CN108437593A - A kind of polyolefin-based copper-clad plate of thermoplastics type of low cost - Google Patents
A kind of polyolefin-based copper-clad plate of thermoplastics type of low cost Download PDFInfo
- Publication number
- CN108437593A CN108437593A CN201810337747.4A CN201810337747A CN108437593A CN 108437593 A CN108437593 A CN 108437593A CN 201810337747 A CN201810337747 A CN 201810337747A CN 108437593 A CN108437593 A CN 108437593A
- Authority
- CN
- China
- Prior art keywords
- polyolefin
- clad plate
- thermoplastics type
- copper
- low cost
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Pending
Links
Classifications
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B27/00—Layered products comprising a layer of synthetic resin
- B32B27/32—Layered products comprising a layer of synthetic resin comprising polyolefins
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B15/00—Layered products comprising a layer of metal
- B32B15/04—Layered products comprising a layer of metal comprising metal as the main or only constituent of a layer, which is next to another layer of the same or of a different material
- B32B15/08—Layered products comprising a layer of metal comprising metal as the main or only constituent of a layer, which is next to another layer of the same or of a different material of synthetic resin
- B32B15/085—Layered products comprising a layer of metal comprising metal as the main or only constituent of a layer, which is next to another layer of the same or of a different material of synthetic resin comprising polyolefins
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B15/00—Layered products comprising a layer of metal
- B32B15/20—Layered products comprising a layer of metal comprising aluminium or copper
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B27/00—Layered products comprising a layer of synthetic resin
- B32B27/18—Layered products comprising a layer of synthetic resin characterised by the use of special additives
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B27/00—Layered products comprising a layer of synthetic resin
- B32B27/18—Layered products comprising a layer of synthetic resin characterised by the use of special additives
- B32B27/20—Layered products comprising a layer of synthetic resin characterised by the use of special additives using fillers, pigments, thixotroping agents
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B33/00—Layered products characterised by particular properties or particular surface features, e.g. particular surface coatings; Layered products designed for particular purposes not covered by another single class
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B2307/00—Properties of the layers or laminate
- B32B2307/20—Properties of the layers or laminate having particular electrical or magnetic properties, e.g. piezoelectric
- B32B2307/204—Di-electric
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B2307/00—Properties of the layers or laminate
- B32B2307/70—Other properties
- B32B2307/726—Permeability to liquids, absorption
Landscapes
- Compositions Of Macromolecular Compounds (AREA)
- Laminated Bodies (AREA)
Abstract
The invention belongs to communicate Material Field, and in particular to a kind of polyolefin-based copper-clad plate of thermoplastics type of low cost.It is basis material that the present invention, which selects thermoplastics type's polyolefin, it is aided with the modified resin of suitable species and ratio, compatilizer, inorganic filler, fire retardant and auxiliary agent, on the one hand the material cost of substrate is reduced, on the other hand the technology difficulty of substrate and copper foil hot pressing cladding is reduced, it further reduced processing cost, thus not only filler is uniformly dispersed for the copper-clad plate being prepared, satisfactory mechanical property, dielectric properties are excellent, water absorption rate and coefficient of thermal expansion are low, peel strength of copper foil is high, and with traditional epoxy resin-matrix, fluorine resin base, heat curing type is polyolefin-based to be compared with copper-clad plates such as heat curing type polyarylether bases, the market competitiveness is stronger, every comprehensive performance requirement of the temperature in use communications field of less demanding to copper-clad plate material can be met.
Description
Technical field
The invention belongs to communicate Material Field, and in particular to a kind of to be suitable for the communications field of less demanding to temperature in use
With the polyolefin-based copper-clad plate of inexpensive thermoplastics type that, dielectric properties are excellent.
Background technology
Currently, the electronics and information industry of various countries is in the high speed development stage.As covering for one of the industry critical material
Copper coin has been widely used in communication base station, satellite, automatic vending machine, computer, mobile phone and the wearable device risen, void
The fields such as quasi- reality technology, pilotless automobile, unmanned plane and intelligent robot.
Traditional epoxy resin-matrix copper-clad plate is quality-high and inexpensive, versatile, but its excessively high dielectric constant and dielectric loss,
Limiting it can only use at low frequency, have been unable to meet instantly high-frequency communication field to the performance requirements of baseplate material.
It is normal as the perfluorinated resin of representative because of its own distinctive chemical constitution to possess extremely low dielectric using polytetrafluoroethylene (PTFE)
A variety of excellent performances such as number and dielectric loss, high thermal stability and chemical stability.It is preferentially reported from United States Patent (USP) US3136680
Since road, polytetrafluoroethylene (PTFE) has been widely used for making all kinds of high performance copper-clad plates, has been commonly utilized in high-gain planar
The fields such as microstrip antenna.However, just gradually entering into the communication equipment of people's daily life every aspect, it is made the valence of material
Lattice are more sensitive, and PTFE base copper-clad plate is expensive, and limiting it is more widely applied, and energy is sent out behind market
Power is insufficient.
Emerging heat curing type it is polyolefin-based it is hard with heat curing type polyarylether base copper-clad plate matter, dielectric loss is low, thermomechanical property
It is good, particularly useful for making multilayer copper-clad plate.The present of intensive micromation and slimming is constantly pursued in wireless communication system
It, the polyolefin-based best replacement that PTFE base copper-clad plate is considered to be with heat curing type polyarylether base copper-clad plate of heat curing type
Product.Although its price is more slightly lower than PTFE base copper-clad plate, but still it is far above epoxy resin-matrix copper-clad plate.Moreover, heat curing type
Vistanex and heat curing type polyarylether resin are during colloidal sol, gluing etc. because having used a large amount of organic solvent so that half
Requirement of the preparation process of cured sheets to mating environmental protection equipment is higher and higher, and fringe cost is also substantially improved therewith.In addition, because of it
Glass fabric, the polyolefin-based dielectric constant with heat curing type polyarylether base copper-clad plate of heat curing type have largely been used in preparation process
Generally it is difficult to decrease to 3.0 hereinafter, this, which is applied to range, also brings apparent limitation.
Invention content
It is excellent suitable for the communications field use of less demanding to temperature in use, dielectric properties that the purpose of the present invention is to provide a kind of
The different polyolefin-based copper-clad plate of inexpensive thermoplastics type.
The polyolefin-based copper-clad plate of thermoplastics type of a kind of low cost provided by the invention, by thermoplastics type's vistanex, modification
After the six class component such as resin, compatilizer, inorganic filler, fire retardant and auxiliary agent is uniformly mixed, it is granulated；Then, through injection moulding, mould
Thermoplastics type's polyolefin substrate of 0.127 ~ 5.080mm thickness is prepared in platen press or extrusion-rolling process；Finally, by the substrate with
The polyolefin-based copper-clad plate of thermoplastics type is prepared through hot lamination process in the copper foil for being overlying on its one or both sides.
It is basis material that the present invention, which selects thermoplastics type's polyolefin, be aided with the modified resins of suitable species and ratio, compatilizer,
Inorganic filler, fire retardant and auxiliary agent, on the one hand reduce the material cost of substrate, on the other hand reduce substrate and copper foil hot pressing
Laminating technology difficulty further reduced processing cost, and not only filler is uniformly dispersed for the copper-clad plate being thus prepared, machinery
It is functional, dielectric properties are excellent, water absorption rate and coefficient of thermal expansion are low, peel strength of copper foil is high, and with traditional asphalt mixtures modified by epoxy resin
Aliphatic radical, fluorine resin base, heat curing type are polyolefin-based to be compared with copper-clad plates such as heat curing type polyarylether bases, and the market competitiveness is stronger, energy
Meet every comprehensive performance requirement of the temperature in use communications field of less demanding to copper-clad plate material.
Further preferred technical solution is：Thermoplastics type's vistanex is polyethylene, polypropylene, poly- fourth
The mixture of one or more of alkene -1, poly(4-methyl-1-pentene) and its derivative.
Further preferred technical solution is：The modified resin is ethylene propylene diene rubber (EPDM resins), polyene
Olefin elastomer (POE resin), olefin block copolymers (OBC resins), alkene-methyl acrylate copolymer (EMA resins), ethylene-
The mixture of one or more of vinyl acetate copolymer (EVA resin), butadiene-styrene rubber, nitrile rubber；The modification
Resin accounts for 1 ~ 35wt% of thermoplastics type's vistanex.
Further preferred technical solution is：The compatilizer be polyethylene, polypropylene, polybutene, polybutadiene,
Polypenthylene, polyprene, polystyrene, POE resin, SEBS resins, EVA resin, EPDM resins and maleic anhydride or Malaysia acyl
The graft copolymer of imines and its mixture of one or more of derivative；The compatilizer accounts for thermoplastics type polyolefin tree
2 ~ 30wt% of fat.
Further preferred technical solution is：The inorganic filler is SiO2、Al2O3、TiO2、ZnO、MgO、Bi2O3、
AlN、Si3N4、SiC、Al(OH)3、Mg(OH)2、BaxSr1-xTiO3(x=1~0)、Mg2TiO4、Bi2(TiO3)3、PbTiO3、
NiTiO3、CaTiO3、ZnTiO3、Zn2TiO4、BaSnO3、Bi2(SnO3)3、CaSnO3、PbSnO3、MgSnO3、SrSnO3、ZnSnO3、
BaZrO3、CaZrO3、PbZrO3、MgZrO3、SrZrO3、ZnZrO3, graphite oxide, fluorographite, talcum powder, mica powder, kaolinite
One kind in soil, clay, solid glass micro-bead, hollow glass micropearl, glass fibre and basalt fibre or several mixing
Object；The inorganic filler accounts for 0.5 ~ 80wt% of thermoplastics type's vistanex.
Further preferred technical solution is：The fire retardant is magnalium flame retardant, boron zinc flame retardant, molybdenum tin
It is one or more in flame retardant, bromide fire retardant, antimony oxide, phosphorus flame retardant and nitrogenated flame retardant and its derivative
Mixture；The fire retardant accounts for 5 ~ 500wt% of thermoplastics type's vistanex.
Further preferred technical solution is：The auxiliary agent be coupling agent, antioxidant and releasing agent in one kind or
A variety of mixture, wherein the coupling agent is silane coupling agent, titanate coupling agent, aluminate coupling agent, borate idol
Join agent, zirconium ester coupling agent, rare-earth coupling agent, phosphate coupling agent and one kind in sulfonyl azide coupling agent and its derivative or
A variety of mixtures；The coupling agent accounts for 0.02 ~ 3.5wt% of inorganic filler；The antioxidant is phosphorous acid esters antioxygen
Agent, Hinered phenols antioxidant, suffocated amine antioxidant, containing in sulphur ester antioxidant, matal deactivator, ZnS, ZnO and MgO
One or more mixtures；The antioxidant accounts for 0.05 ~ 5wt% of thermoplastics type's vistanex；The releasing agent is fat
Fat acid, fatty acid salt, aliphatic ester, amides, paraffin, glycerine, vaseline, silicone powder, silicone oil, polyolefin-wax, Oxidized polyolefin
One or more mixtures in chloroflo, talcum powder, mica powder, clay and clay and its derivative；The releasing agent accounts for
0.01 ~ 3.5wt% of thermoplastics type's vistanex.
Further preferred technical solution is：The temperature of the granulation is 210 ~ 270 DEG C；In the injection moulding
Barrel temperature is 210 ~ 280 DEG C, and mold temperature is -10 ~ 90 DEG C, and injection pressure is 40 ~ 110MPa；Mould in the die pressing
It is 150 ~ 270 DEG C to press temperature, and molding pressure is 40 ~ 120kg/cm2, and clamp time is 30min ~ for 24 hours；Extrusion-the calendering
Barrel temperature in method is 210 ~ 280 DEG C, and bowl temperature is -10 ~ 170 DEG C, 0.5 ~ 5m/min of rolling velocity.
Further preferred technical solution is：The hot pressing temperature of the hot lamination process is 240 ~ 310 DEG C, hot pressing pressure
Power is 30 ~ 150kg/cm2, the time is 20min ~ for 24 hours；It is taken out after temperature is down to 120 DEG C or less, obtains a kind of heat of low cost
The polyolefin-based copper-clad plate of plastotype.
Inventor has found, in the case of no coupling agent and compatilizer, inorganic filler and thermoplastics type's vistanex it
Between compatibility it is bad, the whole peel strength of copper foil is relatively low, and in copper-clad plate different parts peel strength of copper foil difference compared with
Greatly, the thermomechanical property of copper-clad plate at this time, dielectric properties equistability are also low.
Compared with traditional epoxy resin-matrix copper-clad plate, the dielectricity of the polyolefin-based copper-clad plate of thermoplastics type provided by the invention
Can be extremely apparent with water absorption rate advantage, dielectric constant can effectively be adjusted between 2.30 ~ 10.50 and dielectric loss
Within 0.002, water absorption rate is also only≤0.05wt% for control；It is used in the present invention each compared with fluorine resin base copper-clad plate
The cost of class material is lower, while decreasing the complicated heat lamination program that prepreg and film layer layer are stacked, and reduces hot pressing
Temperature and time thereby further reduces processing cost；With heat curing type is polyolefin-based and heat curing type polyarylether base copper-clad plate phase
Than the invention avoids a large amount of uses of glass-fiber-fabric, organic solvent, improve the adjustable extent of copper-clad plate dielectric constant, also drop
The low additional processing cost of material.Although the temperature tolerance of the polyolefin-based copper-clad plate of thermoplastics type provided by the invention is not so good as asphalt mixtures modified by epoxy resin
Aliphatic radical, fluorine resin base, heat curing type be polyolefin-based and the copper-clad plates such as heat curing type polyarylether base are still required to temperature in use
In the not high communications field, the comprehensive performance of the polyolefin-based copper-clad plate of thermoplastics type provided by the invention is more excellent, the market competitiveness more
By force！
Operating process of the present invention is simple, preparation condition is mild, production cost is low, is easy to mass and large-scale production, universality
By force, there is good industrialized production basis and wide application prospect.
Specific implementation mode
A kind of thermoplastics type for low cost that present invention be described in more detail by the following examples provides is polyolefin-based to be covered
Copper coin.However, the embodiment is merely possible to provide explanation, rather than limit the present invention.
Embodiment 1
Weigh 100 parts of polyethylene（Daqing petrochemical 2200J types HDPE）, 10 parts of EPDM resins（Chinese Jilin Chemical EP3072E）, 10 parts it is poly-
Alpha-olefin-maleic anhydride graft copolymer（Long poly- JY-029）, 20 parts of silica（Xinyi Hong Run）, 1 part of antioxidant 1010（Nanjing
Milan chemical industry）, 0.4 part of polyethylene wax（Honeywell RLC657）, 40 parts of main flame retardant magnesium hydroxides（The refined treasured MAGNIFIN in the U.S.
H-5）, 2 parts combustion inhibitor bisphenol A bis-it is bis-（Diphenyl phosphoester）（Normal space chemical industry）With 0.25 part of coupling agent KH550（Nanjing dawn
Chemical general factory）, it is agitated uniformly after be granulated between 230 ~ 250 DEG C；Then, then extruded-rolling process is prepared
The polyvinyl dieelctric sheet of 0.77 ~ 0.81mm thickness, wherein the extruder temperature of extruder is 230 ~ 250 DEG C, and calendering bowl temperature is
70 ~ 90 DEG C, extrusion-rolling velocity is 1.6m/min；Finally, loz copper foils are enclosed respectively on the polyvinyl dieelctric sheet two sides,
Pressure is 65 ~ 85kg/cm2, temperature be 290 DEG C in the case of be laminated 1h after, polyvinyl copper-clad plate has been prepared.
Embodiment 2
Weigh 100 parts of polyethylene（Daqing petrochemical 2200J types HDPE）, 12 parts of polypropylene（Yanshan Petrochemical K9026）, 10 parts of POE trees
Fat（Dow POE7387）, 35 parts of EPDM- maleic anhydride graft copolymers（Long poly- JY-9016）, 5 parts of silica（Xinyi is macro
Profit）, 370 parts of titanium oxide（Just magnificent science and technology in Tianjin）, 1.4 parts of antioxidant 1010s（Nanjing Milan chemical industry）, 0.75 part of polyethylene
Wax（Honeywell RLC657）, 27 parts of main flame retardant decabromodiphenylethane（Shandong sea Wang Huaxue limited liability companies）, 3 parts resistances
It is bis- to fire agent bisphenol-A-（Diphenyl phosphoester）（Normal space chemical industry）With 3 parts of coupling agent KH550（Nanjing Shuguang Chemical General Plant）, agitated
It is granulated between 250 ~ 270 DEG C after uniformly；Then, then the poly- second of 1.01 ~ 1.04mm thickness is prepared in extruded-rolling process
Alkenyl dieelctric sheet, wherein the extruder temperature of extruder is 250 ~ 270 DEG C, and calendering bowl temperature is 80 ~ 100 DEG C, extrusion-calendering
Speed is 1.0m/min；Finally, loz copper foils are enclosed respectively on the polyvinyl dieelctric sheet two sides, be 85 ~ 105kg/ in pressure
After cm2, temperature are laminated 2h in the case of being 300 DEG C, polyvinyl copper-clad plate has been prepared.
Embodiment 3
Weigh 30 parts of poly(4-methyl-1-pentene)s（Mitsui chemistry MX001 types PMP）, 70 parts of polypropylene（Yanshan Petrochemical
K9026）, 20 parts of EPDM resins（Chinese Jilin Chemical EP3072E）, 10 parts of EPDM- maleic anhydride graft copolymers（Long poly- JY-
9016）, 20 parts of aluminium oxide（Zibo perseverance nation）, 1.5 parts of antioxidant 1010s（Nanjing Milan chemical industry）, 0.5 part of polyethylene wax（Huo Niwei
You are RLC657）, 37 parts of main flame retardant magnesium hydroxides（The refined treasured MAGNIFIN H-5 in the U.S.）, 23 parts fire retardant aluminium hydroxides（The Weihe River
Mill Far East rubber and plastic science and technology）With 0.5 part of coupling agent KH550（Nanjing Shuguang Chemical General Plant）, it is agitated uniformly after in 250 ~ 280 DEG C it
Between be granulated；Then, then the polypropylene and poly(4-methyl-1-pentene) of 0.76 ~ 0.80mm thickness is prepared in extruded-rolling process
Composite base dieelctric sheet, wherein the extruder temperature of extruder is 250 ~ 280 DEG C, and calendering bowl temperature is 120 ~ 150 DEG C, extrusion-pressure
It is 1.3m/min to prolong speed；Finally, loz copper foils are enclosed respectively on the composite base dieelctric sheet two sides, be 75 ~ 105kg/ in pressure
cm2, temperature be 300 DEG C in the case of be laminated 1.5h after, polypropylene has been prepared and poly(4-methyl-1-pentene) composite base covers copper
Plate.
Embodiment 4
Weigh 100 parts of polypropylene（Yanshan Petrochemical K9026）, 5 parts of POE resins（Dow POE7387）, 10 parts of polypropylene-horses
Maleic anhydride grafted copolymer（Long poly- JY-9010）, 15 parts of silica（Xinyi Hong Run）, 1 part of antioxidant 1010（Nanjing Milan
Work）, 0.5 part of polyethylene wax（Honeywell RLC657）, 15 parts of main flame retardant aluminium hydroxides（Weifang Far East rubber and plastic science and technology）, 20 parts
Secondary flame retardant decabromodiphenylethane（Shandong sea Wang Huaxue limited liability companies）With 0.2 part of coupling agent KH550（Nanjing dawn chemical industry
Head factory）, it is agitated uniformly after be granulated between 245 ~ 260 DEG C；Then, then extruded-rolling process be prepared 0.50 ~
The polypropylene-base dieelctric sheet of 0.52mm thickness, wherein the extruder temperature of extruder be 245 ~ 260 DEG C, calendering bowl temperature be 115 ~
135 DEG C, extrusion-rolling velocity is 2.0m/min；Finally, loz copper foils are enclosed respectively on the polypropylene-base dieelctric sheet two sides, pressing
Power is 65 ~ 85kg/cm2, temperature be 300 DEG C in the case of be laminated 1h after, polypropylene-base copper-clad plate has been prepared.
Embodiment 5
Weigh 70 parts of polypropylene（Yanshan Petrochemical K9026）, 30 parts of polyethylene（Daqing petrochemical 2200J types HDPE）, 15 parts of EPDM trees
Fat（Chinese Jilin Chemical EPJ0050）, 10 parts of polypropylene-maleic anhydride graft copolymers（Long poly- JY-9010）, 20 parts of silica（Newly
Yihe River Hong Run）, 15 parts of aluminium oxide（Zibo perseverance nation）, 1.2 parts of antioxidant 1010s（Nanjing Milan chemical industry）, 0.55 part of polyethylene wax（Suddenly
Ni Weier RLC657）, 80 parts of main flame retardant aluminium hydroxides（Weifang Far East rubber and plastic science and technology）, 3 parts combustion inhibitor bisphenol A bis-it is bis-（Hexichol
Base phosphate）（Normal space chemical industry）With 0.5 part of coupling agent KH550（Nanjing Shuguang Chemical General Plant）, it is agitated uniformly after in 250 ~ 265
It is granulated between DEG C；Then, then extruded-rolling process be prepared 0.76 ~ 0.80mm thickness polypropylene and polyethylene it is compound
Base dieelctric sheet, wherein the extruder temperature of extruder is 250 ~ 265 DEG C, and calendering bowl temperature is 100 ~ 120 DEG C, extrusion-calendering speed
Degree is 1.2m/min；Finally, loz copper foils are enclosed respectively on the composite base dieelctric sheet two sides, be 75 ~ 95kg/cm in pressure2, temperature
After degree is laminated 1.5h in the case of being 300 DEG C, polypropylene and polyethylene composite-based copper clad plate has been prepared.
Comparative example 1
Weigh 100 parts of polyethylene（Daqing petrochemical 2200J types HDPE）, 10 parts of EPDM resins（Chinese Jilin Chemical EP3072E）, 20 parts of oxygen
SiClx（Xinyi Hong Run）, 1 part of antioxidant 1010（Nanjing Milan chemical industry）, 0.4 part of polyethylene wax（Honeywell RLC657）, 40 parts
Main flame retardant magnesium hydroxide（The refined treasured MAGNIFIN H-5 in the U.S.）It is bis- with 2 parts combustion inhibitor bisphenol A bis-（Diphenyl phosphoester）（Often
Space chemical industry）, it is agitated uniformly after be granulated between 230 ~ 250 DEG C；Then, then extruded-rolling process be prepared 0.77 ~
The polyvinyl dieelctric sheet of 0.80mm thickness, wherein the extruder temperature of extruder is 230 ~ 250 DEG C, and calendering bowl temperature is 75 ~ 95
DEG C, extrusion-rolling velocity is 1.5m/min；Finally, loz copper foils are enclosed respectively on the polyvinyl dieelctric sheet two sides, in pressure
For 75 ~ 95kg/cm2, temperature be 290 DEG C in the case of be laminated 1h after, polyvinyl copper-clad plate has been prepared.
As shown in comparative example 1, not plus compatilizer and the case where coupling agent, inorganic filler and thermoplastics type's vistanex it
Between compatibility it is bad, the whole peel strength of copper foil is relatively low, and in copper-clad plate different parts peel strength of copper foil difference compared with
Greatly, the coefficient of thermal expansion of copper-clad plate at this time, dielectric properties etc. are also not so good as embodiment 1.It is base that the present invention, which selects thermoplastics type's polyolefin,
Body material is aided with modified resin, compatilizer, inorganic filler, fire retardant and the auxiliary agent of suitable species and ratio, on the one hand reduces
On the other hand the material cost of substrate reduces the technology difficulty of substrate and copper foil hot pressing cladding, further reduced and be processed into
This, not only filler is uniformly dispersed for the copper-clad plate being thus prepared, satisfactory mechanical property, dielectric properties are excellent, water absorption rate and heat
The coefficient of expansion is low, peel strength of copper foil is high, and with traditional epoxy resin-matrix, fluorine resin base, heat curing type it is polyolefin-based and
The copper-clad plates such as heat curing type polyarylether base are compared, and the market competitiveness is stronger, can meet the temperature in use communications field pair of less demanding
Every comprehensive performance requirement of copper-clad plate material.
In addition, operating process of the present invention is simple, preparation condition is mild, and production cost is low, is easy to mass, scale metaplasia
Production has good industrialized production basis and wide application prospect.
Above example not imposes any restrictions the content of composition in the present invention.Every technology according to the present invention is real
Matter or composition composition or content still fall within this to any subtle modifications, equivalent variations and modifications made by above example
In the range of inventive technique scheme.
Claims (9)
1. a kind of polyolefin-based copper-clad plate of thermoplastics type of low cost, it is characterised in that：By thermoplastics type's vistanex, modified tree
After the six class component such as fat, compatilizer, inorganic filler, fire retardant and auxiliary agent is uniformly mixed, it is granulated；Then, through injection moulding, molding
Thermoplastics type's polyolefin substrate of 0.127 ~ 5.080mm thickness is prepared in method or extrusion-rolling process；Finally, by the substrate with cover
The polyolefin-based copper-clad plate of thermoplastics type is prepared through hot lamination process in the copper foil of its one or both sides.
2. a kind of polyolefin-based copper-clad plate of thermoplastics type of low cost according to claim 1, it is characterised in that：The heat
Plastotype vistanex is one kind or several in polyethylene, polypropylene, PB Polybutene-1, poly(4-methyl-1-pentene) and its derivative
The mixture of kind.
3. a kind of polyolefin-based copper-clad plate of thermoplastics type of low cost according to claim 1, it is characterised in that：Described changes
Property resin be ethylene propylene diene rubber (EPDM resins), polyolefin elastomer (POE resin), olefin block copolymers (OBC resins),
Alkene-methyl acrylate copolymer (EMA resins), vinyl-vinyl acetate copolymer (EVA resin), butadiene-styrene rubber, nitrile rubber
One or more of mixture；The modified resin accounts for 1 ~ 35wt% of thermoplastics type's vistanex.
4. a kind of polyolefin-based copper-clad plate of thermoplastics type of low cost according to claim 1, it is characterised in that：The phase
Appearance agent is polyethylene, polypropylene, polybutene, polybutadiene, polypenthylene, polyprene, polystyrene, POE resin, SEBS trees
One or more of the graft copolymer and its derivative of fat, EVA resin, EPDM resins and maleic anhydride or maleimide
Mixture；The compatilizer accounts for 2 ~ 30wt% of thermoplastics type's vistanex.
5. a kind of polyolefin-based copper-clad plate of thermoplastics type of low cost according to claim 1, it is characterised in that：The nothing
Machine filler is SiO2、Al2O3、TiO2、ZnO、MgO、Bi2O3、AlN、Si3N4、SiC、Al(OH)3、Mg(OH)2、BaxSr1-xTiO3(x
=1~0)、Mg2TiO4、Bi2(TiO3)3、PbTiO3、NiTiO3、CaTiO3、ZnTiO3、Zn2TiO4、BaSnO3、Bi2(SnO3)3、
CaSnO3、PbSnO3、MgSnO3、SrSnO3、ZnSnO3、BaZrO3、CaZrO3、PbZrO3、MgZrO3、SrZrO3、ZnZrO3, oxidation
Graphite, fluorographite, talcum powder, mica powder, kaolin, clay, solid glass micro-bead, hollow glass micropearl, glass fibre and
One kind in basalt fibre or several mixtures；The inorganic filler account for thermoplastics type's vistanex 0.5 ~
80wt%。
6. a kind of polyolefin-based copper-clad plate of thermoplastics type of low cost according to claim 1, it is characterised in that：The resistance
Combustion agent is magnalium flame retardant, boron zinc flame retardant, molybdenum tin flame retardant, bromide fire retardant, antimony oxide, phosphorus flame retardant
With one or more mixtures in nitrogenated flame retardant and its derivative；The fire retardant accounts for thermoplastics type's vistanex
5~500wt%。
7. a kind of polyolefin-based copper-clad plate of thermoplastics type of low cost according to claim 1, it is characterised in that：Described helps
Agent is one or more mixtures in coupling agent, antioxidant and releasing agent, wherein the coupling agent be silane coupling agent,
Titanate coupling agent, aluminate coupling agent, boric acid ester coupler, zirconium ester coupling agent, rare-earth coupling agent, phosphate coupling agent and
One or more mixtures in sulfonyl azide coupling agent and its derivative；The coupling agent account for inorganic filler 0.02 ~
3.5wt%；The antioxidant is phosphite antioxidant, Hinered phenols antioxidant, suffocated amine antioxidant, contains thioesters
One or more mixtures in kind antioxidant, matal deactivator, ZnS, ZnO and MgO；It is poly- that the antioxidant accounts for thermoplastics type
0.05 ~ 5wt% of olefin resin；The releasing agent be aliphatic acid, fatty acid salt, aliphatic ester, amides, paraffin, glycerine,
In vaseline, silicone powder, silicone oil, polyolefin-wax, oxidized polyolefin waxes, talcum powder, mica powder, clay and clay and its derivative
One or more mixtures；The releasing agent accounts for 0.01 ~ 3.5wt% of thermoplastics type's vistanex.
8. a kind of polyolefin-based copper-clad plate of thermoplastics type of low cost according to claim 1, it is characterised in that：Described makes
The temperature of grain is 210 ~ 270 DEG C；Barrel temperature in the injection moulding is 210 ~ 280 DEG C, and mold temperature is -10 ~ 90 DEG C, note
Blow pressure is 40 ~ 110MPa；Molding temperature in the die pressing is 150 ~ 270 DEG C, and molding pressure is 40 ~ 120kg/cm2,
Clamp time is 30min ~ for 24 hours；Barrel temperature in the extrusion-rolling process is 210 ~ 280 DEG C, bowl temperature is -10 ~
170 DEG C, 0.5 ~ 5m/min of rolling velocity.
9. a kind of polyolefin-based copper-clad plate of thermoplastics type of low cost according to claim 1, it is characterised in that：The heat
The hot pressing temperature of laminating technology is 240 ~ 310 DEG C, and hot pressing pressure is 30 ~ 150kg/cm2, the time is 20min ~ for 24 hours；Wait for that temperature drops
It is taken out after to 120 DEG C or less, obtains a kind of polyolefin-based copper-clad plate of thermoplastics type of low cost.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201810337747.4A CN108437593A (en) | 2018-04-16 | 2018-04-16 | A kind of polyolefin-based copper-clad plate of thermoplastics type of low cost |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201810337747.4A CN108437593A (en) | 2018-04-16 | 2018-04-16 | A kind of polyolefin-based copper-clad plate of thermoplastics type of low cost |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN108437593A true CN108437593A (en) | 2018-08-24 |
Family
ID=63200448
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201810337747.4A Pending CN108437593A (en) | 2018-04-16 | 2018-04-16 | A kind of polyolefin-based copper-clad plate of thermoplastics type of low cost |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN108437593A (en) |
Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN111333965A (en) * | 2020-04-16 | 2020-06-26 | 陕西湍流电子科技有限公司 | Dielectric material, prepreg and laminated board based on ethylene propylene diene monomer |
| CN111363256A (en) * | 2020-04-16 | 2020-07-03 | 陕西湍流电子科技有限公司 | Thermosetting dielectric material based on ethylene propylene diene monomer, preparation method and laminated plate |
| CN112521684A (en) * | 2020-11-16 | 2021-03-19 | 佛山市南方包装有限公司 | High-temperature-cooking-resistant low-temperature-toughness polyolefin plastic and preparation method and application thereof |
| CN113365429A (en) * | 2020-04-21 | 2021-09-07 | 广州市东泓氟塑料股份有限公司 | High-frequency high-speed copper-clad plate with good dielectric constant consistency and preparation and application thereof |
| CN113910703A (en) * | 2021-09-14 | 2022-01-11 | 浙江大学 | Hydrocarbon resin-based flexible high-frequency copper clad laminate material and preparation method thereof |
| CN114889273A (en) * | 2022-03-23 | 2022-08-12 | 电子科技大学 | Glass fiber-free ceramic/hydrocarbon resin-based microwave medium substrate and preparation method thereof |
Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1643070A (en) * | 2002-02-06 | 2005-07-20 | 积水化学工业株式会社 | Resin composition |
| CN102963063A (en) * | 2012-03-16 | 2013-03-13 | 深圳光启创新技术有限公司 | Metamaterial composite plate and machining method |
| JP2014098114A (en) * | 2012-11-15 | 2014-05-29 | Idemitsu Kosan Co Ltd | Surface-treated thermoplastic resin, and thermoplastic resin composition obtained by using the same |
| CN105936745A (en) * | 2015-12-09 | 2016-09-14 | 中山台光电子材料有限公司 | Resin composition |
-
2018
- 2018-04-16 CN CN201810337747.4A patent/CN108437593A/en active Pending
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1643070A (en) * | 2002-02-06 | 2005-07-20 | 积水化学工业株式会社 | Resin composition |
| CN102963063A (en) * | 2012-03-16 | 2013-03-13 | 深圳光启创新技术有限公司 | Metamaterial composite plate and machining method |
| JP2014098114A (en) * | 2012-11-15 | 2014-05-29 | Idemitsu Kosan Co Ltd | Surface-treated thermoplastic resin, and thermoplastic resin composition obtained by using the same |
| CN105936745A (en) * | 2015-12-09 | 2016-09-14 | 中山台光电子材料有限公司 | Resin composition |
Cited By (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN111333965A (en) * | 2020-04-16 | 2020-06-26 | 陕西湍流电子科技有限公司 | Dielectric material, prepreg and laminated board based on ethylene propylene diene monomer |
| CN111363256A (en) * | 2020-04-16 | 2020-07-03 | 陕西湍流电子科技有限公司 | Thermosetting dielectric material based on ethylene propylene diene monomer, preparation method and laminated plate |
| CN113365429A (en) * | 2020-04-21 | 2021-09-07 | 广州市东泓氟塑料股份有限公司 | High-frequency high-speed copper-clad plate with good dielectric constant consistency and preparation and application thereof |
| CN112521684A (en) * | 2020-11-16 | 2021-03-19 | 佛山市南方包装有限公司 | High-temperature-cooking-resistant low-temperature-toughness polyolefin plastic and preparation method and application thereof |
| CN112521684B (en) * | 2020-11-16 | 2023-01-03 | 佛山市南方包装有限公司 | High-temperature-cooking-resistant low-temperature-toughness polyolefin plastic and preparation method and application thereof |
| CN113910703A (en) * | 2021-09-14 | 2022-01-11 | 浙江大学 | Hydrocarbon resin-based flexible high-frequency copper clad laminate material and preparation method thereof |
| CN113910703B (en) * | 2021-09-14 | 2023-03-17 | 浙江大学 | Hydrocarbon resin-based flexible high-frequency copper clad laminate material and preparation method thereof |
| CN114889273A (en) * | 2022-03-23 | 2022-08-12 | 电子科技大学 | Glass fiber-free ceramic/hydrocarbon resin-based microwave medium substrate and preparation method thereof |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN108437593A (en) | A kind of polyolefin-based copper-clad plate of thermoplastics type of low cost | |
| CN108656683B (en) | Fluorine-containing resin-based copper-clad plate with high dielectric constant and preparation method thereof | |
| CN106590452B (en) | A kind of bonding sheet for copper-clad plate | |
| CN104066577B (en) | Multilayer tablet, backboard used for solar batteries and solar module | |
| CN108467532A (en) | A kind of polyolefin-based antenna house of thermoplastics type's saturation of high wave transmission rate | |
| CN112552630B (en) | Resin composition, resin glue solution containing resin composition, prepreg, laminated board, copper-clad plate and printed circuit board | |
| CN108724900B (en) | Preparation method of dry microwave composite dielectric plate | |
| AU2010200472A1 (en) | Composite Material, High-Frequency Circuit Substrate Made Therefrom and Making Method Thereof | |
| CN106589897A (en) | Polyphenyl ether resin mixture | |
| CN113105743B (en) | Heat-conducting ceramic silicon rubber material and preparation method thereof | |
| CN103865165A (en) | Low-smoke, halogen-free and flame retardant polyolefin cable material and preparation method thereof | |
| CN104487244A (en) | Multilayer sheet, backsheet for solar cell and solar cell module | |
| CN108623894A (en) | A kind of silane self-crosslinking bittern-free flame-proof material and its preparation method and application | |
| CN105440450A (en) | BOPP (biaxially-oriented polypropylene) insulating release film | |
| CN105348649A (en) | PP (polypropylene) thermochromic composite release film | |
| CN105440495A (en) | PVC color-variable release film | |
| CN104610633A (en) | Two-step silane crosslinked polyethylene aerial insulation material and preparation technology thereof | |
| CN105001503A (en) | High-extrusion-rate heat-shrinkable tube and production method thereof | |
| CN103073795A (en) | Halogen-free flame-retardant polypropylene master batch, halogen-free flame-retardant polypropylene membrane and preparation method thereof | |
| CN104629251A (en) | Flame retardant composition and application thereof | |
| CN113717489B (en) | Halogen-free flame-retardant thermoplastic elastomer | |
| CN112552604B (en) | Heat-conducting and insulating polypropylene composite material and preparation method and application thereof | |
| CN103849147A (en) | Biaxial orientation type polyphenylene sulfide composite membrane | |
| CN114369428B (en) | Bonding sheet with low thermal expansion coefficient for high-frequency copper-clad plate | |
| CN114437489A (en) | Prepreg prepared from boron nitride modified by continuous method and high-thermal-conductivity thermosetting high-frequency copper-clad plate |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| RJ01 | Rejection of invention patent application after publication |
Application publication date: 20180824 |
|
| RJ01 | Rejection of invention patent application after publication |