CN106381110A - Adhesive for high-Tg, lead-free and low-dielectric type copper-clad plate and preparation method thereof - Google Patents
Adhesive for high-Tg, lead-free and low-dielectric type copper-clad plate and preparation method thereof Download PDFInfo
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- CN106381110A CN106381110A CN201610741824.3A CN201610741824A CN106381110A CN 106381110 A CN106381110 A CN 106381110A CN 201610741824 A CN201610741824 A CN 201610741824A CN 106381110 A CN106381110 A CN 106381110A
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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
-
- 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
- C08G59/00—Polycondensates containing more than one epoxy group per molecule; Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups
- C08G59/18—Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups ; e.g. general methods of curing
- C08G59/40—Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups ; e.g. general methods of curing characterised by the curing agents used
- C08G59/42—Polycarboxylic acids; Anhydrides, halides or low molecular weight esters thereof
- C08G59/4246—Polycarboxylic acids; Anhydrides, halides or low molecular weight esters thereof polymers with carboxylic terminal groups
-
- 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
- C08G59/00—Polycondensates containing more than one epoxy group per molecule; Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups
- C08G59/18—Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups ; e.g. general methods of curing
- C08G59/68—Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups ; e.g. general methods of curing characterised by the catalysts used
- C08G59/686—Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups ; e.g. general methods of curing characterised by the catalysts used containing nitrogen
-
- 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
- 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
-
- 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
-
- 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
-
- 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
Abstract
The invention relates to an adhesive for a high-Tg, lead-free and low-dielectric type copper-clad plate and a preparation method thereof. The adhesive comprises the following components in weight part: 10-80 parts of bromizated modified epoxy resin, 5-80 parts of isocyanate-modified epoxy resin, 20-70 parts of modified polymeric anhydride, 0.005-0.03 part of 2-ethyl-4-methylimidazole, 10.0-60.0 parts of spherical silica, 0.10-0.20 part of silane, 1.00-10.0 parts of flexibilizer, and 10.0-60.0 parts of organic solvent. Compared with the prior art, the adhesive is low in water absorption and excellent in mechanical machining property. Meanwhile, the flame-retardant property of the adhesive is up to the UL94V-O level. Therefore, the adhesive can completely meet the requirements of the lead-free process and the multilayer board production process in the high-frequency and high-speed PCB field.
Description
Technical field
The invention belongs to copper coated foil plate preparation field, especially relate to one kind and be applied to the unleaded low dielectric type of high Tg cover Copper Foil
Adhesive of plate and preparation method thereof.
Background technology
21 century enters the society of advanced IT application, computer, mobile communication, network etc. gradually penetrated into society and
Each of people's life corner, human lives just develop towards the direction of advanced IT application steadily, information processing and information
Communication constitutes the developing two big technology pillars of advanced IT application science and technology field.Develop rapidly institute in order to meet information technology
The vast capacity information transfer brought, and the hard requirement that supper-fast, ultrahigh density is processed, to printed circuit board and cover
Copper coin is put forward higher requirement, and it is swollen that the specific requirement of its product shows as high heat resistance, excellent dielectric properties, low heat
Swollen coefficient and water absorption rate, environmental protection flame retardant performance etc..
On 2 13rd, 2003, European Union《Electrical and electronic product discarded object instruction case (WEEE)》With《With regard to electric
Some Hazardous Substances Directive cases (RoHS) are prohibitted the use of in equipment》Formal announcement, started formal enforcement in 1 day July in 2006,
The formal enforcement of this two instructions, indicates that global electronic industry enters the pb-free solder epoch.Traditional tin-lead solder
(Sn63/Pb37) eutectic point is 183 DEG C.The lead-free solder developed at present, eutectic point is generally higher than tin-lead solder 30
More than DEG C, the raising of welding temperature, necessarily higher requirement is proposed to copper-clad plate heat resistance.
The curing agent that traditional FR-4 substrate is commonly used has polyamines, phenolic resin etc., containing active in this kind of solidification agent molecule
, there is substantial amounts of hydroxyl in the epoxy resin of its solidification in hydrogen, this can lead to the rising of the water absorption rate of solidfied material, wet-hot aging performance and
The decline of dielectric properties.These very important performances cannot meet leadless process or even multi-layer sheet during PCB produces and produce
Demand.
Chinese patent CN104553229A discloses a kind of preparation method of the low dielectric type copper coated foil plate of high Tg Halogen, including
Following steps:One. prepared by adhesive;Two. gluing, prepreg processed;Three. typesetting, compacting.Wherein adhesive is by styrene-first
Base carbic anhydride, low dielectric-epoxy resin, benzoxazine resins, phosphonium flame retardant, high spheroiding silica, imidazoles promote
Enter agent, organic solvent is prepared from.But above-mentioned patent disclosed that Halogen system, Halogen with unleaded be two different bodies
System, Halogen system relative cost is higher, and the resist delamination time is slightly short;And processing characteristics is poor, peel strength is relatively low, and the application is just
It is the improved technique scheme proposing to overcome above-mentioned technical problem, improve the resist delamination time further.
Content of the invention
The purpose of the present invention is exactly to provide to overcome the defect that above-mentioned prior art exists a kind of to possess very low suction
Water rate and the good adhesive of the unleaded low dielectric type copper coated foil plate of the high Tg of production of good machining property, fire resistance and its
Preparation method.
The purpose of the present invention can be achieved through the following technical solutions:
A kind of adhesive being applied to the unleaded low dielectric type copper coated foil plate of high Tg, including following components and weight portion content:
The modified epoxy resin 10-80 of bromination, isocyanate-modified epoxy resin 5-80, modified poly acid anhydrides 20-70,
2- ethyl -4 methylimidazole 0.005-0.03, preparing spherical SiO 2 10.0-60.0, silane 0.10-0.20, toughener 1.00-
10.0th, organic solvent 10.0-60.0.
As preferred embodiment, the weight average molecular weight of the modified epoxy resin of bromination adopts GPC (gel infiltration color
Spectrum) method test.Selected from one of brominated bisphenol a type epoxy resin, bromination phenol aldehyde type or dibromo season pentanediol type epoxy resin
Or it is multiple.For example can using Dow Chemical produce the trade mark be 8005R2 resin, its weight average molecular weight be 500~
3000.
Bromination modified epoxy composition is as follows:
Project | Specifications parameter |
Solid | 75.1% |
Viscosity | 1555mPa*s |
Epoxide equivalent | 410 |
Density | 1.47g/cm3 |
Br% | 42% |
TG >=160 DEG C after brominated epoxy resin solidification, good toughness is it is easy to process, and can improve the resistance of material after solidification
Combustion performance is and good with glass fibre impregnation, the advantages of in hot pressing, the change of resin kinetic viscosity is slow.
As preferred embodiment, isocyanate-modified epoxy resin is aromatic series methyl diphenylene diisocyanate
One of modified epoxy resin or the modified epoxy resin of toluene di-isocyanate(TDI) or two kinds.
As preferred embodiment, modified poly acid anhydrides weight average molecular weight adopts GPC (gel permeation chromatography) method to test.
EF-30, EF-40 that modified poly acid anhydrides produces by Sartomer Company or the resin of the 8005H that Dow Chemical is produced
One or more of.
As more preferred embodiment, the trade mark that modified poly acid anhydrides is produced by Dow Chemical is 8005H
Resin.
Modified poly acid composition is as follows:
Project | Specifications parameter |
Solid | 55% |
Viscosity | 3000~10000mPa*s |
Density | 1.0g/cm3 |
Anhydride equivalent | 700~750 |
Modified poly acid anhydrides can be obviously improved material solidification after adding by a certain percentage after dielectric properties and heat resistance
Energy.
As preferred embodiment, the average grain diameter of preparing spherical SiO 2 is 0.5 μm, and maximum particle diameter is less than 24 μm,
Purity is in more than 99.0wt%.
As preferred embodiment, silane is selected from gamma-aminopropyl-triethoxy-silane, γ-aminopropyl trimethoxy silicon
Alkane, anilinomethyl trimethoxy silane, γ-(β-aminoethyl) aminopropyl trimethoxysilane, γ-(2,3- epoxy the third oxygen) propyl group
One or more of trimethoxy silane, vinyltrimethoxy silane or VTES.
As preferred embodiment, toughener uses FORTEGRA 351 resin or the day of Dow Chemical production
One or more of MX 158 core shell rubbers that this KANEKA company produces.
As preferred embodiment, organic solvent is dimethylformamide, acetone, methyl ethyl ketone, methyl-isobutyl
One or more of ketone or propylene glycol monomethyl ether.
This kind of adhesive can be used for producing copper coated foil plate, using following steps:
(1) get the raw materials ready according to formula composition;
(2) impregnation
(2-1) 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, adding preparing spherical SiO 2, adding and hold after finishing
Continuous stirring 20-60 minute;
(2-2) the modified epoxy resin of bromination, isocyanate-modified epoxy are sequentially added by formula ratio in tank diameter
Resin, modified poly acid anhydrides and 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;
(2-3) weigh 2- ethyl -4 methylimidazole by formula ratio to add in tank diameter, be completely dissolved with organic solvent, confirm
After nodeless mesh, the 2- being completely dissolved ethyl -4 methylimidazole is added in tank diameter and 1-3 is stirred with 1000-1500 rev/min of rotating speed
Hour, prepare adhesive.
Compared with prior art, the present invention has advantages below:
(1) present invention adopts High Bromine epoxy Resin, reaches good flame retardant effect, and fire-retardant rank reaches UL94V-0 level.With
When brominated epoxy resin solidification after TG >=160 DEG C, good toughness it is easy to processing, the fire resistance of material after solidification can be improved, and
Good with glass fibre impregnation, in hot pressing, the change of resin kinetic viscosity is slow.
(2) the epoxy resin cured product function admirable of polymeric anhydride solidification is especially stable with heat resistance and chemically-resistant
Property height is characterized.Acid anhydride curable epoxy resin is although need high temperature, but curing reaction is slower, and exothermic heat of reaction amount is little, and shrinkage factor is little.
It is had compared with amine curing agent, and volatility is little, toxicity is low, little to skin irritation, big with epoxy resin use level, viscosity
Little, can add filler modified, advantageously reduce cost, validity period is long, be easy to construct.
(3) in the epoxy-resin systems of polymeric anhydride solidification, the presence epoxy because of amine type accelerators such as imidazoles tends to
Generate ester bond with anhydride reaction, and suppress part etherification reaction, reduce the hydroxy radical content in system, can significantly improve solid
The dielectric properties of change system and wet-hot aging performance, thus the neck such as high-frequency high-speed speed and high density interconnection can be advantageously applied to
Domain.
Specific embodiment
With reference to specific embodiment, the present invention is described in detail.
Embodiment 1~3
The primary raw material preparing the unleaded low dielectric type copper coated foil plate of high Tg is the modified epoxy resin of bromination, isocyanates changes
The epoxy resin of property, polymeric anhydride curing agent, 2- ethyl -4 methylimidazole, preparing spherical SiO 2, organic solvent and toughener group
Become.
Table 3
Title material | Embodiment 1 | Embodiment 2 | Embodiment 3 |
The modified epoxy resin (%) of bromination | 16.7 | 15.36 | 14.71 |
Isocyanate-modified epoxy resin (%) | 12.6 | 13.4 | 14.3 |
Modified poly anhydride curing agent (%) | 24.6 | 22.5 | 20.4 |
2- ethyl -4 methylimidazole (%) | 0.01 | 0.01 | 0.01 |
Preparing spherical SiO 2 (%) | 21.8 | 24.5 | 27.4 |
Silane (%) | 0.11 | 0.12 | 0.14 |
Organic solvent (%) | 20.6 | 21.6 | 20.28 |
Toughener (%) | 3.58 | 3.51 | 3.38 |
1. specific preparation process is as follows:
A. 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 45 DEG C, add preparing spherical SiO 2, add continuously stirred 60 points after finishing
Clock;
B. the modified epoxy resin of bromination, isocyanate-modified asphalt mixtures modified by epoxy resin are sequentially added by formula ratio in tank diameter
Fat, anhydride curing agent and toughener, stirred 40 minutes with 1500 revs/min of rotating speed, and open cooling water circulation and to turn simultaneously
1800 revs/min of speed stirs 3 hours, and control flume temperature is at 45 DEG C;
C. weigh 2- ethyl -4 methylimidazole by formula ratio to add in tank diameter, little with 1500 revs/min of rotating speed stirring 3
When, that is, prepare adhesive.
Embodiment 4
A kind of adhesive being applied to the unleaded low dielectric type copper coated foil plate of high Tg, using following components and weight portion content:
The modified epoxy resin 10 of bromination, isocyanate-modified epoxy resin 5, modified poly acid anhydrides 20,2- ethyl -4 methylimidazole
0.005th, preparing spherical SiO 2 10.0, silane 0.10, toughener 1.00, organic solvent 10.0.
Wherein, employing the modified epoxy resin of bromination be brominated bisphenol a type epoxy resin, isocyanate-modified ring
Oxygen tree fat is the modified epoxy resin of aromatic series methyl diphenylene diisocyanate, and modified poly acid anhydrides is given birth to for Sartomer Company
The trade mark producing is the resin of EF-30, and the average grain diameter of preparing spherical SiO 2 is 0.5 μm, and maximum particle diameter is less than 24 μm, and purity exists
More than 99.0wt%.Silane adopts gamma-aminopropyl-triethoxy-silane, and toughener uses Dow Chemical to produce
FORTEGRA 351 resin.
A kind of adhesive being applied to the unleaded low dielectric type copper coated foil plate of Tg is used for producing copper coated foil plate, using following step
Suddenly:
(1) get the raw materials ready according to formula composition;
(2) impregnation
(2-1) sequentially add organic solvent, silane by formula ratio in stirring grain, open high speed agitator, rotating speed 1000
Rev/min, keep continuously stirred and control flume temperature at 20 DEG C, adding preparing spherical SiO 2, adding continuously stirred after finishing
20 minutes;
(2-2) the modified epoxy resin of bromination, isocyanate-modified epoxy are sequentially added by formula ratio in tank diameter
Resin, modified poly acid anhydrides and toughener, are stirred 20 minutes with 1000 revs/min of rotating speed, and open cooling water circulation simultaneously simultaneously
With rotating speed, 1800 revs/min are stirred 1 hour, and control flume temperature is at 20 DEG C;
(2-3) weigh 2- ethyl -4 methylimidazole by formula ratio to add in tank diameter, be completely dissolved with organic solvent, confirm
After nodeless mesh, the 2- being completely dissolved ethyl -4 methylimidazole is added in tank diameter and stirred 1 hour with 1000 revs/min of rotating speed, system
Standby obtain adhesive.
Embodiment 5
A kind of adhesive being applied to the unleaded low dielectric type copper coated foil plate of high Tg, including following components and weight portion content:
The modified epoxy resin 50 of bromination, isocyanate-modified epoxy resin 40, modified poly acid anhydrides 40,2- ethyl -4 methylimidazole
0.01st, preparing spherical SiO 2 50.0, silane 0.15, toughener 5.0, organic solvent 40.0.
Wherein, the modified epoxy resin of bromination is bromination phenol aldehyde type epoxy resin, and isocyanate-modified epoxy resin is
The modified epoxy resin of toluene di-isocyanate(TDI), the resin of the 8005H that modified poly acid anhydrides is produced by Dow Chemical, ball
The average grain diameter of shape silica is 0.5 μm, and maximum particle diameter is less than 24 μm, and purity is in more than 99.0wt%.Silane adopt γ-
Aminopropyl trimethoxysilane and the mixture of anilinomethyl trimethoxy silane, toughener uses Dow Chemical to produce
The mixture of the MX158 core shell rubbers that FORTEGRA 351 resin is produced with Japanese KANEKA company.
The adhesive of the unleaded low dielectric type copper coated foil plate of high Tg is used for producing copper coated foil plate, using following steps:
(1) get the raw materials ready according to formula composition;
(2) impregnation
(2-1) sequentially add organic solvent, silane by formula ratio in stirring grain, open high speed agitator, rotating speed 1200
Rev/min, keep continuously stirred and control flume temperature at 30 DEG C, adding preparing spherical SiO 2, adding continuously stirred after finishing
30 minutes;
(2-2) the modified epoxy resin of bromination, isocyanate-modified epoxy are sequentially added by formula ratio in tank diameter
Resin, modified poly acid anhydrides and toughener, are stirred 30 minutes with 1200 revs/min of rotating speed, and open cooling water circulation simultaneously simultaneously
With rotating speed, 1800 revs/min are stirred 2 hours, and control flume temperature is at 30 DEG C;
(2-3) weigh 2- ethyl -4 methylimidazole by formula ratio to add in tank diameter, be completely dissolved with organic solvent, confirm
After nodeless mesh, the 2- being completely dissolved ethyl -4 methylimidazole is added in tank diameter and stirred 2 hours with 1200 revs/min of rotating speed, system
Standby obtain adhesive.
Embodiment 6
A kind of adhesive being applied to the unleaded low dielectric type copper coated foil plate of high Tg, including following components and weight portion content:
The modified epoxy resin 80 of bromination, isocyanate-modified epoxy resin 80, modified poly acid anhydrides 70,2- ethyl -4 methylimidazole
0.03rd, preparing spherical SiO 2 60.0, silane 0.20, toughener 10.0, organic solvent 60.0.
Wherein, the modified epoxy resin of bromination is dibromo season pentanediol type epoxy resin, isocyanate-modified asphalt mixtures modified by epoxy resin
Fat is the modified epoxy resin of the aromatic series methyl diphenylene diisocyanate epoxy resin modified with toluene di-isocyanate(TDI)
Mixture, EF-30, EF-40 resin that modified poly acid anhydrides produces for Sartomer Company.The average grain diameter of preparing spherical SiO 2
For 0.5 μm, maximum particle diameter is less than 24 μm, and purity is in more than 99.0wt%.Silane is vinyltrimethoxy silane, toughener
The MX158 core shell rubbers being produced using Japanese KANEKA company.
The adhesive of the unleaded low dielectric type copper coated foil plate of high Tg is used for producing copper coated foil plate, using following steps:
(1) get the raw materials ready according to formula composition;
(2) impregnation
(2-1) sequentially add organic solvent, silane by formula ratio in stirring grain, open high speed agitator, rotating speed 1500
Rev/min, keep continuously stirred and control flume temperature at 50 DEG C, adding preparing spherical SiO 2, adding continuously stirred after finishing
60 minutes;
(2-2) the modified epoxy resin of bromination, isocyanate-modified epoxy are sequentially added by formula ratio in tank diameter
Resin, modified poly acid anhydrides and toughener, are stirred 40 minutes with 1500 revs/min of rotating speed, and open cooling water circulation simultaneously simultaneously
With rotating speed, 1800 revs/min are stirred 4 hours, and control flume temperature is at 50 DEG C;
(2-3) weigh 2- ethyl -4 methylimidazole by formula ratio to add in tank diameter, be completely dissolved with organic solvent, confirm
After nodeless mesh, the 2- being completely dissolved ethyl -4 methylimidazole is added in tank diameter and stirred 3 hours with 1500 revs/min of rotating speed, system
Standby obtain adhesive.
Claims (7)
1. a kind of adhesive being applied to the unleaded low dielectric type copper coated foil plate of high Tg it is characterised in that this adhesive include following
Component and weight portion content:
The modified epoxy resin 10-80 of bromination, isocyanate-modified epoxy resin 5-80, modified poly acid anhydrides 20-70,2- second
Base -4 methylimidazole 0.005-0.03, preparing spherical SiO 2 10.0-60.0, silane 0.10-0.20, toughener 1.00-10.0, have
Machine solvent 10.0-60.0.
2. a kind of adhesive being applied to the unleaded low dielectric type copper coated foil plate of high Tg according to claim 1, its feature exists
In the modified epoxy resin of described bromination is brominated bisphenol a type epoxy resin, bromination phenol aldehyde type or dibromo season pentanediol type ring
One or more of oxygen tree fat.
3. a kind of adhesive being applied to the unleaded low dielectric type copper coated foil plate of high Tg according to claim 1, its feature exists
In described isocyanate-modified epoxy resin is the modified epoxy resin of aromatic series methyl diphenylene diisocyanate or first
One of modified epoxy resin of phenylene diisocyanate or two kinds.
4. a kind of adhesive being applied to the unleaded low dielectric type copper coated foil plate of high Tg according to claim 1, it is special
Levy and be, EF-30, EF-40 that described modified poly acid anhydrides produces by Sartomer Company or Dow Chemical are produced
One or more of the resin of 8005H.
5. a kind of adhesive being applied to the unleaded low dielectric type copper coated foil plate of high Tg according to claim 1, its feature exists
In the average grain diameter of described preparing spherical SiO 2 is 0.5 μm, and maximum particle diameter is less than 24 μm, and purity is in more than 99.0wt%.
6. a kind of adhesive being applied to the unleaded low dielectric type copper coated foil plate of high Tg according to claim 1, its feature exists
In described silane is selected from gamma-aminopropyl-triethoxy-silane, γ-aminopropyltrimethoxysilane, anilinomethyl trimethoxy
Silane, γ-(β-aminoethyl) aminopropyl trimethoxysilane, γ-(2,3- epoxy the third oxygen) propyl trimethoxy silicane, vinyl
One or more of trimethoxy silane or VTES, described toughener is given birth to using Dow Chemical
One or more of FORTEGRA 351 resin producing or the MX158 core shell rubbers of Japanese KANEKA company production.
7. a kind of preparation method of the adhesive being applied to the unleaded low dielectric type copper coated foil plate of high Tg as claimed in claim 1,
It is characterized in that, for producing copper coated foil plate, using following steps:
(1) get the raw materials ready according to formula composition;
(2) impregnation
(2-1) 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, adding preparing spherical SiO 2, adding and persistently stir after finishing
Mix 20-60 minute;
(2-2) in tank diameter by formula ratio sequentially add the modified epoxy resin of bromination, isocyanate-modified epoxy resin,
Modified poly acid anhydrides and toughener, stir 20-40 minute with 1000-1500 rev/min of rotating speed, and open cooling water circulation simultaneously
And with 1800 revs/min of stirring 1-4 hours of rotating speed, control flume temperature is at 20-50 DEG C;
(2-3) weigh 2- ethyl -4 methylimidazole by formula ratio to add in tank diameter, be completely dissolved with organic solvent, confirm no to tie
After crystalline substance, the 2- being completely dissolved ethyl -4 methylimidazole is added the rotating speed stirring 1-3 with 1000-1500 rev/min in tank diameter little
When, that is, prepare adhesive.
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CN201610741824.3A CN106381110A (en) | 2016-08-26 | 2016-08-26 | Adhesive for high-Tg, lead-free and low-dielectric type copper-clad plate and preparation method thereof |
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CN201610741824.3A CN106381110A (en) | 2016-08-26 | 2016-08-26 | Adhesive for high-Tg, lead-free and low-dielectric type copper-clad plate and preparation method thereof |
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Citations (1)
Publication number | Priority date | Publication date | Assignee | Title |
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CN101481490A (en) * | 2009-01-19 | 2009-07-15 | 东莞联茂电子科技有限公司 | Thermosetting resin composition and use |
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2016
- 2016-08-26 CN CN201610741824.3A patent/CN106381110A/en active Pending
Patent Citations (1)
Publication number | Priority date | Publication date | Assignee | Title |
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CN101481490A (en) * | 2009-01-19 | 2009-07-15 | 东莞联茂电子科技有限公司 | Thermosetting resin composition and use |
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Address after: Shanghai city Chang Cheung Road 201802 Jiading District Nanxiang Town, No. 158 Applicant after: South Asia new materials Polytron Technologies Inc Address before: Shanghai city Chang Cheung Road 201802 Jiading District Nanxiang Town, No. 158 Applicant before: Shanghai Nanya Copper Clad Laminate Co., Ltd. |
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Application publication date: 20170208 |