CN103788576B - Epoxy resin composition and preparation method thereof - Google Patents
Epoxy resin composition and preparation method thereof Download PDFInfo
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- CN103788576B CN103788576B CN201310636997.5A CN201310636997A CN103788576B CN 103788576 B CN103788576 B CN 103788576B CN 201310636997 A CN201310636997 A CN 201310636997A CN 103788576 B CN103788576 B CN 103788576B
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Abstract
The invention discloses an epoxy resin composition which is prepared from novolac epoxy resin, isocyanic acid modified brominated epoxy resin, high-bromine epoxy resin, a phenolic resin curing agent, an epoxy resin curing accelerator, a heat stabilizer, inorganic filler and an organic solvent. A copper-clad laminate prepared by use of the epoxy resin composition disclosed by the invention has the characteristics of high glass transition temperature (higher or equal to 170 DEG C), good heat resistance and peel strength, good machinability and the like, and can meet the requirements for the heat resistance and processability of materials in a PCB (printed circuit board) processing process.
Description
Technical field
The invention belongs to copper-clad plate technical field, relate to a kind of copper foil covered pressure of unleaded high Tg being applicable to high density interconnection HDI
Composition epoxy resin of baseplate material and preparation method thereof.
Background technology
On July 1st, 2006 starts, the instruction of two, European Union (about in electronic and electrical equipment limit use Hazardous Substances Directive and
About scrap electronic and electrical equipment instruction) formal enforcement, indicate global electronic industry will enter the pb-free solder epoch.
Owing to welding temperature is high, improving copper-clad plate thermal reliability accordingly, traditional plumber's solder can not re-use, now
Welding temperature needed for the alternative solders such as SAC all increases substantially.And the copper-clad plate of traditional F R-4, owing to thermostability is low, glass
Glass temperature only has 130-140 DEG C, heat decomposition temperature typically only 300-310 DEG C, although extensively should in general electronic products
With, but can not apply in high density interconnection and integrated circuit fields, existing electronic product quickly grows, and along with printing electricity
Lightening, the multiple stratification on road and the development of semiconductor mount technologies, it is desirable to substrate must have high Tg, high heat-resisting and low bulk
The performances such as coefficient, to improve interconnection and the reliability installed.To this end, exploitation is the heaviest with this resin combination matched
Want.
The developing way that the copper-clad laminate material of the high Tg applied in industry at present is basic mainly uses phenolic cure
System, in terms of the thermostability of material, performance is good, substantially can meet PCB to properties requirements such as thermostabilitys, although
There is the advantage in terms of thermostability in this type of material, but material Shortcomings in terms of toughness, peel strength and PCB processability,
Because the reason that material the most crisp too hard toughness is not enough so that it exists bigger problem in terms of PCB processability, also can simultaneously
Increase PCB processing and fabricating cost.
Summary of the invention
It is an object of the invention to provide a kind of epoxy resin being applicable to the production of PCB industry multi-layer sheet in view of the above problems
Compositions.The copper-clad plate material using this composition epoxy resin to make has good peel strength, toughness and excellent heat-resisting
Property and good PCB processing characteristics, it is possible to be applicable to the making of HDI height multi-layer PCB board.
The present invention provides a kind of ring for making more than Tg170 DEG C copper foil covered pressure baseplate material for achieving the above object
Epoxy resin composition includes brominated epoxy resin (C) the high bromine ring that (A) novolac epoxy resin (B) Carbimide. is modified
Epoxy resins (D) phenolic resin curative；(E) epoxy resin curing accelerator；(F) heat stabilizer；(G) inorganic filler.
The percentage ratio that this composition epoxy resin accounts for composition solid gross weight by each constituent solid weight is as follows:
In a preferred embodiment of the invention, described novolac epoxy resin can be bisphenol A-type novolac epoxy resin, double
One or more mixing in phenol F type novolac epoxy resin, o-cresol formaldehyde epoxy resin.
In a preferred embodiment of the invention, described isocyanate-modified brominated epoxy resin can be aromatic series hexichol
One in modified for methane diisocyanate MDI epoxy resin, toluene di-isocyanate(TDI) TDI modified epoxy or both
Mixing.
In a preferred embodiment of the invention, described High Bromine epoxy Resin is selected from the BEB400 of Changchun, Taiwan Chemical Manufacture
Resin.
In a preferred embodiment of the invention, described phenolic resin curative is the phenolic resin of phenol and formaldehyde crosslinking, institute
State phenol be phenol, xylenols, ethyl-phenol, n-pro-pyl phenol, isopropyl-phenol, normal-butyl phenol, isobutyl group phenol,
One or more mixture in tert-butyl phenol or bisphenol-A.It is phenol and formaldehyde as preferred described phenolic resin
The phenol novolacs of crosslinking, or the bisphenol A phenolic resin of bisphenol-A and formaldehyde crosslinking, or phenol novolacs and bisphenol-A
The mixture of phenolic resin.
In a preferred embodiment of the invention, described epoxy resin curing accelerator select 2-ethyl-4-methylimidazole and
The imidazolium compounds such as 2-methylimidazole, 1 benzyl 2 methyl imidazole, preferably 2-ethyl-4-methylimidazole, it is promoting asphalt mixtures modified by epoxy resin
Consumption in fat solidification should sufficiently lack, and preferable amount is the 0.002～0.016wt% of whole amount of solid.
In a preferred embodiment of the invention, described heat stabilizer can be selected for the XQ82969 that Dow Chemical produces
Resin.
In a preferred embodiment of the invention, described inorganic filler selection aluminium hydroxide and the mixture of silicon dioxide, two
Mass ratio between person is 6～13: 17～25.
Additionally, in addition to the aforementioned components, also can include organic solvent, organic solvent is not specifically limited, such as, and can
Use the one in acetone, methyl ethyl ketone, toluene, dimethylbenzene, methyl iso-butyl ketone (MIBK), propylene glycol monomethyl ether or cyclohexanone or
Two or more mixture, these solvents can each be used alone, and maybe can use the combination of its two or more.
The usage amount of organic solvent is not specifically limited, and is impregnated into by epobond epoxyn from the case of preparing prepreg
From the viewpoint of the good adhesion between easiness and resin combination and matrix in matrix, be preferably added to organic solvent with
Make the solids content of glue be 50% or more than, particularly 60～80% are preferred.
The preparation process of this composition epoxy resin is as follows:
(1) press formula ratio in agitator tank, add part organic solvent, turn on agitator, rotating speed 500～1200 revs/min, protect
Hold continuously stirred and control flume temperature at 20～50 DEG C, add inorganic filler, after interpolation continuously stirred 20～50 points
Clock；
(2) in agitator tank, it is sequentially added into novolac epoxy resin, the brominated epoxy resin of Carbimide. modification, height by formula ratio
Brominated eopxy resin, phenolic resin curative and heat stabilizer, keep with 1000～1500 revs/min of rotating speed stirrings during charging,
Open after interpolation and efficiently shear and emulsifying 1～4 hours, carry out cooling water circulation to keep control flume temperature to exist simultaneously
20～50 DEG C；
(3) weigh epoxy resin curing accelerator by formula ratio, add it to, in remaining organic solvent, be completely dissolved
After, this solution is added in agitator tank, and persistently keeps 1000～1500 revs/min of stirrings 4～13 hours, i.e. prepare asphalt mixtures modified by epoxy resin
Oil/fat composition.
The copper clad laminate using composition epoxy resin of the present invention to prepare has high glass transition temperature (>=170 DEG C), excellent resistance to
The characteristic such as hot, peel strength and good machining property, can meet PCB procedure for processing and for material thermal resistance energy and add
The requirement of work aspect of performance.
Detailed description of the invention
Main material
1. novolac epoxy resin
Novolac epoxy resin of the present invention can be bisphenol A-type novolac epoxy resin, bisphenol-f type novolac epoxy resin or orthoresol
Formaldehyde epoxy resin, or above-mentioned resin can be used alone or can combine more than two kinds persons simultaneously is used in conjunction with.
In the present invention, this kind of resin can be selected for the KEB-3165 that the BNE200 resin of Changchun, Taiwan Chemical Manufacture or Korea S can be grand
Resin, but it is not limited only to this.
2. the brominated epoxy resin that Carbimide. is modified
Resin characteristics parameter:
| Project | Specifications parameter |
| Epoxide equivalent EEW(g/eq) | 300～380 |
| Hydrolyzable chlorine | 300MAX |
| Bromine content (wt%) | 16-23 |
Isocyanate-modified brominated epoxy resin comprises the epoxy resin that aromatic series '-diphenylmethane diisocyanate MDI is modified
And toluene di-isocyanate(TDI) TDI modified epoxy, it is also possible to it is the mixture of the two, its purpose is to give solidification tree
Required for fat and the laminate made with it basic both mechanically and thermally, and there is good toughness and the stripping of excellent copper
From intensity.
In the present invention, this kind of resin can be selected for the XU19074 resin that Dow Chemical produces, but is not not limited only to this.
3. High Bromine epoxy Resin
| Project | Specifications parameter |
| Epoxide equivalent EEW(g/eq) | 380～420 |
| Hydrolyzable chlorine | 300MAX |
| Bromine content (wt%) | 46～50 |
In the present invention, this kind of resin can be selected for the BEB400 resin of Changchun, Taiwan Chemical Manufacture.
4. phenolic resin curative
Phenolic resin is the phenolic resin of phenol and formaldehyde crosslinking, and described phenol is phenol, xylenols, ethyl-phenol, n-pro-pyl
One or more in phenol, isopropyl-phenol, normal-butyl phenol, isobutyl group phenol, tert-butyl phenol or bisphenol-A
Mixture.As the phenol novolacs that preferred described phenolic resin is phenol and formaldehyde crosslinking, or bisphenol-A is handed over formaldehyde
The bisphenol A phenolic resin of connection, or the mixture of phenol novolacs and bisphenol A phenolic resin.
5. heat stabilizer
Heat stabilizer used in the present invention is the epoxy resin of a kind of liquid, plays heat stabilization in the material, promotes
The unfailing performances such as the thermostability of material.
In the present invention, this kind of resin can be selected for the XQ82969 resin that Dow Chemical produces.
6. epoxy resin curing accelerator
Curing accelerator contained in epobond epoxyn in the present invention is generally with promoting consolidating of epoxy resin cure
Change accelerator, commonly use 2-ethyl-4-methylimidazole and the imidazolium compounds such as 2-methylimidazole, 1 benzyl 2 methyl imidazole, preferably
2-ethyl-4-methylimidazole, its consumption in promoting epoxy resin cure should sufficiently lack, and preferable amount is whole amount of solid
0.002～0.016wt%.
The present invention is further illustrated below by embodiment and comparative example.
The characteristic of the copper-clad laminate of embodiment 1-4 and comparative example is measured by following methods (with reference to IPC-TM-650).
(1) vitrification point (Tg)
Glass transition temperature refers to that sheet material is the temperature corresponding to elastomeric state (rubbery state) by glassy transition in the case of being heated
Degree (DEG C).
Detection method: use differential scanning calorimetry (DSC).
(2) thermally stratified layer time (T-260)
The T-260 thermally stratified layer time refer to sheet material under the design temperature of 260 DEG C, due to heat effect lamination occurs,
Duration before this.
Detection method: use thermo-mechanical analysis method (TMA).
(3) peel strength
Test according to IPC-TM-650-2.4.8C method.
(4) scolding tin thermostability
Scolding tin thermostability, refers in the melted scolding tin that sheet material immerses 288 DEG C, without layering occur and bubbling duration.
Detection method: the substrate after etching is cut into 5.0cm × 5.0cm size, and edges of boards are successively with 120 mesh and 800 mesh sand paper
Polishing, pressure-cooks certain time, puts in 288 DEG C of tin melting furnaces, observes with or without phenomenons such as layerings.
Embodiment 1
1. the weight/mass percentage composition of the solid content in composition epoxy resin is 66.5%, and remaining is organic solvent (such as the third two
Alcohol methyl ether),
Wherein, the formula of solid content see table (by weight)
| Raw material | Solid weight (gram) |
| Phenol aldehyde type epoxy resin | 20 |
| The brominated epoxy resin that Carbimide. is modified | 15 |
| High Bromine epoxy Resin | 8 |
| Phenolic resin curative | 23 |
| 2-ethyl-4-methylimidazole (2E4MZ) | 0.05 |
| Heat stabilizer | 2.5 |
| Aluminium hydroxide | 10 |
| Silicon dioxide | 20 |
2. the preparation method of composition epoxy resin:
(1) in agitator tank, organic solvent propylene glycol methyl ether 49 grams, turn on agitator, rotating speed 600 are added by above weight
Rev/min, and continuously stirred 30 minutes；
(2) in agitator tank, it is sequentially added into novolac epoxy resin, the brominated epoxy resin of Carbimide. modification, high bromine by formula ratio
Epoxy resin, phenolic resin and heat stabilizer, keep during charging with 1000 revs/min of rotating speed stirrings；
(3) propylene glycol monomethyl ether is weighed by formula ratio, it is complete with organic solvent propylene glycol monomethyl ether with the ratio of weight ratio 1:10
After CL, this solution is added in agitator tank, and persistently keep 1200 revs/min of stirrings 2 hours, prepare epoxy resin group
Compound.
3. prepare copper-clad laminate
The composition epoxy resin continuously coating prepared in order to top method or impregnated glass fiber cloth, under 170 DEG C of baking conditions
It is dried to obtain prepreg, 8 prepregs are overlapped, the high temperature extension Copper Foil of its upper and lower each 1 35um of placement,
Through 190 DEG C, heat under the pressure of 350PSI, pressurize 90 minutes, obtain the copper-clad laminate of 1.6mm.
4. the performance parameter of the copper-clad laminate that the present embodiment prepares gained is as shown in the table:
| Project | Test result |
| Vitrification point (DSC), DEG C | 175 |
| Peel strength of copper foil (1oz), lb/in | 9.6 |
| T288(TMA),min | 35 |
| Scolding tin thermostability (288 DEG C of wickings), min | >10 |
| CTE (50-260 DEG C, Z axis), % | 2.60 |
Embodiment 2
1. the weight/mass percentage composition of the solid content in composition epoxy resin is 65%, and remaining is organic solvent (such as the third two
Alcohol methyl ether),
Wherein, the formula of solid content see table (by weight)
| Raw material | Solid weight (gram) |
| Phenol aldehyde type epoxy resin | 25 |
| The brominated epoxy resin that Carbimide. is modified | 14 |
| High Bromine epoxy Resin | 6 |
| Phenolic resin curative | 22 |
| 2-ethyl-4-methylimidazole (2E4MZ) | 0.04 |
| Heat stabilizer | 2 |
| Aluminium hydroxide | 7 |
| Silicon dioxide | 22 |
2. the preparation method of composition epoxy resin:
(1) in agitator tank, organic solvent propylene glycol methyl ether 52 grams, turn on agitator, rotating speed 600 are added by above weight
Rev/min, and continuously stirred 30 minutes；
(2) in agitator tank, it is sequentially added into novolac epoxy resin, the brominated epoxy resin of Carbimide. modification, high bromine by formula ratio
Epoxy resin, phenolic resin and heat stabilizer, keep during charging with 1000 revs/min of rotating speed stirrings；
(3) propylene glycol monomethyl ether is weighed by formula ratio, it is complete with organic solvent propylene glycol monomethyl ether with the ratio of weight ratio 1:10
After CL, this solution is added in agitator tank, and persistently keep 1200 revs/min of stirrings 2 hours, prepare epoxy resin group
Polymer resin compositions.
3. prepare copper-clad laminate
The composition epoxy resin continuously coating prepared in order to top method or impregnated glass fiber cloth, under 170 DEG C of baking conditions
It is dried to obtain prepreg, 8 prepregs are overlapped, the high temperature extension Copper Foil of its upper and lower each 1 35um of placement,
Through 190 DEG C, heat under the pressure of 350PSI, pressurize 90 minutes, obtain the copper-clad laminate of 1.6mm.
4. the performance parameter of the copper-clad laminate that the present embodiment prepares gained is as shown in the table:
| Project | Test result |
| Vitrification point (DSC), DEG C | 178 |
| Peel strength of copper foil (1oz), lb/in | 9.5 |
| T288(TMA),min | 39 |
| Scolding tin thermostability (288 DEG C of wickings), min | >10 |
| CTE (50-260 DEG C, Z axis), % | 2.54 |
Embodiment 3
1. the weight/mass percentage composition of the solid content in composition epoxy resin is 62.3%, and remaining is organic solvent (such as the third two
Alcohol methyl ether),
Wherein, the formula of solid content see table (by weight)
| Raw material | Solid weight (gram) |
| Phenol aldehyde type epoxy resin | 30 |
| The brominated epoxy resin that Carbimide. is modified | 12 |
| High Bromine epoxy Resin | 10 |
| Phenolic resin curative | 27 |
| 2-ethyl-4-methylimidazole (2E4MZ) | 0.07 |
| Heat stabilizer | 1.3 |
| Aluminium hydroxide | 13 |
| Silicon dioxide | 17 |
2. the preparation method of composition epoxy resin:
(1) in agitator tank, organic solvent propylene glycol methyl ether 66 grams, turn on agitator, rotating speed 600 are added by above weight
Rev/min, and continuously stirred 30 minutes；
(2) in agitator tank, it is sequentially added into novolac epoxy resin, the brominated epoxy resin of Carbimide. modification, height by formula ratio
Brominated eopxy resin, phenolic resin and heat stabilizer, keep during charging with 1000 revs/min of rotating speed stirrings；
(3) propylene glycol monomethyl ether is weighed by formula ratio, by it with the ratio of weight ratio 1:10 and organic solvent propylene glycol monomethyl ether
After being completely dissolved, this solution is added in agitator tank, and persistently keep 1200 revs/min of stirrings 2 hours, prepare epoxy resin
Compositions.
3. prepare copper-clad laminate
The composition epoxy resin continuously coating prepared in order to top method or impregnated glass fiber cloth, under 170 DEG C of baking conditions
It is dried to obtain prepreg, 8 prepregs are overlapped, the high temperature extension Copper Foil of its upper and lower each 1 35um of placement,
Through 190 DEG C, heat under the pressure of 350PSI, pressurize 90 minutes, obtain the copper-clad laminate of 1.6mm.
4. the performance parameter of the copper-clad laminate that the present embodiment prepares gained is as shown in the table:
| Project | Test result |
| Vitrification point (DSC), DEG C | 182 |
| Peel strength of copper foil (1oz), lb/in | 9.2 |
| T288(TMA),min | 43 |
| Scolding tin thermostability (288 DEG C of wickings), min | >10 |
| CTE (50-260 DEG C, Z axis), % | 2.50 |
Embodiment 4
1. the weight/mass percentage composition of the solid content in composition epoxy resin is 69%, and remaining is organic solvent (such as the third two
Alcohol methyl ether),
Wherein, the formula of solid content see table (by weight)
| Raw material | Solid weight (gram) |
| Phenol aldehyde type epoxy resin | 35 |
| The brominated epoxy resin that Carbimide. is modified | 10 |
| High Bromine epoxy Resin | 4 |
| Phenolic resin curative | 30 |
| 2-ethyl-4-methylimidazole (2E4MZ) | 0.08 |
| Heat stabilizer | 1 |
| Aluminium hydroxide | 6 |
| Silicon dioxide | 25 |
2. the preparation method of composition epoxy resin:
(1) in agitator tank, organic solvent propylene glycol methyl ether 50 grams, turn on agitator, rotating speed 600 are added by above weight
Rev/min, and continuously stirred 30 minutes；
(2) in agitator tank, it is sequentially added into novolac epoxy resin, the brominated epoxy resin of Carbimide. modification, high bromine by formula ratio
Epoxy resin, phenolic resin and heat stabilizer, keep during charging with 1000 revs/min of rotating speed stirrings；
(3) propylene glycol monomethyl ether is weighed by formula ratio, it is complete with organic solvent propylene glycol monomethyl ether with the ratio of weight ratio 1:10
After CL, this solution is added in agitator tank, and persistently keep 1200 revs/min of stirrings 2 hours, prepare epoxy resin group
Compound.
3. prepare copper-clad laminate
The composition epoxy resin continuously coating prepared in order to top method or impregnated glass fiber cloth, under 170 DEG C of baking conditions
It is dried to obtain prepreg, 8 prepregs are overlapped, the high temperature extension Copper Foil of its upper and lower each 1 35um of placement,
Through 190 DEG C, heat under the pressure of 350PSI, pressurize 90 minutes, obtain the copper-clad laminate of 1.6mm.
4. the performance parameter of the copper-clad laminate that the present embodiment prepares gained is as shown in the table:
| Project | Test result |
| Vitrification point (DSC), DEG C | 186 |
| Peel strength of copper foil (1oz), lb/in | 9.0 |
| T288(TMA),min | 50 |
| Scolding tin thermostability (288 DEG C of wickings), min | >10 |
| CTE (50-260 DEG C, Z axis), % | 2.38 |
Comparative example 1
1. the weight/mass percentage composition of the solid content in resin combination is 64%, and remaining is organic solvent (such as propylene glycol first
Ether),
Wherein, the formula of solid content see table (by weight)
| Raw material | Solid weight (gram) |
| Phenol aldehyde type epoxy resin | 35 |
| High Bromine epoxy Resin | 15 |
| Phenolic resin curative | 23 |
| 2-ethyl-4-methylimidazole (2E4MZ) | 0.03 |
| Aluminium hydroxide | 8 |
| Silicon dioxide | 19 |
2. the preparation method of resin combination:
(1) in agitator tank, organic solvent propylene glycol methyl ether 57 grams, turn on agitator, rotating speed 600 are added by above weight
Rev/min, and continuously stirred 30 minutes；
(2) in agitator tank, it is sequentially added into novolac epoxy resin, High Bromine epoxy Resin, phenolic resin by formula ratio, fed
Journey keeps with 1000 revs/min of rotating speed stirrings；
(3) propylene glycol monomethyl ether is weighed by formula ratio, it is complete with organic solvent propylene glycol monomethyl ether with the ratio of weight ratio 1:10
After CL, this solution is added in agitator tank, and persistently keep 1200 revs/min of stirrings 2 hours, prepare resin combination.
3. prepare copper-clad laminate
The resin binder continuously coating prepared in order to top method or impregnated glass fiber cloth, be dried under 170 DEG C of baking conditions
Obtaining prepreg, overlapped by 8 prepregs, the high temperature extension Copper Foil of its upper and lower each 1 35um of placement, through 190
DEG C, heat under the pressure of 350PSI, pressurize 90 minutes, obtain the copper-clad laminate of 1.6mm.
4. the performance parameter of the copper-clad laminate that this comparative example prepares gained is as shown in the table:
| Project | Test result |
| Vitrification point (DSC), DEG C | 174 |
| Peel strength of copper foil (1oz), lb/in | 8.1 |
| T288(TMA),min | 27 |
| Scolding tin thermostability (288 DEG C of wickings), min | >10 |
| CTE (50-260 DEG C, Z axis), % | 2.7 |
Comparative example 2
1. the weight/mass percentage composition of the solid content in resin combination is 66%, and remaining is organic solvent (such as propylene glycol first
Ether),
Wherein, the formula of solid content see table (by weight)
| Raw material | Solid weight (gram) |
| Phenol aldehyde type epoxy resin | 30 |
| High Bromine epoxy Resin | 10 |
| Phenolic resin curative | 20 |
| Tetrabromobisphenol A (TBBA) | 8 |
| 2-ethyl-4-methylimidazole (2E4MZ) | 0.03 |
| Aluminium hydroxide | 10 |
| Silicon dioxide | 18 |
2. the preparation method of resin combination:
(1) in agitator tank, organic solvent propylene glycol methyl ether 49 grams, turn on agitator, rotating speed 600 are added by above weight
Rev/min, it is subsequently adding TBBA, and continuously stirred 30 minutes；
(2) in agitator tank, it is sequentially added into novolac epoxy resin, High Bromine epoxy Resin, phenolic resin by formula ratio, fed
Journey keeps with 1000 revs/min of rotating speed stirrings；
(3) propylene glycol monomethyl ether is weighed by formula ratio, it is complete with organic solvent propylene glycol monomethyl ether with the ratio of weight ratio 1:10
After CL, this solution is added in agitator tank, and persistently keep 1200 revs/min of stirrings 2 hours, prepare resin combination.
3. prepare copper-clad laminate
The resin binder continuously coating prepared in order to top method or impregnated glass fiber cloth, be dried under 170 DEG C of baking conditions
Obtaining prepreg, overlapped by 8 prepregs, the high temperature extension Copper Foil of its upper and lower each 1 35um of placement, through 190
DEG C, heat under the pressure of 350PSI, pressurize 90 minutes, obtain the copper-clad laminate of 1.6mm.
4. the performance parameter of the copper-clad laminate that this comparative example prepares gained is as shown in the table:
| Project | Test result |
| Vitrification point (DSC), DEG C | 170 |
| Peel strength of copper foil (1oz), lb/in | 8.3 |
| T288(TMA),min | 20 |
| Scolding tin thermostability (288 DEG C of wickings), min | >10 |
| CTE (50-260 DEG C, Z axis), % | 2.8 |
To sum up obtained epoxide glass cloth base copper coated foil plate TG >=170 DEG C, have outstanding thermostability, excellent peel strength,
Good PCB processing characteristics, can meet PCB procedure for processing for the requirement in terms of material thermal resistance energy and processing characteristics,
The making of high density interconnection HDI height multi-layer PCB board can be applicable to.
Claims (3)
1. composition epoxy resin, it is characterised in that account for the percentage of composition solid gross weight such as by each constituent solid weight
Under:
Described novolac epoxy resin is bisphenol A-type novolac epoxy resin, bisphenol-f type novolac epoxy resin, o-cresol formaldehyde epoxy
One or more mixing in resin；
The modified brominated epoxy resin of described Carbimide. be modified for aromatic series '-diphenylmethane diisocyanate MDI epoxy resin,
One in toluene di-isocyanate(TDI) TDI modified epoxy or both mixing；
Described High Bromine epoxy Resin is selected from the BEB400 resin of Changchun, Taiwan Chemical Manufacture；
Described phenolic resin curative is the phenol novolacs of phenol and formaldehyde crosslinking, or the bis-phenol of bisphenol-A and formaldehyde crosslinking
A phenolic resin, or the mixture of phenol novolacs and bisphenol A phenolic resin；
Described epoxy resin curing accelerator selects 2-ethyl-4-methylimidazole and 2-methylimidazole or 1-benzyl-2-methyl miaow
Azoles；
The XQ82969 resin that Dow Chemical produces selected by described heat stabilizer；
Aluminium hydroxide and the mixture of silicon dioxide are selected in described inorganic filler, mass ratio between the two be 6～13: 17～
25。
2. composition epoxy resin as claimed in claim 1, it is characterised in that also include organic solvent.
3. the method for preparation composition epoxy resin described in claim 1 or 2, it is characterised in that preparation process is as follows:
(1) press formula ratio in agitator tank, add part organic solvent, turn on agitator, rotating speed 500～1200 revs/min, protect
Hold continuously stirred and control flume temperature at 20～50 DEG C, add inorganic filler, after interpolation continuously stirred 20～50 points
Clock；
(2) in agitator tank, it is sequentially added into novolac epoxy resin, the brominated epoxy resin of Carbimide. modification, height by formula ratio
Brominated eopxy resin, phenolic resin curative and heat stabilizer, keep with 1000～1500 revs/min of rotating speed stirrings during charging,
Open after interpolation and efficiently shear and emulsifying 1～4 hours, carry out cooling water circulation to keep control flume temperature to exist simultaneously
20～50 DEG C；
(3) weigh epoxy resin curing accelerator by formula ratio, add it to, in remaining organic solvent, be completely dissolved
After, this solution is added in agitator tank, and persistently keeps 1000～1500 revs/min of stirrings 4～13 hours, i.e. prepare asphalt mixtures modified by epoxy resin
Oil/fat composition.
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| CN103642446A (en) * | 2013-12-10 | 2014-03-19 | 上海南亚覆铜箔板有限公司 | Lead-free high heat-resisting copper-clad board and preparation method thereof |
| CN104448693B (en) * | 2014-11-20 | 2020-04-10 | 徐东 | Epoxy resin composition and preparation method and application thereof |
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Address after: Shanghai city Chang Cheung Road 201802 Jiading District Nanxiang Town, No. 158 Patentee after: South Asia new materials Polytron Technologies Inc Address before: Shanghai city Chang Cheung Road 201802 Jiading District Nanxiang Town, No. 158 Patentee before: Shanghai Nanya Copper Clad Laminate Co., Ltd. |
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