ℃, 2 normal atmosphere, process after 1 hour, wicking 20s in the tin stove of 288 ℃, whether visual observations has demixing phenomenon.In 3, if any 0,1,2,3 demixing phenomenons are designated as respectively 0/3,1/3,2/3,3/3.
The mensuration > specific inductivity of < specific inductivity and dielectric loss tangent is used flat band method according to IPC-TM-6502.5.5.9, measure the specific inductivity under 1GHz, dielectric loss tangent: use flat band method according to IPC-TM-6502.5.5.9, measure the dielectric loss factor under 1GHz.
Table 1
The footnote of table 1:
The active ester resin (A-1) making in A-1: embodiment 4;
The active ester resin (A-2) making in A-2: embodiment 5;
The active ester resin (A-3) making in A-3: embodiment 6;
The active ester resin (A-4) making in A-4: embodiment 8;
The active ester resin (A-5) making in A-5: embodiment 10;
The multifunctional phenolic compound (P-2) making in P-2: embodiment 2;
Biphenyl type epoxy resin: Japanese chemical drug, epoxy equivalent (weight) 265g/eq, 60 ℃ of softening temperatures;
Common active ester resin: Japanese DIC, HPC-8000-65T;
Phosphorous epoxy resin: epoxy equivalent (weight) is 240q/eq, phosphorus content is 3.2%;
Co-curing agent: dicyclopentadiene type resol, can Longhua work, sense equivalent 170g/eq;
Curing catalyst: dimethyl aminopyridine;
Filler: silicon-dioxide.
From upper table, comparative example 1 is used common active ester resin solidification epoxy resin, although the cured article obtaining has lower specific inductivity, dielectric loss tangent value and good wet-hot aging performance, flame retardant properties is very poor.Comparative example 2 is used nitrogenous phosphorus containing phenolic resin (multifunctional phenolic compound) cured epoxy resin, although the cured article obtaining has good flame retardant properties, specific inductivity and dielectric loss tangent value are all higher, and wet-hot aging performance is very poor.What embodiment 9～14 adopted is the nitrogenous phosphorous active ester resin solidification epoxy resin in the present invention, reduced the addition of phosphorus fire retardant, the cured article obtaining has lower specific inductivity, dielectric loss tangent and excellent wet-hot aging performance, also has good flame retardant resistance simultaneously.
Claims (9)
1. a resin combination, is characterized in that, with solid weight meter, comprising:
(a) active ester resin: 40 ~ 60 parts;
(b) epoxy resin: 30 ~ 60 parts;
The structural formula of described active ester resin is as follows:
,
Wherein, the integer that n is 1 ~ 10, the integer that x is 1 ~ 5, the integer that y is 1 ~ 10;
R is
, R wherein
1be selected from methyl, ethyl, propyl group, phenyl, aminomethyl phenyl, ethylphenyl, xenyl, n-propyl phenyl, isopropyl phenyl, tert-butyl-phenyl, dimaleoyl imino phenyl or nitrophenyl;
Ar is selected from a kind of in following structural:
,
,
,
,
,
,
,
,
,
,
,
,
,
; In formula, R is
, R
1be selected from methyl, ethyl, propyl group, phenyl, aminomethyl phenyl, ethylphenyl, xenyl, n-propyl phenyl, isopropyl phenyl, tert-butyl-phenyl, dimaleoyl imino phenyl or nitrophenyl;
The nitrogen content of described active ester resin is 0.1% ~ 4.5%, and phosphorus content is 0.1% ~ 5.0%.
2. resin combination according to claim 1, is characterized in that: in the structural formula of described active ester resin, Ar is selected from a kind of in following structural:
,
,
, in formula, R is
, R
1be selected from methyl, ethyl, propyl group, phenyl, aminomethyl phenyl, ethylphenyl, xenyl, n-propyl phenyl, isopropyl phenyl, tert-butyl-phenyl, dimaleoyl imino phenyl or nitrophenyl.
3. resin combination according to claim 1, is characterized in that: described R
1be selected from methyl, phenyl or dimaleoyl imino phenyl.
4. resin combination according to claim 1, is characterized in that: the nitrogen content of described active ester resin is 1.5% ~ 3.8%, and phosphorus content is 1.6% ~ 3.0%.
5. resin combination according to claim 1, is characterized in that: described epoxy resin is selected from one or more in biphenyl type epoxy resin, naphthalene nucleus type epoxy resin, dicyclopentadiene type epoxy resin, aralkyl novolac epoxy resin.
6. resin combination according to claim 1, is characterized in that: the ester group functional group equivalent of described active ester resin is 220 ~ 460 g/eq.
7. resin combination according to claim 1, is characterized in that: also comprise co-curing agent, mineral filler and curing catalyst.
8. the prepreg that an employing any one resin combination as described in claim 1 ~ 7 is made, it is characterized in that: any one resin combination described in claim 1 ~ 7 is made to glue by dissolution with solvents, then strongthener is immersed in above-mentioned glue; By after the strongthener heat drying after dipping, can obtain described prepreg.
9. the veneer sheet that an employing any one resin combination as described in claim 1 ~ 7 is made, it is characterized in that: at a single or double by prepreg claimed in claim 8, be covered with tinsel, or after at least 2 are superposeed by prepreg claimed in claim 8, at its single or double, be covered with tinsel, hot compacting, can obtain described veneer sheet.
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Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN106243430A (en) * | 2016-08-29 | 2016-12-21 | 苏州生益科技有限公司 | A kind of compositions of thermosetting resin and use its prepreg made and laminate |
| CN107868228A (en) * | 2016-09-28 | 2018-04-03 | 广东生益科技股份有限公司 | A kind of phosphorous imido organosilicon epoxy resin and its preparation method and application |
| CN111960956A (en) * | 2019-05-20 | 2020-11-20 | 广东生益科技股份有限公司 | Amino-terminated active ester, preparation method thereof, thermosetting resin composition and application thereof |
| WO2020232596A1 (en) * | 2019-05-20 | 2020-11-26 | 广东生益科技股份有限公司 | Active ester with amino groups at two ends, preparation method therefor, thermosetting resin composition and use thereof |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US10252965B2 (en) * | 2015-11-11 | 2019-04-09 | Air Water Inc. | Vinylbenzylated phenol compound, method of manufacturing vinylbenzylated phenol compound, activated ester resin, method of manufacturing activated ester resin, thermoset resin composition, hardened material of thermoset resin composition, interlayer insulating material, prepreg, and method of manufacturing prepreg |
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Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN106243430A (en) * | 2016-08-29 | 2016-12-21 | 苏州生益科技有限公司 | A kind of compositions of thermosetting resin and use its prepreg made and laminate |
| CN107868228A (en) * | 2016-09-28 | 2018-04-03 | 广东生益科技股份有限公司 | A kind of phosphorous imido organosilicon epoxy resin and its preparation method and application |
| CN107868228B (en) * | 2016-09-28 | 2019-09-13 | 广东生益科技股份有限公司 | Phosphorous imido organosilicon epoxy resin of one kind and its preparation method and application |
| CN111960956A (en) * | 2019-05-20 | 2020-11-20 | 广东生益科技股份有限公司 | Amino-terminated active ester, preparation method thereof, thermosetting resin composition and application thereof |
| WO2020232596A1 (en) * | 2019-05-20 | 2020-11-26 | 广东生益科技股份有限公司 | Active ester with amino groups at two ends, preparation method therefor, thermosetting resin composition and use thereof |
| CN111960956B (en) * | 2019-05-20 | 2022-12-30 | 广东生益科技股份有限公司 | Amino-terminated active ester, preparation method thereof, thermosetting resin composition and application thereof |
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