CN106381113A - Adhesive used for high-heat resistance leadless low-dielectric copper-clad plate and preparation method thereof - Google Patents
Adhesive used for high-heat resistance leadless low-dielectric copper-clad plate and preparation method thereof Download PDFInfo
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- CN106381113A CN106381113A CN201610776506.0A CN201610776506A CN106381113A CN 106381113 A CN106381113 A CN 106381113A CN 201610776506 A CN201610776506 A CN 201610776506A CN 106381113 A CN106381113 A CN 106381113A
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- 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
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- 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
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- 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
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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
- C08L2201/00—Properties
- C08L2201/02—Flame or fire retardant/resistant
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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
- C08L2201/00—Properties
- C08L2201/08—Stabilised against heat, light or radiation or oxydation
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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
- C08L2203/00—Applications
- C08L2203/20—Applications use in electrical or conductive gadgets
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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
- 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
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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
- C08L2205/00—Polymer mixtures characterised by other features
- C08L2205/03—Polymer mixtures characterised by other features containing three or more polymers in a blend
Abstract
The invention relates to an adhesive used for a high-heat resistance leadless low-dielectric copper-clad plate and a preparation method thereof. The adhesive comprises the following components in parts by weight: 15-70 parts of low dielectric epoxy resin, 15-40 parts of modified polymerized acid anhydride, 5-40 parts of a cyanate esters curing agent, 2-40 parts of an active esters curing agent, 10-50 parts of a bromine-containing fire retardant, 0.05-1.000 parts of silane, 0.001-0.1 parts of a metals curing accelerator, 0.001-0.1 parts of an amines promoter, 0.005-0.1 parts of an imidazoles promoter, 10-60 parts of an inorganic filling material, and 1-8 parts of a flexibilizer. Compared with the prior art, the copper-clad plate has the advantages of high heat resistance, low water absorption, low dielectric loss and excellent resistance to heat and humidity.
Description
Technical field
The present invention relates to a kind of binding agent, especially relate to a kind of for the unleaded low dielectric type copper coated foil plate of high-fire resistance
Binding agent and preparation method.
Background technology
21 century will become the video signal epoch, and collection multifunction, each electronic product of diversification are increasingly becoming people's life
A central indispensable part, the capacity of the carrying information of electronic product is gradually increased, and conversion speed is also constantly lifted,
This require electronic signal in printed circuit board and its components and parts that loaded in there is higher transfer rate, in order to solve electricity
Sub- product is lightening and intensive the brought thermal losses of high speed is concentrated and is difficult to the problem dissipating it is desirable to baseplate material has relatively
Low dielectric loss tangent value, to reduce the loss of signal and the generation of heat.Meanwhile, " unleaded " and " high density is mutual
The laminate sheet material that the application requirement of connection " technology makes printed circuit board has higher thermostability, and higher vitrification temperature
Degree (Tg) and excellent heat stability and humidity resistance.
In resin combination currently used for high-frequency high-speed substrate, anhydride and cyanate become two kinds of more conventional solidifications
Thing.But in actual application, although the dielectricity of resin can be improved when anhydride type curing agent is used with epoxy resin
Can, but solidification temperature is higher, and hardening time is longer, and processing characteristics is poor, which results between resin and Copper Foil
Cohesive force is poor；The copper-clad plate vitrification point simultaneously prepared is relatively low.
When being used alone cyanate as epoxy hardener, due to cyanate ester resin have in itself excellent mechanical property,
Thermostability and dielectric properties, extremely low dielectric constant and dielectric loss, application therefore in electronic product can ensure higher biography
Defeated speed and efficiency of transmission, but composition epoxy resin manufacturability, toughness and the wet-hot aging performance prepared with it are poor, with
When cyanate price costly, the material cost prepared with it is higher, reduces its range of application to a certain extent.
Content of the invention
The purpose of the present invention is exactly to overcome the defect of above-mentioned prior art presence to provide a kind of so for preparing covers
Copper coin has covering for the unleaded low dielectric type of high-fire resistance of low water absorption rate, low dielectric loss and excellent wet-hot aging performance
The binding agent of copper foil plate and preparation method.
The purpose of the present invention can be achieved through the following technical solutions：
For the binding agent of the unleaded low dielectric type copper coated foil plate of high-fire resistance, former using following components and weight portion content
Material prepares：
Low dielectric-epoxy resin 15-70, modified poly anhydride 15-40, cyanate system firming agent 5-40, the solidification of active ester system
Agent 2-40, brominated flame-retardant 10-50, silane 0.05-1.000, metal system curing accelerator 0.001-0.1, amine system accelerator
0.001-0.1, imidazoles accelerator 0.005-0.1, inorganic filler 10-60, toughener 1-8.
Described low dielectric-epoxy resin be selected from biphenyl type epoxy resin, naphthalene nucleus type epoxy resin, naphthol type epoxy resin,
One or more of naphthylene ether type epoxy, polyphenyl ether type epoxy or dicyclopentadiene type novolac epoxy resin.
Described modified poly anhydride by formed after aromatic amine compound modified phenylethylene copolymer-maleic anhydride three
Membered copolymer, weight average molecular weight 2000～30000, can greatly improve thermostability and the dielectric properties of polymer and its product.
The weight average molecular weight of modified poly anhydride curing agent adopts GPC (gel permeation chromatography) method to test.Described modified poly anhydride
The XQR-147 resin that firming agent is produced by Dow Chemical, chemical constitution such as following formula, its weight average molecular weight 2000～
30000.
Wherein, R represents hydrogen-based, aromatic radical, aliphatic group etc., and Ar represents aromatic radical；Aromatic radical includes phenyl, biphenyl
One or more of base, naphthyl, aliphatic group includes but is not limited to alkyl and alicyclic alkyl.
M in formula, n, r represent molar fraction, wherein m >=0.5 respectively；N and r value from 0.45 to 0.05 respectively；m+n+r
=1.00.The ratio of anhydride and curable epoxide reaction epoxide epoxy group group and anhydride group is 1.0:1.0 to 2.7:1.0, preferably
1.1:1.0 to 1.9:1.0.
In modified poly anhydride there is ring-opening reaction in anhydride group and epoxy resin, and its reaction mechanism is shown below：
Anhydride with epoxy reactive curing mechanism is：First, hydroxyl and carboxylic acid reaction generate the carboxylic acid containing ester chain；Then
There is opening in carboxylic acid and epoxy radicals.After modified poly anhydride can be obviously improved material solidification after adding by a certain percentage
Dielectric properties and heat resistance.
Modified poly anhydride component requirements：
| Project | Specifications parameter |
| Solid (wt%) | 65.4 |
| Viscosity (mPa*s) | 1640 |
| Density (g/cm3) | 1.01 |
| Anhydride equivalent | 700 |
Described cyanate system firming agent is bisphenol type cyanate system firming agent, the solidification of dicyclopentadiene type cyanate system
Agent or phenolic resin type cyanate system firming agent, weight average molecular weight is 500～5000.
Cyanate and epoxide group react complicated, are mainly copolymerized generation five criminal oxazoline rings and hexa-atomic triazine ring
With triple polyisocyanate annulus structure, these copolyreaction are that substep is carried out, and are not simultaneous, are not independently to enter
Row, but be successively cross-linked with each other.Cyanate and the reaction of epoxide group, more specifically can be exemplified as shown in following formula, cyanogen first
Perester radical generates oxazoline ring with epoxy ring opening reaction, and then when temperature is more than 200 DEG C, oxazoline ring structure changes into oxazole
Alkanone ring.
Wherein, a part of triazine network structure generating after ethylene rhodanate resin curing has excellent mechanical property and glass
Change transition temperature, and extremely low dielectric constant and dielectric loss, but simultaneously because this triazine ring structure is regular, degree of crystallinity
Higher, add that crosslink density is big, make the toughness of material not enough.Use it as the firming agent of epoxy resin, generate therebetween
Oxazoline ketone heteroaromatic structure, reduces the crosslink density of triazine ring, thus improve the toughness of solidified resin.
Described active ester system firming agent is selected from the active ester system firming agent containing naphthalene ring, the acetyl of linear phenol-aldehyde resin
The active ester of compound, the active ester of the benzoylate of linear phenol-aldehyde resin or the active ester containing dicyclopentadienyl biphenol structural
One or more of.
Active ester can improve dielectric properties and the wet-hot aging performance of epoxy resin as firming agent.
As the active ester firming agent containing dicyclopentadienyl biphenol structural, the structure of formula more specifically can be listed below：
In formula, X represents phenyl ring, cyclohexyl biphenyl, naphthalene ring, from the sight making the reduction of solidfied material dielectric loss and thermostability raising
Point considers, X is preferably naphthalene ring.J represents 0 or 1, and preferably 1；K represents 0 or 1, preferably 0；N represents and averagely repeats list
Unit is 0.25-2.5.Active ester component requirements are as shown in the table：
| Project | Specifications parameter |
| Solid (wt%) | 65 |
| Solvent | Toluene |
| Functional equivalent (g/eq) | 223 |
| Softening point (DEG C) | 150 |
The reaction of wherein Modified Products By Modification of Active Esters And Epoxy Resin, more specifically can be listed below shown in formula：
As can be seen from the above equation, ester group, as the firming agent of epoxy, is reacted with epoxy resin, is formed and does not generate secondary hydroxyl group
Rack, it is achieved thereby that the low-dielectric that cannot realize of conventional epoxy resin and low water absorption rate.
The XQR-147 resin that the described preferred Dow Chemical of modified poly anhydride is produced,
Double (4- cyanate) phenyl of the described preferred bisphenol A dicyanate of cyanate system firming agent, polyphenol cyanate, 2,2-
Double (4- cyanate phenylmethane) or double (4- cyanate -3, the 5- 3,5-dimethylphenyl) methane of methane, 1,1-, weight average molecular weight is preferred
700～4000,
Described active ester system firming agent preferably contains the active ester of dicyclopentadienyl biphenol structural.
Described metal system curing accelerator is cobalt, copper, the metal-organic complex of zinc, ferrum or stannum or organic metal salt,
Described amine system accelerator be selected from benzyldimethylamine, 2,4, triethylamine, tri-butylamine, 4-dimethylaminopyridine or
One or more of 2,4,6- tri- (dimethylaminomethyl) phenol,
Described imidazoles accelerator is selected from 2-methylimidazole, 2- ethyl -4 Methylimidazole., DMIZ 1,2 dimethylimidazole, 2- benzene
Base imidazoles, 2- phenyl -4 Methylimidazole., 2-methylimidazole quinoline, 2- benzylimidazoline, 1- cyano ethyl -2- undecyl imidazole or
One or more of 1- cyano ethyl -2- phenylimidazole.
The described preferred acetylacetone cobalt of metal system curing accelerator (II), acetylacetone cobalt (III), acetylacetone copper
(II), one or more of zinc acetylacetonate (II), ferric acetyl acetonade zinc octoate, tin octoate or zinc stearate.
The particle diameter that described inorganic filler is be 0.01-24 μm, purity in more than 99.0wt%, selected from aluminium nitride, boric acid
Aluminum, magnesium oxide, magnesium carbonate, cubic boron nitride, crystalline silica, synthetic silica, hollow silica, spherical titanium dioxide
One of silicon, fused silica, Pulvis Talci, aluminium oxide, barium sulfate, Barium metatitanate., strontium titanates, Calcium Carbonate or titanium dioxide or
Multiple.
Described brominated flame-retardant is selected from one of TDE, brominated styrene or deca-BDE or many
Kind.
Described toughener uses FORTEGRA 351 resin of Dow Chemical production or Japanese KANEKA company
One or more of MX158 core shell rubbers producing.
For the preparation method of the binding agent of the unleaded low dielectric type copper coated foil plate of high-fire resistance, using following steps：
(1) sequentially add organic solvent, silane by formula ratio in stirring grain, open high speed agitator, rotating speed 1000-
1500 revs/min, keep continuously stirred and control flume temperature at 20-50 DEG C, add inorganic filler and brominated flame-retardant, add
Continuously stirred 20-60 minute after finishing；
(2) low dielectric-epoxy resin, modified poly anhydride curing agent, cyanate are sequentially added by formula ratio in agitator tank
It is firming agent, active ester system firming agent, toughener, 20-40 minute is stirred with 1000-1500 rev/min of rotating speed, and opens simultaneously
Cooling water circulation and with 1800 revs/min of rotating speed stirring 1-4 hours, control flume temperature is at 20-50 DEG C；
(3) imidazoles accelerator, amine system accelerator, metal system curing accelerator organic solvent are weighed by formula ratio complete
Dissolving, after confirming nodeless mesh adds in agitator tank the mixed accelerators being completely dissolved with 1000-1500 rev/min of rotating speed stirring
1-3 hour, impregnation completes, that is, binding agent is obtained.
Compared with prior art, the present invention has advantages below：
(1) active ester is as the firming agent of epoxy resin, this is because having two or more in active ester solidification agent molecule
There is the ester group of greater activity, curing reaction can be carried out with epoxy resin, generate the rack without secondary hydroxyl group, so solidification
Epoxy resin afterwards has low dielectric loss and water absorption rate, so that the copper-clad plate of preparation has low water absorption rate, low
Dielectric loss and excellent wet-hot aging performance.
(2) the epoxy resin cured product function admirable of modified poly anhydride-cured, especially with heat resistance and chemically-resistant
Stability height is characterized.And in the epoxy-resin systems of polymeric anhydride solidification, because of the presence ring of the amine type accelerators such as imidazoles
Oxygen tends to generate ester bond with anhydride reaction, and suppresses part etherification reaction, reduces the hydroxy radical content in system, thus significantly
The dielectric properties and the wet-hot aging performance that improve curing system, thus can be advantageously applied to high-frequency high-speed and high density interconnection
In field.
(3) to sum up, because the presence of active ester and polymeric anhydride leads to the reduction of hydroxy radical content in system, thus decreasing
Cyanate and hydroxyl reaction generate the content of the poor imido-carbonic ester of wet-hot aging performance, further improve the wet-heat resisting of system
Performance；Play the preferable mechanical property of cyanate ester resin, thermostability and dielectric properties, therefore these three firming agent play simultaneously
Synergism makes its epoxy radicals copper-clad plate prepared possess excellent combination property it is ensured that the higher transfer rate of electronic product
And efficiency of transmission.
(4) adopt 230 DEG C of the epoxide glass cloth base copper coated foil plate Tg ＞ (DMA) of binding agent preparation of the present invention；Z axis
CTE ＜ 2.2%；Thermostability aspect：TD >=370 DEG C, T288 ＞ 180min, T300 ＞ 180min；Electrical property aspect：Dielectric constant
(5GHz)≤3.87；Dielectric loss (5GHz ＜ 0.0068；Peel strength of copper foil (1OZ) ＞ 0.9N/mm；It is provided additionally with very low
Water absorption rate and good machining property, and fire-retardant reach UL94V-0 level, can fully meet in high-frequency high-speed PCB field
Leadless process and the demand of multi-layer sheet production.
Specific embodiment
With reference to specific embodiment, the present invention is described in detail.
Embodiment 1～3 and comparative example 1～3
A kind of binding agent primary raw material being applied to the unleaded low dielectric type copper coated foil plate of high-fire resistance is low dielectric-epoxy resin
Fat, modified poly anhydride curing agent, cyanate system firming agent, active ester system firming agent, brominated flame-retardant, inorganic filler, organic
Solvent and toughener etc. form.
| Title material | Embodiment 1 | Embodiment 2 | Embodiment 3 | Comparative example 1 | Comparative example 2 | Comparative example 3 |
| Low dielectric-epoxy resin | 18 | 17 | 19 | 18 | 21 | 20 |
| Modified poly anhydride | 15 | 16 | 17 | 18 | 16 | ---- |
| Cyanate system firming agent | 12 | 13 | 12 | 12 | ---- | 16 |
| Active ester system firming agent | 3 | 4 | 2 | ---- | 12 | 12 |
| Brominated flame-retardant | 16 | 16 | 16 | 16 | 16 | 16 |
| Silane | 0.18 | 0.15 | 0.15 | 0.18 | 0.15 | 0.16 |
| Metal system curing accelerator | 0.02 | 0.02 | 0.02 | 0.01 | ---- | 0.02 |
| Amine system accelerator | 0.02 | 0.01 | 0.01 | ---- | 0.02 | 0.02 |
| Imidazoles accelerator | 0.01 | 0.01 | 0.01 | 0.01 | 0.01 | 0.01 |
| Inorganic filler | 33 | 33 | 33 | 33 | 33 | 33 |
| Toughener | 1.8 | 1.5 | 1.5 | 1.8 | 1.6 | 1.8 |
1. specific preparation process is as follows：
Sequentially add organic solvent, silane by formula ratio in stirring grain, open high speed agitator, rotating speed 1000-1500
Rev/min, keep continuously stirred and control flume temperature at 20-50 DEG C, add inorganic filler and brominated flame-retardant, interpolation finishes
Continuously stirred 20-60 minute afterwards；
B. low dielectric-epoxy resin, modified poly anhydride curing agent, cyanate are sequentially added by formula ratio in agitator tank
It is firming agent, active ester system firming agent, toughener, 20-40 minute is stirred with 1000-1500 rev/min of rotating speed, and opens simultaneously
Cooling water circulation and with 1800 revs/min of rotating speed stirring 1-4 hours, control flume temperature is at 20-50 DEG C；
C. imidazoles accelerator, amine system accelerator, metal system curing accelerator are weighed with appropriate organic molten by formula ratio
Agent is completely dissolved, confirm nodeless mesh after by the mixed accelerators being completely dissolved add agitator tank in 1000-1500 rev/min turn
Speed stirring 1-3 hour, impregnation completes.
2. gluing baking：
Prepreg gluing speed：10.0m/min.
3. prepreg control parameter：
Gel time：280s
Resin content:56.8%
Resin flow：33.6%
Fugitive constituent:0.31%
4. sheet material composing structure：After 6 2116 prepreg pressings, thickness is 0.781mm
5. pressing plate parameter：
Vacuum：-0.098Mpa
Pressure：261-564psi
Temperature of heat plate：150-220℃
High temperature section hardening time：120min
, being detected, result is as shown in the table to its performance.
When the physical data of upper table understands that comparative example 1 is used polymeric anhydride and cyanate as firming agent, electrical property is relatively
General epoxy resin makes moderate progress, but wet-hot aging performance is poor；Comparative example 2 makees firming agent using active ester and polymeric anhydride
When, its dielectric properties and wet-hot aging performance make moderate progress, but glass transition temperature and peel strength are relatively low；Comparative example 3 makes
During with cyanate and active ester as firming agent, wet-hot aging performance and peel strength have been lifted, but thermal coefficient of expansion is relatively
High.Embodiment 1-3 uses low dielectric type epoxy resin, and solid using modified poly anhydride, cyanate system firming agent, active ester system
Agent three as firming agent, greatly improves the dielectric properties of cured product, heat resistance, glass transition temperature, resistance to
Hygrothermal Properties and processing characteristics.
Embodiment 4
For the binding agent of the unleaded low dielectric type copper coated foil plate of high-fire resistance, former using following components and weight portion content
Material prepares：
Low dielectric-epoxy resin 70, modified poly anhydride 40, cyanate system firming agent 40, active ester system firming agent 40, contain
Bromine flame retardant 50, silane 1, metal system curing accelerator 0.1, amine system accelerator 0.1, imidazoles accelerator 0.1, inorganic filler
60th, toughener 8.
Using low dielectric-epoxy resin be biphenyl type epoxy resin and naphthalene nucleus type epoxy resin mixture, modified poly
Anhydride exists by the terpolymer being formed after aromatic amine compound modified phenylethylene copolymer-maleic anhydride, weight average molecular weight
2000, cyanate system firming agent is bisphenol type cyanate system firming agent, and weight average molecular weight is 500, and active ester system firming agent is selected from
Active ester system firming agent containing naphthalene ring.Metal system curing accelerator is acetylacetone cobalt (II) and acetylacetone cobalt (III)
Mixture, amine system accelerator is benzyldimethylamine, 2,4, and imidazoles accelerator is 2-methylimidazole.The particle diameter that inorganic filler is is
0.01-24 μm, purity is in the aluminium nitride of more than 99.0wt%.Brominated flame-retardant is TDE.Toughener uses the U.S.
FORTEGRA 351 resin that DOW Chemical produces.
For the preparation method of the binding agent of the unleaded low dielectric type copper coated foil plate of high-fire resistance, using following steps：
(1) sequentially add organic solvent, silane by formula ratio in stirring grain, open high speed agitator, 1000 turns of rotating speed/
Point, keep continuously stirred and control flume temperature at 20 DEG C, add inorganic filler and brominated flame-retardant, add and continue after finishing
Stirring 20 minutes；
(2) low dielectric-epoxy resin, modified poly anhydride curing agent, cyanate are sequentially added by formula ratio in agitator tank
It is firming agent, active ester system firming agent, toughener, is stirred 20 minutes with 1000 revs/min of rotating speed, and open cooling water simultaneously and follow
Ring is simultaneously stirred 1 hour with 1800 revs/min of rotating speed, and control flume temperature is at 20-50 DEG C；
(3) imidazoles accelerator, amine system accelerator, metal system curing accelerator organic solvent are weighed by formula ratio complete
The mixed accelerators being completely dissolved is added the rotating speed stirring 1 with 1000 revs/min in agitator tank little after confirming nodeless mesh by dissolving
When, impregnation completes, that is, binding agent is obtained.
Embodiment 5
For the binding agent of the unleaded low dielectric type copper coated foil plate of high-fire resistance, former using following components and weight portion content
Material prepares：
Low dielectric-epoxy resin 20, modified poly anhydride 15, cyanate system firming agent 5, active ester system firming agent 5, brominated
Fire retardant 10, silane 0.05, metal system curing accelerator 0.001, amine system accelerator 0.001, imidazoles accelerator 0.005, no
Machine filler 10, toughener 1.
The low dielectric-epoxy resin using is naphthylene ether type epoxy, and modified poly anhydride is Dow Chemical institute
The XQR-147 resin producing, cyanate system firming agent is double (4- cyanate -3,5- 3,5-dimethylphenyl) methane, weight average molecular weight
700, active ester system firming agent is the active ester containing dicyclopentadienyl biphenol structural.Metal system curing accelerator is acetylacetone,2,4-pentanedione
Ferrum zinc octoate, amine system accelerator is 2,4,6- tri- (dimethylaminomethyl) phenol, and imidazoles accelerator is 2-methylimidazole, 2-
The mixture of ethyl -4 Methylimidazole., the particle diameter that inorganic filler is is 10 μm, and purity is in the crystalline silica of more than 99.0wt%
Silicon, the mixture of synthetic silica.Brominated flame-retardant is brominated styrene.Toughener is produced using Japanese KANEKA company
MX158 core shell rubbers.
For the preparation method of the binding agent of the unleaded low dielectric type copper coated foil plate of high-fire resistance, using following steps：
(1) sequentially add organic solvent, silane by formula ratio in stirring grain, open high speed agitator, 1200 turns of rotating speed/
Point, keep continuously stirred and control flume temperature at 30 DEG C, add inorganic filler and brominated flame-retardant, add and continue after finishing
Stirring 30 minutes；
(2) low dielectric-epoxy resin, modified poly anhydride curing agent, cyanate are sequentially added by formula ratio in agitator tank
It is firming agent, active ester system firming agent, toughener, is stirred 30 minutes with 1200 revs/min of rotating speed, and open cooling water simultaneously and follow
Ring is simultaneously stirred 2 hours with 1800 revs/min of rotating speed, and control flume temperature is at 30 DEG C；
(3) imidazoles accelerator, amine system accelerator, metal system curing accelerator organic solvent are weighed by formula ratio complete
The mixed accelerators being completely dissolved is added the rotating speed stirring 2 with 1200 revs/min in agitator tank little after confirming nodeless mesh by dissolving
When, impregnation completes, that is, binding agent is obtained.
Embodiment 6
For the binding agent of the unleaded low dielectric type copper coated foil plate of high-fire resistance, former using following components and weight portion content
Material prepares：
Low dielectric-epoxy resin 15, modified poly anhydride 18, cyanate system firming agent 12, active ester system firming agent 2, brominated
Fire retardant 19.88, silane 0.1, metal system curing accelerator 0.01, amine system accelerator 0.005, imidazoles accelerator 0.005, no
Machine filler 15, toughener 5.
The low dielectric-epoxy resin using is dicyclopentadiene type novolac epoxy resin, and modified poly anhydride is aromatic amination
The terpolymer being formed after polymer modified styrene maleic anhydride copolymer, 30000, cyanate system is solid for weight average molecular weight
Agent is phenolic resin type cyanate system firming agent, and weight average molecular weight is 5000, and active ester system firming agent is linear phenol-aldehyde resin
Benzoylate active ester.Metal system curing accelerator is tin octoate, and amine system accelerator is tri-butylamine, and imidazoles promote
Agent is 1- cyano ethyl -2- phenylimidazole.The particle diameter that inorganic filler is is 24 μm, and purity is in the strontium titanates of more than 99.0wt%.
Brominated flame-retardant is deca-BDE.Toughener uses FORTEGRA 351 resin that Dow Chemical produces.
For the preparation method of the binding agent of the unleaded low dielectric type copper coated foil plate of high-fire resistance, using following steps：
(1) sequentially add organic solvent, silane by formula ratio in stirring grain, open high speed agitator, 1500 turns of rotating speed/
Point, keep continuously stirred and control flume temperature at 50 DEG C, add inorganic filler and brominated flame-retardant, add and continue after finishing
Stirring 60 minutes；
(2) low dielectric-epoxy resin, modified poly anhydride curing agent, cyanate are sequentially added by formula ratio in agitator tank
It is firming agent, active ester system firming agent, toughener, is stirred 40 minutes with 1500 revs/min of rotating speed, and open cooling water simultaneously and follow
Ring is simultaneously stirred 4 hours with 1800 revs/min of rotating speed, and control flume temperature is at 50 DEG C；
(3) imidazoles accelerator, amine system accelerator, metal system curing accelerator organic solvent are weighed by formula ratio complete
The mixed accelerators being completely dissolved is added the rotating speed stirring 3 with 1500 revs/min in agitator tank little after confirming nodeless mesh by dissolving
When, impregnation completes, that is, binding agent is obtained.
Claims (10)
1. it is used for the binding agent of the unleaded low dielectric type copper coated foil plate of high-fire resistance it is characterised in that adopting following components and weight
The raw material of part content prepares：
Low dielectric-epoxy resin 15-70, modified poly anhydride 15-40, cyanate system firming agent 5-40, active ester system firming agent 2-
40th, brominated flame-retardant 10-50, silane 0.05-1.000, metal system curing accelerator 0.001-0.1, amine system accelerator 0.001-
0.1st, imidazoles accelerator 0.005-0.1, inorganic filler 10-60, toughener 1-8.
2. the binding agent for the unleaded low dielectric type copper coated foil plate of high-fire resistance according to claim 1 it is characterised 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
One or more of type epoxy resin, polyphenyl ether type epoxy or dicyclopentadiene type novolac epoxy resin.
3. the binding agent for the unleaded low dielectric type copper coated foil plate of high-fire resistance according to claim 1 it is characterised in that
Described modified poly anhydride is common by the ternary being formed after aromatic amine compound modified phenylethylene copolymer-maleic anhydride
Polymers, weight average molecular weight 2000～30000,
Described cyanate system firming agent be bisphenol type cyanate system firming agent, dicyclopentadiene type cyanate system's firming agent or
Phenolic resin type cyanate system firming agent, weight average molecular weight is 500～5000,
Described active ester system firming agent is selected from the active ester system firming agent containing naphthalene ring, the acetylate of linear phenol-aldehyde resin
Active ester, the active ester of the benzoylate of linear phenol-aldehyde resin or containing dicyclopentadienyl biphenol structural active ester in
One or more.
4. the binding agent for the unleaded low dielectric type copper coated foil plate of high-fire resistance according to claim 3 it is characterised in that
The XQR-147 resin that the described preferred Dow Chemical of modified poly anhydride is produced,
Double (4- cyanate) the phenyl first of the described preferred bisphenol A dicyanate of cyanate system firming agent, polyphenol cyanate, 2,2-
Double (4- cyanate phenylmethane) or double (4- cyanate -3, the 5- 3,5-dimethylphenyl) methane of alkane, 1,1-, weight average molecular weight is preferred
700～4000,
Described active ester system firming agent preferably contains the active ester of dicyclopentadienyl biphenol structural.
5. the binding agent for the unleaded low dielectric type copper coated foil plate of high-fire resistance according to claim 1 it is characterised in that
Described metal system curing accelerator is cobalt, copper, the metal-organic complex of zinc, ferrum or stannum or organic metal salt,
Described amine system accelerator is selected from benzyldimethylamine, 2,4, triethylamine, tri-butylamine, 4-dimethylaminopyridine or 2,4,
One or more of 6- tri- (dimethylaminomethyl) phenol,
Described imidazoles accelerator is selected from 2-methylimidazole, 2- ethyl -4 Methylimidazole., DMIZ 1,2 dimethylimidazole, 2- phenyl miaow
Azoles, 2- phenyl -4 Methylimidazole., 2-methylimidazole quinoline, 2- benzylimidazoline, 1- cyano ethyl -2- undecyl imidazole or 1- cyanogen
One or more of base ethyl -2- phenylimidazole.
6. the binding agent for the unleaded low dielectric type copper coated foil plate of high-fire resistance according to claim 5 it is characterised in that
The described preferred acetylacetone cobalt of metal system curing accelerator (II), acetylacetone cobalt (III), acetylacetone copper (II), levulinic
One or more of ketone zinc (II), ferric acetyl acetonade, zinc octoate, tin octoate or zinc stearate.
7. the binding agent for the unleaded low dielectric type copper coated foil plate of high-fire resistance according to claim 1 it is characterised in that
The particle diameter that described inorganic filler is be 0.01-24 μm, purity in more than 99.0wt%, selected from aluminium nitride, Alborex M 12, oxidation
Magnesium, magnesium carbonate, cubic boron nitride, crystalline silica, synthetic silica, hollow silica, preparing spherical SiO 2, melting
One or more of silicon dioxide, Pulvis Talci, aluminium oxide, barium sulfate, Barium metatitanate., strontium titanates, Calcium Carbonate or titanium dioxide.
8. the binding agent for the unleaded low dielectric type copper coated foil plate of high-fire resistance according to claim 1 it is characterised in that
Described brominated flame-retardant is selected from one or more of TDE, brominated styrene or deca-BDE.
9. the binding agent for the unleaded low dielectric type copper coated foil plate of high-fire resistance according to claim 1 it is characterised in that
Described toughener uses FORTEGRA 351 resin that Dow Chemical produces or Japanese KANEKA company produces
One or more of MX158 core shell rubbers.
10. it is used for the preparation method of the binding agent of the unleaded low dielectric type copper coated foil plate of high-fire resistance as claimed in claim 1, its
It is characterised by, the method adopts following steps：
(1) sequentially add organic solvent, silane by formula ratio in stirring grain, open high speed agitator, rotating speed 1000-1500
Rev/min, keep continuously stirred and control flume temperature at 20-50 DEG C, add inorganic filler and brominated flame-retardant, interpolation finishes
Continuously stirred 20-60 minute afterwards；
(2) low dielectric-epoxy resin, modified poly anhydride curing agent, cyanate system are sequentially added admittedly by formula ratio in agitator tank
Agent, active ester system firming agent, toughener, stir 20-40 minute with 1000-1500 rev/min of rotating speed, and open cooling simultaneously
Water circulation with 1800 revs/min of rotating speed stirring 1-4 hours, control flume temperature is at 20-50 DEG C；
(3) imidazoles accelerator, amine system accelerator, metal system curing accelerator organic solvent are weighed by formula ratio completely molten
Solution, after confirming nodeless mesh adds the mixed accelerators being completely dissolved in agitator tank and stirs 1- with 1000-1500 rev/min of rotating speed
3 hours, impregnation completed, that is, binding agent is obtained.
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| CN109439257A (en) * | 2018-11-23 | 2019-03-08 | 南亚新材料科技股份有限公司 | A kind of preparation method of the low dielectric type copper coated foil plate of the high Tg of Halogen |
| CN109536107A (en) * | 2018-11-23 | 2019-03-29 | 南亚新材料科技股份有限公司 | A kind of adhesive and preparation method thereof of the low dielectric type copper coated foil plate of the high Tg of Halogen |
| CN111500249A (en) * | 2020-05-20 | 2020-08-07 | 山东金宝电子股份有限公司 | Low-dielectric-property low-water-absorption halogen-free copper-clad plate and preparation method thereof |
| CN112409756A (en) * | 2020-10-20 | 2021-02-26 | 中电科芜湖钻石飞机制造有限公司 | Low-dielectric epoxy resin composition, preparation method thereof and composite material |
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| JP2022092991A (en) * | 2020-12-11 | 2022-06-23 | 昭和電工マテリアルズ株式会社 | Molding resin composition and electronic component device |
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