CN108102594A - It is a kind of to prepare copper coated foil plate polyphenylene oxide resin adhesive and preparation method thereof - Google Patents
It is a kind of to prepare copper coated foil plate polyphenylene oxide resin adhesive and preparation method thereof Download PDFInfo
- Publication number
- CN108102594A CN108102594A CN201711339505.0A CN201711339505A CN108102594A CN 108102594 A CN108102594 A CN 108102594A CN 201711339505 A CN201711339505 A CN 201711339505A CN 108102594 A CN108102594 A CN 108102594A
- Authority
- CN
- China
- Prior art keywords
- polyphenylene oxide
- epoxy resin
- coated foil
- foil plate
- resin
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Pending
Links
- 0 C*CC(C)C1*(*)*(C)CC1 Chemical compound C*CC(C)C1*(*)*(C)CC1 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
- C09J171/00—Adhesives based on polyethers obtained by reactions forming an ether link in the main chain; Adhesives based on derivatives of such polymers
- C09J171/08—Polyethers derived from hydroxy compounds or from their metallic derivatives
- C09J171/10—Polyethers derived from hydroxy compounds or from their metallic derivatives from phenols
- C09J171/12—Polyphenylene oxides
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
- C09J11/00—Features of adhesives not provided for in group C09J9/00, e.g. additives
- C09J11/02—Non-macromolecular additives
- C09J11/04—Non-macromolecular additives inorganic
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
- C09J11/00—Features of adhesives not provided for in group C09J9/00, e.g. additives
- C09J11/02—Non-macromolecular additives
- C09J11/06—Non-macromolecular additives organic
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
- C09J11/00—Features of adhesives not provided for in group C09J9/00, e.g. additives
- C09J11/08—Macromolecular additives
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
- C09J163/00—Adhesives based on epoxy resins; Adhesives based on derivatives of epoxy resins
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K3/00—Use of inorganic substances as compounding ingredients
- C08K3/28—Nitrogen-containing compounds
- C08K2003/282—Binary compounds of nitrogen with aluminium
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L2205/00—Polymer mixtures characterised by other features
- C08L2205/02—Polymer mixtures characterised by other features containing two or more polymers of the same C08L -group
- C08L2205/025—Polymer mixtures characterised by other features containing two or more polymers of the same C08L -group containing two or more polymers of the same hierarchy C08L, and differing only in parameters such as density, comonomer content, molecular weight, structure
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L2205/00—Polymer mixtures characterised by other features
- C08L2205/03—Polymer mixtures characterised by other features containing three or more polymers in a blend
- C08L2205/035—Polymer mixtures characterised by other features containing three or more polymers in a blend containing four or more polymers in a blend
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L2205/00—Polymer mixtures characterised by other features
- C08L2205/06—Polymer mixtures characterised by other features having improved processability or containing aids for moulding methods
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L2207/00—Properties characterising the ingredient of the composition
- C08L2207/53—Core-shell polymer
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Inorganic Chemistry (AREA)
- Adhesives Or Adhesive Processes (AREA)
Abstract
Copper coated foil plate polyphenylene oxide resin adhesive and preparation method thereof is prepared the present invention relates to a kind of, raw material uses following components and parts by weight content：Polyfunctional epoxy resin 1 20, low dielectric-epoxy resin 10 50, cyanate 5 50, active ester curing agent 10 30, polyphenylene oxide 10 60, fire retardant 5 40, silane 0.01 3, metal system curing accelerator 0.005 0.3, imidazoles accelerating agent 0.01 0.3, inorganic filler 10 60, toughener 1 20.Compared with prior art, the present invention can cause the copper-clad plate prepared to have low water absorption rate, low dielectric loss and excellent wet-hot aging performance.
Description
Technical field
The present invention relates to a kind of adhesive and preparation method thereof, more particularly, to a kind of copper coated foil plate for preparing with polyphenylene oxide tree
Fat adhesive and preparation method thereof.
Background technology
21 century enters the society of advanced IT application, and IT industry becomes industry of the 21 century with typical representative.
The important technical basis of development IT industry is high speed, high frequency, the signal transmission of large capacity, therefore, the electricity of support IT industry development
The manufacturing technology of sub- component and electronic product also enters among brand-new change.This means as electronic component and electronics
The printed circuit board (PCB) of product key foundation material must develop to the direction of " high-frequency high-speed ", and function is no longer only
Only it is simple supporting role, but is changed into the work(that must have both signal transmission and strengthening electronic product high reliability simultaneously
Energy.This requires PCB substrate material must have excellent dielectric properties, the heat resistance of protrusion and wet-hot aging performance, excellent
Dimensional stability, good processability and relatively low cost etc..The performance of PCB determined by its baseplate material, resin matrix
It is the basic composition of PCB substrate material, it is an important factor for influencing PCB substrate performance and price, so high performance resin base
Body is the necessary material condition for preparing frequency PCB.Worldwide, the development of frequency PCB substrate resin matrix into
For IT industry and its key of relevant technical progress, also become the key for capturing electronics market.
Polyphenylene oxide (Polyphenylene ether, Poly (phenylene oxide), write a Chinese character in simplified form PPE or PPO) is a kind of
Heat safe thermoplastic resin, nineteen fifty-seven is succeeded in developing by AM General electric appliance (GE) company, and realizes industry in nineteen sixty-five
Metaplasia is produced, and is one of current world's five large-engineering plastics.PPE resins have excellent mechanical strength and heat resistance, good ruler
Very little stability, extremely low hydroscopicity are particularly all shown excellent and stabilization in broad temperature range and frequency range
Dielectric properties.Compared with polyimides (PI) substrate and cyanate (CE) substrate, the dielectric constant and dielectric loss of PPE substrates are just
Cut that value is lower, while the cost of PPE substrates is lower；And heat resistance is suitable with PI substrates.In addition, PPE substrates are also small with density
Characteristic (PI plates density is 1.85, and 1.44) PPE density boards are only about, and adapts to the light-weighted development of current electronic product and becomes
Gesture.Thus, PPE resins become the resin matrix of high-performance high-frequency circuit base material first choice, and are considered most to send out by industry
Open up the frequency PCB substrate resin matrix of potentiality.However thermoplasticity macromolecular PPE, there are melt viscosity height, it is difficult to machine-shaping
The shortcomings of, therefore use small molecule PPE, small molecule PPE (Mw：1000-5000), the processing features of CCL be disclosure satisfy that.
But small molecule PPE is directly used in high performance copper clad laminate there are still problem, terminal hydroxyl steric hindrance is big, activity is low, and reaction is difficult,
Easily reaction is incomplete, so as to be had adverse effect on to dielectric properties and heat resistance.
The content of the invention
It is an object of the present invention to overcome the above-mentioned drawbacks of the prior art and provide a kind of so that is prepared covers
The copper coated foil plate for preparing that copper coin has low water absorption rate, low dielectric loss and excellent wet-hot aging performance is glued with polyphenylene oxide resin
Mixture and preparation method thereof.
The purpose of the present invention can be achieved through the following technical solutions：
It is a kind of to prepare copper coated foil plate polyphenylene oxide resin adhesive, using the raw material of following components and parts by weight content：
Polyfunctional epoxy resin 1-20, low dielectric-epoxy resin 10-50, cyanate 5-50, active ester curing agent 10-
30th, polyphenylene oxide 10-60, fire retardant 5-40, silane 0.01-3, metal system curing accelerator 0.005-0.3, imidazoles accelerating agent
0.01-0.3, inorganic filler 10-60, toughener 1-20.
Preferably, polyfunctional epoxy resin includes 1,1,2,2- tetra- (p-hydroxybenzene) ethane, four diglycidyl ether epoxy
Resin, 4,4- diaminodiphenylmethane epoxy resin, triglycidyl group para-aminophenol, triglycidyl meta-aminophenol
Or the one or more of double (N, the N- 2-glycidyl aminomethyl) hexamethylenes of 1,3-.
It is further preferred that polyfunctional epoxy resin is with the epoxy resin of lower structure：
Preferably, low dielectric-epoxy resin is selected from biphenyl type epoxy resin, naphthalene nucleus type epoxy resin, naphthol type asphalt mixtures modified by epoxy resin
Fat, naphthylene ether type epoxy, polyphenyl ether type epoxy or one kind or more in dicyclopentadiene type novolac epoxy resin
Kind.
Preferably, cyanate is in bisphenol type cyanate, dicyclopentadiene type cyanate or phenolic resin type cyanate
One or more kinds of mixing, it is further preferred that cyanate is the Primaset of Long Sha companies of SwitzerlandTMBA-3000S trees
Fat.
Using cyanate as curing agent, cyanate autohemagglutination forms triazine ring and possesses very excellent dielectric properties, adds in
After the system, the three-dimensional space network to form high crosslink density can be reacted with polyphenylene oxide and epoxy resin, plate Tg is carried
Rising has larger help.
Preferably, active ester curing agent is selected from active ester system curing agent, the acetyl of linear phenol-aldehyde resin containing naphthalene ring
The active ester of the active ester of compound, the active ester of the benzoylate of linear phenol-aldehyde resin or the biphenol structural containing dicyclopentadienyl
In one or more, it is further preferred that active ester curing agent use the biphenol structural containing dicyclopentadienyl active ester.
Using Modified Products By Modification of Active Esters And Epoxy Resin, in active ester cures agent molecule there are two or it is multiple with greater activity
Ester group can carry out curing reaction, rack of the generation without secondary hydroxyl group, so the epoxy resin tool after curing with epoxy resin
There are low dielectric loss and water absorption rate, can cause the copper-clad plate prepared that there is low water absorption rate, low dielectric loss and excellent
Wet-hot aging performance.
Preferably, the weight average molecular weight of polyphenylene oxide is less than 2000, and end group carries phenolic hydroxyl group,
It is further preferred that polyphenylene oxide is the polyphenylene oxide resin of following structural formula, it is the SA90 resins of SABIC companies：
Using phenolic hydroxyl group block polyphenylene oxide resin, can the interreaction between epoxy resin and cyanate three,
Tg higher after reaction product cures, dielectric properties are excellent.In addition, copper-clad plate prepared by the system is also equipped with excellent humidity resistance
Energy.
Preferably, fire retardant uses brominated flame-retardant or phosphonium flame retardant, and used fire retardant is not to reduce dielectricity
It can be preferred.
It is further preferred that brominated fire retardant is deca-BDE, decabromodiphenylethane, brominated styrene or decabrominated dipheny
The one or more of ether；
It is further preferred that phosphonium flame retardant such as three (2,6- 3,5-dimethylphenyl) phosphorus, 10 (2,5- dihydroxy phenyls) -9,10-
Miscellaneous -10- phosphorus phenanthrene -10- the oxides of dihydro-9-oxy, (2,6- 3,5-dimethylphenyls) the phosphorus base benzene of 2,6- bis- or 10- phenyl -9,10- two
Hydrogen -9- oxa- -10- phosphorus phenanthrene -10- oxides are one or more kinds of,
Preferably, silane is selected from gamma-aminopropyl-triethoxy-silane, γ-aminopropyltrimethoxysilane, anilinomethyl three
Methoxy silane, γ-(β-aminoethyl) aminopropyl trimethoxysilane, γ-(2,3- the third oxygen of epoxy) propyl trimethoxy silicane,
One or more in vinyltrimethoxysilane or vinyltriethoxysilane,
Preferably, metal system curing accelerator is cobalt, copper, zinc, iron, the metal-organic complex of tin metal or organic metal
Salt,
It is further preferred that metal-organic complex for acetylacetone cobalt (II), the organic cobalt complex of acetylacetone cobalt (III),
Acetylacetone copper (II) organic copper complex, zinc acetylacetonate (II) organozinc complex or ferric acetyl acetonade (III) one kind or
It is a variety of.
It is further preferred that organic metal salt is zinc octoate, tin octoate or zinc stearate,
Preferably, imidazoles accelerating agent is 2-methylimidazole, -4 methylimidazole of 2- ethyls, 1,2- methylimidazoles, 2- benzene
Base imidazoles, -4 methylimidazole of 2- phenyl, 2-methylimidazole quinoline, 2- benzylimidazolines, 1- cyano ethyl -2- undecyl imidazoles or
The one or more of 1- cyano ethyl -2- phenylimidazoles.
Preferably, inorganic filler for aluminium nitride, aluminium borate, magnesia, magnesium carbonate, cubic boron nitride, crystalline silica,
Synthetic silica, hollow silica, preparing spherical SiO 2, fused silica, talcum powder, aluminium oxide, barium sulfate, metatitanic acid
Barium, strontium titanates, the one or more of calcium carbonate or titanium dioxide, grain size are 0.01-24 μm, purity more than 99.0%,
Preferably, toughener is core shell rubbers, and kernel is butadiene-styrene rubber, and shell is polymethyl methacrylate；Kernel contains
70-80wt%, shell 20-30wt% are measured, what core-shell particles were stablized is distributed in phenolic resin curing agent,
It is further preferred that the trade mark that toughener is Japanese KANEKA companies production is MX227* core shell rubbers.
The preparation method of copper coated foil plate polyphenylene oxide resin adhesive is prepared, using following steps：
A. organic solvent, silane are sequentially added in stirring grain by formula ratio, opens high speed agitator, rotating speed 1000-
1500rpm keeps lasting stirring and control flume temperature is at 20-50 DEG C, inorganic filler and fire retardant added, after addition
Persistently stir 20-60min；
B. polyfunctional epoxy resin, low dielectric-epoxy resin, cyanate, work are sequentially added by formula ratio in tank diameter
Property ester curing agent, polyphenylene oxide, toughener, 20-40min is stirred with the rotating speed of 1000-1500rpm, and opens cooling water simultaneously and follows
Ring simultaneously stirs 1-4h with rotating speed 1800rpm, and control flume temperature is at 20-50 DEG C；
C. weigh imidazoles accelerating agent by formula ratio, metal system curing accelerator is completely dissolved with suitable organic solvent,
The mixed accelerators being completely dissolved is added in tank diameter with the rotating speed stirring 1-3h of 1000-1500rpm after confirming nodeless mesh, is adjusted
Glue is completed, that is, adhesive is prepared.
Preferably, organic solvent is selected from acetone, methyl ethyl ketone, toluene, dimethylbenzene, methyl iso-butyl ketone (MIBK), propylene glycol list
Mixture more than one or both of methyl ether or cyclohexanone.
Compared with prior art, epoxide glass cloth base copper coated foil plate Tg ＞ prepared by the adhesive prepared using the present invention
180℃(DSC)；Z axis CTE ＜ 2.2%；In terms of heat resistance：TD >=370 DEG C, T288 ＞ 120min；In terms of electrical property：Dielectric is normal
Number (10GHz) ＜ 3.9；Dielectric loss (10GHz ＜ 0.0057)；Peel strength of copper foil (1OZ) ＞ 1.2N/mm；It is provided additionally with very
Low water absorption rate and good machining property, and it is fire-retardant reach UL94V-0 grades, the copper-clad plate of preparation possesses very excellent
Comprehensive performance, can be applied to 20 layers of printed circuit board or even above high-end applications market, 180 DEG C of Tg ＞'s is high-end fixed
Position is so that it can which extensive safety is suitable for high-frequency high-speed PCB fields.
Specific embodiment
With reference to specific embodiment, the present invention is described in detail.Following embodiment will be helpful to the technology of this field
Personnel further understand the present invention, but the invention is not limited in any way.It should be pointed out that the ordinary skill to this field
For personnel, without departing from the inventive concept of the premise, various modifications and improvements can be made.These belong to the present invention
Protection domain.
Examples 1 to 3 and comparative example 1~3
A kind of polyphenyl ether resin composition and the use of adhesive primary raw material of its preparation is polyfunctional epoxy resin, low
The compositions such as dielectric-epoxy resin, cyanate, active ester, polyphenylene oxide, fire retardant, inorganic filler, organic solvent and toughener.
Table 1
1. specific preparation process is as follows：
A. organic solvent, silane are sequentially added in stirring grain by formula ratio, opens high speed agitator, rotating speed 1000-
It 1500 revs/min, keeps lasting stirring and control flume temperature is at 20-50 DEG C, add inorganic filler and fire retardant, addition finishes
It persistently stirs 20-60 minutes afterwards；
B. polyfunctional epoxy resin, low dielectric-epoxy resin, cyanate, work are sequentially added by formula ratio in tank diameter
Property ester, polyphenylene oxide, toughener, stirred 20-40 minutes with 1000-1500 revs/min of rotating speed, and open cooling water circulation simultaneously simultaneously
With 1800 revs/min of rotating speed stirring 1-4 it is small when, control flume temperature is at 20-50 DEG C；
C. weigh imidazoles accelerating agent by formula ratio, metal system curing accelerator is completely dissolved with suitable organic solvent,
Confirm after nodeless mesh will the mixed accelerators that be completely dissolved add in it is small with 1000-1500 revs/min of rotating speed stirring 1-3 in tank diameter
When, impregnation is completed, that is, adhesive is made.
Table 2
It was found from the physical data of upper table, Examples 1 to 3 fully combines low molecular weight polycaprolactone phenylate, cyanate, active ester, low
The respective excellent performance of dielectric-epoxy resin and polyfunctional epoxy resin, by adjusting respective proportioning, copper is covered in preparation
Plate possesses more excellent dielectric properties and heat resistance and good processability.Multi-functional epoxy is not added in comparative example 1
Resin, system crosslink density is relatively low, and Tg is relatively low；Comparative example 2 is not added with cyanate, heat resistance and the dielectric properties deficiency of system；
Comparative example 3 is not added with active ester, and the dielectric loss of system is higher.
Embodiment 4
It is a kind of to prepare copper coated foil plate polyphenylene oxide resin adhesive, using the raw material of following components and parts by weight content：It is more
Functional group epoxy resin 1, low dielectric-epoxy resin 10, cyanate 5, active ester curing agent 10, polyphenylene oxide 10, fire retardant 5, silane
0.01st, metal system curing accelerator 0.005, imidazoles accelerating agent 0.01, inorganic filler 10, toughener 1.
The polyfunctional epoxy resin used is four diglycidyl ether epoxy tree of 1,1,2,2- tetra- (p-hydroxybenzene) ethane
Fat, low dielectric-epoxy resin are biphenyl type epoxy resin, and cyanate is bisphenol type cyanate, and active ester curing agent is knot containing naphthalene nucleus
The active ester system curing agent of structure, the weight average molecular weight of polyphenylene oxide are less than 2000, and end group carries phenolic hydroxyl group, used fire retardant with
It does not reduce dielectric properties to be preferred, the present embodiment uses deca-BDE, and silane uses γ-(2,3- the third oxygen of epoxy) third
Base trimethoxy silane.Metal system curing accelerator is acetylacetone cobalt (II), and imidazoles accelerating agent is 2-methylimidazole, inorganic
Filler is aluminium nitride, and grain size is 0.01 μm, and for purity more than 99.0%, toughener is core shell rubbers, and kernel is butadiene-styrene rubber, outside
Shell is polymethyl methacrylate；Kernel content 70wt%, shell 30wt%, the phenolic resin that is distributed in that core-shell particles are stablized are consolidated
In agent.
The preparation method of copper coated foil plate polyphenylene oxide resin adhesive is prepared, using following steps：
A. toluene, silane are sequentially added in stirring grain by formula ratio, opens high speed agitator, rotating speed 1000rpm is kept
Simultaneously control flume temperature at 50 DEG C, adds inorganic filler and fire retardant, 20min is persistently stirred after addition for lasting stirring；
B. polyfunctional epoxy resin, low dielectric-epoxy resin, cyanate, work are sequentially added by formula ratio in tank diameter
Property ester curing agent, polyphenylene oxide, toughener, 40min is stirred with the rotating speed of 1000rpm, and opens cooling water circulation simultaneously and to turn
Fast 1800rpm stirs 1h, and control flume temperature is at 20 DEG C；
C. weigh imidazoles accelerating agent by formula ratio, metal system curing accelerator is completely dissolved with suitable organic solvent,
3h being stirred with the rotating speed of 1000rpm in the mixed accelerators being completely dissolved addition tank diameter after confirming nodeless mesh, impregnation is completed,
Adhesive is prepared.
Embodiment 5
It is a kind of to prepare copper coated foil plate polyphenylene oxide resin adhesive, using the raw material of following components and parts by weight content：It is more
Functional group epoxy resin 10, low dielectric-epoxy resin 20, cyanate 30, active ester curing agent 20, polyphenylene oxide 50, fire retardant 30,
Silane 1, metal system curing accelerator 0.1, imidazoles accelerating agent 0.2, inorganic filler 40, toughener 15.
The polyfunctional epoxy resin used is with the epoxy resin of lower structure：
Low dielectric-epoxy resin is polyphenyl ether type epoxy, and cyanate is the Primaset of Long Sha companies of SwitzerlandTMBA-
3000S resins.Active ester curing agent uses the active ester of the biphenol structural containing dicyclopentadienyl.The weight average molecular weight of polyphenylene oxide is small
In 2000, end group carries phenolic hydroxyl group, and the present embodiment uses the polyphenylene oxide resin of following structural formula, is the SA90 trees of SABIC companies
Fat：
Fire retardant is preferred with not reducing dielectric properties, and the present embodiment is using three (2,6- 3,5-dimethylphenyl) phosphorus, silane
For gamma-aminopropyl-triethoxy-silane.Metal system curing accelerator is tin octoate, and imidazoles accelerating agent is -4 methyl miaow of 2- phenyl
Azoles, 2-methylimidazole quinoline, inorganic filler for hollow silica, preparing spherical SiO 2, grain size be 10 μm, purity 99.0% with
On, toughener is that core shell rubbers use the trade mark that KANEKA companies of Japan produce as MX227* core shell rubbers.
The preparation method of copper coated foil plate polyphenylene oxide resin adhesive is prepared, using following steps：
A. methyl ethyl ketone, silane are sequentially added in stirring grain by formula ratio, opens high speed agitator, rotating speed
1200rpm keeps lasting stirring and control flume temperature is at 30 DEG C, adds inorganic filler and fire retardant, held after addition
Continuous stirring 30min；
B. polyfunctional epoxy resin, low dielectric-epoxy resin, cyanate, work are sequentially added by formula ratio in tank diameter
Property ester curing agent, polyphenylene oxide, toughener, 30min is stirred with the rotating speed of 1200rpm, and opens cooling water circulation simultaneously and to turn
Fast 1800rpm stirs 2h, and control flume temperature is at 30 DEG C；
C. weigh imidazoles accelerating agent by formula ratio, metal system curing accelerator is completely dissolved with suitable organic solvent,
2h being stirred with the rotating speed of 1200rpm in the mixed accelerators being completely dissolved addition tank diameter after confirming nodeless mesh, impregnation is completed,
Adhesive is prepared.
Embodiment 6
It is a kind of to prepare copper coated foil plate polyphenylene oxide resin adhesive, using the raw material of following components and parts by weight content：It is more
Functional group epoxy resin 20, low dielectric-epoxy resin 50, cyanate 50, active ester curing agent 30, polyphenylene oxide 60, fire retardant 40,
Silane 3, metal system curing accelerator 0.3, imidazoles accelerating agent 0.3, inorganic filler 60, toughener 20.
Polyfunctional epoxy resin is using 4,4- diaminodiphenylmethane epoxy resin, triglycidyl group p-aminophenyl
Phenol, low dielectric-epoxy resin are selected from naphthol type epoxy resin, naphthylene ether type epoxy.Cyanate is dicyclopentadiene type
Cyanate, active ester curing agent are the active ester of the biphenol structural containing dicyclopentadienyl.The weight average molecular weight of polyphenylene oxide is less than
2000, end group carries phenolic hydroxyl group, and fire retardant uses decabromodiphenylethane, and silane uses vinyltrimethoxysilane.It is excellent
Selection of land, metal system curing accelerator is acetylacetone copper (II) organic copper complex, zinc acetylacetonate (II).Imidazoles accelerating agent
For 2- benzylimidazolines, inorganic filler is barium titanate, and grain size is 24 μm, and for purity more than 99.0%, toughener is core shell rubbers,
Kernel is butadiene-styrene rubber, and shell is polymethyl methacrylate；Kernel content 80wt%, shell 20wt%.
The preparation method of copper coated foil plate polyphenylene oxide resin adhesive is prepared, using following steps：
A. toluene, silane are sequentially added in stirring grain by formula ratio, opens high speed agitator, rotating speed 1500rpm is kept
Simultaneously control flume temperature at 20 DEG C, adds inorganic filler and fire retardant, 60min is persistently stirred after addition for lasting stirring；
B. polyfunctional epoxy resin, low dielectric-epoxy resin, cyanate, work are sequentially added by formula ratio in tank diameter
Property ester curing agent, polyphenylene oxide, toughener, 20min is stirred with the rotating speed of 1500rpm, and opens cooling water circulation simultaneously and to turn
Fast 1800rpm stirs 4h, and control flume temperature is at 50 DEG C；
C. weigh imidazoles accelerating agent by formula ratio, metal system curing accelerator is completely dissolved with suitable organic solvent,
1h being stirred with the rotating speed of 1500rpm in the mixed accelerators being completely dissolved addition tank diameter after confirming nodeless mesh, impregnation is completed,
Adhesive is prepared.
Specific embodiments of the present invention are described above.It is to be appreciated that the invention is not limited in above-mentioned
Particular implementation, those skilled in the art can make various deformations or amendments within the scope of the claims, this not shadow
Ring the substantive content of the present invention.
Claims (10)
1. a kind of prepare copper coated foil plate polyphenylene oxide resin adhesive, which is characterized in that raw material uses following components and parts by weight
Content：
It is polyfunctional epoxy resin 1-20, low dielectric-epoxy resin 10-50, cyanate 5-50, active ester curing agent 10-30, poly-
Phenylate 10-60, fire retardant 5-40, silane 0.01-3, metal system curing accelerator 0.005-0.3, imidazoles accelerating agent 0.01-
0.3rd, inorganic filler 10-60, toughener 1-20.
2. a kind of copper coated foil plate polyphenylene oxide resin adhesive is prepared according to claim 1, which is characterized in that described
Polyfunctional epoxy resin includes four tetraglycidel ether epoxy resin of 1,1,2,2- tetra- (p-hydroxybenzene) ethane, 4,4- diamino
Double (N, the N- bis- of diphenyl-methane epoxy resin, triglycidyl group para-aminophenol, triglycidyl meta-aminophenol or 1,3-
Glycidol aminomethyl) hexamethylene one or more, preferably with the epoxy resin of lower structure：
3. a kind of copper coated foil plate polyphenylene oxide resin adhesive is prepared according to claim 1, which is characterized in that described
Low dielectric-epoxy resin is selected from biphenyl type epoxy resin, naphthalene nucleus type epoxy resin, naphthol type epoxy resin, naphthylene ether type epoxy
One or more in resin, polyphenyl ether type epoxy or dicyclopentadiene type novolac epoxy resin.
4. a kind of copper coated foil plate polyphenylene oxide resin adhesive is prepared according to claim 1, which is characterized in that described
Cyanate is more than one or both of bisphenol type cyanate, dicyclopentadiene type cyanate or phenolic resin type cyanate
Mixing, preferably Switzerland Long Sha companies PrimasetTMBA-3000S resins.
5. a kind of copper coated foil plate polyphenylene oxide resin adhesive is prepared according to claim 1, which is characterized in that described
Active ester curing agent is selected from the active ester system curing agent containing naphthalene ring, the active ester of the acetylate of linear phenol-aldehyde resin, line
One or more in the active ester of the benzoylate of type phenolic resin or the active ester of the biphenol structural containing dicyclopentadienyl,
It is preferred that the active ester of the biphenol structural containing dicyclopentadienyl.
6. a kind of copper coated foil plate polyphenylene oxide resin adhesive is prepared according to claim 1, which is characterized in that described
The weight average molecular weight of polyphenylene oxide is less than 2000, and end group carries phenolic hydroxyl group, and the polyphenylene oxide resin of preferably following structural formula is SABIC
The SA90 resins of company：
7. a kind of copper coated foil plate polyphenylene oxide resin adhesive is prepared according to claim 1, which is characterized in that
The fire retardant uses brominated flame-retardant or phosphonium flame retardant, and the brominated fire retardant is deca-BDE, ten
The one or more of bromine diphenylethane, brominated styrene or deca-BDE；Such as three (2,6- bis- of the phosphonium flame retardant
Aminomethyl phenyl) phosphorus, the miscellaneous -10- phosphorus phenanthrene -10- oxides of 10 (2,5- dihydroxy phenyls) -9,10- dihydro-9-oxies, bis- (2,6- of 2,6-
3,5-dimethylphenyl) phosphorus base benzene or the miscellaneous -10- phosphorus phenanthrene -10- oxides of 10- phenyl -9,10- dihydro-9-oxies it is one or more kinds of,
The silane is selected from gamma-aminopropyl-triethoxy-silane, γ-aminopropyltrimethoxysilane, anilinomethyl trimethoxy
Base silane, γ-(β-aminoethyl) aminopropyl trimethoxysilane, γ-(2,3- the third oxygen of epoxy) propyl trimethoxy silicane, ethylene
One or more in base trimethoxy silane or vinyltriethoxysilane.
8. a kind of copper coated foil plate polyphenylene oxide resin adhesive is prepared according to claim 1, which is characterized in that
The metal system curing accelerator is cobalt, copper, zinc, iron, the metal-organic complex or organic metal salt of tin metal, is had
Organic metal complex is acetylacetone cobalt (II), the organic cobalt complex of acetylacetone cobalt (III), acetylacetone copper (II) organic copper
The one or more of complex compound, zinc acetylacetonate (II) organozinc complex or ferric acetyl acetonade (III)；Organic metal salt is pungent
Sour zinc, tin octoate or zinc stearate,
The imidazoles accelerating agent is 2-methylimidazole, -4 methylimidazole of 2- ethyls, DMIZ 1,2 dimethylimidazole, 2- phenyl miaows
Azoles, -4 methylimidazole of 2- phenyl, 2-methylimidazole quinoline, 2- benzylimidazolines, 1- cyano ethyl -2- undecyl imidazoles or 1- cyanogen
The one or more of base ethyl -2- phenylimidazoles.
9. a kind of copper coated foil plate polyphenylene oxide resin adhesive is prepared according to claim 1, which is characterized in that
The inorganic filler is aluminium nitride, aluminium borate, magnesia, magnesium carbonate, cubic boron nitride, crystalline silica, synthesis
Silica, hollow silica, preparing spherical SiO 2, fused silica, talcum powder, aluminium oxide, barium sulfate, barium titanate,
The one or more of strontium titanates, calcium carbonate or titanium dioxide, grain size be 0.01-24 μm, purity more than 99.0%,
The toughener is core shell rubbers, and kernel is butadiene-styrene rubber, and shell is polymethyl methacrylate；Kernel content 70-
80wt%, shell 20-30wt%, what core-shell particles were stablized is distributed in phenolic resin curing agent, preferably KANEKA companies of Japan
The trade mark of production is MX227* core shell rubbers.
10. the preparation method for preparing copper coated foil plate polyphenylene oxide resin adhesive according to any one of claim 1-9,
It is characterized in that, this method uses following steps：
A. organic solvent, silane are sequentially added in stirring grain by formula ratio, opens high speed agitator, rotating speed 1000-
1500rpm keeps lasting stirring and control flume temperature is at 20-50 DEG C, inorganic filler and fire retardant added, after addition
20-60min is persistently stirred, the organic solvent is acetone, methyl ethyl ketone, toluene, dimethylbenzene, methyl iso-butyl ketone (MIBK), third
Mixture more than one or both of glycol monomethyl ether or cyclohexanone；
B. polyfunctional epoxy resin, low dielectric-epoxy resin, cyanate, active ester are sequentially added by formula ratio in tank diameter
Curing agent, polyphenylene oxide, toughener stir 20-40min with the rotating speed of 1000-1500rpm, and open cooling water circulation simultaneously simultaneously
1-4h is stirred with rotating speed 1800rpm, control flume temperature is at 20-50 DEG C；
C. imidazoles accelerating agent is weighed by formula ratio, metal system curing accelerator is completely dissolved with suitable organic solvent, confirmation
The mixed accelerators being completely dissolved is added in tank diameter after nodeless mesh, 1-3h is stirred with the rotating speed of 1000-1500rpm, impregnation is complete
Into adhesive is prepared.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201711339505.0A CN108102594A (en) | 2017-12-14 | 2017-12-14 | It is a kind of to prepare copper coated foil plate polyphenylene oxide resin adhesive and preparation method thereof |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201711339505.0A CN108102594A (en) | 2017-12-14 | 2017-12-14 | It is a kind of to prepare copper coated foil plate polyphenylene oxide resin adhesive and preparation method thereof |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN108102594A true CN108102594A (en) | 2018-06-01 |
Family
ID=62215992
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201711339505.0A Pending CN108102594A (en) | 2017-12-14 | 2017-12-14 | It is a kind of to prepare copper coated foil plate polyphenylene oxide resin adhesive and preparation method thereof |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN108102594A (en) |
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN113025212A (en) * | 2021-03-13 | 2021-06-25 | 山东宝龙达实业集团有限公司 | Stainless steel tackifier and preparation method and application thereof |
| CN113897163A (en) * | 2021-12-09 | 2022-01-07 | 武汉市三选科技有限公司 | Adhesive, chip bonding film and preparation method thereof |
| CN114085636A (en) * | 2021-12-10 | 2022-02-25 | 南亚新材料科技(江西)有限公司 | Adhesive suitable for Mini LED high-reliability copper-clad plate and preparation method thereof |
| CN116731314A (en) * | 2022-03-04 | 2023-09-12 | 中国科学院化学研究所 | Cyano resin and preparation method and application thereof |
Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104968725A (en) * | 2013-02-12 | 2015-10-07 | 松下知识产权经营株式会社 | Resin composition, resin varnish, prepreg, metal-clad laminate and printed wiring board |
| CN106381113A (en) * | 2016-08-30 | 2017-02-08 | 上海南亚覆铜箔板有限公司 | Adhesive used for high-heat resistance leadless low-dielectric copper-clad plate and preparation method thereof |
| CN107177030A (en) * | 2016-03-10 | 2017-09-19 | 广东生益科技股份有限公司 | A kind of halogen-free thermosetting resin composite and use its prepreg and laminate for printed circuits |
| CN107298831A (en) * | 2017-07-20 | 2017-10-27 | 南亚新材料科技股份有限公司 | Improve proof tracking index and Drilling operation performance prepreg and its application |
-
2017
- 2017-12-14 CN CN201711339505.0A patent/CN108102594A/en active Pending
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104968725A (en) * | 2013-02-12 | 2015-10-07 | 松下知识产权经营株式会社 | Resin composition, resin varnish, prepreg, metal-clad laminate and printed wiring board |
| CN107177030A (en) * | 2016-03-10 | 2017-09-19 | 广东生益科技股份有限公司 | A kind of halogen-free thermosetting resin composite and use its prepreg and laminate for printed circuits |
| CN106381113A (en) * | 2016-08-30 | 2017-02-08 | 上海南亚覆铜箔板有限公司 | Adhesive used for high-heat resistance leadless low-dielectric copper-clad plate and preparation method thereof |
| CN107298831A (en) * | 2017-07-20 | 2017-10-27 | 南亚新材料科技股份有限公司 | Improve proof tracking index and Drilling operation performance prepreg and its application |
Non-Patent Citations (1)
| Title |
|---|
| 曹惟诚等: "《胶接技术手册》", 31 August 1988, 上海科学技术出版社 * |
Cited By (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN113025212A (en) * | 2021-03-13 | 2021-06-25 | 山东宝龙达实业集团有限公司 | Stainless steel tackifier and preparation method and application thereof |
| CN113025212B (en) * | 2021-03-13 | 2022-05-20 | 山东宝龙达实业集团有限公司 | Stainless steel tackifier and preparation method and application thereof |
| CN113897163A (en) * | 2021-12-09 | 2022-01-07 | 武汉市三选科技有限公司 | Adhesive, chip bonding film and preparation method thereof |
| CN113897163B (en) * | 2021-12-09 | 2022-03-11 | 武汉市三选科技有限公司 | Adhesive, chip bonding film and preparation method thereof |
| US11767450B2 (en) | 2021-12-09 | 2023-09-26 | Wuhan Choice Technology Co, Ltd | Adhesive, die attach film and preparation method therefor |
| CN114085636A (en) * | 2021-12-10 | 2022-02-25 | 南亚新材料科技(江西)有限公司 | Adhesive suitable for Mini LED high-reliability copper-clad plate and preparation method thereof |
| CN116731314A (en) * | 2022-03-04 | 2023-09-12 | 中国科学院化学研究所 | Cyano resin and preparation method and application thereof |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN108102594A (en) | It is a kind of to prepare copper coated foil plate polyphenylene oxide resin adhesive and preparation method thereof | |
| CN101914265B (en) | Non-halogen phosphorus-containing flame retardant high-frequency epoxy resin composition and application thereof to bonding sheet and copper-clad plate | |
| TW201400547A (en) | Low dielectric resin composition, applicable copper-clad laminate and printed circuit board | |
| CN108263068A (en) | A kind of method that copper coated foil plate is prepared using polyphenyl ether resin composition | |
| CN104974520A (en) | Halogen-free resin composition and application thereof | |
| CN107298831A (en) | Improve proof tracking index and Drilling operation performance prepreg and its application | |
| CN102276961A (en) | Halogen-free phosphorus-free epoxy resin composition, and semi-curing sheet and laminated sheet manufactured thereby | |
| CN103980708A (en) | Halogen-free flame-retardant thermosetting resin composition of integrated circuit, prepreg and laminate | |
| CN103992622A (en) | Halogen-free resin composition, prepreg prepared from halogen-free resin composition and laminated board prepared from halogen-free resin composition and used for printed circuit | |
| CN103724944A (en) | Halogen-free epoxy resin composition and application thereof | |
| CN105315615A (en) | Epoxy resin composition and prepreg and copper clad laminate manufactured by using epoxy resin composition | |
| CN103319853A (en) | Resin composition for insulation film, and insulation film and circuit board containing same | |
| CN104109347A (en) | Halogen-free thermosetting resin composition, prepreg and laminated plate | |
| CN103980704A (en) | Halogen-free resin composition for high-frequency and high-speed substrate as well as prepreg and laminated plate | |
| CN103724945A (en) | Halogen-free epoxy resin composition and application thereof | |
| CN106893258B (en) | A kind of composition epoxy resin and prepreg, laminate and printed circuit board containing it | |
| CN105801814B (en) | A kind of halogen-free thermosetting resin composite and use its prepreg and laminate for printed circuits | |
| CN103980667A (en) | Thermosetting resin composition of integrated circuit, prepreg and laminate | |
| CN103965588A (en) | Halogen-free thermosetting resin composition, prepreg and laminated board | |
| CN108047648B (en) | Resin composition suitable for high-speed high-reliability copper-clad plate and preparation method thereof | |
| CN105694451B (en) | A kind of halogen-free resin composition, prepreg, laminate and circuit board | |
| EP2770005B1 (en) | Epoxy resin composition and high frequency electronic-circuit substrate manufactured by using the same | |
| US20140039094A1 (en) | Epoxy resin composition, and prepreg and printed circuit board using the same | |
| CN105131597A (en) | Halogen-free resin composition and prepreg using halogen-free resin composition and printed circuit laminated board | |
| CN109265654A (en) | Resin combination and its manufactured prepreg, laminate |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| RJ01 | Rejection of invention patent application after publication |
Application publication date: 20180601 |
|
| RJ01 | Rejection of invention patent application after publication |