CN109705530A - Compositions of thermosetting resin and prepreg, laminate and high-frequency circuit board containing it - Google Patents
Compositions of thermosetting resin and prepreg, laminate and high-frequency circuit board containing it Download PDFInfo
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Abstract
The present invention provides a kind of compositions of thermosetting resin and containing its prepreg, laminate and high-frequency circuit board, the thermoset composition includes following component in parts by weight: aromatic polycarbodiimide 5-15 parts by weight；Epoxy resin 30-70 parts by weight；The polyphosphonates of hydroxyl and/or phosphonate ester-carbonate copolymer 5-40 parts by weight of hydroxyl；Wherein, the fusing point of the aromatic polycarbodiimide is 100-160 DEG C.Prepreg, laminate and the high-frequency circuit board that compositions of thermosetting resin provided by the present invention is prepared have more excellent dielectric properties, high heat resistance and lower water absorption rate and good processing performance, and fire-retardant can reach V-0 grades of UL94.
Description
Technical field
The invention belongs to compositions of thermosetting resin technical field, be related to a kind of compositions of thermosetting resin and using its
Prepreg, laminate and high-frequency circuit board.
Background technique
The high speed and multifunction handled with electronic product information, applying frequency is continuously improved, in addition to laminate
The heat resistance of material has outside higher requirement, it is desirable that dielectric constant and dielectric loss value are lower and lower, therefore reduce Dk/Df and have become
Hot spot is chased for substrate dealer.Traditional FR-4 material mostly uses dicyandiamide as curing agent, and this curing agent has three-level
Reacting amines have good process operability, but since its C-N key is weaker, is easy cracking at high temperature, leads to solidfied material
Thermal decomposition temperature is lower, is unable to satisfy the heat resistant requirements of leadless process.In this context, with the big model of lead-free process in 2006
Implementation is enclosed, is started in row using curing agent of the phenolic resin as epoxy, phenolic resin has highdensity benzene ring structure, so
With the excellent heat resistance of system after curable epoxide, but the dielectric properties of solidfied material have the tendency that being degraded simultaneously.
Requirement with consumption electronic product to environmental protection is higher and higher, and the non-halogen trend of copper-clad laminate is also increasingly general
All over and therefore reduce that Dk/Df has become substrate dealer chase hot spot.
CN1795223A discloses a kind of polyphosphonate flame retardant curing agent with epoxy resin comprising epoxy resin and
It as effective curing agent and is the epoxy-reactive polyphosphonate of general formula (1).CN106459559A discloses a kind of epoxy combination
Object, the composition epoxy resin include oligomeric phosphonate, carbodiimide, carbodiimide and phenol antioxidant or phosphinate
Antioxidant, oligomeric phosphonate and carbodiimide or oligomeric phosphonate, carbodiimide and phenol antioxidant or phosphinate are anti-
Oxidant, which improve the flame retardant property of material and the glass transition temperatures of composition.But work as polyphosphonates or/and phosphine
When curing agent of the acid esters-carbonate copolymer class as epoxy resin, in order to realize that better electrical property, terminal hydroxy group can use
Aromatic series acyl chlorides or phenols are blocked, and cause its crosslink density to decline, TgThe disadvantages of reduction, heat resistance is insufficient, but without
Terminal hydroxy group sealing end again can extreme influence electrical property.
It is a kind of with more excellent dielectric properties, high heat resistance and lower water absorption rate and good therefore, it is desirable to develop
The compositions of thermosetting resin of processing performance prepare laminate etc..
Summary of the invention
The purpose of the present invention is to provide a kind of compositions of thermosetting resin and use its prepreg, laminate and high frequency
Circuit substrate；Prepreg, laminate and the high-frequency circuit board that compositions of thermosetting resin provided by the present invention is prepared have
More excellent dielectric properties, high heat resistance and lower water absorption rate and good processing performance, and fire-retardant can reach UL94V-0 grades.
To achieve this purpose, the present invention adopts the following technical scheme:
In a first aspect, the thermoset composition is in parts by weight the present invention provides a kind of compositions of thermosetting resin
Including following component:
Aromatic polycarbodiimide 5-15 parts by weight；
Epoxy resin 30-70 parts by weight；
The polyphosphonates of hydroxyl and/or phosphonate ester-carbonate copolymer 5-40 parts by weight of hydroxyl.
Wherein, the fusing point of the aromatic polycarbodiimide be 100-160 DEG C, such as 105 DEG C, 110 DEG C, 115 DEG C,
120 DEG C, 125 DEG C, 130 DEG C, 135 DEG C, 140 DEG C, 145 DEG C, 150 DEG C, 155 DEG C etc..
In the present invention, using aromatic polycarbodiimide and hydroxyl polyphosphonates and/or hydroxyl phosphonic acids
Co-curing agent of the ester-carbonate copolymer as epoxy resin, in the polyphosphonates and/or hydroxyl that ensure that hydroxyl
Guarantee the curing system crosslink density with higher that finally obtains and good while phosphonate ester-carbonate copolymer electrical property
Good humidity resistance, while aromatic carbodiimides has the function of preventing ester groups from hydrolyzing again, and then can be improved
The hydrolytic resistance of esters cured epoxy resin, meanwhile, the polyphosphonates of hydroxyl and/or phosphonate ester-carbonic ester of hydroxyl are total
Polymers also has the function of fire retardant, and in the case where not adding other fire retardants, the fire-retardant of solidfied material of the invention can reach
To UL94V-0 grades.
Resin combination of the invention adds a certain amount of 100-160 DEG C of aromatic polycarbodiimide, can be very big
Improvement resin combination electrical property, while make resin combination have preferable TgAnd the PCT suction of plate can be reduced
Water rate.When the fusing point of aromatic polycarbodiimide is too low, there is volatilization, and its solidfied material heat resistance during gluing
It is poor, dielectric properties are contributed little；But if fusing point is excessively high and there are solubility problems.
In the present invention, the parts by weight of the aromatic polycarbodiimide are 5-15 parts by weight, such as 6 parts by weight, 8 weights
Measure part, 9 parts by weight, 10 parts by weight, 12 parts by weight, 14 parts by weight etc..
The aromatic polycarbodiimide is selected from the poly- carbodiimide of 1,3-, bis--p-methylphenyl, bis- (the 2- methylbenzenes of N, N'-
Base) carbodiimide, the poly- carbodiimide of N- (tert-butyl)-N- [1- (2- chlorphenyl) -1- Methylethyl] or N, N'- benzyl-N- ring
In the poly- carbodiimide of hexyl any one or at least two combination.
In the present invention, the parts by weight of the epoxy resin be 30-70 parts by weight, such as 35 parts by weight, 40 parts by weight,
45 parts by weight, 50 parts by weight, 55 parts by weight, 60 parts by weight, 65 parts by weight etc..
Preferably, the epoxy resin includes bisphenol A type epoxy resin, bisphenol f type epoxy resin, o-cresol phenolic aldehyde ring
Oxygen resin, bisphenol A-type novolac epoxy resin, three phenolic novolac epoxy resins, dicyclopentadiene novolac epoxy resin, biphenyl type phenol
In formaldehyde epoxy resin, alkyl benzene-type novolac epoxy resin or naphthol type novolac epoxy resin any one or at least two group
It closes.
Preferably, the epoxy resin is the epoxy resin with Formulas I structure:
Wherein, X1、X2、X3It is each independently selected fromR1Selected from hydrogen atom,
Any one in substituted or unsubstituted C1-C5 straight chained alkyl or substituted or unsubstituted C1-C5 branched alkyl.
Y1、Y2It is each independently selected from singly-bound ,-CH2-、
In any one, R2Selected from hydrogen atom, substituted or unsubstituted C1-C5 straight chained alkyl or substituted or unsubstituted C1-C5 branch
Any one in alkyl group.
A is the integer of 1-10, such as 1,2,3,4,5,6,7,8,9,10 etc..
In the present invention, phosphonate ester-carbonate copolymer weight of the polyphosphonates of the hydroxyl and/or hydroxyl
Part is 5-40 parts by weight, such as 8 parts by weight, 10 parts by weight, 15 parts by weight, 18 parts by weight, 20 parts by weight, 25 parts by weight, 28 weights
Measure part, 30 parts by weight, 35 parts by weight, 38 parts by weight etc., further preferred 10-25 parts by weight.
Preferably, the structure of the polyphosphonates is as shown in Formula II:
Wherein, Ar is aryl ,-O-Ar-O- the group be selected from resorcinol active group, hydroquinone active group,
The thio diphenol of bisphenol-A active group, Bisphenol F active group, 4,4'- biphenol active group, phenolphthalein active group, 4,4'- is living
Any one in property group, 4,4'- sulphonyl diphenol active group or 3,3,5- trimethylcyclohexyl biphenol active group.
X is substituted or unsubstituted branched alkyl, the C2- of the substituted or unsubstituted straight chained alkyl of C1-C20, C1-C20
The substituted or unsubstituted linear alkene base of C20, the substituted or unsubstituted branched-chain alkene base of C2-C20, C2-C20 substitution or
Unsubstituted straight-chain alkyl-sub, the substituted or unsubstituted branched alkylidene of C2-C20, C5-C20 substituted or unsubstituted ring
Any one in alkyl or the substituted or unsubstituted aryl of C6-C20.
C1-C20 of the present invention can be C2, C3, C4, C5, C8, C9, C10, C12, C14, C16, C18, C19 etc..
N is the arbitrary integer of 1-75, such as 5,10,15,18,20,25,30,35,40,45,50,55,60,65,70 etc..
Preferably, the phosphonate ester-carbonate copolymer has structure shown in formula III or formula IV:
Wherein, Ar1、Ar2、Ar3It is each independently selected from the aryl ,-O-Ar3- O- is selected from resorcinol active group
Group, hydroquinone active group, bisphenol-A active group, Bisphenol F active group, 4,4'- biphenol active group, phenolphthalein activity
The thio diphenol active group of group, 4,4'-, 4,4'- sulphonyl diphenol active group or 3,3,5- trimethylcyclohexyl biphenol are living
Any one in property group.
X1、X2Be each independently the substituted or unsubstituted straight chained alkyl of C1-C20, C1-C20 it is substituted or unsubstituted
Branched alkyl, the substituted or unsubstituted linear alkene base of C2-C20, C2-C20 substituted or unsubstituted branched-chain alkene base,
The substituted or unsubstituted straight-chain alkyl-sub of C2-C20, the substituted or unsubstituted branched alkylidene of C2-C20, C5-C20 take
Generation or unsubstituted naphthenic base or the substituted or unsubstituted aryl of C6-C20.
M be 1-100 arbitrary integer, such as 5,10,15,20,25,30,35,40,45,50,55,60,65,70,75,
80,85,90,95 etc., the preferably arbitrary integer of 5-100, the arbitrary integer of further preferred 10-100.
n1、n2Be each independently the arbitrary integer of 1-75, for example, 5,10,15,20,25,30,35,40,45,50,55,
60,65,70 etc., the preferably arbitrary integer of 5-75, the arbitrary integer of further preferred 10-75.
P is the arbitrary integer of 2-50, such as 5,10,15,20,25,30,35,40,45 etc., the preferably arbitrary integer of 5-50,
The arbitrary integer of further preferred 10-50.
R1、R2It is each independently selected from substituted or unsubstituted aliphatic or aromatic hydrocarbyl, preferably unsubstituted fat
Race or aromatic hydrocarbyl.
In the present invention, aryl refers to that any functional group derived from aromatic rings or substituent group, illustrative aromatic rings have
Toluene, ethylbenzene, n-proplbenzene, isopropylbenzene, styrene, phenol, acetophenone, methyl phenyl ethers anisole, phenetole, benzyl alcohol, benzaldehyde, benzene first
Acyl, chlorobenzoyl chloride, benzoic acid, benzene first cyanogen, nitrobenzene, nitrosobenzene, aniline, fluorobenzene, chlorobenzene, bromobenzene, iodobenzene, benzene sulfonic acid, two
Phenyl ketone, diphenylthanedione, phenylacetic acid, mandelic acid, cinnamic acid, antifebrin, phenyl ethylamine, azobenzene, benzenediazonium chloride,
Benzoyl peroxide, benzyl chloride, benzene sulfonyl chloride, diphenyl-methane, triphenylmenthane, triphenylcarbinol, trityl chloride, Tetrabenzene methane,
Dimethylbenzene (ortho-xylene, meta-xylene, paraxylene), benzenediol (catechol, resorcinol, hydroquinone), benzene diformazan
Sour (phthalic acid, M-phthalic acid, terephthalic acid (TPA)), phenylenediamine (o-phenylenediamine, m-phenylene diamine (MPD), p-phenylenediamine), toluene
Amine (ortho-aminotoluene is shown in toluidines, para-totuidine), benzenedisulfonic acid, p-methyl benzenesulfonic acid, p-aminobenzoic acid, salicylic acid, acetyl
Salicylic acid, paracetamol, metachloroperbenzoic acid, mesitylene, pseudocumene, pyrogallol, picric acid, trinitro- first
Benzene, tribromphenol, pentachlorophenol, mellitic acid, biphenyl, terphenyl, naphthalene, anthracene, phenanthrene, benzoquinones (adjacent benzoquinones, 1,4-benzoquinone) etc., the virtue
Base can be the functional group or substituent group that above-mentioned any aromatic rings is derived.
Preferably, the polyphosphonates or/and phosphonate ester-carbonate copolymer are selected from
In any one or at least two combination.
Wherein, R3、R4It is each independently selected from substituted or unsubstituted aliphatic or aromatic hydrocarbyl, it is preferably unsubstituted
Aliphatic or aromatic hydrocarbyl.
m1For the arbitrary integer of 1-100, for example, 5,10,15,20,25,30,35,40,45,50,55,60,65,70,75,
80,85,90,95 etc., the preferably arbitrary integer of 5-100, the arbitrary integer of further preferred 10-100.
n3、n4、n5Be each independently the arbitrary integer of 1-75, for example, 5,10,15,20,25,30,35,40,45,50,
55,60,65,70 etc., the preferably arbitrary integer of 5-75, the arbitrary integer of further preferred 10-75.
p1For the arbitrary integer of 2-50, such as 5,10,15,20,25,30,35,40,45 etc., preferably 5-50's is any whole
Number, the arbitrary integer of further preferred 10-50.
Preferably, it is 1000- that the polyphosphonates, phosphonate ester-carbonate copolymer weight average molecular weight are independent
60000 (test method of molecular weight be GB/T 21863-2008, weight average molecular weight such as can be based on polystyrene calibration
Measured by gel permeation chromatography), for example, 2000,3000,3500,4000,4500,5000,7000,8000,10000,
15000,20000,25000,30000,35000,40000,45000,50000,55000 etc., preferably 2000-50000, into
One step is preferably 2500-10000.
When weight average molecular weight is less than 1000, solidfied material TgLow, poor heat resistance；When weight average molecular weight is greater than 60000,
The dissolubility of the polyphosphonates or/and phosphonate ester-carbonate copolymer in organic solvent is poor, be unable to get it is good,
Uniform glue, to be difficult to meet the technique requirement of copper-clad plate.
Heretofore described polyphosphonates or/and phosphonate ester-carbonate copolymer additive amount can make solidfied material fire-retardant
Reach UL94V-0 grades.
If it is desired, the compositions of thermosetting resin of the invention further includes curing accelerator.
Preferably, with the phosphine of aromatic polycarbodiimide, epoxy resin, the polyphosphonates of hydroxyl and/or hydroxyl
Acid esters-carbonate copolymer total weight is 100 parts by weight meters, and the additive amount of the curing accelerator is 0.01-1 parts by weight,
Such as 0.02 parts by weight, 0.05 parts by weight, 0.1 parts by weight, 0.5 parts by weight, 0.8 parts by weight etc., further preferred 0.05-0.8
Parts by weight, still more preferably 0.05-0.6 parts by weight.
There is no particular limitation for the curing accelerator, as long as can be catalyzed epoxy-functional reaction, reduce curing system
Reaction temperature；Preferably, the curing accelerator is selected from imidazole curing agent and its derivative, lewis acid, triphen
In base phosphine or piperidines promotor any one or at least two combination.
Preferably, the imidazole curing agent be selected from 2-methylimidazole, 2-ethyl-4-methylimidazole, 2- phenylimidazole or
In 2- undecyl imidazole any one or at least two combination.
If it is desired, the compositions of thermosetting resin of the invention further includes filler.
Preferably, with the phosphine of aromatic polycarbodiimide, epoxy resin, the polyphosphonates of hydroxyl and/or hydroxyl
Acid esters-carbonate copolymer total weight is 100 parts by weight meters, and the additive amount of the filler is 5-300 parts by weight, such as 10
Parts by weight, 15 parts by weight, 20 parts by weight, 50 parts by weight, 80 parts by weight, 100 parts by weight, 150 parts by weight, 180 parts by weight, 250
Parts by weight, 280 parts by weight etc., further preferred 5-200 parts by weight, still more preferably 5-150 parts by weight.
Preferably, the median of the filler be 0.01-50 μm, such as 0.02 μm, 0.05 μm, 0.15 μm, 0.2 μm,
0.5 μm, 0.8 μm, 1 μm, 1.5 μm, 2 μm, 5 μm, 8 μm, 10 μm, 15 μm, 25 μm, 30 μm, 40 μm, 45 μm etc., further preferably
0.01-20 μm, still more preferably 0.1-10 μm.
Preferably, the filler be selected from organic filler or inorganic filler, further preferred inorganic filler, still more preferably
Surface treated inorganic filler, most preferably surface treated silica.
Preferably, it is even to be selected from silane coupling agent, silicone oligomer or titanate esters for the surface treating agent of the surface treatment
Join agent in any one or at least two combination.
Preferably, in terms of by inorganic filler for 100 parts by weight, the dosage of the surface treating agent is 0.1-5.0 parts by weight, example
Such as 0.2 parts by weight, 0.5 parts by weight, 0.8 parts by weight, 1.0 parts by weight, 1.2 parts by weight, 1.5 parts by weight, 2.0 parts by weight, 2.5
Parts by weight, 3.5 parts by weight, 4 parts by weight, 4.5 parts by weight etc., further preferred 0.5-3.0 parts by weight, still more preferably
0.75-2.0 parts by weight.
Preferably, the inorganic filler is selected from nonmetal oxide, metal nitride, non-metal nitride, inorganic hydration
In object or inorganic salts (such as Phos) any one or at least two combination, further preferred fused silica, knot
Crystal form silica, spherical silica, hollow silicon dioxide, aluminium hydroxide, aluminium oxide, talcum powder, aluminium nitride, boron nitride,
In silicon carbide, barium sulfate, barium titanate, strontium titanates, calcium carbonate, calcium silicates or mica any one or at least two combination.
Preferably, the organic filler in polytetrafluoroethylene (PTFE), polyphenylene sulfide or polyether sulfone any one or at least
Two kinds of combination.
Second aspect, the present invention provides a kind of resin adhesive liquid, the resin adhesive liquid is by heat as described in relation to the first aspect
Thermosetting resin composition, which is dissolved or dispersed in solvent, to be obtained.
Resin adhesive liquid customary preparation methods of the invention are as follows: first solid content is put into, liquid solvent is then added, stirring is extremely
After solid content is completely dissolved, liquid resin and promotor are added, continues to stir evenly.
As the solvent in the present invention, there is no particular limitation, as concrete example, can enumerate methanol, ethyl alcohol, butanol
Equal alcohols, the ethers such as ethyl cellosolve, butyl cellosolve, ethylene glycol monomethyl ether, carbitol, butyl carbitol, acetone, butanone, first
The ketones such as methyl ethyl ketone methyl ketone, cyclohexanone, the arenes such as toluene, dimethylbenzene, the esters such as ethyl acetate, ethoxyethyl acetate
Class, the nitrogen-containing solvents such as n,N-Dimethylformamide, n,N-dimethylacetamide；The above solvent can be used alone, can also be two kinds
Or it two or more is used in mixed way；It is preferred that the ketones solvents such as acetone, butanone, methyl ethyl ketone, cyclohexanone.
The third aspect, the present invention provides a kind of prepreg, the prepreg includes reinforcing material and passes through impregnation drying
Adhere to compositions of thermosetting resin as described in relation to the first aspect thereon afterwards.
Preferably, the reinforcing material is organic fiber cloth, inorfil woven cloth or non-woven fabrics.
Preferably, the organic fiber is aramid nonwoven.
Preferably, the inorfil woven cloth is E- glass-fiber-fabric, D- glass-fiber-fabric, S- glass-fiber-fabric, T glass-fiber-fabric, NE- glass
Cloth or quartz fabric.
Preferably, the reinforcing material with a thickness of 0.01-0.2mm, such as 0.02mm, 0.05mm, 0.08mm, 0.1mm,
0.12mm, 0.15mm, 0.18mm etc..
Preferably, the reinforcing material is handled by fibrillation and silane coupling agent is surface-treated；The silane coupling agent is
In epoxy silane coupling agent, amino silicane coupling agent or vinyl silicane coupling agent any one or at least two mixing
Object.
Preferably, the prepreg the preparation method comprises the following steps: reinforcing material to be impregnated with to above-mentioned compositions of thermosetting resin, so
Afterwards under the conditions of 100-250 DEG C, baking 1-15min obtains the prepreg.
Fourth aspect, the present invention provides a kind of laminate, the laminate includes at least one as described in the third aspect
Prepreg.
Preferably, the preparation method of the laminate is to make the prepreg of a piece of or two panels or more by being heated and pressurizeed
It is bonded together and manufactured laminate.
Preferably, the laminate is to solidify to be made in hot press, and solidification temperature is 150-250 DEG C, solidifying pressure
For 10-60Kg/cm2。
5th aspect, the present invention provides a kind of high-frequency circuit board, the high-frequency circuit board contains at least one such as
The metal foil of prepreg described in the third aspect and the prepreg one or both sides being overlying on after overlapping.
Preferably, the metal foil is copper foil, nickel foil, aluminium foil or SUS foil etc..
Compared with the existing technology, the invention has the following advantages:
(1) present invention is with phosphonate ester-carbon of the polyphosphonates and/or hydroxyl of aromatic polycarbodiimide and hydroxyl
Co-curing agent of the acid ester copolymer as epoxy resin, in the phosphonic acids of the polyphosphonates and/or hydroxyl that ensure that hydroxyl
Guarantee the curing system crosslink density with higher that finally obtains and good while ester-carbonate copolymer electrical property
Humidity resistance, while aromatic polycarbodiimide has the function of preventing ester groups from hydrolyzing again, and then esters can be improved
The hydrolytic resistance of cured epoxy resin, and phosphonate ester-carbonate copolymer of the polyphosphonates of hydroxyl and/or hydroxyl also has
There is the function of fire retardant, in the case where not adding other fire retardants, the fire-retardant of solidfied material of the invention can achieve UL94V-0
Grade.
(2) resin combination of the invention adds a certain amount of 100-160 DEG C of aromatic polycarbodiimide, Ke Yiji
The electrical property of big improvement resin combination, while making resin combination that there is preferable TgAnd the PCT of plate can be reduced
Water absorption rate.
Specific embodiment
The technical scheme of the invention is further explained by means of specific implementation.Those skilled in the art should be bright
, the described embodiments are merely helpful in understanding the present invention, should not be regarded as a specific limitation of the invention.
Material involved in following embodiment and comparative examples and trade mark information are as follows:
(A) aromatic polycarbodiimide
A-1: aromatic polycarbodiimide Stabaxol P100 (Lay grace chemistry, 100-120 DEG C of melting range)；
A-2: aromatic polycarbodiimide HYDROSTAB 2 (Lay Anhua is learned, 140 DEG C of softening point)；
A-3: aromatic series carbodiimides monomer HYDROSTAB I (Lay Anhua is learned, 50 DEG C of softening point)；
A-4: aromatic polycarbodiimide Stabaxol P (Lay grace chemistry, 60-90 DEG C of softening point)；
A-5: non-aromatic polycarbodiimide (Rhein chemistry, liquid)；
(B) epoxy resin
B-1: dicyclopentadiene type epoxy resin DNE260A75 (TaiWan, China Changchun, EEW:265g/eq)；
B-2: biphenyl type novolac epoxy resin NC-3000H (Japanese chemical drug, EEW:288g/eq)；
B-3: o-cresol type epoxy resin Epon 164 (momentIve, EEW:200g/eq)；
(C) phosphonate ester-carbonate copolymer of the polyphosphonates of hydroxyl and/or hydroxyl
C-1: the polyphosphonates FRX of Bisphenol A Type containing terminal hydroxy group OL3001 (U.S. FRX Polymers, phosphorus content 10%, point
Son amount is 3000)；
C-2: the polyphosphonates FRX of Bisphenol A Type containing terminal hydroxy group OL5001 (U.S. FRX Polymers, phosphorus content 10%, point
Son amount is 5000)；
C-3: the polyphosphonates FRX of Bisphenol A Type containing terminal hydroxy group HM1100 (U.S. FRX Polymers, phosphorus content 10%, point
Son amount is 11000)；
C-4: the phosphonate ester containing terminal hydroxy group-carbonate copolymer FRX CO95 (U.S. FRX Polymers, phosphorus content
10.6%, molecular weight 25000)；
C-5: the polyphosphonates of biphenyl type containing terminal hydroxy group (U.S. FRX Polymers, phosphorus content 10%, molecular weight 15000)；
C-6: it is free of terminal hydroxy group polyphosphonates FRX OL3000 (U.S. FRX Polymers, phosphorus content 10%)；
(D) fire retardant
D-1: phosphonium flame retardant XP-7866 (the refined treasured in the U.S., phosphorus content 13.5)
D-2:BT-93W (the refined treasured in the U.S., bromine content 67.2%)
(E) promotor
E-1:2- phenylimidazole (Japanese four countries' chemical conversion)；
(F) filler
F-1: fused silica (average grain diameter is 1-10 μm, 99% or more purity)；
F-2: boehmite.
Embodiment 1-11
By group assignment system compositions of thermosetting resin shown in table 1, and makes and be laminated according to the production method of following laminate
Plate sample:
The each component of formula ratio is uniformly mixed in a solvent, control glue solid content is 65%, is soaked with 2116 glass-fiber-fabrics
The above-mentioned glue of stain controls suitable thickness, then toasts 2-15min in 145-175 DEG C of baking oven and prepreg is made, then count
It opens prepreg to stack, descends the stacked on copper foil in two sides on it, be 190-200 DEG C in solidification temperature, solidifying pressure 30-
60Kg/cm2, curing time be 90-120min under the conditions of copper-clad plate is made.
Comparative example 1-8
By assignment system compositions of thermosetting resin is organized shown in table 2, according to the production method system of laminate described in embodiment
Make laminate samples.
Table 1
Table 2
Performance test
The embodiment 1-11 and comparative example 1-8 laminate provided is tested for the property, test method is as follows:
(1) glass transition temperature (Tg): according to differential scanning calorimetry (DSC), according to IPC-TM-650 2.4.25 institute
Defined DSC method is measured；
(2) dielectric constant (Dk) and dielectric loss factor (Df): according to the resonance method for using stripline runs, according to IPC-TM-
Dielectric loss, dielectric loss factors under the method measurement 1GHz of 650 2.5.5.5；
(3) it PCT and PCT water absorption rate: is measured according to the method for IPC-TM-650 2.6.16；
(4) resistance to dip solderability: according to the method observation layering cream time of IPC-TM-650 2.4.13.1；
(5) difficult to burn；It is carried out according to 94 standard method of UL.
3 are shown in Table to the test result of the embodiment 1-11 and comparative example 1-8 laminate provided:
Table 3
By embodiment and performance test it is found that the copper-clad plate that compositions of thermosetting resin provided by the present invention is prepared
With more excellent dielectric properties, high heat resistance and lower water absorption rate and good processing performance, and fire-retardant can reach
UL94V-0 grades.
By embodiment 3-6 it is found that the hydroxyl phosphonate ester and addition fusing point of selection different molecular weight and different structure
For 140 DEG C of aromatic polycarbodiimide, the copper-clad plate finally obtained shows preferable Tg, have simultaneously compared with low-dielectric loss
Lower PCT water absorption rate, 288 DEG C of limit time performances of preferable PCT plate bursting and resistance to immersed solder.
It is by the comparison of embodiment 1-2 and comparative example 1-2 it is found that sub- compared to the fragrant adoption carbonization two of addition low melting point
Amine, addition fusing point can significantly improve the T of the copper-clad plate finally obtained in 100-160 DEG C of aromatic polycarbodiimideg, together
When reduce its dielectric loss and PCT water absorption rate, and 288 DEG C of limit times of PCT plate bursting and resistance to immersed solder can be improved.
By the comparison of embodiment 1-2 and comparative example 3 it is found that compared to addition non-aromatic polycarbodiimide, addition is molten
Point can significantly improve the T of the copper-clad plate finally obtained in 100-160 DEG C of aromatic polycarbodiimideg, while reducing it
Dielectric loss and PCT water absorption rate, and 288 DEG C of limit times of PCT plate bursting and resistance to immersed solder can be improved.
By the comparison of embodiment 5 and comparative example 4 it is found that in the present invention, aromatic polycarbodiimide and contain terminal hydroxy group
Phosphonate ester-carbonate copolymer as the co-curing epoxy resin of co-curing agent, the copper-clad plate finally obtained can be made to have
Higher crosslink density and there is good humidity resistance, while aromatic polycarbodiimide has again prevents ester groups water
The function of solution, and then the hydrolytic resistance of copper-clad plate can be improved.
By the comparison of embodiment 2 and comparative example 5 it is found that the polyphosphate and comparative example 5 containing terminal hydroxy group that embodiment 2 is selected
The polyphosphate for the not hydroxyl selected in addition to without other than terminal hydroxy group, molecular structure is all the same with molecular weight, thus compare it is found that
Although the polyphosphate of hydroxyl can not reduce the dielectric loss of system, but greatly damage the T of systemg, PCT with
And the performances such as resistance to 288 DEG C of limit of immersed solder, and the present invention selects the polyphosphate containing terminal hydroxy group that can reduce system dielectric loss
While improve system Tg, its PCT water absorption rate is reduced, the effect of 288 DEG C of limit times of PCT plate bursting and resistance to immersed solder is improved.
By the comparison of embodiment 8-10 and comparative example 6-8 it is found that in the present invention, the addition of aromatic polycarbodiimide
Amount should within the scope of the present invention, if the additive amount of aromatic polycarbodiimide is too low, to the reducing effect of dielectric loss compared with
It is small；If the adding too much of aromatic polycarbodiimide can be such that dielectric loss increased instead, only in model of the present invention
In enclosing, the dielectric loss value of the copper-clad plate finally obtained is lower.
Therefore, resin combination of the invention do not require nothing more than epoxy resin, aromatic polycarbodiimide, hydroxyl it is poly-
The collocation of phosphonate ester-carbonate copolymer of phosphonate ester and/or hydroxyl etc., is also required to meet the proportion of each component, could make
There must be the copper-clad plate of excellent properties.
The Applicant declares that the present invention is explained by the above embodiments compositions of thermosetting resin of the invention and containing it
Prepreg, laminate and high-frequency circuit board do not mean that the present invention but the invention is not limited to above-mentioned method detailed
Above-mentioned method detailed, which must be relied on, to be implemented.It should be clear to those skilled in the art, any changes to of the invention
Into addition, selection of concrete mode of equivalence replacement and auxiliary element to each raw material of product of the present invention etc. all fall within the present invention
Protection scope and the open scope within.
Claims (10)
1. a kind of compositions of thermosetting resin, which is characterized in that the thermoset composition includes following component in parts by weight:
Aromatic polycarbodiimide 5-15 parts by weight；
Epoxy resin 30-70 parts by weight；
The polyphosphonates of hydroxyl and/or phosphonate ester-carbonate copolymer 5-40 parts by weight of hydroxyl；
Wherein, the fusing point of the aromatic polycarbodiimide is 100-160 DEG C.
2. compositions of thermosetting resin according to claim 1, which is characterized in that the aromatic polycarbodiimide choosing
From the poly- carbodiimide of 1,3-, bis--p-methylphenyl, bis- (2- aminomethyl phenyl) carbodiimides of N, N'-, N- (tert-butyl)-N- [1- (2- chlorine
Phenyl) -1- Methylethyl] in poly- carbodiimide or the poly- carbodiimide of N, N'- benzyl-N- cyclohexyl any one or at least two
The combination of kind；
Preferably, the epoxy resin includes bisphenol A type epoxy resin, bisphenol f type epoxy resin, o-cresol phenolic aldehyde asphalt mixtures modified by epoxy resin
Rouge, bisphenol A-type novolac epoxy resin, three phenolic novolac epoxy resins, dicyclopentadiene novolac epoxy resin, biphenyl type phenolic aldehyde ring
In oxygen resin, alkyl benzene-type novolac epoxy resin or naphthol type novolac epoxy resin any one or at least two combination；
Preferably, the epoxy resin is the epoxy resin with Formulas I structure:
Wherein, X1、X2、X3It is each independently selected fromR1Selected from hydrogen atom, replace or
Any one in unsubstituted C1-C5 straight chained alkyl or substituted or unsubstituted C1-C5 branched alkyl；
Y1、Y2It is each independently selected from singly-bound ,-CH2-、
In any one, R2Selected from hydrogen atom, substituted or unsubstituted C1-C5 straight chained alkyl or substituted or unsubstituted C1-C5 branch
Any one in alkyl group；
The integer that a is 1~10.
3. compositions of thermosetting resin according to claim 1 or 2, which is characterized in that the structure of the polyphosphonates is such as
Shown in Formula II:
Wherein, Ar is aryl, and-O-Ar-O- the group is selected from resorcinol active group, hydroquinone active group, bisphenol-A
Active group, Bisphenol F active group, 4,4'- biphenol active group, phenolphthalein active group, the thio diphenol active group of 4,4'-
Any one in group, 4,4'- sulphonyl diphenol active group or 3,3,5- trimethylcyclohexyl biphenol active group；
X is the substituted or unsubstituted straight chained alkyl of C1-C20, the substituted or unsubstituted branched alkyl of C1-C20, C2-C20
Substituted or unsubstituted linear alkene base, the substituted or unsubstituted branched-chain alkene base of C2-C20, C2-C20 substitution or do not take
The substituted or unsubstituted naphthenic base of the straight-chain alkyl-sub in generation, the substituted or unsubstituted branched alkylidene of C2-C20, C5-C20
Or any one in the substituted or unsubstituted aryl of C6-C20；
N is the arbitrary integer of 1-75；
Preferably, the phosphonate ester-carbonate copolymer has structure shown in formula III or formula IV:
Wherein, Ar1、Ar2、Ar3It is each independently selected from the aryl ,-O-Ar3- O- is selected from resorcinol active group, to benzene
Diphenol active group, bisphenol-A active group, Bisphenol F active group, 4,4'- biphenol active group, phenolphthalein active group, 4,
In the thio diphenol active group of 4'-, 4,4'- sulphonyl diphenol active group or 3,3,5- trimethylcyclohexyl biphenol active group
Any one；
X1、X2It is each independently the substituted or unsubstituted straight chained alkyl of C1-C20, the substituted or unsubstituted branch of C1-C20
Alkyl, the substituted or unsubstituted linear alkene base of C2-C20, C2-C20 substituted or unsubstituted branched-chain alkene base, C2-C20
Substituted or unsubstituted straight-chain alkyl-sub, C2-C20 substituted or unsubstituted branched alkylidene, C5-C20 substitution or not
The substituted substituted or unsubstituted aryl of naphthenic base or C6-C20；
M is the arbitrary integer of 1-100, the preferably arbitrary integer of 5-100, the arbitrary integer of further preferred 10-100；
n1、n2It is each independently the arbitrary integer of 1-75, the preferably arbitrary integer of 5-75, further preferred 10-75's is any whole
Number；
P is the arbitrary integer of 2-50, the preferably arbitrary integer of 5-50, the arbitrary integer of further preferred 10-50；
R1、R2Be each independently selected from substituted or unsubstituted aliphatic or aromatic hydrocarbyl, preferably unsubstituted aliphatic or
Aromatic hydrocarbyl；
Preferably, the polyphosphonates or/and phosphonate ester-carbonate copolymer are selected from
In any one or at least two combination；
Wherein, R3、R4It is each independently selected from substituted or unsubstituted aliphatic or aromatic hydrocarbyl, preferably unsubstituted fat
Race or aromatic hydrocarbyl；
m1For the arbitrary integer of 1-100, the preferably arbitrary integer of 5-100, the arbitrary integer of further preferred 10-100；
n3、n4、n5It is each independently the arbitrary integer of 1-75, the preferably arbitrary integer of 5-75, further preferred 10-75's appoints
Meaning integer；
p1For the arbitrary integer of 2-50, the preferably arbitrary integer of 5-50, the arbitrary integer of further preferred 10-50.
4. compositions of thermosetting resin described in any one of -3 according to claim 1, which is characterized in that the polyphosphonic acid
Ester, phosphonate ester-carbonate copolymer weight average molecular weight it is independent be 1000-60000, preferably 2000-50000, into
One step is preferably 2500-10000.
5. compositions of thermosetting resin described in any one of -4 according to claim 1, which is characterized in that the thermosetting property tree
Oil/fat composition further includes curing accelerator；
Preferably, with the phosphonate ester-of aromatic polycarbodiimide, epoxy resin, the polyphosphonates of hydroxyl and/or hydroxyl
The total weight of carbonate copolymer is 100 parts by weight meters, and the additive amount of the curing accelerator is 0.01-1 parts by weight, further
It is preferred that 0.05-0.8 parts by weight, still more preferably 0.05-0.6 parts by weight；
Preferably, the curing accelerator is selected from imidazole curing agent and its derivative, lewis acid, triphenylphosphine or piperidines
In class promotor any one or at least two combination；
Preferably, the imidazole curing agent is selected from 2-methylimidazole, 2-ethyl-4-methylimidazole, 2- phenylimidazole or 2- ten
In one alkyl imidazole any one or at least two combination.
6. compositions of thermosetting resin described in any one of -5 according to claim 1, which is characterized in that the thermosetting property tree
Oil/fat composition further includes filler；
Preferably, with the phosphonate ester-of aromatic polycarbodiimide, epoxy resin, the polyphosphonates of hydroxyl and/or hydroxyl
The total weight of carbonate copolymer is 100 parts by weight meters, and the additive amount of the filler is 5-300 parts by weight, further preferred 5-
200 parts by weight, still more preferably 5-150 parts by weight；
Preferably, the median of the filler is 0.01-50 μm, further preferred 0.01-20 μm, still more preferably 0.1-
10μm；
Preferably, the filler is selected from organic filler or inorganic filler, and further preferred inorganic filler is still more preferably passed through
The inorganic filler of surface treatment, most preferably surface treated silica；
Preferably, the surface treating agent of the surface treatment is selected from silane coupling agent, silicone oligomer or titanate coupling agent
In any one or at least two combination；
Preferably, in terms of by inorganic filler for 100 parts by weight, the dosage of the surface treating agent is 0.1-5.0 parts by weight, further
It is preferred that 0.5-3.0 parts by weight, still more preferably 0.75-2.0 parts by weight；
Preferably, the inorganic filler be selected from nonmetal oxide, metal nitride, non-metal nitride, inorganic hydrate or
In inorganic salts any one or at least two combination, further preferred fused silica, crystalline sillica, ball
Type silica, hollow silicon dioxide, aluminium hydroxide, aluminium oxide, talcum powder, aluminium nitride, boron nitride, silicon carbide, barium sulfate, titanium
In sour barium, strontium titanates, calcium carbonate, calcium silicates or mica any one or at least two combination；
Preferably, the organic filler in polytetrafluoroethylene (PTFE), polyphenylene sulfide or polyether sulfone any one or at least two
Combination.
7. a kind of resin adhesive liquid, which is characterized in that the resin adhesive liquid is by thermosetting such as of any of claims 1-6
Property resin combination, which is dissolved or dispersed in solvent, to be obtained.
8. a kind of prepreg, which is characterized in that the prepreg includes reinforcing material and by adhering to thereon after impregnation drying
Such as compositions of thermosetting resin of any of claims 1-6.
9. a kind of laminate, which is characterized in that the laminate includes an at least prepreg as claimed in claim 8.
10. a kind of high-frequency circuit board, which is characterized in that the high-frequency circuit board contains at least one such as claim 8 institute
The metal foil of the prepreg and the prepreg one or both sides being overlying on after overlapping stated.
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| CN201811641370.8A CN109705530B (en) | 2018-12-29 | 2018-12-29 | Thermosetting resin composition, prepreg, laminate and high-frequency circuit board containing the same |
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2020133337A1 (en) * | 2018-12-29 | 2020-07-02 | 广东生益科技股份有限公司 | Thermosetting resin composition, and prepreg, laminated board and high frequency circuit substrate which contain same |
| CN114672165A (en) * | 2020-12-24 | 2022-06-28 | 广东生益科技股份有限公司 | Halogen-free flame-retardant resin composition, prepreg prepared from same and laminated board for printed circuit |
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| CN1795223A (en) * | 2003-05-22 | 2006-06-28 | 苏普雷斯塔有限责任公司 | Polyphosphonate flame retardant curing agent for epoxy resin |
| CN102911631A (en) * | 2011-08-05 | 2013-02-06 | 汉高股份有限公司 | Adhesive composition with single-component epoxy structure |
| CN103694642A (en) * | 2013-12-27 | 2014-04-02 | 广东生益科技股份有限公司 | Thermosetting resin composition and application thereof |
| CN104910585A (en) * | 2015-06-10 | 2015-09-16 | 苏州生益科技有限公司 | Thermosetting resin composition as well as prepreg and laminated board made of thermosetting resin composition |
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|---|---|---|---|---|
| CN1795223A (en) * | 2003-05-22 | 2006-06-28 | 苏普雷斯塔有限责任公司 | Polyphosphonate flame retardant curing agent for epoxy resin |
| CN102911631A (en) * | 2011-08-05 | 2013-02-06 | 汉高股份有限公司 | Adhesive composition with single-component epoxy structure |
| CN103694642A (en) * | 2013-12-27 | 2014-04-02 | 广东生益科技股份有限公司 | Thermosetting resin composition and application thereof |
| CN104910585A (en) * | 2015-06-10 | 2015-09-16 | 苏州生益科技有限公司 | Thermosetting resin composition as well as prepreg and laminated board made of thermosetting resin composition |
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2020133337A1 (en) * | 2018-12-29 | 2020-07-02 | 广东生益科技股份有限公司 | Thermosetting resin composition, and prepreg, laminated board and high frequency circuit substrate which contain same |
| CN114672165A (en) * | 2020-12-24 | 2022-06-28 | 广东生益科技股份有限公司 | Halogen-free flame-retardant resin composition, prepreg prepared from same and laminated board for printed circuit |
| CN114672165B (en) * | 2020-12-24 | 2024-03-29 | 广东生益科技股份有限公司 | Halogen-free flame-retardant resin composition and prepreg and printed circuit laminate prepared from same |
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| CN109705530B (en) | 2021-06-04 |
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