CN109810467A - A kind of compositions of thermosetting resin and prepreg and laminate using its preparation - Google Patents
A kind of compositions of thermosetting resin and prepreg and laminate using its preparation Download PDFInfo
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- CN109810467A CN109810467A CN201910075087.1A CN201910075087A CN109810467A CN 109810467 A CN109810467 A CN 109810467A CN 201910075087 A CN201910075087 A CN 201910075087A CN 109810467 A CN109810467 A CN 109810467A
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Abstract
The invention discloses a kind of compositions of thermosetting resin, in parts by weight, comprising: (a) epoxy resin: 100 parts；(b) the modified unsaturated polyester (UP) active ester resin of alkenes crosslinking agent: 50 ~ 300 parts；(c) promotor: 0.05 ~ 4 part.Modified Products By Modification of Active Esters And Epoxy Resin system and hydrocarbon resin curing system can be effectively combined by the modified unsaturated polyester (UP) active ester resin of alkenes crosslinking agent of the invention by way of chemical bond, the excellent properties of the excellent properties of active ester cured epoxy system and hydrocarbon resin are effectively combined, so that resin combination has both excellent dielectric properties, heat resistance, intensity, hard and soft after solidifying, peel strength is high, water absorption rate is low, percent thermal shrinkage is small, can be applied to high speed, high frequency printed wiring board.
Description
Technical field
The present invention relates to the prepregs and laminate of its preparation of a kind of compositions of thermosetting resin and application, belong to electronics
Field of material technology.
Background technique
In recent years, with the continuous propulsion of information processing and information transmission 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 lower
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.
In view of the above technical problems, in the prior art, the epoxy-resin systems using active ester resin solidification are available
The excellent cured product of dielectric properties.But there is heat resistance deficiency in the epoxy resin of active ester resin solidification, it is difficult
To take into account heat resistance and low-k, low-dielectric loss tangent, thus the requirement not being able to satisfy in material practical application.
On the other hand, hydrocarbon resin, for example, polybutadiene, butadiene and styrene the resins such as copolymer also have it is excellent
Dielectric properties, be increasingly becoming one of mainstream technology of this field.However, a large amount of studies have shown that although hydrocarbon resin can
Good dielectric properties are provided, but since hydrocarbon resin is flexible, non-polar carbon chains structure, are existed after causing hydrocarbon resin to solidify
Rigidity is insufficient, intensity is low, poor heat resistance, the problems such as glass transition temperature is low, cementability is poor, and there are still very in practical application
More problems need to solve.
Thus, develop a kind of new compositions of thermosetting resin, using its production printed circuit board material high speed,
The signals transmission of high frequency can show substantially low low-k and low-dielectric loss tangent, at this field
One of main R&D direction.
Summary of the invention
Goal of the invention of the invention is to provide a kind of thermosetting epoxy resin composition and the prepreg using its preparation
And laminate.
To achieve the above object of the invention, the technical solution adopted by the present invention is that: a kind of compositions of thermosetting resin, with weight
Part meter, comprising:
(a) epoxy resin: 100 parts；
(b) the modified unsaturated polyester (UP) active ester resin of alkenes crosslinking agent: 50~300 parts；
(c) promotor: 0.05~4 part；
The modified unsaturated polyester (UP) active ester of the alkenes crosslinking agent is by vinyl monomer, unsaturated polyester (UP)
The mixture or prepolymer that active ester, initiator mix, the unsaturated polyester (UP) active ester
Structural formula is as follows:
Wherein:
N value is 0.5~10；
X1Selected from-CH=CH-,One or more of, and must containing-CH=
CH-；
Y1Selected from one of following groups or several:
Ya Naiji ether,
Middle Z1It is isopropylidene, cyclopentadienylidene, sulfuryl, methylene or oxygen atom, Rx is hydrogen atom or carbon atom
Number is less than or equal to 5 alkyl；
Ra is hydrogen atom, benzoyl, substituted benzoyl or alkyl acyl；
Rb is hydrogen atom, phenyl or substituted-phenyl.
Above, the modified unsaturated polyester (UP) active ester of the alkenes crosslinking agent is that vinyl monomer, unsaturated polyester (UP) is living
The mixture or prepolymer that property ester, initiator mix；When for vinyl monomer, unsaturated polyester (UP) active ester, initiator
When mixture, refer to the state of its physical blending, but in subsequent temperature-rise period, vinyl monomer and unsaturated polyester (UP) active ester are also
It is that can be chemically reacted under the action of initiator, forms polymer.
The amount of the modified unsaturated polyester (UP) active ester resin of the alkenes crosslinking agent can be 55 parts, 60 parts, 65 parts, 70
Part, 90 parts, 100 parts, 120 parts, 150 parts, 180 parts, 200 parts, 210 parts, 230 parts, 250 parts, 260 parts, 270 parts, 280 parts, 290
Part, 295 parts.
In the structural formula of the unsaturated polyester (UP) active ester, n value is 0.5~10, can be 1,2,3,4,5,6,7,8,9,
Preferably 1~10 integer, more preferably 1~8, more preferably 2~6, more preferably 3~5.
The X1Selected from-CH=CH-,One or more of, and must contain-
CH=CH-；
X1Can have in group a certain proportion ofGroup；Work as X1Group has centainly
RatioWhen, it can effectively improve the tacky problem of hydrocarbon resin,Ratio be preferably total X110%~50% molar ratio of group.
It further include the initiator for having 0.05~25 part in the modified unsaturated polyester (UP) active ester of the alkenes crosslinking agent.This draws
Hair agent refer to the compound that free radical is resolved by thermal energy, can be used for causing alkenes, double vinyl monomers free radical polymerization and altogether
Polymerization reaction, it can also be used to which the crosslinking curing and high molecular crosslink of unsaturated polyester (UP) react.The initiator can be azo
Initiator, peroxide initiator, redox type initiators can be one or more of following initiator: tert-butyl mistake
Hydrogen oxide, cumyl peroxide, di-t-butyl peroxide, peroxidized t-butyl perbenzoate, di-cyclohexylperoxy di-carbonate,
Isopropyl benzene hydroperoxide, azodiisobutyronitrile, benzoyl peroxide.The preferred tert-butyl hydroperoxide of the initiator, peroxidating
One or more of diisopropylbenzene (DIPB), di-t-butyl peroxide, peroxidized t-butyl perbenzoate.The initiator additive amount is
0.005~10 parts by weight, specific additive amount may is that 0.005 parts by weight, 0.01 parts by weight, 0.02 parts by weight, 0.05 weight
Part, 0.10 parts by weight, 0.20 parts by weight, 0.50 parts by weight, 1 parts by weight, 3 parts by weight, 5 parts by weight, 8 parts by weight, 10 parts by weight.
Above, in the molecular structure of the unsaturated polyester (UP) active ester in the component (b) in addition to reactive
Except unsaturated double-bond, also there is the active ester groups that reaction can be cured with epoxy resin, reaction official in entire strand
Energy group is more, and the crosslink density after solidifying crosslinking is big, can effectively improve the heat resistance and mechanical strength of resin curing system.Group
The special construction for dividing (b), Modified Products By Modification of Active Esters And Epoxy Resin system and hydrocarbon resin curing system are had by way of chemical bond
Effect combines, and active ester cured epoxy system imparts the preferable adhesive property of resin system, improves laminate copper foil layer
Peel strength between resin layer, while the dielectric properties of resin system are had no effect on, hydrocarbon resin curing system imparts
The extraordinary dielectric properties of material and toughness.
In above-mentioned technical proposal, the epoxy resin is selected from bisphenol A epoxide resin, bisphenol F epoxy resin, phosphorous asphalt mixtures modified by epoxy resin
Rouge, nitrogen-containing epoxy thermoset, o-cresol formaldehyde epoxy resin, bisphenol-A phenolic epoxy resin, phenol novolac epoxy resins, cresol novolac
Epoxy resin, 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, polyphenyl ether modified epoxy
One of resin, alicyclic based epoxy resin, glycidyl amine type epoxy resin, glycidyl ester type epoxy resin are several
Kind.
Preferably, the epoxy resin is selected from biphenyl type epoxy resin, naphthalene nucleus type epoxy resin, dicyclopentadiene type epoxy
One or more of resin, aralkyl novolac epoxy resin.
In above-mentioned technical proposal, the promotor is selected from one or more of following substance: dimethyl aminopyridine, uncle
Amine and its salt, imidazoles, organic metal salt, triphenylphosphine are Ji Qi phosphonium salt.It is preferred that dimethyl aminopyridine；Specific additive amount can be with
It is: 0.005 parts by weight, 0.01 parts by weight, 0.02 parts by weight, 0.05 parts by weight, 0.10 parts by weight, 0.20 parts by weight, 0.50 weight
Measure part, 1 parts by weight, 2 parts by weight, 3 parts by weight, 4 parts by weight.
In above-mentioned technical proposal, the ratio of the vinyl monomer and unsaturated polyester (UP) active ester, with the official of unsaturated double-bond
Energy equivalent meter is 0.05:1~5:1.Preferably 0.5:1~4:1, more preferably 1:1~3:1, more preferably 2:1~3:1, it is excellent
It is selected as 2.5:1.
In above-mentioned technical proposal, the vinyl monomer is selected from styrene, substituted phenylethylene, methyl acrylate, replaces propylene
One or more of sour methyl esters, maleimide resin, and must wherein contain maleimide resin.Preferably, alkenes
Contain maleimide resin in monomer；The maleimide resin is bismaleimide, single maleimide, More Malay
Acid imide.The mass ratio of the maleimide resin and other alkenes crosslinking agent summations is 5:100~50:100.The alkene
The addition of class monomer can be very good to improve aathermoset resin system to the wellability of glass fabric.
It further include component (d) in above-mentioned technical proposal, the component (d) is selected from hydrocarbon resin, vinyl modified span comes
Acid imide, vinyl modified polyphenylene oxide, vinyl modified benzoxazine resin, vinyl modified phenolic resin, olefin copolymer,
One or more of Petropols, mono-component polyurethane resin.The component (d) is preferably hydrocarbon resin, vinyl modified
Bismaleimide, vinyl modified polyphenylene oxide, vinyl modified benzoxazine resin, one in vinyl modified phenolic resin
Kind is several.
Preferably, the vinyl modified phenolic resin is vinyl modified dimaleoyl imino phenolic resin, vinyl
Modified linear phenol-aldehyde resin or dicyclopentadiene-ethylene benzyl phenylate.The dicyclopentadiene-ethylene benzyl phenylene ether resins have
Such as flowering structure:
；
Wherein Ry2It is hydrogen atom or alkyl, the integer that n is 1~10.
In above-mentioned technical proposal, hydrocarbon resin in butadiene styrene resin, polybutadiene, polyisobutene resin one
Kind is several.Preferably, hydrocarbon resin is that number-average molecular weight is greater than less than 11000, contents of ethylene in above-mentioned technical proposal
It 60%, is at room temperature the hydrocarbon resin of liquid.Preferably, hydrocarbon resin is number-average molecular weight less than 7000.In the component (d)
Hydrocarbon resin is specifically as follows: 10 parts by weight, 20 parts by weight, 40 parts by weight, 50 parts by weight, 60 parts by weight, 80 parts by weight, 100
Parts by weight, 150 parts by weight, 200 parts by weight.
Component (d) the medium vinyl modified bismaleimide is selected from by allyl compound and maleimide resin
The prepolymer that prepolymerization generates, the allyl compound are selected from allyl ether compound, allyl phenoxy resin, allyl phenol
One or more of urea formaldehyde, diallyl bisphenol, diallyl bisphenol S；The maleimide resin is selected from 4,4 '-
Diphenyl methane dimaleimide resin, 4,4 '-Diphenyl Ether Bismaleimide resins, 4,4 '-hexichol isopropyl spans carry out acyl
One or more of imide resin, 4,4 '-diphenyl sulphone (DPS) bimaleimide resins.Preferably, the vinyl modified span
Carrying out imido number-average molecular weight is 2000~5000g/mol.
The vinyl modified polyphenylene oxide of the component (d) is selected from phenylethene modified polyphenylene oxide, substituted phenylethylene modified polyphenyl
Ether, acrylate modified polyphenylene oxide, substituted acrylate Noryl etc. contain one in unsaturated double-bond Noryl
Kind is several.The adding proportion of the vinyl modified polyphenylene oxide is 20~200 parts by weight.The vinyl modified polyphenylene oxide can
To advanced optimize heat resistance and dielectric properties, especially there is positive effect to the dielectric loss tangent value for reducing resin system,
But addition excessively will limit the raising of resin system adhesive property.Preferably, the molecular weight of the vinyl modified polyphenylene oxide
Less than 5000.Preferably, the vinyl modified polyphenylene oxide is in compound shown in following structural formula (one), (two), (three)
One or several kinds:
Structural formula (one):
；
Wherein X2Selected from having structure:
Wherein R1、R3、R6、R8、R9、R11、R14、R16、R17、R19、R22、
R24It is same or different, respectively halogen atom, alkyl or phenyl；Wherein R2、R4、R5、R7、R10、R12、R15、R18、R20、
R21、R23It is same or different, it is hydrogen atom, halogen atom, alkyl or phenyl respectively；
- Y in structural formula (one)2- O- structure are as follows:Wherein R26、R28It is same or different, point
It is not halogen atom, alkyl or phenyl, R25、R27It is respectively selected from hydrogen atom, halogen atom, alkyl or phenyl；
M, n respectively represent 0~30 integer in structural formula (one), and cannot simultaneously be 0.
Structural formula (two):
Wherein n is greater than 5 integer.
Structural formula (three):
；
Wherein Y3Are as follows: Wherein m, n are greater than the integer equal to 1 respectively.
Vinyl modified benzoxazine resin in the component (d) is selected from allyl modified bisphenol A type benzoxazine, alkene
Modified bis-phenol g type benzoxazine, allyl modified bisphenol S type benzoxazine, two amine type benzoxazine of bis-phenol, allyl change
One or more of property dicyclopentadiene phenolic benzoxazine.Preferably, the allyl modified benzoxazine resin adds
Adding ratio is 1~20 parts by weight.Add suitable component (d) allyl modified benzoxazine resin can advanced optimize it is heat-resisting
Performance and adhesive property, but add excessively can dielectric properties to resin system and toughness cause adverse effect.
Vinyl modified phenolic resin in the component (d) is preferably vinyl modified linear phenol-aldehyde resin, vinyl
One or more of modified maleimide base phenolic resin, dicyclopentadiene-ethylene benzyl phenylate, more preferably bicyclic penta
Diene-ethylene benzyl phenylate.
The resin that the vinyl modified linear phenol-aldehyde resin has the following structure:
Wherein Ry1It is hydrogen atom or alkyl, the integer that n is 1~10.
Vinyl modified dimaleoyl imino phenolic resin in the component (d) is the resin having the following structure:
Wherein, it be 1~10, k is 1~10 that m, which is 2~20, n,.
Petropols in the component (d) are selected from alicyclic petroleum resin (DCPD), aromatic petroleum resin (C9), rouge
One or more of fat race/aromatic copolyester Petropols (C5/C9).Preferably, the molecular weight of the Petropols is
1000~3000g/mol.Preferably, the adding proportion of the Petropols is 5~25 parts by weight.Add suitable component (d)
Petropols, while the dielectric properties and adhesive property of resin system can be advanced optimized, moreover it is possible to improve resin system
Mobile performance improves processing performance.
In above-mentioned technical proposal, the compositions of thermosetting resin can also include amine compound, amide based compound,
The co-curings agent components (e) such as acid anhydrides based compound, phenol system compound, cyanate.Specifically, amine system curing agent can be diamino
Base diphenyl methane, diaminodiphenylsulfone, diethylenetriamines, double carboxyl phthalimides, imidazoles etc.；Amide system chemical combination
Object can be dicyandiamide, Versamid etc.；Acid anhydrides based compound can be phthalic anhydride, trimellitic anhydride,
Pyromellitic dianhydride, maleic anhydride, hydrogenated phthalic anhydride, carbic anhydride etc.；Phenol system compound can be phosphorus-containing phenolic aldehyde
Resin, Nitrogen-containing Phenolic Resins, bisphenol A phenolic resin, phenol novolacs, naphthol novolac resin, biphenyl phenol-formaldehyde resin modified, connection
Benzene is modified naphthol resin, dicyclopentadiene phenol add-on type resin, phenol aralkyl resin, naphthols aralkyl resin, three hydroxyl first
Methylmethane resin, benzoxazine resin etc..The co-curing agent preferred acid anhydride curing agent, cyanate curing agent.The cyanic acid
Ester resin refers to the compound containing cyanic acid ester group in structure, can be bisphenol A cyanate ester resin, bisphenol A cyanate resin, double
Phenol M cyanate ester resin, o-cresol aldehyde type epoxy resin, phenol type cyanate ester resin, gathers dicyclopentadiene type ethylene rhodanate resin
One or more of phenylate modified cyanic acid ester resin.Preferably, the adding proportion of component (e) cyanate ester resin be 10~
200 parts by weight.Add suitable component (e) cyanate ester resin can advanced optimize the heat resistance of resin system, cementability and
Dielectric properties, but add the decline that excessively will lead to the wet-hot aging performance of resin system.
It further include curing agent in above-mentioned technical proposal, the curing agent is amine compound, amide based compound, acid anhydrides
Based compound, phenol system compound or cyanate.
Based on the above technical solution, the compositions of thermosetting resin can also include the group of 1~80 parts by weight
Divide (f) fire retardant.The fire retardant can be bromide fire retardant, phosphorus flame retardant, nitrogenated flame retardant, organic silicon fibre retardant, have
Machine metal salt fire retardant, inorganic flame retardant etc..Wherein, bromide fire retardant can be deca-BDE, decabromodiphenylethane, bromine
Change styrene or tetrabromo-phthalic diformamide.Phosphorus flame retardant can be Phos, phosphate compound, phosphinic acid compounds,
Phosphinic compounds, phosphine oxide compound and 9, the miscellaneous phenanthrene -10- oxide of -9 oxa- -10- phosphine of 10- dihydro, 10- (2,5 dihydroxies
Base phenyl) -9 miscellaneous phenanthrene -10- oxide of oxa- -10- phosphine of -9,10- dihydro, the miscellaneous -10- phosphine of 10- phenyl -9,10- dihydro-9-oxy be luxuriant and rich with fragrance -
The organophosphorus compounds such as 10- oxide, three (2,6 3,5-dimethylphenyl) phosphines, phosphine nitrile.Nitrogenated flame retardant can be triazine chemical combination
Object, cyanuric acid compound, isocyanide acid compound, phenthazine 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 carbonyls
Deng.Inorganic fire retardants can be aluminium hydroxide, magnesium hydroxide, aluminium oxide, barium monoxide etc..Added fire retardant can be according to layer
The concrete application field of pressing plate and select, it is such as phosphorous or nitrogenous to the application field that halogen requires, preferably non-halogen fire retardant
Fire retardant.It preferably, can be with the nitrogen shape of maleimide ester in above-mentioned technical proposal when selecting phosphonium flame retardant
At nitrogen phosphorus cooperative flame retardant, flame retarding efficiency is improved.Preferably, the fire retardant additive amount in above-mentioned compositions of thermosetting resin be 5~
50 parts by weight.
Based on the above technical solution, the compositions of thermosetting resin can also include component (g) filler, described
The additive amount of filler is the 1%~80% of hard resin component.The inorganic filler is selected from crystalline sillica, melting dioxy
SiClx, preparing spherical SiO 2, aluminium oxide, aluminium hydroxide, aluminium nitride, boron nitride, titanium dioxide, strontium titanates, barium titanate, sulfuric acid
One or more of barium, talcum powder, calcium silicates, calcium carbonate, mica, polytetrafluoroethylene (PTFE), graphene filler.
In above-mentioned compositions of thermosetting resin, it can also be added according to practical feelings and use toughener, silane coupling agent, face
The addition such as material, emulsifier, dispersing agent, antioxidant, antistatic agent, heat stabilizer, ultraviolet absorbing agent, colorant, lubricant
One or more of agent.
It is close to can be used for manufacturing prepreg, laminate, printed circuit board, semiconductor for above-mentioned compositions of thermosetting resin
Closure material, lamination adhering film, binder, resin cast material, conductive paste etc..
A kind of prepreg made by above-mentioned resin combination is claimed simultaneously in the present invention, by the resin combination
Glue is made with solvent dissolution, then reinforcing material is immersed in above-mentioned glue, by the reinforcing material heat drying after dipping
Afterwards, the prepreg can be obtained.
The preparation of the glue, it is preferred that first by the modified unsaturated polyester (UP) active ester of component (b) alkenes crosslinking agent one
Prepolymerization is carried out under conditions of fixed, is then added in the modified unsaturated polyester (UP) active ester of the alkenes crosslinking agent for getting togather pre-polymerization
Glue is blended into composition.After prepolymerization, it is possible to reduce vinyl monomer waving during making semi-solid preparation bonding sheet
Hair.
When the component (d) contained in composition, and component (d) be selected from hydrocarbon resin, vinyl modified bismaleimide,
Vinyl modified polyphenylene oxide, vinyl modified benzoxazine resin, cyanate ester resin (Cyanate Ester Resin Modified with Polyphenylene Oxide), ethylene
Base phenol-formaldehyde resin modified (vinyl modified dimaleoyl imino phenolic resin, vinyl modified phenolic resin, dicyclopentadiene-
Ethylene benzyl phenylate) one of or it is several when, component (b) and component (d) are first preferably mixed into carry out prepolymerization.
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, propylene glycol methyl ether acetate.The reinforcing material can be adopted
With natural fiber, organic synthetic fibers, organic fabric or inorganic fabric.
A kind of laminate is claimed simultaneously in the present invention, is covered with gold in a single or double by above-mentioned prepreg
Belong to foil, or by least 2 by above-mentioned prepreg superposition after, be covered with metal foil in its single or double, hot forming, i.e.,
The laminate can be obtained.
The quantity of the prepreg is determined according to desired laminate thickness, can use one or more.The gold
Belong to foil, can be copper foil, be also possible to aluminium foil, their thickness is not particularly limited.
Due to the above technical solutions, the present invention has the following advantages over the prior art:
1. the present invention develops a kind of unsaturated polyester (UP) active ester resin that new alkenes crosslinking agent is modified, removed in structure
Have except reactive unsaturated double-bond, also there are the active ester groups that can be cured reaction with epoxy resin, entirely
Reactive functionality is more in strand, and therefore, the crosslink density after solidifying crosslinking is big, has after resin system solidification preferably heat-resisting
Performance and mechanical strength；
2. the present invention develops a kind of unsaturated polyester (UP) active ester resin that new alkenes crosslinking agent is modified, unsaturated polyester (UP)
The special construction of active ester has Modified Products By Modification of Active Esters And Epoxy Resin system and hydrocarbon resin curing system by way of chemical bond
Combining for effect, the excellent properties of the excellent properties of active ester cured epoxy system and hydrocarbon resin have been effectively combined
Come, active ester cured epoxy system imparts the preferable low-shrinkage of resin system, adhesive property, improve laminate copper foil layer and
Peel strength between resin layer, while the dielectric properties of resin system are had no effect on, hydrocarbon resin curing system imparts material
Expect extraordinary dielectric properties and toughness；
3. experiment show to have both after resin combination of the invention solidifies excellent dielectric properties, heat resistance, intensity,
Hard and soft, peel strength is high, water absorption rate is low, percent thermal shrinkage is small, can be applied to high speed, high frequency printed wiring board.
Specific embodiment
The present invention will be further described below with reference to examples:
Synthesis example 1~2 and comparative example 1~2 are the synthesis of resin, and Examples 1 to 4 is the synthesis of prepolymer in the present invention,
Embodiment 5~9 and comparative example 3~4 are preparation and the evaluation of physical property of compositions of thermosetting resin provided by the invention.
Synthesis example 1
Tetrahydrofuran 1000g, dicyclohexylcarbodiimide 100g, maleic anhydride 58.8g, double is put into three neck reaction flasks
Phenol A 228g is placed in three neck reaction flasks after completely dissolution and is sufficiently mixed, and the 4- dimethylamino of catalytic amount is then added under stiring
Pyridine reacts 5 hours at room temperature, product separating-purifying is obtained active ester Resin A -1 later, the active ester resin (A-1)
In hydroxy functional group equivalent 690 grams/equivalent is calculated as with input ratio, ester group function equivalent with input ratio be calculated as 230 grams/when
Amount, unsaturated double-bond function equivalent are 460 grams/equivalent；
In the flask that thermometer, dropping funel, condenser pipe, isocon, blender are housed, solvent methyl isobutyl group is put into
Then ketone 1000g takes in -1 276g of active ester Resin A investment flask, sufficiently dissolves；Logical nitrogen will be depressurized in reaction system, and
System temperature is controlled at 65 DEG C or less；Then, 70g chlorobenzoyl chloride is put into, then, 20% was added dropwise into system with 3 hours
Sodium hydroxide solution 210g after being added dropwise, maintains reaction 3 hours at 65 DEG C；After the reaction was completed, it is separated off water layer；It connects
Water is added into system again, stirring and washing is separated off water layer；It repeats above cleaning operation 3~5 times；Then it vacuumizes and subtracts
Pressure removes methyl iso-butyl ketone (MIBK), obtains active ester resin (B-1), ester group function equivalent is in the active ester resin (B-1) to throw
Entering than being calculated as 198 grams/equivalent unsaturated double-bond function equivalent is 529 grams/equivalent.
Synthesis example 2
Tetrahydrofuran 1000g, dicyclohexylcarbodiimide 100g, maleic anhydride 58.8g, 2 are put into three neck reaction flasks,
7 dihydroxy naphthlene 160g are placed in three neck reaction flasks after completely dissolution and are sufficiently mixed, and the 4- bis- of catalytic amount is then added under stiring
Methylamino pyridine reacts 5 hours at room temperature, product separating-purifying is obtained active ester resin (A-2) later, the active ester tree
Hydroxy functional group equivalent in rouge (A-2) is calculated as 520 grams/equivalent with input ratio, and ester group function equivalent is calculated as with input ratio
173 grams/equivalent, unsaturated double-bond function equivalent is 347 grams/equivalent；
In the flask that thermometer, dropping funel, condenser pipe, isocon, blender are housed, solvent methyl isobutyl group is put into
Then ketone 1000g takes in -2 208g of Resin A investment flask, sufficiently dissolves；Logical nitrogen will be depressurized in reaction system, and by system
Temperature is controlled at 65 DEG C or less；Then, 70g chlorobenzoyl chloride is put into, then, 20% hydroxide was added dropwise into system with 3 hours
Sodium solution 210g after being added dropwise, maintains reaction 3 hours at 65 DEG C；After the reaction was completed, it is separated off water layer；Then past again
Water is added in system, stirring and washing is separated off water layer；It repeats above cleaning operation 3~5 times；Then decompression is vacuumized by first
Base isobutyl ketone removes, and obtains active ester resin (B-2), ester group function equivalent is in terms of input ratio in the active ester resin (B-2)
Calculating is 156 grams/equivalent, and unsaturated double-bond function equivalent is 416 grams/equivalent.
Comparative example 1
In the flask for being equipped with thermometer, fractionator, condenser pipe, blender, bisphenol-A 228g and methyl tert-butyl are put into
Base ketone solvent 1000g, which is placed in flask, is sufficiently mixed dissolution, logical nitrogen will be depressurized in reaction system, and system temperature control is existed
65℃；Then, 121.8g paraphthaloyl chloride is put into, then, 20% sodium hydroxide solution was added dropwise into system with 3 hours
210g after being added dropwise, maintains reaction 3 hours at 65 DEG C；After the reaction was completed, it is separated off water layer；Then again into system
Water is added, stirring and washing is separated off water layer；It repeats above cleaning operation 3~5 times；Then decompression is vacuumized by methyl tert-butyl
Base ketone removes, and obtains active ester resin (A-3), the hydroxy functional group equivalent in the active ester resin (A-3) is calculated with input ratio
For 765 grams/equivalent, ester group function equivalent is calculated as 255 grams/equivalent with input ratio；
In the flask for being equipped with thermometer, fractionator, condenser pipe, blender, investment active ester resin (A-3) 255g and
Methyl isobutyl ketone solvent 1000g, which is placed in flask, is sufficiently mixed dissolution, will depressurize logical nitrogen in reaction system, and by system temperature
Degree control is at 65 DEG C；Then, 70g chlorobenzoyl chloride is put into, then, 20% sodium hydroxide solution was added dropwise into system with 3 hours
210g after being added dropwise, maintains reaction 3 hours at 65 DEG C；After the reaction was completed, it is separated off water layer；Then again into system
Water is added, stirring and washing is separated off water layer；It repeats above cleaning operation 3~5 times；Then decompression is vacuumized by methyl tert-butyl
Base ketone removes, and obtains active ester resin (B-3), the functional equivalent of the active ester resin (B-3) is about 217 according to input ratio
Gram/equivalent.
Comparative example 2
Referring to the method for comparative example 1, active ester resin (A-3) is obtained, thermometer is being installed, fractionator, condenser pipe, is being stirred
It mixes in the flask of device, investment active ester resin (A-3) 255g and methyl isobutyl ketone solvent 1000g are placed in flask and are sufficiently mixed
Dissolution will depressurize logical nitrogen, and system temperature controlled at 65 DEG C in reaction system；Then, 45.0g acryloyl chloride is put into, is connect
, 20% sodium hydroxide solution 210g was added dropwise into system with 3 hours, after being added dropwise, maintains reaction 3 small at 65 DEG C
When；After the reaction was completed, it is separated off water layer；Then water is added into system again, stirring and washing is separated off water layer；Repeat with
Upper cleaning operation 3~5 times；Then it vacuumizes decompression to remove methyl iso-butyl ketone (MIBK), obtains active ester resin (B-4), the activity
The functional equivalent of ester resin (B-4) is about 205 grams/equivalent according to input ratio.
Examples 1 to 9 and comparative example 3~5
Embodiment 1
In the flask for being equipped with thermometer, fractionator, condenser pipe, blender, 500g butanone is put into, B-1 resin is added
120g, styrene 20g, peroxidized t-butyl perbenzoate 3g after dissolution is sufficiently stirred, will depressurize logical nitrogen in reaction system, and
System temperature control is reacted 2 hours at 85 DEG C, room temperature is then naturally cooled to, it is spare that prepolymer C-1 is made.
Embodiment 2
In the flask for being equipped with thermometer, fractionator, condenser pipe, blender, 500g butanone is put into, B-1 resin is added
120g, styrene 20g, bimaleimide resin 10g, peroxidized t-butyl perbenzoate 3g after dissolution is sufficiently stirred, will react
Logical nitrogen is depressurized in system, and system temperature control is reacted 2 hours at 85 DEG C, then naturally cools to room temperature, pre-polymerization is made
Object C-2 is spare.
Embodiment 3
In the flask for being equipped with thermometer, fractionator, condenser pipe, blender, 500g butanone is put into, B-1 resin is added
120g, styrene 20g, hydrocarbon resin 20g, peroxidized t-butyl perbenzoate 3g after dissolution is sufficiently stirred, will subtract in reaction system
Logical nitrogen is pressed, and system temperature control is reacted 2 hours at 85 DEG C, room temperature is then naturally cooled to, it is standby that prepolymer C-3 is made
With.
Embodiment 4
In the flask for being equipped with thermometer, fractionator, condenser pipe, blender, 200g butanone is put into, B-2 resin is added
50g, styrene 10g, peroxidized t-butyl perbenzoate 1g after dissolution is sufficiently stirred, will depressurize logical nitrogen, and will in reaction system
System temperature control is reacted 1 hour within the scope of 85 DEG C, then naturally cools to room temperature, and it is spare that prepolymer C-4 is made.
Then, according still further to the proportion in table 1, other components are added, by each component be uniformly mixed be made 60% resin it is molten
Liquid uses glass-fiber-fabric to be impregnated with above-mentioned resin solution as reinforcing material, then by the glass-fiber-fabric being impregnated in 175 DEG C of baking oven
Printed circuit pre-preg material is made in 2~10 minutes in heating, laminate is then made under the following conditions, and pass through following methods
The performances such as its dielectric properties, heat resistance, adhesive property, toughness, intensity are evaluated, as the result is shown in table 1.
The formula of embodiment 5~9 and comparative example 3~5 ginseng is shown in Table 1, it is necessary first to gather the unsaturation in embodiment 6
Ester active ester, alkenes crosslinking agent, initiator pre-polymerization synthetic prepolymer according to the method for embodiment 1, the unsaturation in embodiment 7 are poly-
According to the method pre-polymerization synthetic prepolymer of embodiment 2, the unsaturation in embodiment 8 is poly- for ester active ester, alkenes crosslinking agent, initiator
According to the method pre-polymerization synthetic prepolymer of embodiment 3, the unsaturation in embodiment 9 is poly- for ester active ester, alkenes crosslinking agent, initiator
Ester active ester, alkenes crosslinking agent, initiator, hydrocarbon resin according to embodiment 4 method pre-polymerization synthetic prepolymer；5 He of embodiment
Comparative example 3~5 is prepared by General Physics blending method.
<laminate manufacturing conditions>
Substrate: 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 DEG C/5min；
Condition of cure: 180 DEG C/120min.
<measurement of dielectric constant and dielectric loss tangent>dielectric constant uses plate according to IPC-TM-6502.5.5.9
Method measures the dielectric constant under 1GHz, dielectric loss tangent: using flat band method, measurement according to IPC-TM-650 2.5.5.9
Dielectric loss factor under 1GHz.
<peel strength>characterizes the adhesive property of compositions of thermosetting resin using the peel strength of laminate, according to IPC-
" after thermal stress " experiment condition in TM-6502.8 method, tests the peel strength of metal cladding.
<water absorption rate>is measured according to the method for IPC-TM-6502.6.2.1.
<thermally stratified layer time T-288>is measured according to IPC-TM-6502.4.24.1 method.
<glass transition temperature>is measured using DMA method.
<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.
Table 1
The footnote of table 1:
Epoxy resin: DIC HP-7200H, epoxide equivalent 278g/eq；
B-1: unsaturated polyester (UP) active ester (B-1) obtained in synthesis example 1；
B-2: unsaturated polyester (UP) active ester (B-2) obtained in synthesis example 2；
B-3: unsaturated polyester (UP) active ester (B-3) obtained in comparative example 1；
B-4: unsaturated polyester (UP) active ester (B-4) obtained in comparative example 2；
Alkenes crosslinking agent -1: styrene；
Alkenes crosslinking agent -2: bimaleimide resin；
Initiator: peroxidized t-butyl perbenzoate；
Promotor: dimethyl aminopyridine；
Hydrocarbon resin: butadiene styrene resin (Sartomdr, Ricon 100)；
Co-curing agent: styrene-maleic anhydride copolymer, self-control；
Filler: ball-type silicon powder.
As can be known from the results of Table 1: embodiment 5~9 is heat-resisting compared to using the cured comparative example 3 of active ester, comparative example 5
Performance, bending strength are all significantly improved, and dielectric properties improve significantly.Embodiment 5~9 is compared to the pure carbon of comparative example 4
The system of hydrogen resin solidification, heat resistance, peel strength, bending strength are all significantly improved.Embodiment 7 is compared to embodiment
6, heat resistance, peel strength, bending strength are all significantly improved.Embodiment 8 compared to embodiment 6, dielectric constant Dk and
Dielectric loss tangent value Df significantly decreases.
To sum up, using the printed circuit prepreg and lamination of compositions of thermosetting resin of the invention and its preparation
Plate, has both that excellent dielectric properties, heat resistance, bending strength, peel strength are high, water absorption rate is low, and process industrial art performance is excellent
The features such as.
The foregoing description of the disclosed embodiments enables those skilled in the art to implement or use the present invention.
Various modifications to these embodiments will be readily apparent to those skilled in the art, as defined herein
General Principle can be realized in other embodiments without departing from the spirit or scope of the present invention.Therefore, of the invention
It is not intended to be limited to the embodiments shown herein, and is to fit to and the principles and novel features disclosed herein phase one
The widest scope of cause.
Claims (10)
1. a kind of compositions of thermosetting resin, which is characterized in that in parts by weight, comprising:
(a) epoxy resin: 100 parts；
(b) the modified unsaturated polyester (UP) active ester resin of alkenes crosslinking agent: 50~300 parts；
(c) promotor: 0.05~4 part；
The modified unsaturated polyester (UP) active ester of the alkenes crosslinking agent is by vinyl monomer, unsaturated polyester (UP) active ester, initiator
The structural formula of the mixture or prepolymer mixed, the unsaturated polyester (UP) active ester is as follows:
Wherein:
N value is 0.5~10；
X1Selected from-CH=CH-,One or more of, and-CH=must be contained
CH-；
Y1Selected from one of following groups or several:
Ya Naiji ether, wherein
Z1It is isopropylidene, cyclopentadienylidene, sulfuryl, methylene or oxygen atom, Rx is that hydrogen atom or carbon atom number are less than or equal to 5
Alkyl；
Ra is hydrogen atom, benzoyl, substituted benzoyl or alkyl acyl；
Rb is hydrogen atom, phenyl or substituted-phenyl.
2. compositions of thermosetting resin according to claim 1, it is characterised in that: the epoxy resin is selected from bisphenol-A ring
Oxygen 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, polyphenyl ether modified epoxy resin, alicyclic based epoxy resin, glycidyl amine type epoxy resin, contracting
One or more of water glycerol ester type epoxy resin.
3. compositions of thermosetting resin according to claim 1, it is characterised in that: the promotor is in following substance
One or more: dimethyl aminopyridine, tertiary amine and its salt, imidazoles, organic metal salt, triphenylphosphine are Ji Qi phosphonium salt.
4. compositions of thermosetting resin according to claim 1, it is characterised in that: the vinyl monomer and unsaturation are poly-
The ratio of ester active ester works as meter with the function of unsaturated double-bond, is 0.05:1~5:1.
5. compositions of thermosetting resin according to claim 1, it is characterised in that: the vinyl monomer be selected from styrene,
One or more of substituted phenylethylene, methyl acrylate, substitutional crylic acid methyl esters, maleimide resin, and it is wherein necessary
Contain maleimide resin.
6. compositions of thermosetting resin according to claim 1, it is characterised in that: it further include component (d), the component
(d) hydrocarbon resin, vinyl modified bismaleimide, vinyl modified polyphenylene oxide, vinyl modified benzoxazine tree are selected from
One or more of rouge, vinyl modified phenolic resin, olefin copolymer, Petropols, mono-component polyurethane resin.
7. compositions of thermosetting resin according to claim 6, it is characterised in that: the vinyl modified phenolic resin is
Vinyl modified dimaleoyl imino phenolic resin, vinyl modified linear phenol-aldehyde resin or dicyclopentadiene-ethylene benzyl benzene
Ether.
8. compositions of thermosetting resin according to claim 1, it is characterised in that: it further include curing agent, the curing agent
For amine compound, amide based compound, acid anhydrides based compound, phenol system compound or cyanate.
9. a kind of prepreg made of resin combination as described in claim 1, it is characterised in that: by the resin
Glue is made in the dissolution of composition solvent, and then reinforcing material is immersed in above-mentioned glue, the reinforcing material after dipping is added
After heated drying, the prepreg can be obtained.
10. a kind of laminate, it is characterised in that: be covered in a single or double by prepreg as claimed in claim 9
Metal foil, or will at least 2 by prepreg as claimed in claim 9 superposition after, be covered with metal foil in its single or double,
The laminate can be obtained in hot forming.
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Cited By (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN110218415A (en) * | 2019-05-31 | 2019-09-10 | 广东生益科技股份有限公司 | Resin combination, prepreg, laminate, metal-clad laminate and printed wiring board |
| WO2020237634A1 (en) * | 2019-05-31 | 2020-12-03 | 广东生益科技股份有限公司 | Resin composition, prepreg, laminate, metal foil-clad laminate, and printed circuit board |
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Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US20100240811A1 (en) * | 2009-03-18 | 2010-09-23 | He Yufang | Thermosetting Resin Composition and Application Thereof |
| CN104448700A (en) * | 2013-09-18 | 2015-03-25 | 味之素株式会社 | Resin composition |
| CN106256862A (en) * | 2015-06-22 | 2016-12-28 | 味之素株式会社 | Resin composition |
| CN108299793A (en) * | 2016-09-12 | 2018-07-20 | 味之素株式会社 | Resin combination |
| CN108727942A (en) * | 2017-04-24 | 2018-11-02 | 味之素株式会社 | Resin combination |
| CN108727837A (en) * | 2017-04-24 | 2018-11-02 | 味之素株式会社 | Resin combination |
-
2019
- 2019-01-25 CN CN201910075087.1A patent/CN109810467B/en active Active
Patent Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US20100240811A1 (en) * | 2009-03-18 | 2010-09-23 | He Yufang | Thermosetting Resin Composition and Application Thereof |
| CN104448700A (en) * | 2013-09-18 | 2015-03-25 | 味之素株式会社 | Resin composition |
| CN106256862A (en) * | 2015-06-22 | 2016-12-28 | 味之素株式会社 | Resin composition |
| CN108299793A (en) * | 2016-09-12 | 2018-07-20 | 味之素株式会社 | Resin combination |
| CN108727942A (en) * | 2017-04-24 | 2018-11-02 | 味之素株式会社 | Resin combination |
| CN108727837A (en) * | 2017-04-24 | 2018-11-02 | 味之素株式会社 | Resin combination |
Cited By (17)
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| JP2022534306A (en) * | 2019-05-31 | 2022-07-28 | ▲広▼▲東▼生益科技股▲ふん▼有限公司 | Resin composition, prepreg, laminate, metal foil-clad laminate and printed wiring board |
| WO2020237634A1 (en) * | 2019-05-31 | 2020-12-03 | 广东生益科技股份有限公司 | Resin composition, prepreg, laminate, metal foil-clad laminate, and printed circuit board |
| CN110218415B (en) * | 2019-05-31 | 2021-07-06 | 广东生益科技股份有限公司 | Resin composition, prepreg, laminate, metal-clad laminate, and printed wiring board |
| CN110218415A (en) * | 2019-05-31 | 2019-09-10 | 广东生益科技股份有限公司 | Resin combination, prepreg, laminate, metal-clad laminate and printed wiring board |
| KR20220010518A (en) * | 2019-05-31 | 2022-01-25 | 셍기 테크놀로지 코포레이션 리미티드 | Resin composition, prepreg, laminate, metal foil laminate and printed circuit board |
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| JP7201846B2 (en) | 2019-05-31 | 2023-01-10 | ▲広▼▲東▼生益科技股▲ふん▼有限公司 | Resin composition, prepreg, laminate, metal foil-clad laminate and printed wiring board |
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| CN113248917A (en) * | 2020-02-13 | 2021-08-13 | 台光电子材料(昆山)有限公司 | Resin composition and product thereof |
| TWI777149B (en) * | 2020-02-13 | 2022-09-11 | 大陸商台光電子材料（昆山）有限公司 | A resin composition and its products |
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