CN105368001B - A kind of halogen-free epoxy resin composition and preparation method and applications - Google Patents
A kind of halogen-free epoxy resin composition and preparation method and applications Download PDFInfo
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- CN105368001B CN105368001B CN201510852626.XA CN201510852626A CN105368001B CN 105368001 B CN105368001 B CN 105368001B CN 201510852626 A CN201510852626 A CN 201510852626A CN 105368001 B CN105368001 B CN 105368001B
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Abstract
A kind of halogen-free epoxy resin composition disclosed by the invention, it is made up of solid content and organic solvent, wherein, the weight percentage of solid content is 50 80%, organic solvent is surplus, and its solid content is prepared by phosphorous epoxy resin, the epoxy resin of isocyanic acid modification, DCPD types epoxy resin, phosphorus containing phenolic resin curing agent, DDS curing agent, benzene ethene horse Lai sour copolymers, epoxy resin curing accelerator, phosphate ester flame retardants, inorganic filler.The invention also discloses the preparation method and application of the halogen-free epoxy resin composition.The halogen-less high frequency high speed copper-clad plate prepared using the halogen-free epoxy resin composition of the present invention has high glass-transition temperature (Tg >=150 DEG C), excellent heat resistance and low thermal coefficient of expansion (CTE≤3.3%), low dielectric constant/dielectric loss (Dk≤3.9, Df≤0.009).
Description
Technical field
The invention belongs to copper-clad plate technical field, is related to a kind of halogen-free epoxy resin suitable for high-frequency high-speed baseplate material
Composition and preparation method and applications.
Background technology
In the last few years, with the development of information industry, advanced communication apparatus and technology, it is widely used in each of communication field
The demand of kind of high frequency electronic equipment is also substantially improved in rapid growth, the signal transacting and transmission frequency of electronic equipment, by megahertz
Hereby (MHz) strides forward to GHz (GHz), meanwhile, it is information-based with the continuous high-technicalization and height of human lives, information processing and
Information communication has turned into the pith of human lives, the height that the mankind constantly pursue the high speed of information processing, phonotape and videotape transmits
Integrality, the miniaturization of tech electronic product and multifunction etc., are defended with catenet work station, mobile phone wireless communication, automobile
Star navigates and Bluetooth technology improves constantly applying frequency for the new technique of representative, tends to high frequency or hyperfrequency field, signal
Transmission high frequency and high speed propose the requirement with high-frequency high-speed characteristic to the electronic circuit base material transmitted for signal.When
Before, for PCB with the cutting edge technology that the high speed of baseplate material, high frequency are in copper-clad plate industry development, it has become the whole world
The important topic of raw material factory used in PCB substrate material producer and baseplate material.
Since the concept of Halogen is after copper-clad plate industry is fashionable, copper-clad plate performance it is continuous it is progressive in, bromine it is fire-retardant and
The product research development of the different system branch of halogen-free flameproof two also all exists simultaneously, so that PCB industries are different for terminal
Application field demand make corresponding selection.But proposed from the concept of Halogen to being developed so far, electronic product environment friendly non-halogen
Change is trend of the times all the time, and the use of the applicable Halogen product in low middle each field of height increasingly increases.Halogen-free copper-clad plate is from initial
Just face that fragility is big, water suction is big and the retardance of two big defects with high costs during starting development always, even to this day, the day of technology
Beneficial maturation makes the processability of Halogen product and water absorption rate more and more better, and processing of the PCB manufacturers to Halogen product uses also increasingly
It is handy, and high cost is also gradually digested in the requirement of each industrial chain halogen-free environmental and the surging of terminal promote.
Halogen-free material already turns into a kind of development trend.In recent years, various electronic equipments are carried with the increase of information processing capacity
The encapsulation technologies such as highly integrated, distribution the densification and multiple stratification of semiconductor devices hastily develop.For various
The insulating materials of printed substrate used in electronic equipment etc., in order to improve the transmission speed of signal and lower signal transmission
When loss, it is desirable to dielectric constant and dielectric loss angle tangent are low, therefore, develop the resin combination that matches with this also extremely
It is important.
The content of the invention
Jian states Wen Ti ﹐ it is an object of the invention to provide a kind of Halogen asphalt mixtures modified by epoxy resin for being applicable high-frequency high-speed baseplate material in Shang
Oil/fat composition and preparation method and applications.The copper-clad plate material made using the composition epoxy resin has medium glass
Change transition temperature (Tg≤150 DEG C), excellent heat resistance and low thermal coefficient of expansion (CTE≤3.3%), low dielectric constant/
Dielectric loss (Dk≤3.9, Df≤0.009), the making of high-frequency high-speed printed wiring board (PCB) can be applied to.
One kind is provided for making the copper foil covered pressure substrate material of more than 150 DEG C Halogens of Tg to state the Mu ﹐ present invention Shang realizing
The Halogen ring oxygen resin combination ﹐ of material includes：(A) phosphorous epoxy resin；(B) isocyanic acid modified epoxy；(C) DCPD type rings
Oxygen tree fat；(D) phosphorus containing phenolic resin curing agent；(E) DDS curing agent；(F) styrene-Ma Lai Suan copolymers；(G) asphalt mixtures modified by epoxy resin
Fat curing accelerator；(H) phosphate ester flame retardants；(I) inorganic filler.
The percentage that the halogen-free epoxy resin composition is accounted for composition solid gross weight by each component solid weight is as follows：
In addition, in addition to the aforementioned components, can also include organic solvent, organic solvent is not specifically limited, for example, can
More than one or both of methyl ethyl ketone, toluene, dimethylbenzene, methyl iso-butyl ketone (MIBK), propylene glycol monomethyl ether or cyclohexanone
Mixture, these solvents can each be used alone, or its combination of two or more can be used.
Further, the usage amount of organic solvent is not specifically limited, and glues epoxy resin from the case where preparing prepreg
Mixture is impregnated into from the viewpoint of the good adhesion between the easiness in matrix and resin combination and matrix, is preferably added to
Organic solvent is so that the solids content of glue is preferred for 50% or more, particularly 55~75%.
In the preferred embodiment of the present invention, the phosphorous epoxy resin is DOPO types epoxy resin, DOPO-HQ type rings
Oxygen tree fat, one kind in DOPO-NQ type epoxy resin or any two or more mixing.
It is DOPO, DOPO-HQ and DOPO-NQ chemical constitution below：
In the preferred embodiment of the present invention, epoxy resin its resin characteristics requirement that the isocyanic acid is modified is shown in Table 1.
Table 1
| Project | Specifications parameter |
| Epoxide equivalent EEW (g/eq) | 260~320 |
| Hydrolyzable chlorine (p propylene glycol monomethyl ethers) | 300MAX |
| Solid (wt%) | 73~77 |
The isocyanate-modified epoxy resin includes the asphalt mixtures modified by epoxy resin that aromatic series '-diphenylmethane diisocyanate MDI is modified
The mixing of one or both of fat, toluene di-isocyanate(TDI) TDI modified epoxies.Its purpose is to assign solidified resin
And with required for laminate made of it is basic both mechanically and thermally, and there is good toughness and excellent copper-stripping
Intensity.
The XZ97103 resins of Dow Chemical production can be selected in such resin in the present invention, but are not limited only to this.
In the preferred embodiment of the present invention, the DCPD types epoxy resin physical property requirement is shown in Table 2.
Table 2
| Project | Specifications parameter |
| Epoxide equivalent EEW (g/eq) | 265~285 |
| Hydrolyzable chlorine (p propylene glycol monomethyl ethers) | 500MAX |
| Solid (wt%) | 74~76 |
The molecular structure of the DCPD types epoxy resin is as follows：
Taiwan Changchun chemical industry DNE260BA75 resins can be selected in such resin in the present invention, but are not limited only to this.
In the preferred embodiment of the present invention, used its resin characteristics of phosphorus containing phenolic resin curing agent requirement is shown in Table
3。
Table 3
| Project | Specifications parameter |
| Hydroxyl equivalent (g/eq) | 330~560 |
| Hydrolyzable chlorine (p propylene glycol monomethyl ethers) | 300MAX |
| Phosphorus content (wt%) | 8-10 |
| Solid (wt%) | 54~60 |
The phosphorus containing phenolic resin curing agent is bisphenol A-type phosphorus containing phenolic resin, and it is by phosphorus-containing compound and bisphenol-A type ring
Oxygen resin reaction is made, and the resin of DOW Chemical production, trade mark XZ-92741 can be selected, but be not limited only to this.
In the preferred embodiment of the present invention, the styrene-Ma Lai Suan copolymers have good thermal reliability
With low-down dielectric properties, be below styrene-Ma Lai Suan copolymers molecular structure：
Such curing agent selects the SMA EF-30 or EF-40 of Sartomer Company in the present invention, but is not limited only to this.
In the preferred embodiment of the present invention, phosphate ester flame retardants select big eight chemistry of Japan in the present invention
PX-200, but it is not limited only to this.
In the preferred embodiment of the present invention, the epoxy resin curing accelerator is imidazolium compounds, preferable amount
For 0.005~0.1wt% of whole amount of solid.Preferably one or both of 2-ethyl-4-methylimidazole, 2-methylimidazole
Mixing.
In the preferred embodiment of the present invention, appropriate filler is added in the resin combination, to reduce resin group
The coefficient of expansion of the making copper-clad plate material of compound, can also play a part of reducing the dielectric constant of material, and this filler can be
One kind or any two or more mixing in silica, aluminum oxide, mica, talcum powder, boron nitride etc..The silica
For one kind in powdered quartz, fusion silica, hollow type silica and spherical silicon dioxide or any two
The mixing of the kind above.The preferred silicon of filler of the present invention but is not limited only to this than 525 fusion silica of section.
As the preparation method of the halogen-free epoxy resin composition of second aspect of the present invention, comprise the following steps：
(1) part organic solvent is added in tank diameter by formula ratio and DDS curing agent, styrene-Ma Lai Suan is copolymerized
Thing and phosphate ester flame retardants, turn on agitator, 600~1400 revs/min of rotating speed, keeps lasting stirring and control flume temperature exists
20~50 DEG C, inorganic filler is added, is persistently stirred after addition 90~120 minutes；
(2) by epoxy resin, the DCPD types that formula ratio sequentially adds phosphorous epoxy resin, isocyanic acid is modified in tank diameter
Epoxy resin, phosphorus containing phenolic resin curing agent, keep stirring with 1000~1500 revs/min of rotating speeds during charging, addition finishes
Efficiently shearing is opened afterwards and is emulsified 1~4 hour, while carries out cooling water circulation to keep control flume temperature at 20~50 DEG C；
(3) epoxy resin curing accelerator is weighed by formula ratio, adds it in remaining organic solvent, be completely dissolved
Afterwards, the solution is added in tank diameter, and continues 1000~1500 revs/min of holding and stir 4~13 hours, that is, Halogen epoxy is made
Resin combination.
As the application of the halogen-free epoxy resin composition of third aspect present invention, it is used to make high-frequency high-speed track
Road plate.
The copper clad laminate prepared using composition epoxy resin of the present invention have medium glass transition temperature (Tg≤
150 DEG C), excellent heat resistance and low thermal coefficient of expansion (CTE≤3.3%), low dielectric constant/dielectric loss (Dk≤
3.9, Df≤0.009) making of high-frequency high-speed printed wiring board (PCB) can, be applied to.
Embodiment
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 (with reference to IPC-TM-650) measure.
(1) glass transition temperature (Tg)
Detection method：Use differential scanning calorimetry (DS degree refer to sheet material in the case of heated by glassy transition to be high
Play the temperature (DEG C) corresponding to state (rubbery state).
(2) thermally stratified layer time (T-288)
The T-288 thermally stratified layer times refer to sheet material under 288 DEG C of design temperature, because there is lamination in the effect of heat,
Duration before this.
Detection method：Using thermo-mechanical analysis method (TMA).
(3) peel strength
According to the test of IPC-TM-650-2.4.8C methods.
(4) scolding tin heat resistance
Scolding tin heat resistance, refer to that sheet material is immersed in 288 DEG C of melting scolding tin, during without occurring being layered and bubble lasting
Between.
Detection method：Substrate after etching is cut into 5.0cm × 5.0cm sizes, edges of boards are successively with 120 mesh and 800 mesh sand
Phenomena such as paper is polished, and is pressure-cooked certain time, is put into 288 DEG C of tin melting furnaces, and observation whether there is layering.
(5)Dk/Df
According to the test of IPC-TM-650-2.5.5.9 methods.
Embodiment 1
1. the weight/mass percentage composition of the solid content in halogen-free epoxy resin composition is 66%, remaining is organic solvent (example
Such as methyl ethyl ketone), wherein, the formula of solid content see the table below 4 (by weight)
Table 4
| Raw material | Solid weight (gram) |
| Phosphorous epoxy resin | 7 |
| The epoxy resin that isocyanic acid is modified | 13 |
| DCPD type epoxy resin | 7 |
| Phosphorus containing phenolic resin curing agent | 7 |
| DDS curing agent | 0.5 |
| Styrene-Ma Lai Suan copolymers | 20 |
| 2-ethyl-4-methylimidazole (2E4MZ) | 0.03 |
| PX-200 | 5 |
| Silica | 17 |
2. the preparation method of halogen-free epoxy resin composition：
(1) by above weight added in tank diameter 39 grams of organic solvent methyl ethyl ketone and DDS curing agent, styrene-
Ma Lai Suan copolymers and phosphate ester flame retardants, turn on agitator, 900 revs/min of rotating speed, and continue stirring 120 minutes directly
It is complete to DDS curing agent, styrene-Ma Lai Suan copolymers and PX-200 dissolving；Silica is added, after addition
Persistently stir 90 minutes.
(2) by the ring that formula ratio sequentially adds novolac epoxy resin phosphorous epoxy resin, isocyanic acid is modified in tank diameter
Oxygen tree fat, DCPD types epoxy resin, phosphorus containing phenolic resin curing agent, efficient shearing and emulsification 2 hours is opened after addition, together
Shi Jinhang cooling water circulations keep stirring with 1200 revs/min of rotating speeds to keep control flume temperature at 20~50 DEG C, during charging
Mix；
(3) weigh 2-ethyl-4-methylimidazole by formula ratio, by its with weight than 1：10 ratio and organic solvent methyl
After ethyl ketone is completely dissolved, the solution is added in tank diameter, and continues to be kept for 1200 revs/min stir 2 hours, Halogen ring is made
Epoxy resin composition.
3. prepare copper-clad laminate
To halogen-free epoxy resin composition continuously coating made from the method for top or impregnated glass fiber cloth, in 170 DEG C of bakings
Prepreg is dried to obtain under the conditions of roasting, 8 prepregs are overlapped, its upper and lower high temperature expanded copper for respectively placing 1 35um
Paper tinsel, through heating, pressurization 90 minutes under 190 DEG C, 350PSI pressure, obtain 1.0mm copper-clad laminate.
4. the performance parameter that the present embodiment prepares the copper-clad laminate of gained is as shown in table 5 below：
Table 5
| Project | Test result |
| Glass transition temperature (DSC), DEG C | 155 |
| Peel strength of copper foil (1oz), lb/in | 7.5 |
| T288(TMA),min | >60 |
| Scolding tin heat resistance (288 DEG C of wickings), min | >10 |
| CTE (50-260 DEG C, Z axis), % | 3.10 |
| Dk(10GHZ) | 3.86 |
| Df(10GHZ) | 0.0088 |
Embodiment 2
1. the weight/mass percentage composition of the solid content in halogen-free epoxy resin composition is 63%, remaining is organic solvent (example
Such as methyl ethyl ketone), wherein, the formula of solid content see the table below 6 (by weight)
Table 6
| Raw material | Solid weight (gram) |
| Phosphorous epoxy resin | 9 |
| The epoxy resin that isocyanic acid is modified | 10 |
| DCPD type epoxy resin | 14 |
| Phosphorus containing phenolic resin curing agent | 10 |
| DDS curing agent | 0.3 |
| Styrene-Ma Lai Suan copolymers | 23 |
| 2-ethyl-4-methylimidazole (2E4MZ) | 0.02 |
| PX-200 | 6 |
| Silica | 23 |
2. the preparation method of halogen-free epoxy resin composition：
(1) by above weight added in tank diameter 56 grams of organic solvent methyl ethyl ketone and DDS curing agent, styrene-
Ma Lai Suan copolymers and phosphate ester flame retardants, turn on agitator, 900 revs/min of rotating speed, and continue stirring 120 minutes directly
It is complete to DDS curing agent, styrene-Ma Lai Suan copolymers and PX-200 dissolving；Silica is added, after addition
Persistently stir 90 minutes.
(2) by the ring that formula ratio sequentially adds novolac epoxy resin phosphorous epoxy resin, isocyanic acid is modified in tank diameter
Oxygen tree fat, DCPD types epoxy resin, phosphorus containing phenolic resin curing agent, efficient shearing and emulsification 2 hours is opened after addition, together
Shi Jinhang cooling water circulations keep stirring with 1200 revs/min of rotating speeds to keep control flume temperature at 20~50 DEG C, during charging
Mix；
(3) weigh 2-ethyl-4-methylimidazole by formula ratio, by its with weight than 1：10 ratio and organic solvent methyl
After ethyl ketone is completely dissolved, the solution is added in tank diameter, and continues to be kept for 1200 revs/min stir 2 hours, Halogen ring is made
Epoxy resin composition.
3. prepare copper-clad laminate
To halogen-free epoxy resin composition continuously coating made from the method for top or impregnated glass fiber cloth, in 170 DEG C of bakings
Prepreg is dried to obtain under the conditions of roasting, 8 prepregs are overlapped, its upper and lower high temperature expanded copper for respectively placing 1 35um
Paper tinsel, through heating, pressurization 90 minutes under 190 DEG C, 350PSI pressure, obtain 1.0mm copper-clad laminate.
4. the performance parameter that the present embodiment prepares the copper-clad laminate of gained is as shown in table 7 below：
Table 7
| Project | Test result |
| Glass transition temperature (DSC), DEG C | 152 |
| Peel strength of copper foil (1oz), lb/in | 7.1 |
| T288(TMA),min | >60 |
| Scolding tin heat resistance (288 DEG C of wickings), min | >10 |
| CTE (50-260 DEG C, Z axis), % | 3.15 |
| Dk(10GHZ) | 3.83 |
| Df(10GHZ) | 0.0082 |
Embodiment 3
1. the weight/mass percentage composition of the solid content in halogen-free epoxy resin composition is 58%, remaining is organic solvent (example
Such as methyl ethyl ketone), wherein, the formula of solid content see the table below 8 (by weight)
Table 8
| Raw material | Solid weight (gram) |
| Phosphorous epoxy resin | 15 |
| The epoxy resin that isocyanic acid is modified | 16 |
| DCPD type epoxy resin | 15 |
| Phosphorus containing phenolic resin curing agent | 8 |
| DDS curing agent | 0.6 |
| Styrene-Ma Lai Suan copolymers | 25 |
| 2-ethyl-4-methylimidazole (2E4MZ) | 0.05 |
| PX-200 | 4 |
| Silica | 30 |
2. the preparation method of halogen-free epoxy resin composition：
(1) by above weight added in tank diameter 80 grams of organic solvent methyl ethyl ketone and DDS curing agent, styrene-
Ma Lai Suan copolymers and phosphate ester flame retardants, turn on agitator, 900 revs/min of rotating speed, and continue stirring 120 minutes directly
It is complete to DDS curing agent, styrene-Ma Lai Suan copolymers and PX-200 dissolving；Silica is added, after addition
Persistently stir 90 minutes.
(2) by the ring that formula ratio sequentially adds novolac epoxy resin phosphorous epoxy resin, isocyanic acid is modified in tank diameter
Oxygen tree fat, DCPD types epoxy resin, phosphorus containing phenolic resin curing agent, efficient shearing and emulsification 2 hours is opened after addition, together
Shi Jinhang cooling water circulations keep stirring with 1200 revs/min of rotating speeds to keep control flume temperature at 20~50 DEG C, during charging
Mix；
(3) weigh 2-ethyl-4-methylimidazole by formula ratio, by its with weight than 1：10 ratio and organic solvent methyl
After ethyl ketone is completely dissolved, the solution is added in tank diameter, and continues to be kept for 1200 revs/min stir 2 hours, Halogen ring is made
Epoxy resin composition.
3. prepare copper-clad laminate
To halogen-free epoxy resin composition continuously coating made from the method for top or impregnated glass fiber cloth, in 170 DEG C of bakings
Prepreg is dried to obtain under the conditions of roasting, 8 prepregs are overlapped, its upper and lower high temperature expanded copper for respectively placing 1 35um
Paper tinsel, through heating, pressurization 90 minutes under 190 DEG C, 350PSI pressure, obtain 1.0mm copper-clad laminate.
4. the performance parameter that the present embodiment prepares the copper-clad laminate of gained is as shown in table 9 below：
Table 9
| Project | Test result |
| Glass transition temperature (DSC), DEG C | 156 |
| Peel strength of copper foil (1oz), lb/in | 7.4 |
| T288(TMA),min | >60 |
| Scolding tin heat resistance (288 DEG C of wickings), min | >10 |
| CTE (50-260 DEG C, Z axis), % | 3.11 |
| Dk(10GHZ) | 3.85 |
| Df(10GHZ) | 0.0080 |
Embodiment 4
1. the weight/mass percentage composition of the solid content in halogen-free epoxy resin composition is 70%, remaining is organic solvent (example
Such as methyl ethyl ketone), wherein, the formula of solid content see the table below 10 (by weight)
Table 10
| Raw material | Solid weight (gram) |
| Phosphorous epoxy resin | 8 |
| The epoxy resin that isocyanic acid is modified | 17 |
| DCPD type epoxy resin | 18 |
| Phosphorus containing phenolic resin curing agent | 14 |
| DDS curing agent | 0.5 |
| Styrene-Ma Lai Suan copolymers | 20 |
| 2-ethyl-4-methylimidazole (2E4MZ) | 0.06 |
| PX-200 | 7 |
| Silica | 35 |
2. the preparation method of halogen-free epoxy resin composition：
(1) by above weight added in tank diameter 51 grams of organic solvent methyl ethyl ketone and DDS curing agent, styrene-
Ma Lai Suan copolymers and PX-200, turn on agitator, 900 revs/min of rotating speed, and continue stirring 120 minutes until DDS solidifies
Agent, styrene-Ma Lai Suan copolymers and PX-200 dissolvings are complete；Silica is added, is persistently stirred after addition
90 minutes.
(2) by the ring that formula ratio sequentially adds novolac epoxy resin phosphorous epoxy resin, isocyanic acid is modified in tank diameter
Oxygen tree fat, DCPD types epoxy resin, phosphorus containing phenolic resin curing agent, efficient shearing and emulsification 2 hours is opened after addition, together
Shi Jinhang cooling water circulations keep stirring with 1200 revs/min of rotating speeds to keep control flume temperature at 20~50 DEG C, during charging
Mix；
(3) weigh 2-ethyl-4-methylimidazole by formula ratio, by its with weight than 1：10 ratio and organic solvent methyl
After ethyl ketone is completely dissolved, the solution is added in tank diameter, and continues to be kept for 1200 revs/min stir 2 hours, Halogen ring is made
Epoxy resin composition.
3. prepare copper-clad laminate
To halogen-free epoxy resin composition continuously coating made from the method for top or impregnated glass fiber cloth, in 170 DEG C of bakings
Prepreg is dried to obtain under the conditions of roasting, 8 prepregs are overlapped, its upper and lower high temperature expanded copper for respectively placing 1 35um
Paper tinsel, through heating, pressurization 90 minutes under 190 DEG C, 350PSI pressure, obtain 1.0mm copper-clad laminate.
4. the performance parameter that the present embodiment prepares the copper-clad laminate of gained is as shown in table 11 below：
Table 11
| Project | Test result |
| Glass transition temperature (DSC), DEG C | 158 |
| Peel strength of copper foil (1oz), lb/in | 7.8 |
| T288(TMA),min | >60 |
| Scolding tin heat resistance (288 DEG C of wickings), min | >10 |
| CTE (50-260 DEG C, Z axis), % | 3.15 |
| Dk(10GHZ) | 3.80 |
| Df(10GHZ) | 0.0086 |
Comparative example 1
1. the weight/mass percentage composition of the solid content in resin combination is 65%, remaining is organic solvent (such as propane diols
Methyl ether),
Wherein, the formula of solid content see the table below 12 (by weight)
Table 12
| Raw material | Solid weight (gram) |
| Phosphorous epoxy resin | 15 |
| The epoxy resin that isocyanic acid is modified | 28 |
| Phosphorus containing phenolic resin curing agent | 10 |
| Styrene-Ma Lai Suan copolymers | 22 |
| 2-ethyl-4-methylimidazole (2E4MZ) | 0.06 |
| PX-200 | 8 |
| Silica | 40 |
2. the preparation method of composition epoxy resin：
(1) 66 grams of organic solvent methyl ethyl ketone is added in tank diameter by above weight and styrene-Ma Lai Suan are total to
Polymers and PX-200, turn on agitator, 900 revs/min of rotating speed, and continue stirring 120 minutes until styrene-Ma Lai Suan are total to
Polymers and PX-200 dissolvings are complete；Silica is added, is persistently stirred after addition 90 minutes.
(2) by epoxy resin, the phosphorous phenol that formula ratio sequentially adds phosphorous epoxy resin, isocyanic acid is modified in tank diameter
Urea formaldehyde curing agent, efficiently shearing is opened after addition and is emulsified 2 hours, while carry out cooling water circulation to keep control flume
Temperature keeps stirring with 1200 revs/min of rotating speeds at 20~50 DEG C, during charging；
(3) weigh 2-ethyl-4-methylimidazole by formula ratio, by its with weight than 1：10 ratio and organic solvent the third two
After alcohol methyl ether is completely dissolved, the solution is added in tank diameter, and continues to be kept for 1200 revs/min stir 2 hours, resin group is made
Compound.
3. prepare 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
Prepreg is dried to obtain, 8 prepregs are overlapped, its upper and lower high temperature extension copper foil for respectively placing 1 35um, through 190
DEG C, heating, pressurization 90 minutes under 350PSI pressure, obtain 1.0mm copper-clad laminate.
4. the performance parameter that the present embodiment prepares the copper-clad laminate of gained is as shown in table 13 below：
Table 13
| Project | Test result |
| Glass transition temperature (DSC), DEG C | 148 |
| Peel strength of copper foil (1oz), lb/in | 7.0 |
| T288(TMA),min | 35 |
| Scolding tin heat resistance (288 DEG C of wickings), min | >10 |
| CTE (50-260 DEG C, Z axis), % | 3.35 |
| Dk(10GHZ) | 4.02 |
| Df(10GHZ) | 0.0102 |
Comparative example 2
1. the weight/mass percentage composition of the solid content in resin combination is 60%, remaining is organic solvent (such as propane diols
Methyl ether), wherein, the formula of solid content see the table below 14 (by weight)
Table 14
| Raw material | Solid weight (gram) |
| Phosphorous epoxy resin | 25 |
| The epoxy resin that isocyanic acid is modified | 32 |
| Phosphorus containing phenolic resin curing agent | 15 |
| Styrene-Ma Lai Suan copolymers | 25 |
| 2-ethyl-4-methylimidazole (2E4MZ) | 0.07 |
| Silica | 38 |
2. the preparation method of composition epoxy resin：
(1) 92 grams of organic solvent methyl ethyl ketone is added in tank diameter by above weight and styrene-Ma Lai Suan are total to
Polymers, turn on agitator, 900 revs/min of rotating speed, and continue stirring 120 minutes until styrene-Ma Lai Suan copolymers have dissolved
Entirely；Silica is added, is persistently stirred after addition 90 minutes.
(2) by epoxy resin, the phosphorous phenol that formula ratio sequentially adds phosphorous epoxy resin, isocyanic acid is modified in tank diameter
Urea formaldehyde curing agent, efficiently shearing is opened after addition and is emulsified 2 hours, while carry out cooling water circulation to keep control flume
Temperature keeps stirring with 1200 revs/min of rotating speeds at 20~50 DEG C, during charging；
(3) weigh 2-ethyl-4-methylimidazole by formula ratio, by its with weight than 1：10 ratio and organic solvent the third two
After alcohol methyl ether is completely dissolved, the solution is added in tank diameter, and continues to be kept for 1200 revs/min stir 2 hours, resin group is made
Compound.
3. prepare 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
Prepreg is dried to obtain, 8 prepregs are overlapped, its upper and lower high temperature extension copper foil for respectively placing 1 35um, through 190
DEG C, heating, pressurization 90 minutes under 350PSI pressure, obtain 1.0mm copper-clad laminate.
4. the performance parameter that the present embodiment prepares the copper-clad laminate of gained is as shown in table 15 below：
Table 15
| Project | Test result |
| Glass transition temperature (DSC), DEG C | 149 |
| Peel strength of copper foil (1oz), lb/in | 7.2 |
| T288(TMA),min | 43 |
| Scolding tin heat resistance (288 DEG C of wickings), min | >10 |
| CTE (50-260 DEG C, Z axis), % | 3.45 |
| Dk(5GHZ) | 4.12 |
| Df(5GHZ) | 0.0123 |
To sum up obtained epoxide glass cloth base copper coated foil plate has medium glass transition temperature (Tg≤150 DEG C), excellent
Good heat resistance and low thermal coefficient of expansion (CTE≤3.3%), low dielectric constant/dielectric loss (Dk≤3.9, Df≤
0.009) making of halogen-less high frequency high speed printed wiring board (PCB) can, be applied to.
Claims (13)
1. a kind of halogen-free epoxy resin composition, it is made up of solid content and organic solvent, wherein, the weight percent of solid content contains
It is surplus to measure as 50-80%, organic solvent, it is characterised in that the solid content is made up of the component of following weight percentage：
High-frequency high-speed printed wiring board is made using the halogen-free epoxy resin composition, its performance is as follows：
Glass transition temperature Tg≤150 DEG C, thermal coefficient of expansion CTE≤3.3%, dielectric constant Dk≤3.9, dielectric loss Df≤
0.009。
2. halogen-free epoxy resin composition as claimed in claim 1, it is characterised in that the weight percentage of the solid content
For 55-75%, organic solvent is surplus.
3. halogen-free epoxy resin composition as claimed in claim 1, it is characterised in that the phosphorous epoxy resin is DOPO types
Epoxy resin, DOPO-HQ types epoxy resin, one kind in DOPO-NQ type epoxy resin or any two or more mixing.
4. halogen-free epoxy resin composition as claimed in claim 1, it is characterised in that the epoxy resin that the isocyanic acid is modified
From the XZ97103 resins of Dow Chemical production.
A kind of 5. halogen-free epoxy resin composition as claimed in claim 1, it is characterised in that the DCPD types epoxy resin choosing
With Taiwan Changchun chemical industry DNE260BA75 resins.
6. a kind of halogen-free epoxy resin composition as claimed in claim 1, it is characterised in that described phosphorus containing phenolic resin is consolidated
Agent is the XZ-92741 of DOW Chemical.
7. halogen-free epoxy resin composition as claimed in claim 1, it is characterised in that the styrene-maleic anhydride copolymer
Thing selects the SMAEF-30 or EF-40 of Sartomer Company.
8. halogen-free epoxy resin composition as claimed in claim 1, it is characterised in that the phosphate ester flame retardants select day
The PX-200 of this big eight chemistry.
9. halogen-free epoxy resin composition as claimed in claim 1, it is characterised in that the epoxy resin curing accelerator is
The mixing of one or both of 2-ethyl-4-methylimidazole, 2-methylimidazole.
10. halogen-free epoxy resin composition as claimed in claim 1, it is characterised in that the filler is selected from 525 of silicon than section
Fusion silica.
11. halogen-free epoxy resin composition as claimed in claim 1, it is characterised in that the organic solvent is dimethyl methyl
Mixture more than one or both of acid amides, acetone, methyl ethyl ketone, methyl iso-butyl ketone (MIBK), propylene glycol monomethyl ether.
12. the preparation method of the halogen-free epoxy resin composition described in any one of claim 1 to 11 claim, its feature exist
In comprising the following steps：
(1) by formula ratio added in tank diameter part organic solvent and DDS curing agent, styrene-maleic anhydride copolymer and
Phosphate ester flame retardants, turn on agitator, 600~1400 revs/min of rotating speed, keep lasting stirring and control flume temperature 20~
50 DEG C, inorganic filler is added, is persistently stirred after addition 90~120 minutes；
(2) by epoxy resin, the DCPD type ring oxygen that formula ratio sequentially adds phosphorous epoxy resin, isocyanic acid is modified in tank diameter
Resin, phosphorus containing phenolic resin curing agent, keep stirring with 1000~1500 revs/min of rotating speeds during charging, opened after addition
Open efficiently shearing and emulsify 1~4 hour, while carry out cooling water circulation to keep control flume temperature at 20~50 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 tank diameter, and continues 1000~1500 revs/min of holding and stirs 4~13 hours, that is, Halogen asphalt mixtures modified by epoxy resin is made
Oil/fat composition.
13. the halogen-free epoxy resin composition described in any one of claim 1 to 11 claim prints to make high-frequency high-speed
Wiring board processed.
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| CN106009532A (en) * | 2016-06-29 | 2016-10-12 | 上海南亚覆铜箔板有限公司 | Halogen-free thermosetting resin composition as well as preparation method and application thereof |
| CN106832778B (en) * | 2017-02-13 | 2019-04-02 | 广州仑利奇合成树脂有限公司 | A kind of halogen-free flameproof epoxy systems and preparation method thereof |
| CN107839902B (en) * | 2017-10-24 | 2019-08-09 | 哈尔滨玻璃钢研究院 | A kind of spaceborne unfolding mechanism composite material brace bar and preparation method thereof |
| CN109851991A (en) * | 2018-12-04 | 2019-06-07 | 吉安市宏瑞兴科技有限公司 | A kind of halogen-free epoxy resin composition and preparation method thereof and application thereof |
| CN110588103A (en) * | 2019-04-09 | 2019-12-20 | 吉安市宏瑞兴科技有限公司 | Flame-retardant copper-clad plate and preparation method thereof |
| CN113844130A (en) * | 2021-09-13 | 2021-12-28 | 山东金宝电子股份有限公司 | Preparation method of high-Tg high-frequency copper-clad plate |
| CN113861603A (en) * | 2021-09-27 | 2021-12-31 | 山东金宝电子股份有限公司 | Halogen-free resin composition for high-frequency high-speed copper-clad plate and preparation method and application thereof |
| CN114889265A (en) * | 2022-04-12 | 2022-08-12 | 江西省宏瑞兴科技股份有限公司 | High-reliability copper-clad plate suitable for high-speed field and preparation method thereof |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| US6645631B2 (en) * | 1999-12-13 | 2003-11-11 | Dow Global Technologies Inc. | Flame retardant phosphorus element-containing epoxy resin compositions |
| CN102039701A (en) * | 2009-10-19 | 2011-05-04 | 台光电子材料股份有限公司 | Prepreg and metal foil substrate |
| CN102975430B (en) * | 2012-11-27 | 2016-03-23 | 上海南亚覆铜箔板有限公司 | A kind of anti-flammability copper coated foil plate applying the solid content of phosphor-containing halogen-free element and preparation method thereof |
| 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 |
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