CN106009532A - Halogen-free thermosetting resin composition as well as preparation method and application thereof - Google Patents
Halogen-free thermosetting resin composition as well as preparation method and application thereof Download PDFInfo
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- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L63/00—Compositions of epoxy resins; Compositions of derivatives of epoxy resins
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- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
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- C08L63/00—Compositions of epoxy resins; Compositions of derivatives of epoxy resins
- C08L63/04—Epoxynovolacs
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- H—ELECTRICITY
- H05—ELECTRIC TECHNIQUES NOT OTHERWISE PROVIDED FOR
- H05K—PRINTED CIRCUITS; CASINGS OR CONSTRUCTIONAL DETAILS OF ELECTRIC APPARATUS; MANUFACTURE OF ASSEMBLAGES OF ELECTRICAL COMPONENTS
- H05K1/00—Printed circuits
- H05K1/02—Details
- H05K1/03—Use of materials for the substrate
- H05K1/0313—Organic insulating material
- H05K1/0353—Organic insulating material consisting of two or more materials, e.g. two or more polymers, polymer + filler, + reinforcement
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- C08L2201/00—Properties
- C08L2201/02—Flame or fire retardant/resistant
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
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- C08L2203/20—Applications use in electrical or conductive gadgets
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- H—ELECTRICITY
- H05—ELECTRIC TECHNIQUES NOT OTHERWISE PROVIDED FOR
- H05K—PRINTED CIRCUITS; CASINGS OR CONSTRUCTIONAL DETAILS OF ELECTRIC APPARATUS; MANUFACTURE OF ASSEMBLAGES OF ELECTRICAL COMPONENTS
- H05K2201/00—Indexing scheme relating to printed circuits covered by H05K1/00
- H05K2201/01—Dielectrics
- H05K2201/0137—Materials
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- H05—ELECTRIC TECHNIQUES NOT OTHERWISE PROVIDED FOR
- H05K—PRINTED CIRCUITS; CASINGS OR CONSTRUCTIONAL DETAILS OF ELECTRIC APPARATUS; MANUFACTURE OF ASSEMBLAGES OF ELECTRICAL COMPONENTS
- H05K2201/00—Indexing scheme relating to printed circuits covered by H05K1/00
- H05K2201/02—Fillers; Particles; Fibers; Reinforcement materials
- H05K2201/0203—Fillers and particles
- H05K2201/0206—Materials
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Abstract
The invention discloses a halogen-free thermosetting resin composition which comprises a composition solid and an organic solvent, wherein the composition solid comprises: (A) phosphorus-containing epoxy resin; (B) isocyanic acid modified epoxy resin; (C) novolac epoxy; (D) phosphorus-containing phenolic resin curing agent; (E) DDS curing agent; (F) phenolic resin; (G) epoxy resin curing accelerator; and (H) inorganic filler. The invention also discloses a preparation method of the halogen-free thermosetting resin composition and an application in the preparation of a high-frequency printed circuit board. The prepared high-frequency printed circuit board (PCB) has high glass-transition temperature (Tg>=170 DEG C), good heat resistance and low thermal expansion coefficient (CTE<=3.0%) and low dielectric loss (Df<=0.011).
Description
Technical field
The invention belongs to copper-clad plate technical field, relate to a kind of halogen-free thermosetting resin composite being applicable to high frequency substrate material
And its preparation method and application.
Background technology
Since the concept of Halogen is after copper-clad plate industry is fashionable, copper-clad plate performance constantly progressive in, bromine is fire-retardant and Halogen
The product research development of fire-retardant two different system branches exists the most simultaneously, for PCB industry for different the answering of terminal
Corresponding selection is made with domain requirement.For adapting to world's environmental protection trend and green consumer, halogen-free for Present Global electronics product
When its electronic product is formulated the volume production of halogen-free electronic product by the environmental protection trend of industry, countries in the world and the big factory of associated electrical successively
Journey table.Printed circuit board is the basis of electronic motor product, halogen-free with to printed circuit board for first emphasis control object,
International organization has been strict with for the content of halogen of printed circuit board, and that green peace organization promotes present stage energetically is green
Change policy, it is desirable to all of manufacturer gets rid of the polrvinyl chloride in its electronic product and bromide fire retardant completely, has concurrently to meet
Unleaded and halogen-free environment-friendly electronic.The concept of Halogen proposes to being developed so far, and electronic product environment friendly non-halogenization is the general trend of events all the time
Being become, the use of the Halogen product that the low each field of middle height is suitable for increases day by day.Halogen-free copper-clad plate when initial starting development just
Facing that fragility is big, the retardance of the big defect of big and with high costs two that absorb water, even to this day, the increasingly mature of technology makes nothing always
Processability and the water absorption rate of halogen product are more and more better, and it is more and more handy that the processing of Halogen product is used by PCB manufacturer,
And high cost is also the most digested in the requirement of each industrial chain halogen-free environmental and the surging of terminal promote.Halogen-free material is
So become a kind of development trend.
In the last few years, along with the high speed development of electronics technology, the electronic product such as mobile communication, server, mainframe computer
Information processing constantly develops towards the direction of " signal transmission high frequency and high-speed digitization ", is widely used in communication field
The demand of various high frequency electronic equipment is also quickly increasing, and signal processing and the transmission frequency of electronic equipment are substantially improved, by million
Hertz (MHz) strides forward to GHz (GHz), with catenet work station, mobile phone wireless communication, automobile satellite navigation and
Bluetooth technology is that the new technique of representative makes applying frequency improve constantly, and tends to high frequency or hyperfrequency field, signal transmission high frequency
Change and high speed has the requirement of high-frequency high-speed characteristic to the electronic circuit base material proposition transmitted for signal.Currently, PCB uses
The high speed of baseplate material, high frequency are the cutting edge technologies in copper-clad plate industry development, are wherein adapted to the base of high frequency application
Panel material becomes the emphasis direction of material manufacturer exploitation now.
Summary of the invention
An object of the present invention is to provide a kind of halogen-free thermosetting tree being suitable for high frequency substrate material in view of the above problems
Oil/fat composition.
The two of the purpose of the present invention are to provide the preparation of the above-mentioned halogen-free thermosetting resin composite being suitable for high frequency substrate material
Method.
The three of the purpose of the present invention are to provide the application of the above-mentioned halogen-free thermosetting resin composite being suitable for high frequency substrate material.
The present invention provides a kind of halogen-free thermosetting resin composite to include composition solid and organic for achieving the above object
Solvent, wherein said composition solid includes (A) phosphorous epoxy resin (B) Carbimide. modified epoxy (C)
Phenol aldehyde type epoxy resin；(D) phosphorus containing phenolic resin firming agent；(E) DDS firming agent；(F) phenolic resin；(G) epoxy resin
Curing accelerator；(H) inorganic filler；
The percentage ratio that this halogen-free thermosetting resin composite accounts for composition solid gross weight by each constituent solid weight is as follows:
Additionally, in addition to the aforementioned components, also can include organic solvent, organic solvent is not specifically limited, such as, and can
Use in methyl ethyl ketone, toluene, dimethylbenzene, methyl iso-butyl ketone (MIBK), propylene glycol monomethyl ether or cyclohexanone one or both with
On mixture, these solvents can each be used alone, maybe can use the combination of its two or more.
The usage amount of organic solvent is not specifically limited, and is impregnated by halogen-free thermosetting resin composite from the case of preparing prepreg
From the viewpoint of the good adhesion between easiness and halogen-free thermosetting resin composite and matrix in matrix, preferably add
Enter organic solvent so that the solids content of glue be 50% or more than, particularly 55～75% are preferred.
Should. halogen-free thermosetting resin composite preparation process is as follows:
(1) press formula ratio in agitator tank, add part organic solvent and DDS firming agent, turn on agitator, rotating speed
600～1500 revs/min, keep continuously stirred and control the temperature of described agitator tank at 20～50 DEG C, add inorganic filler,
After interpolation continuously stirred 90～120 minutes；
(2) in described agitator tank, it is sequentially added into phosphorous epoxy resin, the epoxy resin of Carbimide. modification, phenolic aldehyde by formula ratio
Type epoxy resin, phosphorus containing phenolic resin firming agent and phenolic resin, keep during charging with 1000～1500 revs/min of rotating speeds
Stirring, opens after interpolation and efficiently shears and emulsifying 1～4 hours, carry out cooling water circulation to keep control flume body temperature simultaneously
Degree is at 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 described agitator tank, and persistently keeps 1000～1500 revs/min of stirrings 4～13 hours, i.e. prepare nothing
Halogen compositions of thermosetting resin.
As the application of the above-mentioned halogen-free thermosetting resin composite of third aspect present invention, it can be used to prepare high frequency and prints
Wiring board (PCB).
In a preferred embodiment of the invention, described high frequency printed wiring board (PCB) has high glass transition temperature
Degree (Tg 170 DEG C), excellent thermostability and low thermal coefficient of expansion (CTE 3.0%), low dielectric loss (Df
0.011)。
Detailed description of the invention
Main material
1. phosphorous epoxy resin
Phosphorous epoxy resin of the present invention can be DOPO type epoxy resin, DOPO-HQ type epoxy resin or DOPO
-NQ type epoxy resin, or above-mentioned resin can be used alone or can combine more than two kinds persons simultaneously is used in conjunction with.It is below
The chemical constitution of DOPO, DOPO-HQ and DOPO-NQ:
2. the epoxy resin that Carbimide. is modified
Resin characteristics requires:
Isocyanate-modified epoxy resin comprises epoxy resin modified for aromatic series '-diphenylmethane diisocyanate MDI and first
Phenylene diisocyanate TDI modified epoxy, it is also possible to be the mixture of the two, its purpose is to give solidification resin and
Required for the laminate that it is made basic both mechanically and thermally, and there is good toughness and excellent copper-stripping is strong
Degree.
In the present invention, this kind of resin can be selected for the XZ97103 resin that Dow Chemical produces, but is not limited only to this.
3. phenol aldehyde type epoxy resin
Novolac epoxy resin of the present invention can be bisphenol A-type novolac epoxy resin, bisphenol-f type novolac epoxy resin or adjacent first
Novolac 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 KEB-3165, KEB-3180 resin etc. that Korea S can be grand, but is not limited only to this.
4. phosphorus containing phenolic resin firming agent
Resin characteristics requires:
This phosphorus containing phenolic resin firming agent is bisphenol A-type phosphorus containing phenolic resin, and it is by phosphorus-containing compound and bisphenol A-type ring
Epoxy resins reaction prepares, and can be selected for the resin of DOW Chemical production, trade mark XZ-92741, but is not limited only to this.
5. phenolic resin
At the phenolic resin that phenolic resin of the present invention is phenol and formaldehyde crosslinking, described phenol is phenol, xylenols, ethyl
In phenol, n-pro-pyl phenol, isopropyl-phenol, normal-butyl phenol, isobutyl group phenol, tert-butyl phenol or bisphenol-A
One or more mixture.As the phenol novolacs that preferred described phenolic resin is phenol and formaldehyde crosslinking, or
The bisphenol A phenolic resin of bisphenol-A and formaldehyde crosslinking, or the mixture of phenol novolacs and bisphenol A phenolic resin.
In the present invention, this kind of resin can be selected for the PF8020 phenolic resin of Shandong holy well Chemical Manufacture.But it is not limited only to this.
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, excellent
Selecting 2-ethyl-4-methylimidazole, its consumption in promoting epoxy resin cure should sufficiently lack, and preferable amount is whole solid
The 0.005～0.08wt% of the scale of construction.
7. inorganic filler
Halogen-free thermosetting resin composite of the present invention adds suitable filler, to reduce the making copper-clad plate material of resin combination
The coefficient of expansion, it can comprise silicon dioxide, aluminium oxide, aluminium hydroxide, magnesium oxide, magnesium hydroxide, aluminium nitride, carbonization
One or more mix with silicon dioxide related inorganic powder body for silicon, quartz, Muscovitum, boehmite, Pulvis Talci etc., or have and have
Machine core outer shell is the powder particle that insulator is modified, and inorganic filler can be ball-type, granular, lamellar or pin palpus shape etc., and
Alternative via silane coupling agent pretreatment.The preferred aluminium hydroxide of inorganic filler of the present invention and the combination of silicon dioxide, hydrogen-oxygen
Change H-42M, the ML0109 of silicon dioxide preferred Chongqing brocade skill of aluminum preferably Japan Showa electrician, but be not limited only to this.
The dielectric loss that the present invention is low is working in coordination with by phosphorus containing phenolic resin firming agent, phosphorous epoxy resin and inorganic filler combination
Act on and obtain.
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)
Detection method: use differential scanning calorimetry (DSC) test, vitrification point refer to sheet material in the case of being heated by
Glassy transition is the temperature (DEG C) corresponding to elastomeric state (rubbery state).
(2) thermally stratified layer time (T-288)
The T-288 thermally stratified layer time refer to sheet material under the design temperature of 288 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 beaten with 120 mesh and 800 mesh sand paper successively
Mill, pressure-cooks certain time, puts in 288 DEG C of tin melting furnaces, observes with or without phenomenons such as layerings.
(5) anti-flammability
Detection method: use the method for UL-94 to test.
(6)Dk/Df
Test according to IPC-TM-650-2.5.5.9 method.
Embodiment 1
1. the weight/mass percentage composition of the solid content in halogen-free thermosetting resin composite is 65%, remaining be organic solvent (such as
Methyl ethyl ketone), wherein, the formula of solid content see table 1 (by weight)
Table 1
| Raw material | Solid weight (gram) |
| Phosphorous epoxy resin | 4 |
| The epoxy resin that Carbimide. is modified | 11 |
| Phenol aldehyde type epoxy resin | 20 |
| Phosphorus containing phenolic resin firming agent | 16 |
| DDS firming agent | 1.1 |
| Phenolic resin | 8 |
| 2-ethyl-4-methylimidazole (2E4MZ) | 0.03 |
| Aluminium hydroxide | 13 |
| Silicon dioxide | 7 |
2. the preparation method of halogen-free thermosetting resin composite:
(1) in agitator tank, add organic solvent methyl ethyl ketone 43 grams and DDS firming agent by above weight, open stirring
Device, rotating speed 800 revs/min, and dissolve completely until DDS firming agent for continuously stirred 120 minutes；Add aluminium hydroxide and
Silicon dioxide, after interpolation continuously stirred 90 minutes.
(2) in agitator tank, it is sequentially added into phosphorous epoxy resin, the epoxy resin of Carbimide. modification, phenol aldehyde type ring by formula ratio
Epoxy resins, phosphorus containing phenolic resin firming agent and phenolic resin, open after interpolation and efficiently shear and emulsifying 2 hours, simultaneously
Carry out cooling water circulation to keep control flume temperature at 20～50 DEG C, keep during charging with 1200 revs/min of rotating speed stirrings；
(3) 2-ethyl-4-methylimidazole is weighed by formula ratio, by it with the ratio of weight ratio 1:10 and organic solvent methyl
After ethyl ketone is completely dissolved, this solution is added in agitator tank, and persistently keep 1200 revs/min of stirrings 2 hours, prepare nothing
Halogen compositions of thermosetting resin.
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 1.0mm.
4. the performance parameter of the copper-clad laminate that the present embodiment prepares gained is as shown in table 2 below:
Table 2
| Project | Test result |
| Vitrification point (DSC), DEG C | 175 |
| Peel strength of copper foil (1oz), lb/in | 7.5 |
| T288(TMA),min | >60 |
| Scolding tin thermostability (288 DEG C of wickings), min | >10 |
| CTE (50-260 DEG C, Z axis), % | 2.8 |
| Dk(5GHZ) | 4.66 |
| Df(5GHZ) | 0.0105 |
| Content of halogen (ppm) | 301 |
| Anti-flammability | UL-94V0 |
Embodiment 2
1. the weight/mass percentage composition of the solid content in halogen-free thermosetting resin composite is 63%, and remaining is organic solvent (example
Such as methyl ethyl ketone), wherein, the formula of solid content see table 3 (by weight)
Table 3
2. the preparation method of halogen-free thermosetting resin composite:
(1) in agitator tank, add organic solvent methyl ethyl ketone 57 grams and DDS firming agent by above weight, open stirring
Device, rotating speed 800 revs/min, and dissolve completely until DDS firming agent for continuously stirred 120 minutes；Add aluminium hydroxide and
Silicon dioxide, after interpolation continuously stirred 90 minutes.
(2) in agitator tank, it is sequentially added into phosphorous epoxy resin, the epoxy resin of Carbimide. modification, phenol aldehyde type ring by formula ratio
Epoxy resins, phosphorus containing phenolic resin firming agent and phenolic resin, open after interpolation and efficiently shear and emulsifying 2 hours, simultaneously
Carry out cooling water circulation to keep control flume temperature at 20～50 DEG C, keep during charging with 1200 revs/min of rotating speed stirrings；
(3) 2-ethyl-4-methylimidazole is weighed by formula ratio, by it with the ratio of weight ratio 1:10 and organic solvent methyl second
After base ketone is completely dissolved, this solution is added in agitator tank, and persistently keep 1200 revs/min of stirrings 2 hours, prepare Halogen
Compositions of thermosetting resin.
3. prepare copper-clad laminate
The halogen-free thermosetting resin composite continuously coating prepared in order to top method or impregnated glass fiber cloth, 170 DEG C of bakings
Under the conditions of be dried to obtain prepreg, 8 prepregs are overlapped, the high temperature of its upper and lower each 1 35um of placement extends
Copper Foil, through 190 DEG C, heat under the pressure of 350PSI, pressurize 90 minutes, obtain the copper-clad laminate of 1.0mm.
4. the performance parameter of the copper-clad laminate that the present embodiment prepares gained is as shown in table 4 below:
Table 4
| Project | Test result |
| Vitrification point (DSC), DEG C | 173 |
| Peel strength of copper foil (1oz), lb/in | 8.1 |
| T288(TMA),min | >60 |
| Scolding tin thermostability (288 DEG C of wickings), min | >10 |
| CTE (50-260 DEG C, Z axis), % | 2.9 |
| Dk(5GHZ) | 4.69 |
| Df(5GHZ) | 0.0102 |
| Content of halogen (ppm) | 331 |
| Anti-flammability | UL-94V0 |
Embodiment 3
1. the weight/mass percentage composition of the solid content in halogen-free thermosetting resin composite is 59%, and remaining is organic solvent (example
Such as methyl ethyl ketone), wherein, the formula of solid content see table 5 (by weight)
Table 5
| Raw material | Solid weight (gram) |
| Phosphorous epoxy resin | 8 |
| The epoxy resin that Carbimide. is modified | 8 |
| Phenol aldehyde type epoxy resin | 24 |
| Phosphorus containing phenolic resin firming agent | 15 |
| DDS firming agent | 0.8 |
| Phenolic resin | 12 |
| 2-ethyl-4-methylimidazole (2E4MZ) | 0.06 |
| Aluminium hydroxide | 24 |
| Silicon dioxide | 5 |
2. the preparation method of halogen-free thermosetting resin composite:
(1) in agitator tank, add organic solvent methyl ethyl ketone 67 grams and DDS firming agent by above weight, open stirring
Device, rotating speed 800 revs/min, and dissolve completely until DDS firming agent for continuously stirred 120 minutes；Add aluminium hydroxide and
Silicon dioxide, after interpolation continuously stirred 90 minutes.
(2) in agitator tank, it is sequentially added into phosphorous epoxy resin, the epoxy resin of Carbimide. modification, phenol aldehyde type ring by formula ratio
Epoxy resins, phosphorus containing phenolic resin firming agent and phenolic resin, open after interpolation and efficiently shear and emulsifying 2 hours, simultaneously
Carry out cooling water circulation to keep control flume temperature at 20～50 DEG C, keep during charging with 1200 revs/min of rotating speed stirrings；
(3) 2-ethyl-4-methylimidazole is weighed by formula ratio, by it with the ratio of weight ratio 1:10 and organic solvent methyl
After ethyl ketone is completely dissolved, this solution is added in agitator tank, and persistently keep 1200 revs/min of stirrings 2 hours, prepare nothing
Halogen compositions of thermosetting resin.
3. prepare copper-clad laminate
The halogen-free thermosetting resin composite continuously coating prepared in order to top method or impregnated glass fiber cloth, 170 DEG C of bakings
Under the conditions of be dried to obtain prepreg, 8 prepregs are overlapped, the high temperature of its upper and lower each 1 35um of placement extends
Copper Foil, through 190 DEG C, heat under the pressure of 350PSI, pressurize 90 minutes, obtain the copper-clad laminate of 1.0mm.
4. the performance parameter of the copper-clad laminate that the present embodiment prepares gained is as shown in table 6 below:
Table 6
Embodiment 4
1. the weight/mass percentage composition of the solid content in halogen-free thermosetting resin composite is 70%, and remaining is organic solvent (example
Such as methyl ethyl ketone), wherein, the formula of solid content see table 7 (by weight)
Table 7
| Raw material | Solid weight (gram) |
| Phosphorous epoxy resin | 11 |
| The epoxy resin that Carbimide. is modified | 10 |
| Phenol aldehyde type epoxy resin | 20 |
| Phosphorus containing phenolic resin firming agent | 12 |
| DDS firming agent | 2.2 |
| Phenolic resin | 3 |
| 2-ethyl-4-methylimidazole (2E4MZ) | 0.01 |
| Aluminium hydroxide | 23 |
| Silicon dioxide | 10 |
2. the preparation method of halogen-free thermosetting resin composite:
(1) in agitator tank, add organic solvent methyl ethyl ketone 39 grams and DDS firming agent by above weight, open stirring
Device, rotating speed 800 revs/min, and dissolve completely until DDS firming agent for continuously stirred 120 minutes；Add aluminium hydroxide and
Silicon dioxide, after interpolation continuously stirred 90 minutes.
(2) in agitator tank, it is sequentially added into phosphorous epoxy resin, the epoxy resin of Carbimide. modification, phenol aldehyde type ring by formula ratio
Epoxy resins, phosphorus containing phenolic resin firming agent and phenolic resin, open after interpolation and efficiently shear and emulsifying 2 hours, simultaneously
Carry out cooling water circulation to keep control flume temperature at 20～50 DEG C, keep during charging with 1200 revs/min of rotating speed stirrings；
(3) 2-ethyl-4-methylimidazole is weighed by formula ratio, by it with the ratio of weight ratio 1:10 and organic solvent methyl
After ethyl ketone is completely dissolved, this solution is added in agitator tank, and persistently keep 1200 revs/min of stirrings 2 hours, prepare nothing
Halogen compositions of thermosetting resin.
3. prepare copper-clad laminate
The halogen-free thermosetting resin composite continuously coating prepared in order to top method or impregnated glass fiber cloth, 170 DEG C of bakings
Under the conditions of be dried to obtain prepreg, 8 prepregs are overlapped, the high temperature of its upper and lower each 1 35um of placement extends
Copper Foil, through 190 DEG C, heat under the pressure of 350PSI, pressurize 90 minutes, obtain the copper-clad laminate of 1.0mm.
4. the performance parameter of the copper-clad laminate that the present embodiment prepares gained is as shown in table 8 below:
Table 8
| Project | Test result |
| Vitrification point (DSC), DEG C | 180 |
| Peel strength of copper foil (1oz), lb/in | 7.4 |
| T288(TMA),min | >60 |
| Scolding tin thermostability (288 DEG C of wickings), min | >10 |
| CTE (50-260 DEG C, Z axis), % | 2.73 |
| Dk(5GHZ) | 4.55 |
| Df(5GHZ) | 0.01 |
| Content of halogen (ppm) | 287 |
| Anti-flammability | UL-94V0 |
Comparative example 1
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 9 (by weight)
Table 9
2. the preparation method of composition epoxy resin:
(1) in agitator tank, add organic solvent propylene glycol methyl ether 56 grams by above weight, add aluminium hydroxide and added
Finish latter continuously stirred 90 minutes.
(2) in agitator tank, it is sequentially added into phosphorous epoxy resin, phenol aldehyde type epoxy resin, phosphorus containing phenolic resin by formula ratio solid
Agent and phenolic resin, open after interpolation and efficiently shear and emulsifying 2 hours, carry out cooling water circulation to keep controlling simultaneously
Cell body temperature processed, at 20～50 DEG C, keeps during charging with 1200 revs/min of rotating speed stirrings；
(3) 2-ethyl-4-methylimidazole is weighed by formula ratio, by it with the ratio of weight ratio 1:10 and organic solvent methyl
After ethyl ketone is completely dissolved, this solution is added in agitator tank, and persistently keep 1200 revs/min of stirrings 2 hours, prepare tree
Oil/fat composition.
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 1.0mm.
4. the performance parameter of the copper-clad laminate that the present embodiment prepares gained is as shown in table 10 below:
Table 10
| Project | Test result |
| Vitrification point (DSC), DEG C | 164 |
| Peel strength of copper foil (1oz), lb/in | 7.6 |
| T288(TMA),min | 31 |
| Scolding tin thermostability (288 DEG C of wickings), min | 8 |
| CTE (50-260 DEG C, Z axis), % | 3.1 |
| Dk(5GHZ) | 4.71 |
| Df(5GHZ) | 0.0127 |
| Content of halogen (ppm) | 403 |
| Anti-flammability | UL-94V0 |
Comparative example 2
1. the weight/mass percentage composition of the solid content in resin combination is 61%, and remaining is organic solvent (such as propylene glycol first
Ether),
Wherein, the formula of solid content see table 11 (by weight)
Table 11
| Raw material | Solid weight (gram) |
| Phosphorous epoxy resin | 36 |
| Phenol aldehyde type epoxy resin | 25 |
| Phosphorus containing phenolic resin firming agent | 13 |
| DDS firming agent | 2.0 |
| 2-ethyl-4-methylimidazole (2E4MZ) | 0.08 |
| Aluminium hydroxide | 20 |
| Silicon dioxide | 7 |
2. the preparation method of composition epoxy resin:
(1) in agitator tank, add organic solvent propylene glycol methyl ether 66 grams and DDS firming agent by above weight, open stirring
Device, rotating speed 800 revs/min, and dissolve completely until DDS firming agent for continuously stirred 120 minutes；Add aluminium hydroxide and
Silicon dioxide, after interpolation continuously stirred 90 minutes.
(2) in agitator tank, it is sequentially added into phosphorous epoxy resin, phenol aldehyde type epoxy resin, phosphorus containing phenolic resin by formula ratio solid
Agent and phenolic resin, open after interpolation and efficiently shear and emulsifying 2 hours, carry out cooling water circulation to keep controlling simultaneously
Cell body temperature processed, at 20～50 DEG C, keeps during charging with 1200 revs/min of rotating speed stirrings；
(3) 2-ethyl-4-methylimidazole is weighed by formula ratio, by it with the ratio of weight ratio 1:10 and organic solvent methyl
After ethyl ketone is completely dissolved, this solution is added in agitator tank, and persistently keep 1200 revs/min of stirrings 2 hours, prepare tree
Oil/fat composition.
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 1.0mm.
4. the performance parameter of the copper-clad laminate that the present embodiment prepares gained is as shown in table 12 below:
Table 12
| Project | Test result |
| Vitrification point (DSC), DEG C | 171 |
| Peel strength of copper foil (1oz), lb/in | 7.2 |
| T288(TMA),min | 46 |
| Scolding tin thermostability (288 DEG C of wickings), min | 9 |
| CTE (50-260 DEG C, Z axis), % | 3.2 |
| Dk(5GHZ) | 4.77 |
| Df(5GHZ) | 0.0129 |
| Content of halogen (ppm) | 454 |
| Anti-flammability | UL-94V0 |
To sum up obtained epoxide glass cloth base copper coated foil plate has high glass transition temperature (Tg 170 DEG C), excellent
Thermostability and low thermal coefficient of expansion (CTE 3.0%), low dielectric constant/dielectric loss (Df 0.011), it is possible to suitable
Making for halogen-less high frequency printed wiring board (PCB).
Claims (9)
1. halogen-free thermosetting resin composite includes that composition solid and organic solvent, wherein said composition solid include
(A) phosphorous epoxy resin (B) Carbimide. modified epoxy (C) phenol aldehyde type epoxy resin；(D) phosphorus-containing phenolic aldehyde tree
Fat firming agent；(E) DDS firming agent；(F) phenolic resin；(G) epoxy resin curing accelerator；(H) inorganic filler；
The percentage ratio that this halogen-free thermosetting resin composite accounts for composition solid gross weight by each constituent solid weight is as follows:
2. halogen-free thermosetting resin composite as claimed in claim 1, it is characterised in that described halogen-free thermosetting resin group
In compound, the content of composition solid is 55～75%.
3. halogen-free thermosetting resin composite as claimed in claim 1, it is characterised in that described phosphorous epoxy resin is
One or any two in DOPO type epoxy resin, DOPO-HQ type epoxy resin or DOPO-NQ type epoxy resin
Plant mixed above.
4. halogen-free thermosetting resin composite as claimed in claim 1, it is characterised in that described isocyanate-modified
Epoxy resin is in the epoxy resin of aromatic series '-diphenylmethane diisocyanate modification, toluene di-isocyanate(TDI) modified epoxy
A kind of or mixing of two kinds.
5. halogen-free thermosetting resin composite as claimed in claim 1, it is characterised in that described phosphorus containing phenolic resin is solid
Agent is bisphenol A-type phosphorus containing phenolic resin.
6. halogen-free thermosetting resin composite as claimed in claim 1, it is characterised in that described inorganic filler is hydrogen-oxygen
Change aluminum and the combination of silicon dioxide.
7. the preparation method of the halogen-free thermosetting resin composite described in any one of claim 1 to 6 claim, its feature exists
In, comprise the steps:
(1) press formula ratio in agitator tank, add part organic solvent and DDS firming agent, turn on agitator, rotating speed
600～1500 revs/min, keep continuously stirred and control the temperature of described agitator tank at 20～50 DEG C, add inorganic filler,
After interpolation continuously stirred 90～120 minutes；
(2) in described agitator tank, it is sequentially added into phosphorous epoxy resin, the epoxy resin of Carbimide. modification, phenol by formula ratio
Aldehyde type epoxy resin, phosphorus containing phenolic resin firming agent and phenolic resin, keep during charging turning with 1000～1500 revs/min
Speed stirring, opens after interpolation and efficiently shears and emulsifying 1～4 hours, carry out cooling water circulation to keep controlling cell body simultaneously
Temperature is at 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 described agitator tank, and persistently keeps 1000～1500 revs/min of stirrings 4～13 hours, the most prepared
Halogen-free thermosetting resin composite.
8. the halogen-free thermosetting resin composite described in any one of claim 1 to 6 claim is preparing high frequency printed wiring
Application in plate.
Apply the most as claimed in claim 8, the Tg of described high frequency printed wiring board 170 DEG C, CTE 3.0%, Df
≦0.011。
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN107011625A (en) * | 2017-04-21 | 2017-08-04 | 山东圣泉新材料股份有限公司 | A kind of resin combination, laminate, prepreg and preparation method thereof, application |
Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102964777A (en) * | 2012-11-27 | 2013-03-13 | 上海南亚覆铜箔板有限公司 | Phosphorus-containing and halogen-free flame retardant resin adhesive as well as preparation method and application thereof |
| CN102975430A (en) * | 2012-11-27 | 2013-03-20 | 上海南亚覆铜箔板有限公司 | Flame-retarding copper clad laminate coated with solid content containing phosphorous and no halogen and preparation method thereof |
| CN104119639A (en) * | 2013-04-24 | 2014-10-29 | 台光电子材料(昆山)有限公司 | Halogen-free resin composition, and copper foil substrate and printed circuit board applying it |
| CN104559068A (en) * | 2014-12-23 | 2015-04-29 | 上海南亚覆铜箔板有限公司 | Thermosetting resin composition as well as preparation method and application thereof |
| CN105368001A (en) * | 2015-11-27 | 2016-03-02 | 上海南亚覆铜箔板有限公司 | Halogen-free epoxy resin composition, preparation method therefor and application of halogen-free epoxy resin composition |
-
2016
- 2016-06-29 CN CN201610494548.5A patent/CN106009532A/en active Pending
Patent Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102964777A (en) * | 2012-11-27 | 2013-03-13 | 上海南亚覆铜箔板有限公司 | Phosphorus-containing and halogen-free flame retardant resin adhesive as well as preparation method and application thereof |
| CN102975430A (en) * | 2012-11-27 | 2013-03-20 | 上海南亚覆铜箔板有限公司 | Flame-retarding copper clad laminate coated with solid content containing phosphorous and no halogen and preparation method thereof |
| CN104119639A (en) * | 2013-04-24 | 2014-10-29 | 台光电子材料(昆山)有限公司 | Halogen-free resin composition, and copper foil substrate and printed circuit board applying it |
| CN104559068A (en) * | 2014-12-23 | 2015-04-29 | 上海南亚覆铜箔板有限公司 | Thermosetting resin composition as well as preparation method and application thereof |
| CN105368001A (en) * | 2015-11-27 | 2016-03-02 | 上海南亚覆铜箔板有限公司 | Halogen-free epoxy resin composition, preparation method therefor and application of halogen-free epoxy resin composition |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN107011625A (en) * | 2017-04-21 | 2017-08-04 | 山东圣泉新材料股份有限公司 | A kind of resin combination, laminate, prepreg and preparation method thereof, application |
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Address after: Shanghai city Chang Cheung Road 201802 Jiading District Nanxiang Town, No. 158 Applicant after: South Asia new materials Polytron Technologies Inc Address before: Shanghai city Chang Cheung Road 201802 Jiading District Nanxiang Town, No. 158 Applicant before: Shanghai Nanya Copper Clad Laminate Co., Ltd. |
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Application publication date: 20161012 |