CN109988298A - A kind of modified polyphenylene ether resin, compositions of thermosetting resin and application thereof - Google Patents
A kind of modified polyphenylene ether resin, compositions of thermosetting resin and application thereof Download PDFInfo
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- CN109988298A CN109988298A CN201711470773.6A CN201711470773A CN109988298A CN 109988298 A CN109988298 A CN 109988298A CN 201711470773 A CN201711470773 A CN 201711470773A CN 109988298 A CN109988298 A CN 109988298A
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B15/00—Layered products comprising a layer of metal
- B32B15/04—Layered products comprising a layer of metal comprising metal as the main or only constituent of a layer, which is next to another layer of the same or of a different material
- B32B15/08—Layered products comprising a layer of metal comprising metal as the main or only constituent of a layer, which is next to another layer of the same or of a different material of synthetic resin
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B27/00—Layered products comprising a layer of synthetic resin
- B32B27/06—Layered products comprising a layer of synthetic resin as the main or only constituent of a layer, which is next to another layer of the same or of a different material
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B27/00—Layered products comprising a layer of synthetic resin
- B32B27/28—Layered products comprising a layer of synthetic resin comprising synthetic resins not wholly covered by any one of the sub-groups B32B27/30 - B32B27/42
- B32B27/285—Layered products comprising a layer of synthetic resin comprising synthetic resins not wholly covered by any one of the sub-groups B32B27/30 - B32B27/42 comprising polyethers
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B37/00—Methods or apparatus for laminating, e.g. by curing or by ultrasonic bonding
- B32B37/06—Methods or apparatus for laminating, e.g. by curing or by ultrasonic bonding characterised by the heating method
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G65/00—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule
- C08G65/34—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule from hydroxy compounds or their metallic derivatives
- C08G65/38—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule from hydroxy compounds or their metallic derivatives derived from phenols
- C08G65/44—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule from hydroxy compounds or their metallic derivatives derived from phenols by oxidation of phenols
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G65/00—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule
- C08G65/34—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule from hydroxy compounds or their metallic derivatives
- C08G65/48—Polymers modified by chemical after-treatment
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L63/00—Compositions of epoxy resins; Compositions of derivatives of epoxy resins
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L71/00—Compositions of polyethers obtained by reactions forming an ether link in the main chain; Compositions of derivatives of such polymers
- C08L71/08—Polyethers derived from hydroxy compounds or from their metallic derivatives
- C08L71/10—Polyethers derived from hydroxy compounds or from their metallic derivatives from phenols
- C08L71/12—Polyphenylene oxides
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B2260/00—Layered product comprising an impregnated, embedded, or bonded layer wherein the layer comprises an impregnation, embedding, or binder material
- B32B2260/04—Impregnation, embedding, or binder material
- B32B2260/046—Synthetic resin
Abstract
The present invention relates to a kind of modified polyphenylene ether resins, compositions of thermosetting resin and application thereof；The modified polyphenylene ether resin is resin structure obtained from being reacted as the low molecular weight both-end hydroxyl polyphenylene oxide of formula (1-1) with two carboxylic acid halides or dicarboxylic acids, monofunctional, aromatic's phenol or monofunctional, aromatic's carboxylic acid halides or monofunctional, aromatic's carboxylic acid for containing formula (1-2) structural unit；The compositions of thermosetting resin is using epoxy resin and the modified polyphenylene ether resin as neccessary composition；The present invention also provides purposes of the compositions of thermosetting resin in prepreg, circuit substrate and laminated film.Prepreg made of compositions of thermosetting resin provided by the invention, circuit substrate and laminated film have low-k, low-dielectric loss angle tangent, high glass-transition temperature and excellent heat resistance, humidity resistance, agent of low hygroscopicity and with the good binding force of metal.
Description
Technical field
Technical field of macromolecules of the present invention, and in particular to a kind of modified polyphenylene ether resin, compositions of thermosetting resin and its
Modified polyphenylene ether resin and its compositions of thermosetting resin in purposes more particularly to a kind of main chain containing active ester groups, and
The solidfied material made of the compositions of thermosetting resin, prepreg, circuit substrate and laminated film.
Background technique
In recent years, with the development of electronic information technology, electronic equipment installation miniaturization, densification, information it is big
Capacity, high frequency, to the dielectric properties of circuit substrate, heat resistance, humidity resistance, mechanical performance, dimensional stability, water suction
More stringent requirements are proposed for the comprehensive performances such as property, chemical resistance.
Contain a large amount of benzene ring structure in polyphenylene oxide resin (PPO) molecular structure, and without highly polar group, imparts PPO
Excellent performance, such as glass transition temperature height, good stability of the dimension, linear expansion coefficient is small, water absorption rate is low, especially remarkably
Low-k, low-dielectric loss, therefore have tried to for PPO being introduced into circuit substrate, to improve the electricity of circuit substrate
Gas performance makes it in high frequency substrate material.But PPO is thermoplastic resin, and there are melting point resin height, processing performance is owed
Good, the disadvantages of resistance to halogenated hydrocarbons and poor aromatic hydrocarbon equal solvent, simultaneously as PPO resin molecular weight is big, symmetry is high, cause its with
Epoxy resin structural difference is big, makes its poor compatibility with epoxy resin, causes to occur PPO in curing system tight with epoxy resin
The phenomenon that heavy phase separates, the performance level and its stability of resin cured matter and uniform sex expression be not good enough.
PPO has attracted many companies and research because of its outstanding physical property, heat resistance, mechanical performance and electrical property etc.
Personnel are modified it, such as by PPO small molecule and/or are modified as thermosetting resin, and achieve certain achievement.
ASAHI company (EP382,312A1) uses the resin through allyl modified PPO, curing agent TAIC and initiator PH25B composition
Composition makes substrate, but the PPE of allylation, and reaction condition and process control needs are more harsh, need in high temperature
It is lower just to crosslink reaction, it can not be as the curing agent of epoxy resin.Disclosed in US4,853,423A1 by PPO with
Epoxy resin mixing, is added zinc acetylacetonate or zinc stearate, can solve consistency problem to a certain extent, but introduce
Two kinds of metal salts to will lead to electric property bad.US5 is disclosed PPO small molecule, Mn molecular weight in 834,565A1
Less than 3000, the problem of phase separation with epoxy resin can effectively solve, but electric property declines, Tg is reduced, and introduces the meaning of PPO
It declines to a great extent.
CN103102484B provides a kind of cross-linking polyphenyl ether resin, and horse is mainly introduced in polyphenylene oxide resin
Carry out imide group, while on the phenyl ring of PPO or the substituent group of both-end base may be selected to be ester group, alkene or span structure,
Rather than the polyphenylene oxide resin containing active ester group is embedded on main chain, molecular structure steric hindrance is big, and alkene and span come
The reaction condition of acid imide etc. is more harsh, needs just crosslink reaction at high temperature, and reaction process technique is more difficult
Control.
A kind of both-end Quito functional activity ester resin containing PPO main chain, the PPO resin are disclosed in CN104761719B
By introducing multiple active ester reactive groups at resin both ends, the crosslinking of PPO and epoxy is improved, but only because of its active ester group
At the both ends of PPO resin, therefore its cross-linking dot density is still lower, while multiple active ester groups groups concentrate on PPO resin both ends,
Its steric hindrance is big, and reaction is difficult, and part ester group is difficult to happen effecting reaction, and such as more unreacted ester group of remaining can dislike instead
Change the properties of solidfied material.
Summary of the invention
In order to solve, PPO and epoxy resin compatibility are bad, it is low that the functional group densities of effective cross-linking reaction can occur, solidification
The problems such as condition is harsh, solidfied material appearance mutually separates, is low with the binding force of metal, poor in processability, an object of the present invention exists
It is to be modified to obtain by the both-end hydroxyl polyphenylene oxide to low molecular weight in providing a kind of modified polyphenylene ether resin.
Modified polyphenylene ether resin obtained from the present invention is modified as the both-end hydroxyl polyphenylene oxide to low molecular weight,
It is backbone structure and the molecule both ends that active ester groups are introduced into PPO, because of the molecule of PPO continuous segment in designed resin structure
Measuring smaller and embedded active ester groups and epoxy group has good reactivity and compatibility, therefore effectively improves poly-
The problem of poor compatibility of phenylate and epoxy resin；Meanwhile there is active ester group in modified PPO main chain and both ends, it can
The crosslink density for effectively improving solidfied material avoids the solidfied material Tg occurred because the molecular weight of PPO continuous segment reduces and substantially drops
Low problem.
On the other hand, secondary hydroxyl is not generated after active ester groups Yu the epoxy group solidification of the modified polyphenylene ether resin,
Its solidfied material has good dielectric properties, while also having excellent adhesive property and good toughness, low water absorption, resistance to
Hot and humidity resistance, thus modified excellent properties intrinsic on PPO influence it is smaller, and improve PPO cohesive force and
With the disadvantage of the binding force difference of metal.
It is a further object to provide a kind of compositions of thermosetting resin containing above-mentioned modified polyphenylene ether resin
And application thereof, there is low-k, low-dielectric loss angle tangent, high glass transition after compositions of thermosetting resin solidification
Temperature and excellent heat resistance, humidity resistance, agent of low hygroscopicity and with the good binding force of metal.
In order to achieve the above object, present invention employs following technical solutions:
It is the low molecular weight both-end hydroxyl polyphenylene oxide by formula (1-1) the present invention provides a kind of modified polyphenylene ether resin
With two carboxylic acid halides or dicarboxylic acids, monofunctional, aromatic's phenol or monofunctional, aromatic's carboxylic acid halides or simple function containing formula (1-2) structural unit
Resin structure obtained from aromatic carboxylic acid is reacted:
Wherein, n1、n2For the positive integer greater than 0, and meet 2≤n1+n2≤ 30, such as n1+n2For 2,3,5,8,10,12,
13,15,18,20,22,25,26,28 or 30, preferably 2≤n1+n2≤20。
Both-end hydroxyl polyphenylene oxide is a series of n1+n2It is worth different resin compounds, low molecular weight selected by the present invention is double
Terminal hydroxy group polyphenylene oxide, n1+n2Value falls in 2≤n1+n2Quality accounting in≤30 ranges is 90% or more；Such as n1+n2> 30 account for
It is higher than too, it will affect the dissolubility of modified polyphenylene oxide resin and its compatibility with epoxy resin.
R1It is identical or different, selected from H, F, substituted or unsubstituted C1~C6 (such as C1, C2, C3, C4, C5 or C6) it is straight
Alkyl group or branched alkyl.
X is selected from In any one.
R2It is identical or different, selected from H, F, substituted or unsubstituted C1~C6 (such as C1, C2, C3, C4, C5 or C6) it is straight
Alkyl group or branched alkyl,In any one.
Any one of Y in substituted or unsubstituted phenyl ring, substituted or unsubstituted diphenyl ether.
In the present invention, the modified polyphenylene ether resin preferably has structure shown in formula (I) or formula (II):
Wherein, n1、n2For the positive integer greater than 0, and meet 2≤n1+n2≤ 30, such as n1+n2For 2,3,5,8,10,12,
13,15,18,20,22,25,26,28 or 30, preferably 2≤n1+n2≤20；n3For the positive integer greater than 1, for example, 2,3,5,8,
10 etc.；n4For the positive integer greater than 0, such as 1,2,3,5,8,10 etc..
R1It is identical or different, selected from H, F, substituted or unsubstituted C1~C6 (such as C1, C2, C3, C4, C5 or C6) it is straight
Alkyl group or branched alkyl.
X is selected from In any one.
R2It is identical or different, selected from H, F, substituted or unsubstituted C1~C6 (such as C1, C2, C3, C4, C5 or C6) it is straight
Alkyl group or branched alkyl,In any one.
Y is substituted or unsubstituted phenyl ring, any one in substituted or unsubstituted diphenyl ether.
Z is substituted or unsubstituted phenyl ring, in substituted or unsubstituted naphthalene nucleus, substituted or unsubstituted aromatic fused ring
Any one.
Preferably, the preparation method of the modified polyphenylene ether resin of formula (I) structure includes:
With the low molecular weight both-end hydroxyl polyphenylene oxide of formula (1-1), containing formula (1-2) structural unit two carboxylic acid halides or dicarboxylic acids and
Monofunctional, aromatic's phenol be raw material, with the phenolic hydroxyl group in the low molecular weight both-end hydroxyl polyphenylene oxide be 1 mole calculating, first plus
Enter 0.5~1.5 (such as 0.5,0.8,0.9,1.0,1.2,1.4 or 1.5) mole two carboxylic acid halides containing formula (1-2) structural unit or
Then dicarboxylic acids adds 0.05~0.6 (such as 0.05,0.08,0.1,0.12,0.15,0.2,0.3,0.4,0.5 or 0.6)
Mole monofunctional, aromatic's phenol react and obtain.
In the preparation method of the modified polyphenylene ether resin of formula (I) structure, the appropriate mistake of two carboxylic acid halides or dicarboxylic acids of addition
Amount, need to be added monofunctional, aromatic's phenol and close to unreacted carboxylic acid halides or carboxylic acid；If two carboxylic acid halides or dicarboxylic acids that are added are super
1.5 moles are crossed, on the one hand will cause waste of raw materials, two more carboxylic acid halides of another aspect residual amount or dicarboxylic acids can be with single officials
Energy aromatic series phenol reaction generates the active ester of small molecule, and certain influence can be generated to the heat resistance of final modified resin.
Preferably, the preparation method of the modified polyphenylene ether resin of formula (II) structure includes:
With the low molecular weight both-end hydroxyl polyphenylene oxide of formula (1-1), containing formula (1-2) structural unit two carboxylic acid halides or dicarboxylic acids and
Monofunctional, aromatic's carboxylic acid halides or monofunctional, aromatic's carboxylic acid are raw material, with the phenol in the low molecular weight both-end hydroxyl polyphenylene oxide
Hydroxyl is 1 mole of calculating, and 0.25~0.5 (such as 0.25,0.3,0.32,0.35,0.4,0.45 or 0.5) mole is first added and contains formula
Two carboxylic acid halides or dicarboxylic acids of (1-2) structural unit, then add 0.05~0.6 (such as 0.05,0.08,0.1,0.12,
0.15,0.2,0.3,0.4,0.5 or 0.6) mole monofunctional, aromatic's carboxylic acid halides or monofunctional, aromatic's carboxylic acid react and
?.
In the preparation method of the modified polyphenylene ether resin of formula (II) structure, the both-end hydroxyl polyphenylene oxide of addition is excessive,
Monofunctional, aromatic's carboxylic acid halides need to be added or monofunctional, aromatic's carboxylic acid closes unreacted phenolic hydroxyl group；If two acyls being added
Halogen or dicarboxylic acids are less than 0.25 mole, and the more both-end base polyphenylene oxide of residual amount can be with monofunctional, aromatic's carboxylic acid halides or simple function
Aromatic carboxylic acid directly reacts the bifunctional modified polyphenylene ether resin for generating only both ends group containing active ester, so that cross-linking density
It reduces, certain influence is generated on the glass transition temperature of modified resin solidfied material.
The present invention also provides a kind of compositions of thermosetting resin comprising epoxy resin and foregoing modified polyphenyl
Ether resin, that is, the compositions of thermosetting resin is using epoxy resin and the modified polyphenylene ether resin as essential component, preferably with ring
Modified polyphenylene ether resin shown in oxygen resin and structural formula as described above (I) and/or (II) is essential component.
Preferably, the modified polyphenylene ether resin accounts for the 10%~80% of the compositions of thermosetting resin total weight, example
Such as 10%, 12%, 15%, 17%, 18%, 20%, 25%, 28%, 30%, 32%, 35%, 38%, 41%, 43%, 45%,
50%, 55%, 60%, 65%, 70%, 72%, 75% or 80%, preferably 25%~60%.
Preferably, the epoxy resin accounts for the 20%~65% of the compositions of thermosetting resin total weight, such as 20%,
22%, 25%, 27%, 28%, 30%, 35%, 38%, 40%, 42%, 45%, 48%, 51%, 53%, 55%, 60% or
65%, preferably 30%~55%.
Preferably, in the compositions of thermosetting resin, the epoxy resin refer in 1 molecule tool there are two or two
The epoxy resin of a above epoxy group is particularly preferred as bifunctional bisphenol's A type epoxy resin, bifunctional bisphenol's F type asphalt mixtures modified by epoxy resin
Rouge, bifunctional bisphenol's S type epoxy resin, epoxy resins of phenol formaldehyde type, methylphenol phenol aldehyde type epoxy resin, bisphenol A-type phenol
Formaldehyde epoxy resin, biphenyl epoxy resin, resorcinol type epoxy resin, naphthalene system epoxy resin, contains DCPD-containing epoxy resin
Phosphorus epoxy resin contains epoxy silicone, glycidyl amine type epoxy resin, alicyclic based epoxy resin, polyglycol type epoxy
Resin, four phenol ethane, four glycidol ether, triphenol methane type epoxy resin, bifunctional cyanate or bifunctional isocyanate with
The condensation product of epoxy resin and other kinds of epoxy resin, but it is not limited only to this, it can be one of which or at least two
Mixture, wherein typical but non-limiting mixture are as follows: bifunctional bisphenol's A type epoxy resin and bifunctional bisphenol's F type ring
Oxygen resin；Bifunctional bisphenol's S type epoxy resin and epoxy resins of phenol formaldehyde type；Resorcinol type epoxy resin and naphthalene system epoxy
Resin；Alicyclic based epoxy resin and polyglycol type epoxy resins.
It preferably, can also include it in addition to modified polyphenylene ether resin of the invention in the compositions of thermosetting resin
His epoxy curing agent, other epoxy curing agents account for the 0%~30% of the compositions of thermosetting resin total weight, example
Such as 1%, 3%, 5%, 10%, 12%, 15%, 20%, 25%, 28%, 30%；It can be selected from dicyandiamide, aromatic amine, phenolic aldehyde
Resin, benzoxazine resin, active ester, cyanate ester resin, polystyrene-maleic anhydride resin (SMA), both-end hydroxyl polyphenylene oxide
In resin or bismaleimide-triazine resin any one or at least two mixture, wherein typical but non-limiting
Mixture are as follows: dicyandiamide and aromatic amine；Aromatic amine and phenolic resin, preferably active ester, cyanate ester resin, polystyrene-
One of maleic anhydride resin (SMA) or bismaleimide-triazine resin or at least two mixture.
Preferably, the active ester is active ester shown in following structural formula (1-3) or structural formula (1-4)；
Wherein, the integer that j is 0~20, such as 0,1,2,3,5,8,10,12,14,15,16,18 or 20；K is 0~20
Integer, such as 0,1,2,3,5,8,10,12,14,15,16,18 or 20.
Ar1For substituted or unsubstituted phenyl ring, substituted or unsubstituted naphthalene nucleus.
Z is methylene, bivalent aliphatic cyclic hydrocarbon group, phenylene dimethylene, any in biphenylene-dimethylene
It is a kind of.
Ar2It is selected from In any one.
Preferably, it can also include fire retardant in compositions of thermosetting resin of the present invention, be selected from organic fire-retardant
And/or inorganic fire retardants.
Preferably, the organic fire-retardant is selected from halogen system organic fire-retardant, phosphorus system organic fire-retardant, nitrogen system organic fire-resisting
In agent, siliceous organic fire-retardant, phosphorous and/or nitrogen and/or silicon organic fire-retardant any one or at least two mixture.
It preferably, can also include curing accelerator in compositions of thermosetting resin of the present invention.
Preferably, the additive amount of the curing accelerator be epoxy resin, modified polyphenylene ether resin and it is above-mentioned optionally
The 0.01%~2% of the gross mass of other thermosetting resins, for example, 0.01%, 0.05%, 0.1%, 0.2%, 0.5%,
0.8%, 1%, 1.2%, 1.5% or 2%.
Preferably, the curing accelerator is selected from glyoxaline compound, the derivative of glyoxaline compound, piperidines chemical combination
In object, pyridine compounds and their, organic metal salt lewis acid or triphenylphosphine any one or at least two mixture.
Preferably, can also include filler in compositions of thermosetting resin of the present invention, selected from organic filler and/or
Inorganic filler.
Preferably, with the additive amount of Noryl, epoxy resin and the above-mentioned optionally other components that may be added
The sum of be 100 parts by weight meters, the additive amount of the filler is 5~300 parts by weight, such as 5 parts by weight, 10 parts by weight, 15 weight
Part, 20 parts by weight, 30 parts by weight, 40 parts by weight, 50 parts by weight, 80 parts by weight, 100 parts by weight, 120 parts by weight, 150 weight
Part, 180 parts by weight, 200 parts by weight, 250 parts by weight, 280 parts by weight or 300 parts by weight, preferably 25~150 parts by weight.
Preferably, the organic filler is any one in polytetrafluorethylepowder powder, polyphenylene sulfide or polyether sulfone powder
Kind or at least two mixture.
Preferably, the inorganic filler is selected from nonmetal oxide, metal nitride, non-metal nitride, inorganic hydration
In object, inorganic salts, metal hydrate or Phos any one or at least two mixture, preferred molten titanium dioxide
Silicon, crystalline sillica, spherical silica, hollow silicon dioxide, aluminium hydroxide, aluminium oxide, talcum powder, aluminium nitride, nitrogen
Change boron, silicon carbide, barium sulfate, barium titanate, strontium titanates, calcium carbonate, in calcium silicates or mica any one or at least two
Mixture.
Heretofore described " comprising ", it is intended that it can also include other components, these other groups especially except described group
Part assigns the compositions of thermosetting resin different characteristics.In addition to this, " comprising " of the present invention, may be replaced by
Enclosed " for " or " by ... form ".
For example, the compositions of thermosetting resin, which can also include various additives as concrete example, can enumerate antioxygen
Agent, heat stabilizer, antistatic agent, ultraviolet absorbing agent, pigment, colorant or lubricant etc..These various additives can be single
It solely uses, two or more can also be used in mixed way.
The customary preparation methods of compositions of thermosetting resin of the invention are as follows: first solid content is put into, liquid is then added
Solvent adds liquid resin and promotor, continues to stir evenly after stirring is completely dissolved to solid content.
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, DMAC N,N' dimethyl acetamide.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 such as acetone, butanone, methyl ethyl ketone, cyclohexanone.The additive amount of the solvent by
Those skilled in the art select according to oneself experience, so that resin adhesive liquid reaches the viscosity for being suitble to use.
It is that foregoing compositions of thermosetting resin is solidified and is prepared into the present invention also provides a kind of solidfied material
It arrives.
The present invention also provides a kind of prepregs, are prepared with the following method: by reinforcing material and impregnation
The compositions of thermosetting resin as described above being attached to after drying on reinforcing material, under the conditions of 100~250 DEG C, baking 1~
Obtain the prepreg within 15 minutes.The present invention limits used reinforcing material without special, can be organic fiber, inorganic
Fibre knitting cloth or non-woven fabrics.The organic fiber can choose aramid nonwoven, and the inorfil woven cloth can be with
For E- glass-fiber-fabric, D- glass-fiber-fabric, S- glass-fiber-fabric, T glass-fiber-fabric, NE- glass-fiber-fabric or quartz fabric.The thickness of the reinforcing material is without spy
It does not limit, has the considerations of good dimensional stability in laminate, the woven cloth and nonwoven thickness preferably 0.01~
0.2mm, and preferably by fibrillation processing and silane coupling agent surface treatment, in order to provide good water resistance and heat-resisting
Property, the silane coupling agent is preferably appointing in epoxy silane coupling agent, amino silicane coupling agent or vinyl silicane coupling agent
It anticipates a kind of or at least two mixtures.
The present invention also provides a kind of circuit substrates, are prepared with the following method: by being heated and pressurizeed,
So that the prepreg of a piece of or two panels or more is bonded together and manufactured laminate, and be bonded in laminate one or both sides with
On metal foil.The laminate is to solidify to be made in hot press, and solidification temperature is 150 DEG C~250 DEG C, and solidifying pressure is
10~60kg/cm2.The metal foil is copper foil, nickel foil, aluminium foil and SUS foil etc., and material is unlimited.
The present invention also provides a kind of laminated films, are prepared with the following method: by above-mentioned thermosetting property tree
Oil/fat composition is dissolved or dispersed in organic solvent, is then coated in base film or metal foil, is made it dry, thus
Obtain the laminated film.
Compared with prior art, the present invention at least has the advantages that
(1) Noryl tree obtained from the present invention is modified as the both-end hydroxyl polyphenylene oxide to low molecular weight
Rouge is backbone structure and the molecule both ends that active ester groups are introduced into PPO, because of PPO continuous segment in designed resin structure
The smaller and embedded active ester groups of molecular weight and epoxy group there is good reactivity and compatibility, therefore effectively change
The problem of being apt to the poor compatibility of polyphenylene oxide and epoxy resin；Meanwhile there are active ester groups in modified PPO main chain and both ends
Group, can effectively improve the crosslink density of solidfied material, and it is big to avoid the solidfied material Tg occurred because the molecular weight of PPO continuous segment reduces
The problem of width reduces；
(2) secondary hydroxyl is not generated after active ester groups Yu the epoxy group solidification of modified polyphenylene ether resin provided by the present invention
Base, solidfied material has good dielectric properties, while also having excellent adhesive property and good toughness, low water suction
Rate, heat resistance and humidity resistance, thus the modified excellent properties influence intrinsic on PPO is smaller, and improves the bonding of PPO
Power and disadvantage with the binding force difference of metal；
(3) compositions of thermosetting resin provided by the invention containing the modified polyphenylene ether resin has after solidification
Low-k, low-dielectric loss angle tangent, high glass-transition temperature and excellent heat resistance, humidity resistance, low moisture absorption
Property and with the good binding force of metal.
Specific embodiment
Of the invention for ease of understanding, it is as follows that the present invention enumerates embodiment.Those skilled in the art are it will be clearly understood that the implementation
Example is only to aid in the understanding present invention, should not be regarded as a specific limitation of the invention.
Embodiment
(1) synthesis of the modified polyphenylene ether resin of formula (I) structure
1mol (425g) RPE-HL and 1500g tetrahydro is put into the flask for being equipped with thermometer, dropping funel, blender
Furans, is passed through nitrogen, and stirring is to being completely dissolved.Then, 0.7mol (142.1g) m-phthaloyl chloride stirring and dissolving is put into, so
Afterwards, system temperature is controlled at 20 DEG C and (is configured to hereinafter, being slowly added dropwise and (being greater than 0.5 hour) 1.4mol (141.4g) triethylamine
20% triethylamine/tetrahydrofuran solution is added dropwise).Then, continue to be stirred to react 2.0~3.0 hours at 20 DEG C or less.Then,
0.4mol (37.6g) phenol is put into, continues to be stirred to react 2.0 hours at 20 DEG C or less.It stands after the reaction was completed, is filtered to remove three
Ethylamine hydrochloride solid carries out vacuum distillation concentration in solution, then adds methanol and resin product is precipitated, filtering is washed with water
PH value to final water layer is 7, again with methanol washing, then dry product.The ester equivalent root of prepared Noryl
It is 396g/eq according to feed ratio.
(2) synthesis of the modified polyphenylene ether resin of formula (II) structure
1mol (425g) RPE-HL and 1500g tetrahydro is put into the flask for being equipped with thermometer, dropping funel, blender
Furans, is passed through nitrogen, and stirring is to being completely dissolved.Then, 0.4mol (81.2g) m-phthaloyl chloride stirring and dissolving is put into, then,
System temperature is controlled at 20 DEG C hereinafter, being slowly added dropwise and (be greater than 0.5 hour) 1mol (101.2g) triethylamine (is configured to 20%
Triethylamine/tetrahydrofuran solution is added dropwise).Then, continue to be stirred to react 2.0~3.0 hours at 20 DEG C or less.Then, it puts into
0.2mol (28.2g) chlorobenzoyl chloride continues to be stirred to react 2.0 hours at 20 DEG C or less.It stands after the reaction was completed, is filtered to remove three
Ethylamine hydrochloride solid carries out vacuum distillation concentration in solution, then adds methanol and resin product is precipitated, filtering is washed with water
PH value to final water layer is 7, again with methanol washing, then dry product.The ester equivalent root of prepared Noryl
It is 498g/eq according to feed ratio.
The operation for repeating above (1) or (2) changes different reactant and its ratio, available difference modified polyphenyl
Ether resin, shown in table 1 specific as follows.
Table 1
The synthetic raw material information being related to is as follows:
RPE-HL: refined gram, Mn 1233 of Jiangsu, phenolic hydroxyl equivalent about 425g/eq
SA90: Sha Baiji, Mn 2059, phenolic hydroxyl equivalent about 840g/eq
RPE-HHH: refined gram, Mn 7644 of Jiangsu, phenolic hydroxyl equivalent about 2650g/eq
Isophthalic dibenzoyl chlorine: molecular weight 203
Chlorobenzoyl chloride: molecular weight 140.6
Equal four formyl chloride of benzene of 1,2,4,5-: molecular weight 328
Phenol: molecular weight 94
Triethylamine: molecular weight 101.2
(3) resin combination containing modified polyphenylene ether resin and epoxy resin
The preparation method of resin combination and its copper-clad plate containing modified polyphenylene ether resin and epoxy resin in the present invention,
It specifically includes: epoxy resin, modified polyphenylene ether resin or other active esters, curing accelerator is mixed in solvent by a certain percentage
Close uniformly, control glue solid content is 65%, impregnate above-mentioned glue with 2116 glass-fiber-fabrics, control suitable thickness, then 145~
2~15min being toasted in 175 DEG C of baking oven, prepreg being made, then several prepregs stack, and descend the stacked on copper in two sides on it
Foil is 190 DEG C~200 DEG C in solidification temperature, and solidifying pressure is 30~60kg/cm2, under the conditions of curing time is 90~120min
Copper-clad plate is made, specific ingredient, content and plate property are as shown in table 2-1 and table 2-2.Table 2-1
Table 2-2
Performance evaluation:
It can be seen that both-end hydroxyl polyphenyl used in synthesis modification polyphenylene oxide from embodiment and comparative example 1-1,1-2,1-3
The molecular weight of ether should not be too big, and the molar ratio of the phenolic hydroxyl group and diacid chloride in both-end hydroxyl polyphenylene oxide is controlled in 1:(0.25
~1.5) performance is more excellent in the range of；Can be seen that patent of invention CN104761719B is related to from comparative example 1-4 contains PPO
Both-end Quito functional activity ester resin of main chain, active ester groups concentrate on resin both ends, and steric hindrance is big, completely solid to resin
The condition requirement of change is very harsh, tends to not exclusively properties be caused to fall flat because of solidification.
(4) resin combination containing modified polyphenylene ether resin, epoxy resin and cyanate
The system of resin combination and its copper-clad plate containing modified polyphenylene ether resin, epoxy resin and cyanate in the present invention
Preparation Method specifically includes: by epoxy resin, modified polyphenylene ether resin and optional cyanate ester resin or other active esters, consolidating
Change promotor, filler to be uniformly mixed in solvent by a certain percentage, control glue solid content is 65%, is impregnated with 2116 glass-fiber-fabrics
Above-mentioned glue controls suitable thickness, then toasts 2~15min in 145~175 DEG C of baking oven and prepreg is made, and then several
Prepreg stacks, and descends the stacked on copper foil in two sides on it, solidification temperature be 190 DEG C~210 DEG C, solidifying pressure be 30~
60kg/cm2, curing time be 90~120min under the conditions of copper-clad plate is made.Specific ingredient, content and plate property such as table 3
It is shown.
Table 3
Performance evaluation:
It can be seen that comparative example 2-1 and comparative example 2-2 from the comparison result of embodiment and comparative example to use lower than the present invention
Modified polyphenylene ether resin content or comparative example 2-3 in middle compositions of thermosetting resin, which use, is higher than thermosetting resin in the present invention
When modified polyphenylene ether resin content in composition, copper-clad plate obtained is in terms of dielectric properties, humidity resistance and water absorption rate
It is inferior to the present invention；Only with DCPD active ester in comparative example 2-4, and do not contain modified polyphenylene ether resin of the invention when,
Heat resistance, dielectric properties and water absorption rate etc. are inferior to the present invention.
It can thus be seen that the compositions of thermosetting resin of modified polyphenylene ether resin provided by the invention, has after solidification
There are low-k, low-dielectric loss angle tangent, high glass-transition temperature and excellent heat resistance, humidity resistance, low suction
It is moist and with copper foil have good binding force.
Embodiment and comparative example is related to material and trade mark information is as follows:
(A) modified polyphenylene ether resin
S1~S5: the modified polyphenylene ether resin that synthetic example 1~5 is prepared
S6~S8: the modified polyphenylene ether resin that synthesis comparative example 6~8 is prepared
S9: both-end Quito functional activity ester resin disclosed in patent CN103221442B containing PPO main chain
(B) other resins and promotor
HP-7200HHH:DIC, DCPD type epoxy resin, epoxide equivalent 286
HP-7200H-75M:DIC, DCPD type epoxy resin, epoxide equivalent 278
HP-9900:DIC, naphthol type epoxy resin, epoxide equivalent 274
NC-2000-L: Japanese chemical drug, aralkyl base epoxy, epoxide equivalent 238
SKE-1: Shang Kete, special epoxy resin, epoxide equivalent 120
BA-3000S:LONZA, bisphenol type cyanate
CY-40: Wuqiao resin processing plant, DCPD type cyanate
HPC-8000-65T:DIC, DCPD active ester, ester equivalent 223
DMAP:4- dimethylamino naphthyridine
BICATZ: zinc Isoocatanoate, The Shepherd Chemical Company
(C) filler
Fused silica (average grain diameter is 1 to 10 μm, 99% or more purity)
The test method of the above characteristic is as follows:
(1) glass transition temperature (Δ Tg): being tested using DSC, according to the DSC of IPC-TM-650 2.4.24 defined
Test method is measured.
(2) glass transition temperature (Tg): being tested using DMA, is surveyed according to the DMA of IPC-TM-650 2.4.24 defined
Method for testing is measured.
(3) it dielectric constant and dielectric loss factor: is tested according to SPDR method.
(4) humidity resistance (PCT) is evaluated: after the copper foil on copper-clad plate surface is etched, evaluating substrate；By substrate placement force
In pot, after handling a few hours under the conditions of 120 DEG C, 105KPa, it is immersed in 288 DEG C of tin furnace, remembers when substrate de-lamination plate bursting
Between picture recording is seasonable；It can terminate to evaluate when substrate also does not occur blistering or being layered in tin furnace more than 5min.
(5) T288, T300: TMA instrument is used, according to the test side T288 or T300 of IPC-TM-650 2.4.24.1 defined
Method is measured.
(6) it water imbibition: is measured according to the water imbibition test method of IPC-TM-650 2.6.2.1 defined.
(7) it thermal decomposition temperature (Td/5%): is surveyed using the TG 209F3 type thermogravimetric analyzer of NETZSHC company, Germany production
Fixed, temperature elevating range is room temperature to 800 DEG C, and heating rate 10 DEG C/min, N2 protection, record sample weight loss reaches temperature when 5%
For Td5%.
(8) peel strength (PS): according to " receiving state " experiment condition in IPC-TM-650 2.4.8 method, metal is tested
The peel strength of cap rock.
The Applicant declares that the present invention is explained by the above embodiments detailed process equipment and process flow of the invention,
But the present invention is not limited to the above detailed process equipment and process flow, that is, it is above-mentioned detailed not mean that the present invention must rely on
Process equipment and process flow could be implemented.It should be clear to those skilled in the art, any improvement in the present invention,
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 of the invention
Within protection scope and the open scope.
Claims (10)
1. a kind of modified polyphenylene ether resin, which is characterized in that the modified polyphenylene ether resin is double by the low molecular weight of formula (1-1)
Terminal hydroxy group polyphenylene oxide and two carboxylic acid halides or dicarboxylic acids, monofunctional, aromatic's phenol or monofunctional, aromatic for containing formula (1-2) structural unit
Resin structure obtained from carboxylic acid halides or monofunctional, aromatic's carboxylic acid react:
Wherein, n1、n2For the positive integer greater than 0, and meet 2≤n1+n2≤30；
R1It is identical or different, straight chained alkyl or branched alkyl selected from H, F, substituted or unsubstituted C1~C6；
X is selected from In any one；
R2It is identical or different, selected from H, F, the straight chained alkyl of substituted or unsubstituted C1~C6 or branched alkyl,In any one；
Any one of Y in substituted or unsubstituted phenyl ring, substituted or unsubstituted diphenyl ether.
2. modified polyphenylene ether resin as described in claim 1, which is characterized in that the modified polyphenylene ether resin has formula (I)
Or structure shown in formula (II):
Wherein, n1、n2、n4For the positive integer greater than 0, and meet 2≤n1+n2≤30；n3For the positive integer greater than 1；
R1It is identical or different, straight chained alkyl or branched alkyl selected from H, F, substituted or unsubstituted C1~C6；
X is selected from In any one；
R2It is identical or different, selected from H, F, the straight chained alkyl of substituted or unsubstituted C1~C6 or branched alkyl,In any one；
Y is substituted or unsubstituted phenyl ring, any one in substituted or unsubstituted diphenyl ether；
Z is substituted or unsubstituted phenyl ring, substituted or unsubstituted naphthalene nucleus, any in substituted or unsubstituted aromatic fused ring
It is a kind of.
3. modified polyphenylene ether resin as claimed in claim 2, which is characterized in that the Noryl tree of formula (I) structure
The preparation method of rouge includes:
With the low molecular weight both-end hydroxyl polyphenylene oxide of formula (1-1), two carboxylic acid halides containing formula (1-2) structural unit or dicarboxylic acids and single official
Energy aromatic series phenol is raw material, is in terms of 1 mole by the phenolic hydroxyl group in the low molecular weight both-end hydroxyl polyphenylene oxide of the formula (1-1)
It calculates, 0.5~1.5 mole of two carboxylic acid halides or dicarboxylic acids for containing formula (1-2) structural unit is first added, then adds 0.05~0.6 and rubs
Your monofunctional, aromatic's phenol is reacted and is obtained；
Preferably, the preparation method of the modified polyphenylene ether resin of formula (II) structure includes:
With the low molecular weight both-end hydroxyl polyphenylene oxide of formula (1-1), two carboxylic acid halides containing formula (1-2) structural unit or dicarboxylic acids and single official
Energy aromatic series carboxylic acid halides or monofunctional, aromatic's carboxylic acid are raw material, with the phenol in the low molecular weight both-end hydroxyl polyphenylene oxide of formula (1-1)
Property hydroxyl be 1 mole calculating, first be added 0.25~0.5 mole contain formula (1-2) structural unit two carboxylic acid halides or dicarboxylic acids, then again
The monofunctional, aromatic's carboxylic acid halides or monofunctional, aromatic's carboxylic acid for being added 0.05~0.6 mole are reacted and are obtained.
4. a kind of compositions of thermosetting resin, which is characterized in that the compositions of thermosetting resin includes epoxy resin and right
It is required that modified polyphenylene ether resin described in any one of 1-3.
5. compositions of thermosetting resin as claimed in claim 4, which is characterized in that the modified polyphenylene ether resin accounts for the heat
The 10%~80% of thermosetting resin composition total weight, preferably 25%~60%.
Preferably, the epoxy resin accounts for the 20%~65% of the compositions of thermosetting resin total weight, preferably 30%~
55%.
6. compositions of thermosetting resin as described in claim 4 or 5, which is characterized in that the compositions of thermosetting resin is also
Including other epoxy curing agents；
Preferably, other described epoxy curing agents are dicyandiamide, aromatic amine, phenolic resin, benzoxazine resin, activity
Ester, cyanate ester resin, polystyrene-maleic anhydride resin, both-end hydroxyl polyphenylene oxide resin or bismaleimide-triazine resin
In any one or at least two mixture；
Preferably, the compositions of thermosetting resin further includes fire retardant；
Preferably, the fire retardant is organic fire-retardant and/or inorganic fire retardants；
Preferably, the compositions of thermosetting resin further includes filler and/or curing accelerator.
7. a kind of solidfied material, which is characterized in that the solidfied material is by thermosetting resin described in any one of claim 4-6
Composition solidifies and is made.
8. a kind of prepreg, which is characterized in that the prepreg is prepared with the following method: will appoint in claim 4-6
Compositions of thermosetting resin described in one is dissolved or dispersed in organic solvent, is then infiltrated up in reinforcing material, will
The prepreg is made in obtained infiltration substrate semi-solid preparation.
9. a kind of circuit substrate, which is characterized in that the circuit substrate be by least prepreg according to any one of claims 8 with
Metal foil is hot-forming, and the circuit substrate is made.
10. a kind of laminated film, which is characterized in that the laminated film is prepared with the following method: by claim 4-6
Any one of described in compositions of thermosetting resin be dissolved or dispersed in organic solvent, be then coated on base film or
In metal foil, makes it dry and the laminated film is made.
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| CN110724261A (en) * | 2019-09-30 | 2020-01-24 | 艾蒙特成都新材料科技有限公司 | High-heat-resistance low-dielectric polyphenylene ether type bismaleimide resin, laminated board and preparation method thereof |
| CN110746594A (en) * | 2019-11-14 | 2020-02-04 | 杭州聚丰新材料有限公司 | Low-molecular-weight fluorine-containing polyphenyl ether and preparation method and application thereof |
| CN110776739A (en) * | 2019-09-05 | 2020-02-11 | 艾蒙特成都新材料科技有限公司 | Thermosetting resin composition for high-speed substrate, copper-clad plate and preparation method of copper-clad plate |
| CN110885441A (en) * | 2019-12-06 | 2020-03-17 | 中国科学院大连化学物理研究所 | Supported catalyst and application thereof in preparation of remote-claw type low molecular weight polyphenylene ether |
| CN112898561A (en) * | 2021-01-27 | 2021-06-04 | 大连理工大学 | Maleimide-terminated polyphenylene ether and preparation method thereof |
| CN113214630A (en) * | 2021-05-17 | 2021-08-06 | 常州中英科技股份有限公司 | Flame-retardant polyarylether composition, prepreg prepared from flame-retardant polyarylether composition and thermosetting high-frequency copper-clad plate |
| CN113292718A (en) * | 2021-05-17 | 2021-08-24 | 常州中英科技股份有限公司 | Flame-retardant polyarylether composition |
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| CN110776739A (en) * | 2019-09-05 | 2020-02-11 | 艾蒙特成都新材料科技有限公司 | Thermosetting resin composition for high-speed substrate, copper-clad plate and preparation method of copper-clad plate |
| CN110776739B (en) * | 2019-09-05 | 2022-04-05 | 艾蒙特成都新材料科技有限公司 | Thermosetting resin composition for high-speed substrate, copper-clad plate and preparation method of copper-clad plate |
| CN110724261B (en) * | 2019-09-30 | 2022-03-01 | 艾蒙特成都新材料科技有限公司 | High-heat-resistance low-dielectric polyphenylene ether type bismaleimide resin, laminated board and preparation method thereof |
| CN110724261A (en) * | 2019-09-30 | 2020-01-24 | 艾蒙特成都新材料科技有限公司 | High-heat-resistance low-dielectric polyphenylene ether type bismaleimide resin, laminated board and preparation method thereof |
| CN110746594A (en) * | 2019-11-14 | 2020-02-04 | 杭州聚丰新材料有限公司 | Low-molecular-weight fluorine-containing polyphenyl ether and preparation method and application thereof |
| CN110746594B (en) * | 2019-11-14 | 2020-08-04 | 杭州聚丰新材料有限公司 | Low-molecular-weight fluorine-containing polyphenyl ether and preparation method and application thereof |
| CN110885441A (en) * | 2019-12-06 | 2020-03-17 | 中国科学院大连化学物理研究所 | Supported catalyst and application thereof in preparation of remote-claw type low molecular weight polyphenylene ether |
| CN112898561A (en) * | 2021-01-27 | 2021-06-04 | 大连理工大学 | Maleimide-terminated polyphenylene ether and preparation method thereof |
| CN113292718A (en) * | 2021-05-17 | 2021-08-24 | 常州中英科技股份有限公司 | Flame-retardant polyarylether composition |
| CN113214630A (en) * | 2021-05-17 | 2021-08-06 | 常州中英科技股份有限公司 | Flame-retardant polyarylether composition, prepreg prepared from flame-retardant polyarylether composition and thermosetting high-frequency copper-clad plate |
| CN113214630B (en) * | 2021-05-17 | 2023-04-21 | 常州中英科技股份有限公司 | Flame-retardant polyarylether-based composition, prepreg prepared from flame-retardant polyarylether-based composition and thermosetting high-frequency copper-clad plate prepared from flame-retardant polyarylether-based composition |
| CN113292718B (en) * | 2021-05-17 | 2023-06-13 | 常州中英科技股份有限公司 | Flame-retardant polyarylether-based composition |
| CN114516956A (en) * | 2021-12-17 | 2022-05-20 | 久耀电子科技（江苏）有限公司 | Preparation method of organosilane-modified intrinsic flame-retardant polyphenyl ether |
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