CN109535651A - A kind of resin combination and preparation method thereof - Google Patents
A kind of resin combination and preparation method thereof Download PDFInfo
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- CN109535651A CN109535651A CN201811295615.6A CN201811295615A CN109535651A CN 109535651 A CN109535651 A CN 109535651A CN 201811295615 A CN201811295615 A CN 201811295615A CN 109535651 A CN109535651 A CN 109535651A
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L63/00—Compositions of epoxy resins; Compositions of derivatives of epoxy resins
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K3/00—Use of inorganic substances as compounding ingredients
- C08K3/18—Oxygen-containing compounds, e.g. metal carbonyls
- C08K3/20—Oxides; Hydroxides
- C08K3/22—Oxides; Hydroxides of metals
- C08K2003/2227—Oxides; Hydroxides of metals of aluminium
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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
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- C08L2203/20—Applications use in electrical or conductive gadgets
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- 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
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- 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
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Abstract
The invention discloses a kind of resin combinations, which is characterized in that the percentages that composition solid total weight is accounted for by solid weight, the solid composite including following component: base epoxy resin 1%~15%；The modified brominated epoxy resin 5%~25% of isocyanic acid；Low brominated epoxy 10%~35%；Four-functional group epoxy resin 0.5%~5%；High bromine resin curing agent 0.1%~20%；Phenolic resin curing agent 5%~40%；Dicyandiamide 0.1%~3%；Epoxy resin curing accelerator 0.002~0.050%；Inorganic filler 10%~40%.The invention also discloses preparation methods.Epoxide glass cloth base copper coated foil plate obtained by the present invention has simple glass transition temperature (Tg≤130 DEG C), excellent heat resistance and high peel strength (Peel≤9lb/in), good PCB processing performance, can be suitable for the production of PCB industry leadless process printed wiring board.
Description
Technical field
The present invention relates to copper-clad plate preparation technical fields, and in particular to a kind of resin combination and preparation method thereof.
Background technique
With the high density and high performance of PCB, HDI/BUM plate, potting component multi-layer board and high multi-layer board etc. obtain fast
Hail exhibition, and PCB layer number, thickness increase and the increase of area, in high-temperature soldering, especially pb-free solder, in order to protect
The reliability for demonstrate,proving welding, is subjected to higher welding temperature or longer weld interval, thus, its baseplate material is proposed more
High requirement, compared with conventional material, this kind of plate should have higher glass transition temperature and heat resistance.
On July 1st, 2006 starts, and two instructions of European Union (are referred to about limiting in electronic and electrical equipment using harmful substance
Enable and about scrap electronic and electrical equipment instruction) formal implementation, indicate that global electronic industry will enter the pb-free solder epoch.
Due to welding temperature height, copper-clad plate thermal reliability is correspondinglyd increase, traditional plumber's solder cannot reuse, tin now
Welding temperature needed for the alternative solders such as silver-bearing copper all increases substantially.
And tradition FR-4 copper-clad plate, since heat resistance is low, glass transition temperature only has 130-140 DEG C, and thermal decomposition temperature is general
Only 300-310 DEG C, although being widely applied in general electronic products, in high density interconnection and integrated circuit fields not
It can apply, existing electronic product is quickly grown, and with the hair of the lightening of printed circuit, multiple stratification and semiconductor mount technologies
Exhibition, it is desirable that substrate must have good heat resistance and PCB processing performance, to improve the reliability of interconnection with installation.
Developed lead-free product Tg is mostly at 150 DEG C or more in industry at present, such copper-clad laminate material kind
There are many class, also more and more mature, and for these materials in order to improve heat resistance, the curing system used in general formula is solid for phenolic aldehyde
Change.Although being improved in terms of the heat resistance of material, material Shortcomings in terms of peel strength and PCB processability.Cause
For the too hard too crisp reason of material, it can make drill point serious wear in the drilling processing procedure of PCB processing, and drill point cost depletions are higher,
Increase PCB processing procedure cost.
Another design direction is the curing system of dicyandiamide, although the material toughness of this curing system is relatively good, PCB
Processability, but then there is very big deficiency in material, it is heat-resisting for material not to be able to satisfy PCB procedure for processing in terms of heat resistance
The requirement of aspect of performance, that is, leadless process cannot be applicable in.
Therefore, develop that a kind of heat resistance is good and peel strength is high, the good general T g lower cost materials gesture of PCB processability
It must go.
Summary of the invention
In order to overcome drawbacks described above present in the prior art, one of the objects of the present invention is to provide one kind to be suitable for
The compositions of thermosetting resin of PCB industry leadless process production；The copper-clad plate material made using the compositions of thermosetting resin
With good peel strength, toughness and excellent heat resistance and good PCB processing performance, and material cost is lower.
The second object of the present invention is to provide the preparation method of the resin combination of one of the object of the invention.
One of in order to achieve the object of the present invention, provided technical solution is:
A kind of resin combination is accounted for the percentages of total weight amount by solid weight, including following component
Solid composite:
In a preferred embodiment of the invention, the resin combination further includes organic solvent, so that the solid
Accounting of the composition levels in total amount is not less than 50%.
In a preferred embodiment of the invention, accounting range of the solid composite content in total amount is 60
~75%.
In a preferred embodiment of the invention, the organic solvent includes acetone, methyl ethyl ketone, toluene, diformazan
Benzene, methyl iso-butyl ketone (MIBK), propylene glycol monomethyl ether, any one or two or more mixtures in cyclohexanone.
In a preferred embodiment of the invention, the modified brominated epoxy resin of the isocyanic acid includes aromatic series hexichol
Any one in methane diisocyanate MDI modified epoxy resin, toluene di-isocyanate(TDI) TDI modified epoxy or two
The mixture of kind.
In a preferred embodiment of the invention, the phenolic resin curing agent includes the phenolic aldehyde tree of phenol and formaldehyde crosslinking
Rouge, the phenol are phenol, dimethlbenzene, ethyl -phenol, n-propyl phenol, isopropyl-phenol, normal-butyl phenol, isobutyl-benzene
Any one in phenol, tert-butyl phenol.
In a preferred embodiment of the invention, the phenolic resin curing agent includes pair of bisphenol-A and formaldehyde crosslinking
The mixing of any one or two kinds of phenol A phenolic resin, phenol novolacs and bisphenol A phenolic resin.
In a preferred embodiment of the invention, the epoxy resin curing accelerator includes 2- ethyl -4- methyl miaow
Azoles, 2-methylimidazole, any one or two or more mixing in 1 benzyl 2 methyl imidazole.
In a preferred embodiment of the invention, the inorganic filler includes talcum powder, silica flour, ceramic powder, hydrogen-oxygen
Change aluminium, metal oxide particle such as silica, clay, any one or two or more mixing in boron nitride.
In order to achieve the object of the present invention two, used technical solution is:
A kind of preparation method of resin combination, includes the following steps:
(1) dicyandiamide, the high bromine resin curing agent of part organic solvent and whole is added in stirred tank by formula ratio, opens
Blender is opened, 500~1000 revs/min of revolving speed, is persistently stirred 1.5~2.5 hours, guarantees that all dissolution is complete for solid in slot, together
When control groove body temperature at 20~45 DEG C；Then inorganic filler is added, is persistently stirred after addition 80~120 minutes；
(2) the modified bromine of base epoxy resin, low brominated epoxy, isocyanic acid is sequentially added by formula ratio in stirred tank
Change epoxy resin, four-functional group epoxy resin and phenolic resin curing agent, keeps turning with 900~1400 revs/min during charging
Efficiently shearing and emulsification 1~3 hour are opened in speed stirring after addition, while carrying out cooling water circulation to keep control groove body
Temperature is at 20~45 DEG C；
(3) epoxy resin curing accelerator is weighed by formula ratio, adds it in remaining organic solvent, is completely dissolved
Afterwards, which is added in stirred tank, and continues 1000~1500 revs/min of holding and stirs 4~12 hours, obtain resin combination
Object.
The beneficial effects of the present invention are:
Epoxide glass cloth base copper coated foil plate obtained by the present invention have simple glass transition temperature (Tg≤130 DEG C),
Excellent heat resistance and high peel strength (Peel≤9lb/in), good PCB processing performance, can be suitable for PCB industry
The production of leadless process printed wiring board.
Specific embodiment
Main material
Base epoxy resin
Base epoxy resin physical parameter is referring to table 1:
Table 1
| Project | Specifications parameter |
| Epoxide equivalent EEW (g/eq) | 160~210 |
| Hydrolyzable chlorine | 300MAX |
The BE188 resin of Taiwan Changchun chemical company can be selected in such base epoxy resin in the present invention, but is not limited only to
This.
2. the modified brominated epoxy resin of isocyanic acid
The modified brominated epoxy resin physical parameter of isocyanic acid is referring to table 2:
Table 2
| Project | Specifications parameter |
| Epoxide equivalent EEW (g/eq) | 260~310 |
| Hydrolyzable chlorine | 300MAX |
| Bromine content (wt%) | 13-18 |
Isocyanate-modified brominated epoxy resin includes the modified asphalt mixtures modified by epoxy resin of aromatic series '-diphenylmethane diisocyanate MDI
Rouge and toluene di-isocyanate(TDI) TDI modified epoxy are also possible to the mixture of the two, and its purpose is to assign solidification tree
Rouge and with required for laminate made of it is basic both mechanically and thermally, and with good toughness and excellent copper stripping
From intensity.
The XQ82937 tree of Dow Chemical production can be selected in the modified brominated epoxy resin of such isocyanic acid in the present invention
Rouge, but it is not limited only to this.
3. high bromine resin curing agent
High bromine resin curing agent specifications parameter is referring to table 3:
Table 3
| Project | Specifications parameter |
| Epoxide equivalent EEW (g/eq) | 250~290 |
| Hydrolyzable chlorine | 300MAX |
| Bromine content (wt%) | 55-60 |
The TBBA resin of Shandong Tianyi Chemical Co., Ltd. can be selected in such high bromine resin curing agent in the present invention, but not only
It is limited to this.
4. low brominated epoxy
Low brominated epoxy physical parameter is referring to table 4:
Table 4
| Project | Specifications parameter |
| Epoxide equivalent EEW (g/eq) | 380~450 |
| Hydrolyzable chlorine | 300MAX |
| Bromine content (wt%) | 17~24 |
The GEBR454A80 epoxy resin of Guangzhou Hong Chang Electronic Materials Corp production can be selected in such low brominated epoxy, but
It is without being limited thereto.
5. phenolic resin curing agent
In the phenolic resin that phenolic resin of the present invention is phenol and formaldehyde crosslinking, the phenol is phenol, dimethlbenzene, second
Base phenol, n-propyl phenol, isopropyl-phenol, normal-butyl phenol, isobutyl group phenol, tert-butyl phenol or bisphenol A phenolic resin,
Or bisphenol-A and formaldehyde crosslinking bisphenol A phenolic resin or phenol novolacs and bisphenol A phenolic resin mixture.
In the present invention such phenolic resin curing agent can be selected South Korea can Longhua work KPH-2003 resin, but be not limited only to
This.
6. four-functional group epoxy resin
Four-functional group epoxy resin used in the present invention is a kind of epoxy resin of liquid, plays UV resistance in the material
Function is kept off, reliability of material energy is promoted
In the present invention such four-functional group epoxy resin can be selected South Korea can Longhua work KET-4131 resin, but not only limit
In this.
7. epoxy resin curing accelerator
Curing accelerator contained in epobond epoxyn in the present invention is usual promotion epoxy resin cure
Curing accelerator, commonly use the imidazolium compounds such as 2-ethyl-4-methylimidazole and 2-methylimidazole, 1 benzyl 2 methyl imidazole,
It is preferred that 2-methylimidazole, is promoting the dosage in epoxy resin cure that should adequately lack, preferable amount is entire amount of solid
0.002~0.050wt%.
8. filler
Filler appropriate is added in invention resin composition, with reduce resin combination production copper-clad plate material it is swollen
Swollen coefficient, inorganic filler can improve the chemical property and electrical property of solidified resin, such as reduce thermal expansion coefficient (CTE), increase
Modulus is accelerated Heat transmission and is assisted fire-retardant etc..Applicable inorganic filler includes but is not limited to: talcum powder, silica flour, ceramics
Powder, aluminium hydroxide, metal oxide particle such as silica, clay, boron nitride etc. and their mixture.Wherein, dioxy
SiClx, aluminium hydroxide and talcum powder can be considered as the first choice of filler used.
In addition, also may include having organic solvent in addition to the aforementioned components, organic solvent is not specifically limited, for example, can
Use one or both of acetone, methyl ethyl ketone, toluene, dimethylbenzene, methyl iso-butyl ketone (MIBK), propylene glycol monomethyl ether or cyclohexanone
Above mixture, these solvents each can be used alone, or its two or more of combination can be used.
The usage amount of organic solvent is not specifically limited, and soaks epobond epoxyn from the case where preparing prepreg
From the viewpoint of good adhesion of the stain between the easiness and resin combination and matrix into matrix, it is preferably added to organic molten
Agent is so that the solid content of glue is that 50% or more, especially 60~75% are preferred.
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 by following methods (referring to IPC-TM-650) measurement.
(1) glass transition temperature (Tg)
Glass transition temperature
Detection method: using differential scanning calorimetry (DSC), refers to that plate is height by glassy transition in heated situation
Play temperature (DEG C) corresponding to state (rubbery state).
(2) thermally stratified layer time (T-288)
The T-288 thermally stratified layer time refers to plate under 288 DEG C of set temperature, since there is lamination in the effect of heat,
Duration before this.
Detection method: it uses thermo-mechanical analysis method (TMA).
(3) peel strength
It is tested according to IPC-TM-650-2.4.8C method.
(4) scolding tin heat resistance
Scolding tin heat resistance refers to that plate immerses in 288 DEG C of melting scolding tin, when without occurring being layered and blister lasting
Between.
Detection method: the substrate after etching is cut into 5.0cm × 5.0cm size, edges of boards successively use 120 mesh and 800 mesh sand
Paper polishing, pressure-cooks certain time, is put into 288 DEG C of tin melting furnaces, and whether there is or not be layered for observation.
Water absorption rate
It is tested according to IPC-TM-650-2.6.2.1 method.
Embodiment 1
1. the mass percentage of the solid content in resin combination is 66.8%, remaining is organic solvent (such as methyl
Ethyl ketone) wherein, the formula of solid content see the table below 5 (by weight).
Table 5
2. the preparation method of composition epoxy resin:
(1) 54 grams of organic solvent methyl ethyl ketone and high bromine resin curing agent, double are added in stirred tank by the above weight
Cyanamide, turn on agitator, 900 revs/min of revolving speed, to and continue stirring 120 minutes until high bromine resin curing agent, dicyandiamide dissolve
Completely, inorganic filler is then added, is persistently stirred after addition 100 minutes；
(2) the modified brominated epoxy resin of base epoxy resin, isocyanic acid, low is sequentially added by formula ratio in stirred tank
Brominated eopxy resin, four-functional group epoxy resin phenolic resin curing agent keep stirring with 1000 revs/min of revolving speeds during charging；
(3) 2-methylimidazole is weighed by formula ratio, by it with the ratio of weight ratio 1:10 and organic solvent methyl ethyl ketone
After being completely dissolved, which is added in stirred tank, and continues to be kept for 1200 revs/min stir 2 hours, resin combination is made.
3. preparing copper-clad laminate
To resin binder continuously coating made from the method for top or impregnated glass fiber cloth, under 170 DEG C of baking conditions
It is dried to obtain prepreg, 8 prepregs are overlapped, the upper and lower high temperature extension copper foil for respectively placing 1 35um, through 190
DEG C, heating, pressurization 60 minutes under the pressure of 350PSI, obtain the copper-clad laminate of 1.5mm.
4. the performance parameter that the present embodiment prepares resulting copper-clad laminate is as shown in table 6 below:
Table 6
Embodiment 2
1. the mass percentage of the solid content in resin combination is 62%, remaining is organic solvent (such as methyl second
Base ketone),
Wherein, the formula of solid content see the table below 7 (by weight).
Table 7
| Raw material | Solid weight (gram) |
| Base epoxy resin | 6 |
| The modified brominated epoxy resin of isocyanic acid | 16 |
| Low brominated epoxy | 31 |
| Four-functional group epoxy resin | 1 |
| High bromine resin curing agent | 2 |
| Phenolic resin curing agent | 17 |
| Dicyandiamide | 0.35 |
| 2-methylimidazole (2-MI) | 0.03 |
| Aluminium hydroxide | 8 |
| Silica | 10 |
| Talcum powder | 4 |
2. the preparation method of composition epoxy resin:
(1) 56 grams of organic solvent methyl ethyl ketone and high bromine resin curing agent, double are added in stirred tank by the above weight
Cyanamide, turn on agitator, 900 revs/min of revolving speed, and continue stirring 120 minutes until high bromine resin curing agent, dicyandiamide have dissolved
Entirely, inorganic filler is then added, is persistently stirred after addition 100 minutes；
(2) the modified brominated epoxy resin of base epoxy resin, isocyanic acid, low is sequentially added by formula ratio in stirred tank
Brominated eopxy resin, four-functional group epoxy resin phenolic resin curing agent keep stirring with 1000 revs/min of revolving speeds during charging；
(3) 2-methylimidazole is weighed by formula ratio, by it with the ratio of weight ratio 1:10 and organic solvent methyl ethyl ketone
After being completely dissolved, which is added in stirred tank, and continues to be kept for 1200 revs/min stir 2 hours, resin combination is made.
3. preparing copper-clad laminate
To resin binder continuously coating made from the method for top or impregnated glass fiber cloth, under 170 DEG C of baking conditions
It is dried to obtain prepreg, 8 prepregs are overlapped, the upper and lower high temperature extension copper foil for respectively placing 1 35um, through 190
DEG C, heating, pressurization 60 minutes under the pressure of 350PSI, obtain the copper-clad laminate of 1.5mm.
4. the performance parameter that the present embodiment prepares resulting copper-clad laminate is as shown in table 8 below:
Table 8
Embodiment 3
1. the mass percentage of the solid content in resin combination is 60%, remaining is organic solvent (such as methyl second
Base ketone), wherein the formula of solid content see the table below 9 (by weight).
Table 9
2. the preparation method of composition epoxy resin:
(1) 77 grams of organic solvent methyl ethyl ketone and high bromine resin curing agent, double are added in stirred tank by the above weight
Cyanamide, turn on agitator, 900 revs/min of revolving speed, and continue stirring 120 minutes until high bromine resin curing agent, dicyandiamide have dissolved
Entirely, inorganic filler is then added, is persistently stirred after addition 100 minutes；
(2) the modified brominated epoxy resin of base epoxy resin, isocyanic acid, low is sequentially added by formula ratio in stirred tank
Brominated eopxy resin, four-functional group epoxy resin phenolic resin curing agent keep stirring with 1000 revs/min of revolving speeds during charging；
(3) 2-methylimidazole is weighed by formula ratio, by it with the ratio of weight ratio 1:10 and organic solvent methyl ethyl ketone
After being completely dissolved, which is added in stirred tank, and continues to be kept for 1200 revs/min stir 2 hours, resin combination is made.
3. preparing copper-clad laminate
To resin binder continuously coating made from the method for top or impregnated glass fiber cloth, under 170 DEG C of baking conditions
It is dried to obtain prepreg, 8 prepregs are overlapped, the upper and lower high temperature extension copper foil for respectively placing 1 35um, through 190
DEG C, heating, pressurization 60 minutes under the pressure of 350PSI, obtain the copper-clad laminate of 1.5mm.
4. the performance parameter that the present embodiment prepares resulting copper-clad laminate is as shown in the following table 10:
Table 10
| Project | Test result |
| Glass transition temperature (DSC, DEG C) | 141 |
| Copper foil peel strength (1oz, lb/in) | 9.2 |
| T288(TMA,min) | 48 |
| Scolding tin heat resistance (288 DEG C of wickings, min) | >10 |
| CTE (%) | 3.50 |
| Td (DEG C, 5%wt loss) | 346 |
| Water absorption rate (%) | 0.10 |
| Anti-flammability | V0 |
| PCB processability (the new most access times of drill point) | 1950 |
Embodiment 4
The mass percentage of solid content in resin combination is 70%, remaining is organic solvent (such as Methylethyl
Ketone), wherein the formula of solid content see the table below 11 (by weight).
Table 11
| Raw material | Solid weight (gram) |
| Base epoxy resin | 12 |
| The modified brominated epoxy resin of isocyanic acid | 6 |
| Low brominated epoxy | 39 |
| Four-functional group epoxy resin | 3.1 |
| High bromine resin curing agent | 0.5 |
| Phenolic resin curing agent | 10 |
| Dicyandiamide | 2.3 |
| 2-methylimidazole (2-MI) | 0.041 |
| Aluminium hydroxide | 27 |
| Silica | 7 |
| Talcum powder | 5 |
2. the preparation method of composition epoxy resin:
(1) 47 grams of organic solvent methyl ethyl ketone and high bromine resin curing agent, double are added in stirred tank by the above weight
Cyanamide, turn on agitator, 900 revs/min of revolving speed, and continue stirring 120 minutes until high bromine resin curing agent, dicyandiamide have dissolved
Entirely, inorganic filler is then added, is persistently stirred after addition 100 minutes；
(2) the modified brominated epoxy resin of base epoxy resin, isocyanic acid, low is sequentially added by formula ratio in stirred tank
Brominated eopxy resin, four-functional group epoxy resin phenolic resin curing agent keep stirring with 1000 revs/min of revolving speeds during charging；
(3) 2-methylimidazole is weighed by formula ratio, by it with the ratio of weight ratio 1:10 and organic solvent methyl ethyl ketone
After being completely dissolved, which is added in stirred tank, and continues to be kept for 1200 revs/min stir 2 hours, resin combination is made.
3. preparing copper-clad laminate
To resin binder continuously coating made from the method for top or impregnated glass fiber cloth, under 170 DEG C of baking conditions
It is dried to obtain prepreg, 8 prepregs are overlapped, the upper and lower high temperature extension copper foil for respectively placing 1 35um, through 190
DEG C, heating, pressurization 60 minutes under the pressure of 350PSI, obtain the copper-clad laminate of 1.5mm.
4. the performance parameter that the present embodiment prepares resulting copper-clad laminate is as shown in table 12 below:
Table 12
Comparative example 1
1. the mass percentage of the solid content in resin combination is 66.4%, remaining is organic solvent (such as diformazan
Base formamide), wherein the formula of solid content see the table below 13 (by weight).
Table 13
| Raw material | Solid weight (gram) |
| Low brominated epoxy | 100 |
| Dicyandiamide | 2.5 |
| 2-methylimidazole (2-MI) | 0.09 |
2. the preparation method of composition epoxy resin:
(1) dicyandiamide and 52 grams of organic solvent dimethylformamide are added in stirred tank by the above weight, unlatching is stirred
Mix device, 600 revs/min of revolving speed, and continue stirring 30 minutes, until dicyandiamide solid all dissolves；
(2) low brominated epoxy is added by formula ratio in stirred tank, keeps stirring with 1000 revs/min of revolving speeds during charging
It mixes；
(3) 2-methylimidazole 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, which is added in stirred tank, and continues to be kept for 1200 revs/min stir 2 hours, resin combination is made.
3. preparing copper-clad laminate
To resin binder continuously coating made from the method for top or impregnated glass fiber cloth, under 170 DEG C of baking conditions
It is dried to obtain prepreg, 8 prepregs are overlapped, the upper and lower high temperature extension copper foil for respectively placing 1 35um, through 190
DEG C, heating, pressurization 40 minutes under the pressure of 350PSI, obtain the copper-clad laminate of 1.5mm.
4. the performance parameter that the present embodiment prepares resulting copper-clad laminate is as shown in table 14 below:
Table 14
Comparative example 2
1. the mass percentage of the solid content in resin combination is 70%, remaining is organic solvent (such as propylene glycol
Methyl ether),
Wherein, the formula of solid content see the table below 15 (by weight).
Table 15
2. the preparation method of composition epoxy resin:
(1) 44 grams of organic solvent propylene glycol monomethyl ether are added in stirred tank by the above weight, turn on agitator, revolving speed 600
Rev/min, and continue stirring 30 minutes, inorganic filler is then added, is persistently stirred after addition 100 minutes；
(2) the modified brominated epoxy resin of novolac epoxy resin, isocyanic acid, low is sequentially added by formula ratio in stirred tank
Brominated eopxy resin, four-functional group epoxy resin and phenolic resin curing agent keep stirring with 1000 revs/min of revolving speeds during charging
It mixes；
(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, which is added in stirred tank, and continues to be kept for 1200 revs/min stir 2 hours, resin combination is made.
3. preparing copper-clad laminate
To resin binder continuously coating made from the method for top or impregnated glass fiber cloth, under 170 DEG C of baking conditions
It is dried to obtain prepreg, 8 prepregs are overlapped, the upper and lower high temperature extension copper foil for respectively placing 1 35um, through 190
DEG C, heating, pressurization 90 minutes under the pressure of 350PSI, obtain the copper-clad laminate of 1.5mm.
4. the performance parameter that the present embodiment prepares resulting copper-clad laminate is as shown in table 16 below:
Table 16
To sum up, obtained epoxide glass cloth base copper coated foil plate has simple glass transition temperature (Tg≤130
DEG C), excellent heat resistance and high peel strength (Peel≤9lb/in), good PCB processing performance, PCB can be suitable for
The production of industry leadless process printed wiring board.
Claims (10)
1. a kind of resin combination, which is characterized in that account for the percentages of composition solid total weight by solid weight, including such as
The solid composite of lower component:
2. a kind of resin combination as described in claim 1, which is characterized in that the resin combination further includes organic molten
Agent, so that accounting of the solid composite content in total amount is not less than 50%.
3. a kind of resin combination as claimed in claim 2, which is characterized in that the solid composite content is in total amount
Accounting range be 60-75%.
4. a kind of resin combination as claimed in claim 2, which is characterized in that the organic solvent includes acetone, methyl second
Base ketone, toluene, dimethylbenzene, methyl iso-butyl ketone (MIBK), propylene glycol monomethyl ether, any one or two or more mixing in cyclohexanone
Object.
5. a kind of resin combination as described in claim 1-4 any one, which is characterized in that the modified bromine of the isocyanic acid
Changing epoxy resin includes the epoxy resin of aromatic series '-diphenylmethane diisocyanate MDI modification, toluene di-isocyanate(TDI) TDI modification
The mixture of any one or two kinds in epoxy resin.
6. a kind of resin combination as described in claim 1-4 any one, which is characterized in that the phenolic resin curing agent
Phenolic resin including phenol and formaldehyde crosslinking, the phenol are phenol, dimethlbenzene, ethyl -phenol, n-propyl phenol, cumene
Phenol, normal-butyl phenol, isobutyl group phenol, any one in tert-butyl phenol.
7. a kind of resin combination as described in claim 1-4 any one, which is characterized in that the phenolic resin curing agent
Bisphenol A phenolic resin, phenol novolacs and bisphenol A phenolic resin including bisphenol-A and formaldehyde crosslinking any one or two
The mixing of kind.
8. a kind of resin combination as described in claim 1-4 any one, which is characterized in that the epoxy resin cure promotees
Into agent include 2-ethyl-4-methylimidazole, 2-methylimidazole, in 1 benzyl 2 methyl imidazole any one or it is two or more
Mixing.
9. a kind of resin combination as described in claim 1-4 any one, which is characterized in that the inorganic filler includes sliding
Mountain flour, silica flour, ceramic powder, aluminium hydroxide, metal oxide particle such as silica, clay, any one in boron nitride
Or two or more mixing.
10. the preparation method of the resin combination as described in any one of working as claim 1-9, which is characterized in that including such as
Lower step:
(1) part organic solvent and dicyandiamide, high bromine resin curing agent are added in stirred tank by formula ratio, turn on agitator,
It 500~1000 revs/min of revolving speed, persistently stirs 1.5~2.5 hours, guarantees that all dissolution is complete for solid in slot, while controlling groove body
Temperature is at 20~45 DEG C；Then inorganic filler is added, is persistently stirred after addition 80~120 minutes；
(2) the modified brominated of base epoxy resin, low brominated epoxy, isocyanic acid is sequentially added by formula ratio in stirred tank
Oxygen resin, four-functional group epoxy resin and phenolic resin curing agent keep stirring with 900~1400 revs/min of revolving speeds during charging
It mixes, efficiently shearing and emulsification 1~3 hour is opened after addition, while carrying out cooling water circulation to keep control flume temperature
At 20~45 DEG C；
(3) epoxy resin curing accelerator is weighed by formula ratio, added it in remaining organic solvent, after being completely dissolved,
The solution is added in stirred tank, and continues 1000~1500 revs/min of holding and stirs 4~12 hours, obtains resin combination.
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN110116541A (en) * | 2019-05-13 | 2019-08-13 | 广德龙泰电子科技有限公司 | A kind of middle TG reheating deformation solidification copper-clad laminate production technology |
| CN110437585A (en) * | 2019-08-15 | 2019-11-12 | 重庆德凯实业股份有限公司 | One kind covering copper foil epoxy glass fiber fabric base laminate and its preparation process |
| CN111909488A (en) * | 2020-06-30 | 2020-11-10 | 广东裕丰威禾新材料科技股份有限公司 | Thermosetting resin composition, thermosetting laminated board and preparation method |
| CN113290978A (en) * | 2021-05-13 | 2021-08-24 | 莱州鹏洲电子有限公司 | CEM-1 copper-clad plate with high CTI (comparative tracking index) and high peel strength and preparation method thereof |
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| CN104559888A (en) * | 2014-12-23 | 2015-04-29 | 上海南亚覆铜箔板有限公司 | Copper-clad plate applicable to production of high multi-layer PCB (printed circuit board) and preparation method of copper-clad plate |
| CN107298831A (en) * | 2017-07-20 | 2017-10-27 | 南亚新材料科技股份有限公司 | Improve proof tracking index and Drilling operation performance prepreg and its application |
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| CN101864146A (en) * | 2010-06-13 | 2010-10-20 | 宏昌电子材料股份有限公司 | Epoxy resin composition for printed circuit copper-clad plate |
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| CN111909488A (en) * | 2020-06-30 | 2020-11-10 | 广东裕丰威禾新材料科技股份有限公司 | Thermosetting resin composition, thermosetting laminated board and preparation method |
| CN113290978A (en) * | 2021-05-13 | 2021-08-24 | 莱州鹏洲电子有限公司 | CEM-1 copper-clad plate with high CTI (comparative tracking index) and high peel strength and preparation method thereof |
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