CN105620000B - A kind of composite plate and its manufacturing method - Google Patents
A kind of composite plate and its manufacturing method Download PDFInfo
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- CN105620000B CN105620000B CN201410583528.6A CN201410583528A CN105620000B CN 105620000 B CN105620000 B CN 105620000B CN 201410583528 A CN201410583528 A CN 201410583528A CN 105620000 B CN105620000 B CN 105620000B
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Abstract
The present invention provides a kind of manufacturing methods of composite plate, comprising: is melted using screw extruder to resin raw material；Epoxy modified polybutadiene resin is injected from the spout of screw extruder；It will be in resin combination salivation to conductor plate；And conductor plate and resin combination are carried out shaping.Compared with traditional copper-clad plate processing technology, the present invention does not use any organic solvent completely, environment friendly and pollution-free, and simple process, and cost is relatively low.And the composite plate with low-k and low-dielectric loss that the present invention also provides a kind of.
Description
Technical field
The present invention relates to a kind of composite plate and its manufacturing methods.
Background technique
With the development of microwave technology, all kinds of communication electronic equipments start to develop toward high frequency direction, it is desirable that by large capacity
Information is in the low-loss high-speed transfer of high band and processing, but frequency is higher, the easier decaying of electric signal, therefore for work
In all kinds of devices of high frequency band, it is desirable that substrate has dielectric constant low as far as possible and loss.
For commercialization high frequency printed circuit boards in the market based on the high frequency plate of PTFE substrate, such product electrical property is excellent
It is different, but cost is very high, and because fluororesin mechanical property is very low, processing performance and dimensional stability are excessively poor.Although
Non-polar polymeric material dielectric constant is lower, but it is poor with the surface binding force of copper foil or other anakinetomers.In addition,
In copper-clad plate production process, the thermosetting resins such as epoxy resin are compounded in glass fibers with gluing machine in such a way that solution mixes
On Wei Bu, then by being heating and curing to obtain copper-clad plate.This technique must use a large amount of organic solvent dissolving resin, higher cost.
Summary of the invention
Aiming at the problem that using a large amount of organic solvents and complex process in composite plate production process in the prior art, the present invention
Provide the manufacturing method and composite plate of composite plate.
According to an aspect of the invention, there is provided a kind of manufacturing method of composite plate, comprising:
Resin raw material is melted using screw extruder；
Epoxy modified polybutadiene resin is injected from the spout of screw extruder；
It will be in resin combination salivation to conductor plate；And
Conductor plate and resin combination are carried out shaping.
In some embodiments, epoxy modified polybutadiene resin is injected from the middle section side spout of screw extruder.
In some embodiments, screw extruder is double screw extruder.
In some embodiments, resin raw material includes thermoplastic resin.
In some embodiments, resin raw material further comprises the group being made of curing agent, grafting compatilizer and initiator
One of or it is a variety of.
In some embodiments, it before the step of being melted using screw extruder to resin raw material, further wraps
Include: by thermoplastic resin with by one of curing agent, grafting compatilizer and group for forming of initiator or a variety of mix.
In some embodiments, implement to form resin with by curing agent, compatilizer and initiator in a high speed mixer
One of group or a variety of the step of being mixed.
In some embodiments, in the step of being melted using screw extruder to resin raw material, by Screw Extrusion
The temperature of machine is set as in the range of 150 DEG C and 320 DEG C.
In some embodiments, thermoplastic resin include polyolefin, polyethers, polysulfones, polyether-ether-ketone, polyamide and/or it
Combination.
In some embodiments, curing agent is alkene curing agent.
In some embodiments, alkene curing agent includes styrene, 1,3 butadiene, isoprene, styrene, butadiene
And/or their combination.
In some embodiments, grafting compatilizer include maleic anhydride, glycidyl methacrylate, acrylic acid and/
Or their combination.
In some embodiments, initiator is radical initiator.
In some embodiments, radical initiator includes azo compound, peroxide compound and/or their group
It closes.
In some embodiments, azo compound includes azobisisobutyronitrile, the different eyeball in heptan of azo two and/or their group
It closes.
In some embodiments, peroxide compound includes benzoyl peroxide, isopropyl benzene hydroperoxide, t-butyl peroxy
Change hydrogen, cumyl peroxide and/or their combination.
In some embodiments, by the thermoplastic resin of 47-95 parts by weight and curing agent, the 0.2-3 by 1-20 parts by weight
One of group of the grafting compatilizers of parts by weight and the initiator of 0.05-1 parts by weight composition a variety of is mixed；And from
The epoxy-modified polybutadiene of 2-30 parts by weight is injected in the spout of screw extruder.In invention, by injecting 2-
The epoxy-modified polybutadiene of 30 parts by weight can reduce the dielectric constant and dielectric loss of finished product composite plate.
In some embodiments, conductor plate is metal plate.
In some embodiments, metal plate is copper foil, aluminium foil, goldleaf or silver foil.
In some embodiments, after the salivation and before sizing, the thickness of the resin combination on conductor plate between
In the range of 0.2mm to 8mm.
In some embodiments, conductor plate and resin combination are carried out shaping using calender.
In some embodiments, after being formed using calender, the thickness of composite plate is in the range of 0.1mm to 4mm.
According to another aspect of the present invention, a kind of composite plate is additionally provided, composite plate includes: two conductor plates and is clipped in
Resin layer between two conductor plates, the resin layer are made of resin combination, which includes:
The resin of 47-95 parts by weight；And
The epoxy-modified polybutadiene of 2-30 parts by weight.
In some embodiments, resin combination further comprises:
The curing agent of 1-20 parts by weight；
The grafting compatilizer of 0.2-3 parts by weight；And
The initiator of 0.05-1 parts by weight.
In some embodiments, resin is thermoplastic resin.
In some embodiments, thermoplastic resin include polyolefin, polyethers, polysulfones, polyether-ether-ketone, polyamide and/or it
Combination.
In some embodiments, curing agent is alkene curing agent.
In some embodiments, alkene curing agent includes styrene, 1,3 butadiene, isoprene, styrene, butadiene
And/or their combination.
In some embodiments, grafting compatilizer include maleic anhydride, glycidyl methacrylate, acrylic acid and/
Or their combination.
In some embodiments, initiator is radical initiator.
In some embodiments, radical initiator includes azo compound, peroxide compound and/or their group
It closes.
In some embodiments, azo compound includes azobisisobutyronitrile, the different eyeball in heptan of azo two and/or their group
It closes.
In some embodiments, peroxide compound includes benzoyl peroxide, isopropyl benzene hydroperoxide, t-butyl peroxy
Change hydrogen, cumyl peroxide and/or their combination.
In some embodiments, conductor plate is metal plate.
In some embodiments, metal plate is copper foil, aluminium foil, goldleaf or silver foil.
In some embodiments, the thickness of composite plate is in the range of 0.1mm to 4mm.
Due to the present invention by screw extruder leading portion be added one of grafting compatilizer, curing agent and initiator or
A variety of pairs of resins are adjusted, and improve the cohesive force of resin Yu conductor plate (such as copper foil), then by screw extruder
Liquid epoxy modified polybutadiene resin is added in section, is drawn using leading portion grafting compatilizer residual free radical in screw extruder middle section
Hair ring oxygen modified polybutadiene resin free radical polymerization, causes the crosslinking of resin system, improves heat resistance, the solvent resistant of resin
Property from screw extruder mouth mold direct extrusion molding and covers conductor plate and obtains low-k composite plate.Add with traditional composite plate
Work technique is compared, and the present invention does not use any organic solvent completely, environment friendly and pollution-free, and simple process, and cost is relatively low.And lead to
Crossing the composite plate that this method is prepared has low-k and low-dielectric loss.
Detailed description of the invention
Fig. 1 is according to an embodiment of the present invention for manufacturing the side of the composite plate with low-k and low-dielectric loss
The flow chart of method.
Specific embodiment
Following will be combined with the drawings in the embodiments of the present invention, and technical solution in the embodiment of the present invention carries out clear, complete
Site preparation description, it is clear that described embodiments are only a part of the embodiments of the present invention, instead of all the embodiments.It is based on
Embodiment in the present invention, those of ordinary skill in the art's every other embodiment obtained belong to what the present invention protected
Range.
The preparation method of composite plate:
It is that the flow chart for preparing the method for composite plate uses Screw Extrusion shown in S101 as shown in figure 1 with reference to Fig. 1, Fig. 1
Machine melts resin raw material, and the temperature of screw extruder is set as in the range of 150 DEG C and 320 DEG C；In the step
In, resin raw material includes thermoplastic resin, it is preferable that resin raw material further comprises by curing agent, grafting compatilizer and initiation
One of group of agent composition is a variety of.Wherein, thermoplastic resin includes polyolefin, polyethers, polysulfones, polyether-ether-ketone, polyamide
And/or their combination；Curing agent is alkene curing agent, and alkene curing agent includes styrene, 1,3 butadiene, isoprene, benzene
Ethylene, butadiene and/or their combination；Being grafted compatilizer includes maleic anhydride, glycidyl methacrylate, acrylic acid
And/or their combination；Initiator is radical initiator, and radical initiator includes azo compound, peroxide chemical combination
Object and/or their combination, azo compound include azobisisobutyronitrile, the different eyeball in heptan of azo two and/or their combination, mistake
Oxygen class compound include benzoyl peroxide, isopropyl benzene hydroperoxide, tert-butyl hydroperoxide, cumyl peroxide and/or
Their combination.The preferred double screw extruder of screw extruder.
In S101 step, the resin raw material that is melted can also include antioxidant, nucleating agent, release agent, lubricant,
Pigment, antistatic agent etc., due to they be it is well known to those of ordinary skill in the art, for purposes of simplicity, herein
It is not described in detail.
Before S101 step, further comprise: by the thermoplastic resin of 47-95 parts by weight and consolidating by 1-20 parts by weight
One of group of initiator composition of agent, the grafting compatilizer of 0.2-3 parts by weight and 0.05-1 parts by weight is a variety of in height
Fast mixing machine is mixed to obtain resin raw material.
Shown in S103 as shown in figure 1, the liquid epoxy that 2-30 parts by weight are injected from the spout of screw extruder is modified
Polybutadiene, it is preferable that injected from the middle section side spout of screw extruder.
Shown in S105 as shown in figure 1, by resin combination salivation to conductor plate, wherein conductor plate is metal plate, including
Copper foil, aluminium foil, goldleaf or silver foil.After the completion of salivation operation, the thickness of the resin combination on conductor plate is between 0.2mm to 8mm
In the range of.
Shown in S107 as shown in figure 1, conductor plate and resin combination are carried out shaping using calender, it is fixed using calender
After type, the thickness of composite plate is in the range of 0.1mm to 4mm.
1 the present invention is described in further detail to embodiment 4 by the following examples.
Embodiment 1
1. resin formula
A kind of polyphenylene oxide (PPO) composite substrate, resin formula are as follows:
2. the preparation process of composite plate
Step a: each component is weighed by above-mentioned weight percent；
Step b: weighed polyphenylene oxide resin, maleic anhydride, DCP, styrene, antioxidant 1098 and irgasfos 168 are added
Enter and is mixed into high-speed mixer；
Step c: uniformly mixed above-mentioned each group is placed in the hopper of double screw extruder, each temperature of double screw extruder
Degree is set in 250-320 degrees Celsius；Liquid epoxy modified butadiene resin is measured to injection from the side spout of middle section；By resin
Composition is cast to two continuous copper foils up and down from mouth mold, after the completion of salivation, resin combination on copper foil with a thickness of 4mm；
Copper foil and resin combination are carried out shaping through calender again, obtain the copper-clad plate with a thickness of 2mm.
Embodiment 2
1. resin formula
A kind of polypropylene composite materials substrate, resin formula are as follows:
2. the preparation process of composite plate
Step a: each component is weighed by above-mentioned weight percent；
Step b: by weighed acrylic resin, maleic anhydride, azobisisobutyronitrile, 1,3 butadiene, antioxidant 1010 and
Irgasfos 168 is added in high-speed mixer and mixes；
Step c: uniformly mixed above-mentioned each group is placed in the hopper of double screw extruder, and each section of double screw extruder
Temperature is set in 150-250 degrees Celsius；Liquid epoxy modified butadiene resin is measured to injection from the side spout of middle section；It will tree
Oil/fat composition is cast to two continuous aluminium foils up and down from mouth mold, after the completion of salivation, resin combination on aluminium foil with a thickness of
6mm；Aluminium foil and resin combination are carried out shaping through calender again, obtain the metal plate with a thickness of 3mm.
Embodiment 3
1. resin formula
A kind of polystyrene composite substrate, resin formula are as follows:
2. the preparation process of composite plate
Step a: each component is weighed by above-mentioned weight percent；
Step b: by weighed polystyrene resin, glycidyl methacrylate, benzoyl peroxide, styrene,
Antioxidant 1010 and irgasfos 168, which are added in high-speed mixer, to be mixed；
Step c: uniformly mixed above-mentioned each group is placed in the hopper of double screw extruder, and each section of double screw extruder
Temperature is set in 150-250 degrees Celsius；Liquid epoxy modified butadiene resin is measured to injection from the side spout of middle section；It will tree
Oil/fat composition is cast to two continuous copper foils up and down from mouth mold, after the completion of salivation, resin combination on copper foil with a thickness of
3mm；Copper foil and resin combination are carried out shaping through calender again, obtain the copper-clad plate with a thickness of 1.6mm.
Embodiment 4
1. resin formula
A kind of polystyrene composite substrate, resin formula are as follows:
2. the preparation process of composite plate
Step a: each component is weighed by above-mentioned weight percent；
Step b: weighed polystyrene resin, GMA, MAH, BPO, styrene, antioxidant 1010 and irgasfos 168 are added
Enter and is mixed into high-speed mixer；
Step c: uniformly mixed above-mentioned each group is placed in the hopper of double screw extruder, and each section of double screw extruder
Temperature is set in 150-250 degrees Celsius；Liquid epoxy modified butadiene resin is measured to injection from the side spout of middle section；It will tree
Oil/fat composition is cast to two continuous copper foils up and down from mouth mold, after the completion of salivation, resin combination on copper foil with a thickness of
7mm；Copper foil and resin combination are carried out shaping through calender again, obtain the copper-clad plate with a thickness of 3.6mm.
Dielectric constant test and dielectric loss test
Using AET high frequency (microwave) dielectric constant analyzer respectively to composite plate made in embodiment 1 to embodiment 4
Carry out dielectric constant test and dielectric loss test.Test result is as follows:
| Dielectric constant | Dielectric loss | |
| Embodiment 1 | 2.7 | 0.005 |
| Embodiment 2 | 2.6 | 0.007 |
| Embodiment 3 | 2.9 | 0.009 |
| Embodiment 4 | 2.6 | 0.005 |
1 dielectric constant of table and dielectric loss test result
As shown in table 1, composite plate of the invention all has lower dielectric constant and low-dielectric loss, uses embodiment 1
Dielectric constant to the composite plate of method as described in example 4 manufacture is respectively less than 2.9 and its dielectric loss is respectively less than 0.009.Cause
This, the method for the preparation composite plate provided through the invention, in the case where not using any organic solvent, final be made has
The composite plate of lower dielectric constant and low-dielectric loss, this method simple process and cost is relatively low.
The foregoing is merely illustrative of the preferred embodiments of the present invention, is not intended to limit the invention, all in essence of the invention
Within mind and principle, any modification, equivalent replacement, improvement and so on be should all be included in the protection scope of the present invention.
Claims (10)
1. a kind of manufacturing method of composite plate characterized by comprising
Resin raw material is melted using screw extruder；
Epoxy modified polybutadiene resin is injected from the spout of the screw extruder；
It will be in resin combination salivation to conductor plate；And
The conductor plate and the resin combination are carried out shaping；
Wherein, the resin raw material further includes grafting compatilizer, and the grafting compatilizer includes maleic anhydride, methacrylic acid contracting
Water glyceride, acrylic acid or their combination, the grafting compatilizer is added in the leading portion of the screw extruder, described
Epoxy-modified polybutadiene is added in the middle section of the screw extruder.
2. the method according to claim 1, wherein being injected from the middle section side spout of the screw extruder
The epoxy-modified polybutadiene.
3. the method according to claim 1, wherein the screw extruder is double screw extruder.
4. the method according to claim 1, wherein the resin raw material includes thermoplastic resin.
5. according to the method described in claim 4, it is characterized in that, the resin raw material further comprises by curing agent and initiation
One of group of agent composition is a variety of.
6. according to the method described in claim 5, it is characterized in that, being melted using screw extruder to resin raw material described
Before the step of melting, further comprise: by one in the thermoplastic resin and the group being made of curing agent and initiator
Kind or a variety of mixed.
7. the method according to claim 1, wherein being melted using screw extruder to resin raw material described
In the step of melting, the temperature of the screw extruder is set as in the range of 150 DEG C and 320 DEG C.
8. according to the method described in claim 5, it is characterized in that, the curing agent is alkene curing agent.
9. according to the method described in claim 5, it is characterized in that, the initiator is radical initiator.
10. according to the method described in claim 6, it is characterized in that, by the thermoplastic resin of 47-95 parts by weight and by 1-20 weight
Measure one of group of initiator composition of the curing agent of part, the grafting compatilizer of 0.2-3 parts by weight and 0.05-1 parts by weight or
It is a variety of to be mixed, and from the spout of the screw extruder inject 2-30 parts by weight the epoxy-modified polybutadiene
Olefine resin.
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| CN105620000B true CN105620000B (en) | 2019-10-25 |
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Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1745142A (en) * | 2003-01-28 | 2006-03-08 | 松下电工株式会社 | Poly(phenylene ether) resin composition, prepreg, and laminated sheet |
| US20080113187A1 (en) * | 2005-02-03 | 2008-05-15 | Kaoru Toyouchi | Resin Composition For High-Frequency Electronic And Electric Parts And Shaped Article Thereof |
Family Cites Families (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH0669746B2 (en) * | 1985-06-13 | 1994-09-07 | 松下電工株式会社 | Laminated board and its manufacturing method |
| JPS62104825A (en) * | 1985-08-23 | 1987-05-15 | Matsushita Electric Works Ltd | Production of polyphenylene oxide cured product |
| CN102942878A (en) * | 2012-11-29 | 2013-02-27 | 彭代信 | Thermoplastic resin adhesive film |
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2014
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Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1745142A (en) * | 2003-01-28 | 2006-03-08 | 松下电工株式会社 | Poly(phenylene ether) resin composition, prepreg, and laminated sheet |
| US20080113187A1 (en) * | 2005-02-03 | 2008-05-15 | Kaoru Toyouchi | Resin Composition For High-Frequency Electronic And Electric Parts And Shaped Article Thereof |
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