CN106590452B - A kind of bonding sheet for copper-clad plate - Google Patents
A kind of bonding sheet for copper-clad plate Download PDFInfo
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- CN106590452B CN106590452B CN201611051432.0A CN201611051432A CN106590452B CN 106590452 B CN106590452 B CN 106590452B CN 201611051432 A CN201611051432 A CN 201611051432A CN 106590452 B CN106590452 B CN 106590452B
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
- C09J7/00—Adhesives in the form of films or foils
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- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
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- C09J11/00—Features of adhesives not provided for in group C09J9/00, e.g. additives
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- C09J11/00—Features of adhesives not provided for in group C09J9/00, e.g. additives
- C09J11/02—Non-macromolecular additives
- C09J11/06—Non-macromolecular additives organic
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- C09J125/00—Adhesives based on homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by an aromatic carbocyclic ring; Adhesives based on derivatives of such polymers
- C09J125/02—Homopolymers or copolymers of hydrocarbons
- C09J125/04—Homopolymers or copolymers of styrene
- C09J125/06—Polystyrene
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- C09J127/00—Adhesives based on homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a halogen; Adhesives based on derivatives of such polymers
- C09J127/02—Adhesives based on homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a halogen; Adhesives based on derivatives of such polymers not modified by chemical after-treatment
- C09J127/12—Adhesives based on homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a halogen; Adhesives based on derivatives of such polymers not modified by chemical after-treatment containing fluorine atoms
- C09J127/18—Homopolymers or copolymers of tetrafluoroethene
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- C09J171/00—Adhesives based on polyethers obtained by reactions forming an ether link in the main chain; Adhesives based on derivatives of such polymers
- C09J171/08—Polyethers derived from hydroxy compounds or from their metallic derivatives
- C09J171/10—Polyethers derived from hydroxy compounds or from their metallic derivatives from phenols
- C09J171/12—Polyphenylene oxides
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- C08L2205/00—Polymer mixtures characterised by other features
- C08L2205/02—Polymer mixtures characterised by other features containing two or more polymers of the same C08L -group
- C08L2205/025—Polymer mixtures characterised by other features containing two or more polymers of the same C08L -group containing two or more polymers of the same hierarchy C08L, and differing only in parameters such as density, comonomer content, molecular weight, structure
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Abstract
The invention belongs to the Material Field that communicates, and in particular to a kind of bonding sheet for copper-clad plate.After resin, inorganic filler and auxiliary agent are well mixed by the present invention, controllable area, surfacing, thickness uniformly easily-controllable, toughness and sticky suitable bonding sheet have been prepared through techniques such as hot pressed sintering turning.According to practical application scene, all kinds of compoiste adhering pieces have been prepared by selecting suitable resin and inorganic filler by the present invention, realize multiple polymers base, different dielectric properties, different surfaces structure prepreg between it is good compound.Especially significantly improved because reinforcing material, the adjustable scopes of bonding sheet dielectric properties such as glass fibre is not used, effectively enhance the practicality and universality of bonding sheet.Compatibility is good in the present invention, between bonding sheet and prepreg, cohesive force is strong, preparation-obtained multi-layer sheet thermomechanical property is good, it is stable it is high, hygroscopicity is low, every combination property requirement of the different communication field to copper-clad plate can be met.
Description
Technical field
The invention belongs to the Material Field that communicates, and in particular to a kind of bonding sheet for copper-clad plate.
Background technology
Nowadays, information electronics industry is in the high speed development stage, just progressively as one of pillar industry of various countries.As
The copper-clad plate of one of information electronic industries critical material, have been widely used in communication base station, satellite, navigation positioning system, automatic
The fields such as vending machine, computer, mobile phone.One of the basic component units of prepreg as copper-clad plate, the compound feelings between them
Condition is most important to the final performance of copper-clad plate.The wearable device that especially rises recently, pilotless automobile, unmanned plane and
The fields such as intelligent robot have also been proposed higher requirement to the combination property of copper-clad plate, and usually needing in some cases will be a variety of
Polymer matrix, different dielectric properties, the prepreg of different surfaces structure are combined to together, to realize the polynary of copper-clad plate performance
Change, can normal, stabilization the work in multiple frequency ranges simultaneously.The use of bonding sheet, the performance of its own are to prepreg
Between composite effect play particularly important role.
United States Patent (USP) US3676566, US3770566 and US4647508 report the bonding sheet using commercialization（As gathered
The compound Kapton series membranes of acid imide-fluorine material）For manufacturing high performance copper-clad plate.However, commercialization bonding sheet forms
Fixed, usable scope is small and expensive.Chinese patent CN101885900A, CN102794949B, CN103731980A,
CN105898984A, CN101880441A and CN102558861B etc. provide the preparation method of a variety of bonding sheet for copper-clad plate,
But the dielectric properties adjustable extent that bonding sheet be present is narrower, solidification process is complicated, technique is unmanageable and causes production difficulty to increase
Greatly, and due to being related to the use of a variety of organic solvents cause environmental problem and safety problem serious.
The content of the invention
It is an object of the invention to provide a kind of bonding sheet for copper-clad plate and preparation method thereof.
A kind of bonding sheet for copper-clad plate provided by the invention, its specific preparation process are：Weigh resin, inorganic filler and help
Agent, it is agitated to be well mixed and then bonding sheet is prepared through hot pressed sintering-turning process；The thickness of the bonding sheet is
0.005~5mm。
Inventor has found, bonding sheet for copper-clad plate prepares it and all refers to glass-fiber-fabric or glass fibre etc. in the prior art
The use of reinforcing material, or do bonding sheet using curable system；The former causes because reinforcing material itself dielectric constant is high
The dielectric properties adjustable extent of bonding sheet significantly narrows；The latter's solidification process is complicated, technique is unmanageable and causes production difficult
Degree increase.
After resin, inorganic filler and auxiliary agent are well mixed by the present invention, can quickly it connect through techniques such as hot pressed sintering-turning
Controllable area, surfacing, thickness uniformly easily-controllable, toughness and sticky suitable bonding sheet have been prepared continuously.According to reality
All kinds of compoiste adhering pieces have been prepared by selecting suitable resin and inorganic filler, have realized by application scenarios, the present invention
Multiple polymers base, different dielectric properties, different surfaces structure prepreg between it is good compound.Especially because being not used
The reinforcing materials such as glass fibre, the adjustable scope of bonding sheet dielectric properties is greatly improved, effectively enhance the reality of bonding sheet
With property and universality.Compatibility is good in the present invention, between bonding sheet and prepreg, cohesive force is strong, preparation-obtained multilayer
Plate heat-mechanical performance is good, stabilization is high, hygroscopicity is low, can meet every combination property requirement of the different communication field to copper-clad plate.
Operating process of the present invention is simple, universality is strong, preparation condition is gentle, production cost is low, is easy to mass and scale
Metaplasia is produced, and has the basic and wide application prospect of good industrialized production.
The multi-layer sheet that bonding sheet of the present invention obtains afterwards with prepreg pressing handles 5min, is repeated 5 times not at high temperature
Generation is bubbled, is not stratified, and outward appearance, intensity and toughness are several unchanged.Z axis CTE (0 ~ 100oC, ppm/oC it is) 5 ~ 475, it is fire-retardant
Property (UL-94) reaches V1 or V0, and 288oIt is resistance to dip solderability more than 20 times under C, 288 after pressure cooker boilingoUnder C it is resistance to it is dip solderability still above
20 times.
In the present invention, described resin is fluorine resin（As polytetrafluoroethylene (PTFE) (PTFE), perfluoroethylene-propylene (FEP,
F46), tetrafluoroethylene-perfluoro alkoxy vinyl ethers copolymer (PFA) etc.）, polyolefin（Such as polypropylene, polybutadiene, polyphenyl
Ethene etc.）, it is polyamide, polyimides, polyether-ketone, polyether-ether-ketone, makrolon, polyarylether, poly arylidene thio-ester, polyether sulphone, poly-
Aromatic sulfide sulfone, PAEK, polyarylene sulfide ketone, polyethersulfone ketone, polyether sulphone nitrile, polyaryl thioether sulfone nitrile, polyphenylene quinoxaline, phenol
Urea formaldehyde, epoxy resin, cyanate ester resin, polyester, polyformaldehyde, polyureas, polyurethane, acrylonitrile-styrene-acrylic ester copolymerization
Thing, acrylonitritrile-styrene resin, methacrylate-styrol copolymer, acrylonitrile-butadiene-styrene copolymer,
Ethylene-tetrafluoroethylene copolymer, SEBS, styrene-butadiene-styrene, styrene-isoprene-phenylethene are common
Polymers, styrene-polyolefin-styrol copolymer, SAN, butadiene-styrene rubber, nitrile rubber and cellulose
And its one or more mixtures in derivative.
In the present invention, described 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, graphene oxide, fluorographite, talcum powder, mica powder, in kaolin and clay etc.
A kind of or several mixture；Described inorganic filler accounts for 0 ~ 85wt% of resin.
In the present invention, described auxiliary agent is one or more mixing in coupling agent, fire retardant, antioxidant and releasing agent
Thing.
In the present invention, described coupling agent is silane coupler（Such as KH550, KH570）, titanate coupling agent（Such as
TMC-201, TMC-102, DN-101 etc.）, aluminate coupling agent（Such as SG-Al821, DL-411-A, DL-411-B）, borate
Coupling agent, zirconium ester coupling agent（Such as ZR-801, ZR-802）, rare-earth coupling agent（Such as DN-903, DN-931）, phosphate it is even
Join agent（Such as DN-27, DN-37）With one or more mixtures in sulfonyl azide coupling agent and its derivative, its dosage
Account for 0 ~ 5wt% of inorganic filler.
In the present invention, described fire retardant is phosphorus flame retardant（Such as resorcinol double (diphenyl phosphoester), phosphoric acid triphens
Ester etc.）, nitrogenated flame retardant（Such as melamine cyanurate, polyphosphoric acid melamine）, magnalium flame retardant（As magnesium hydroxide,
Aluminium hydroxide etc.）, boron zinc flame retardant（Such as borax, kodalk, Firebrake ZB）, molybdenum tin flame retardant（Such as zinc stannate, oxidation
Molybdenum etc.）, one or more mixtures in antimony oxide and its derivative；Its dosage is 0 ~ 50wt% of resin.
In the present invention, described antioxidant is phosphite antioxidant（Such as three (2,4- di-tert-butyl-phenyls) phosphorous
Acid esters, two (2,6- di-t-butyl -4- aminomethyl phenyls) pentaerythritol diphosphites etc.）, Hinered phenols antioxidant（Such as four [β-
(3,5- di-tert-butyl-hydroxy phenyls) propionic acid] pentaerythritol ester, hexylene glycol [β-(3,5- di-tert-butyl-hydroxy phenyls) third
Acid] ester etc.）, suffocated amine antioxidant（Such as secondary diarylamine, ketoamine）, containing sulphur ester antioxidant（Such as thiodipropionic acid dilauryl
Osmanthus ester etc.）, matal deactivator（Such as N, the hydrazides of N- diacetyl adipyls base two etc.）, one or more in ZnS, ZnO and MgO
Mixture；Its dosage is 0 ~ 3wt% of resin.
In the present invention, described releasing agent is aliphatic acid（Such as stearic acid, palmitic acid, laurate）, soap（As firmly
Resin acid calcium, zinc stearate etc.）, fatty acid ester（Such as stearyl stearate, glycerol tristearate, the double stearates of pentaerythrite
Deng）, amide-type（Erucyl amide）, paraffin, glycerine, vaseline, silicone powder, silicone oil（Such as dimethyl silicone polymer）, polyolefin
Wax（Such as Tissuemat E, polypropylene wax）, oxidized polyolefin waxes（Such as OPE, its chlorinated polypropylene wax）, talcum powder,
One or more mixtures in mica powder, clay and clay and its derivative；Its dosage is 0 ~ 5wt% of resin.
In the present invention, described hot pressed sintering temperature is 120 ~ 430oC, pressure is 40 ~ 200kg/cm2, the time is 2 ~ 72h.
In the present invention, described turning speed is 10 ~ 250m/min, 0.005 ~ 5mm/r of the amount of feeding, cutting depth 0.005 ~
5mm。
Embodiment
A kind of bonding sheet for copper-clad plate provided by the invention and its preparation side are further described by the following examples
Method.However, the embodiment is merely possible to provide explanation, rather than limit the present invention.
Embodiment 1
Weigh 75 parts of PTFE（Daikin PTFE M-18）, 75 parts of PFA（Du Pont Teflon PFA340）, 70 parts of titanium dioxides
Titanium（Just magnificent science and technology in Tianjin）With 1 part of KH550（Nanjing Shuguang Chemical General Plant）, after being well mixed through homogenizer,
360oC、120 kg/cm2After lower hot pressed sintering 24h, bonding sheet is obtained through turning, its thickness about 0.095 ~ 0.105mm；Should
Bonding sheet after PTFE plate high-temperature laminatings with obtaining multi-layer sheet, then 300o5min is handled under C, after being repeated 5 times, can be observed more
Laminate is non-foaming, not stratified, and outward appearance, intensity and toughness are several unchanged.
Embodiment 2
Weigh 150 parts of PTFE（Daikin PTFE M-18）, 10 parts of PFA（Du Pont Teflon PFA340）, 80 parts of dioxies
Change titanium（Just magnificent science and technology in Tianjin）With 2 parts of KH550（Nanjing Shuguang Chemical General Plant）, after being well mixed through homogenizer,
430oC、200 kg/cm2After lower hot pressed sintering 24h, bonding sheet is obtained through turning, its thickness about 0.095 ~ 0.105mm；Will
The bonding sheet after PTFE plate high-temperature laminatings with obtaining multi-layer sheet, then 300o5min is handled under C, after being repeated 5 times, can be observed
Multi-layer sheet is non-foaming, not stratified, and outward appearance, intensity and toughness are several unchanged.
Embodiment 3
Weigh 110 parts of PTFE（Daikin PTFE L-5）, 30 parts of FEP（Daikin Neoflon FEP NC-1539）、
10 parts of ethylene-tetrafluoroethylene copolymers (ETFE)（Du Pont Teflon Tefzel ETFE750）, 50 parts of titanium dioxide（In Tianjin
Just magnificent science and technology）, 30 parts of silica（Xinyi Hong Run）With 1 part of KH550（Nanjing Shuguang Chemical General Plant）, mixed through homogenizer
After closing uniformly, 380oC、150 kg/cm2After lower hot pressed sintering 24h, bonding sheet is obtained through turning, its thickness about 0.0105
~0.115mm；Multi-layer sheet will be obtained after the bonding sheet and PTFE plate high-temperature laminatings, then 300o5min is handled under C, is repeated 5 times
Afterwards, it is non-foaming, not stratified that multi-layer sheet can be observed, and outward appearance, intensity and toughness are several unchanged.
Embodiment 4
Weigh 45 parts of PTFE（Daikin PTFE L-5）, 15 parts of ethylene-tetrafluoroethylene copolymers (ETFE)（Du Pont
Teflon Tefzel ETFE750）, 70 parts of polyphenylene oxide（Husky Bick PPO640）, 20 parts of ABS resins（Strange beautiful PA-717C）, 70 parts
Aluminum oxide（Zibo perseverance nation）, 1 part of KH550（Nanjing Shuguang Chemical General Plant）, 0.8 part of antioxidant 225（Ciba refines）, 10 parts of bis-phenols
A- is double（Diphenyl phosphoester）（The normal space chemical industry in Changzhou）With 0.5 part of zinc stearate（Hebei celebrating protects plastic additive and processes limited public affairs
Department）, after being well mixed through homogenizer, 270oC、130 kg/cm2Lower hot pressed sintering 12h and then 350oC、150
kg/cm2Lower hot pressed sintering 12h, bonding sheet is obtained after through turning, its thickness about 0.010 ~ 0.110mm；By the bonding sheet two sides
PTFE plates and polyphenylene oxide plate are covered with respectively, multi-layer sheet are obtained after high-temperature laminating, then 240o5min is handled under C, is repeated 5 times
Afterwards, it is non-foaming that multi-layer sheet can be observed, bonding sheet and PTFE plates and the compound place of polyphenylene oxide plate are not stratified, and outward appearance, intensity and
Toughness is several unchanged.
Embodiment 5
By 40 parts of polyphenylene oxide resins（Husky Bick PPO640）, 70 parts of polystyrene（Strange beautiful PG-383）, 20 parts of silica（Newly
Yihe River Hong Run）, 20 parts of titanium oxide（Just magnificent science and technology in Tianjin）, 0.5 part of Silane coupling agent KH550（Nanjing Shuguang Chemical General Plant）、1
Part antioxidant 1010（Nanjing Milan chemical industry）, 1 part of Fischer-Tropsch wax（Japan Sekiscoat Co., Ltd. FT115）, 30 parts of aluminium hydroxides（Weifang
Far East rubber and plastic science and technology）With 2 parts of bisphenol-As-bis-（Diphenyl phosphoester）（BDP, the normal space chemical industry in Changzhou）It is well mixed through high-speed stirred.
After being well mixed through homogenizer, 220oC、110 kg/cm2Lower hot pressed sintering 16h and then 280oC、140 kg/
cm2Lower hot pressed sintering 8h, bonding sheet is obtained after through turning, its thickness about 0.105 ~ 0.110mm；The bonding sheet two sides is distinguished
Polyphenylene oxide plate is covered with, multi-layer sheet is obtained after high-temperature laminating, then 160o5min is handled under C, after being repeated 5 times, can be observed more
Laminate is non-foaming, and bonding sheet and the compound place of polyphenylene oxide plate are not stratified, and outward appearance, intensity and toughness are several unchanged.
Embodiment 6
Weigh 95 parts of polyphenylene oxide（Husky Bick PPO640）, 30 parts of polypropylene（Yanshan Petrochemical K9026）, 25 parts of ABS resins（Very
Beautiful PA-717C）, 70 parts of aluminum oxide（Zibo perseverance nation）, 1 part of KH550（Nanjing Shuguang Chemical General Plant）, 1 part of antioxidant 225（Ciba
Refine）, 6 parts of bisphenol-As-bis-（Diphenyl phosphoester）（The normal space chemical industry in Changzhou）With 0.5 part of zinc stearate（Plastic additive is protected in Hebei celebrating
Process Co., Ltd）, after being well mixed through homogenizer, 260oC、130 kg/cm2Lower hot pressed sintering 16h and then
300oC、150 kg/cm2Lower hot pressed sintering 8h, bonding sheet is obtained after through turning, its thickness about 0.095 ~ 0.105mm；Should
Bonding sheet two sides is covered with polyphenylene oxide plate respectively, multi-layer sheet is obtained after high-temperature laminating, then 210o5min is handled under C, is repeated 5 times
Afterwards, it is non-foaming, not stratified that multi-layer sheet can be observed, and outward appearance, intensity and toughness are several unchanged.
Embodiment 7
Weigh 90 parts of polyphenylene oxide（Husky Bick PPO640）, 50 parts of ASA resins（Strange beautiful PW-978B）, 20 parts of ABS resins（Very
Beautiful PA-717C）, 50 parts of aluminum oxide（Zibo perseverance nation）, 10 parts of silica（Xinyi Hong Run）, 1 part of KH550（Nanjing dawn chemical industry is total
Factory）, 1 part of antioxidant 225（Ciba refines）, 5 parts of bisphenol-As-bis-（Diphenyl phosphoester）（The normal space chemical industry in Changzhou）, 10 parts of hydroxides
Aluminium（Weifang Far East rubber and plastic science and technology）With 0.5 part of zinc stearate（Plastic additive processing Co., Ltd is protected in Hebei celebrating）, through high-speed stirred
After machine is well mixed, 220oC、120 kg/cm2Lower hot pressed sintering 16h and then 280oC、150 kg/cm2Lower hot pressing
8h is sintered, obtains bonding sheet through turning after, its thickness about 0.105 ~ 0.115mm；The bonding sheet two sides is covered with polyphenyl respectively
Ether plate and FR-4 plates, multi-layer sheet are obtained after high-temperature laminating, then 190o5min is handled under C, after being repeated 5 times, can be observed more
Laminate is non-foaming, and bonding sheet and FR-4 plates and the compound place of polyphenylene oxide plate are not stratified, and outward appearance, intensity and toughness are several unchanged.
Embodiment 8
Weigh 90 parts of polystyrene（Strange beautiful PG-383）, 20 parts of ASA resins（Strange beautiful PW-978B）, 10 parts of ABS resins（Very
Beautiful PA-717C）, 1 part of antioxidant 225（Ciba refines）, 10 parts of bisphenol-As-bis-（Diphenyl phosphoester）（The normal space chemical industry in Changzhou）、
0.5 part of KH550（Nanjing Shuguang Chemical General Plant）, 50 parts of aluminium hydroxides（Weifang Far East rubber and plastic science and technology）With 0.5 part of zinc stearate（River
Plastic additive processing Co., Ltd is protected in north celebrating）, after being well mixed through homogenizer, 120oC、40 kg/cm2Lower hot pressing is burnt
Tie 16h and then 180oC、100 kg/cm2Lower hot pressed sintering 8h, bonding sheet is obtained after through turning, and its thickness about 0.105 ~
0.115mm；The bonding sheet two sides is covered with polyphenylene oxide plate respectively, multi-layer sheet is obtained after high-temperature laminating, then 120oHandled under C
5min, after being repeated 5 times, it can be observed that multi-layer sheet is non-foaming, and bonding sheet and the compound place of polyphenylene oxide plate are not stratified, and it is outward appearance, strong
Degree and toughness are several unchanged.
Embodiment 9
By 50 parts of polyphenylene oxide resins（Husky Bick PPO640）, 30 parts of polystyrene（Strange beautiful PG-383）, 30 parts of ASA resins
（Strange beautiful PW-978B）, 20 parts of silica（Xinyi Hong Run）, 20 parts of titanium oxide（Just magnificent science and technology in Tianjin）, 0.8 part it is silane coupled
Agent KH550（Nanjing Shuguang Chemical General Plant）, 1 part of antioxidant 1010（Nanjing Milan chemical industry）, 1 part of silicone powder（Triumphant outstanding polymer plastic
Expect toughening material Co., Ltd）, 30 parts of aluminium hydroxides（Weifang Far East rubber and plastic science and technology）With 2 parts of bisphenol-As-bis-（Diphenyl phosphoester）
（BDP, the normal space chemical industry in Changzhou）It is well mixed through high-speed stirred.After being well mixed through homogenizer, 190oC、130 kg/
cm2Lower hot pressed sintering 12h and then 260oC、150kg/cm2Lower hot pressed sintering 12h, bonding sheet is obtained after through turning, its
Thickness about 0.110 ~ 0.115mm；The bonding sheet two sides is covered with polyphenylene oxide plate and FR-4 plates respectively, multilayer is obtained after high-temperature laminating
Plate, then 170o5min is handled under C, after being repeated 5 times, can be observed that multi-layer sheet is non-foaming, and bonding sheet and polyphenylene oxide plate are compound
Place is not stratified, and outward appearance, intensity and toughness are several unchanged.
Comparative example 1
In the case of inapplicable bonding sheet, multilayer is prepared through technique pressing in the same manner as in Example 1 in PTFE plates
Plate.
Comparative example 2
In the case of inapplicable bonding sheet, PTFE plates and polyphenylene oxide plate are pressed into system through technique in the same manner as in Example 4
It is standby to obtain multi-layer sheet.
Comparative example 3
In the case of inapplicable bonding sheet, polyphenylene oxide plate is prepared through technique pressing in the same manner as in Example 5 more
Laminate.
Comparative example 4
In the case of inapplicable bonding sheet, polyphenylene oxide plate and FR-4 plates are pressed through technique in the same manner as in Example 7 and made
It is standby to obtain multi-layer sheet.
Compared to traditional handicraft, the present invention can quickly and easily adjust the area of bonding sheet by adjusting turning process parameter
And thickness, the bonding sheet uniformity being thus prepared are good.Turning process is widely used, universality is strong.For different applications
Scene, the present invention is from suitable resin material, inorganic filler and processing aid, optimum organization so that the dielectricity of bonding sheet
The suitable corresponding use occasion such as energy, toughness and viscosity, realization can be with multiple polymers base, different dielectric properties, different surfaces
It is good compound between the prepreg of structure.Compatibility is good between prepreg, cohesive force is strong, preparation-obtained multi-layer sheet
Heat-mechanical performance is good, stabilization is high, hygroscopicity is low, can meet every combination property requirement of the different communication field to copper-clad plate.This
Outside, operating process of the present invention is simple, universality is strong, preparation condition is gentle, production cost is low, is easy to mass and scale metaplasia
Production, there is the basic and wide application prospect of good industrialized production.
Note：It is characteristic value above；Z axis CTE is tested to obtain by the TMA of IPC TM-650 2.4.24 Mettler 3000.
Above example is not that the content of composition in the present invention is imposed any restrictions.Every technology according to the present invention is real
Any subtle modifications, equivalent variations and modifications that matter or composition composition or content are made to above example, still fall within this
In the range of inventive technique scheme.
Claims (6)
1. a kind of bonding sheet for copper-clad plate, it is characterised in that the specific preparation process of bonding sheet for copper-clad plate is：Weigh resin, nothing
Machine filler and auxiliary agent, it is agitated to be well mixed and then bonding sheet is prepared through hot pressed sintering-turning process；It is described viscous
The thickness of sheeting is 0.005 ~ 5mm；
Described resin is polyolefin, polyamide, polyimides, polyether-ketone, polyether-ether-ketone, makrolon, polyarylether, polyarylphosphorus
Ether, polyether sulphone, polyaryl thioether sulfone, PAEK, polyarylene sulfide ketone, polyethersulfone ketone, polyether sulphone nitrile, polyaryl thioether sulfone nitrile,
Polyphenylene quinoxaline, phenolic resin, epoxy resin, cyanate ester resin, polyester, polyformaldehyde, polyureas, polyurethane, acrylonitrile-benzene second
Alkene-acrylate copolymer, acrylonitritrile-styrene resin, methacrylate-styrol copolymer, acrylic nitrile-butadiene two
Alkene-styrol copolymer, ethylene-tetrafluoroethylene copolymer, SEBS, styrene-butadiene-styrene, styrene-different
Isoprene-styrene copolymer, styrene-polyolefin-styrol copolymer, SAN, butadiene-styrene rubber,
One or more mixtures in nitrile rubber and cellulose and its derivates；
Described inorganic filler is 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, stone
One kind or several mixtures in ink, graphite oxide, fluorographite, talcum powder, mica powder, kaolin and clay；It is described
Inorganic filler account for 0 ~ 85wt% of resin；
Described hot pressed sintering temperature is 120 ~ 430oC, pressure is 40 ~ 200kg/cm2, the time is 2 ~ 72h；
Described turning speed is 10 ~ 250m/min, 0.005 ~ 5mm/r of the amount of feeding, 0.005 ~ 5mm of cutting depth.
2. bonding sheet for copper-clad plate as claimed in claim 1, it is characterised in that described auxiliary agent is coupling agent, fire retardant, resisted
One or more mixtures in oxygen agent and releasing agent.
3. bonding sheet for copper-clad plate as claimed in claim 2, it is characterised in that described coupling agent is silane coupler, metatitanic acid
Ester coupling agent, aluminate coupling agent, boric acid ester coupler, zirconium ester coupling agent, rare-earth coupling agent, phosphate coupling agent and sulphonyl
One or more mixtures in nitrine coupling agent and its derivative, its dosage account for 0 ~ 5wt% of inorganic filler.
4. bonding sheet for copper-clad plate as claimed in claim 2, it is characterised in that described fire retardant is phosphorus flame retardant, nitrogen system
Fire retardant, magnalium flame retardant, boron zinc flame retardant, molybdenum tin flame retardant, antimony oxide and its one kind in derivative or
A variety of mixtures；Its dosage is 0 ~ 50wt% of resin.
5. bonding sheet for copper-clad plate as claimed in claim 2, it is characterised in that described 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；Its dosage is 0 ~ 3wt% of resin.
6. bonding sheet for copper-clad plate as claimed in claim 2, it is characterised in that described releasing agent is aliphatic acid, aliphatic acid
Salt, fatty acid ester, amide-type, paraffin, glycerine, vaseline, silicone powder, silicone oil, polyolefin-wax, oxidized polyolefin waxes, talcum powder,
One or more mixtures in mica powder, clay and clay and its derivative；Its dosage is 0 ~ 5wt% of resin.
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| CN107641483A (en) * | 2017-07-17 | 2018-01-30 | 常州中英科技股份有限公司 | A kind of high heat conduction bonding sheet and preparation method thereof |
| CN110733225B (en) * | 2018-10-19 | 2021-07-09 | 嘉兴学院 | Preparation method of high-thermal-conductivity high-toughness copper-clad plate |
| CN109628050A (en) * | 2018-10-23 | 2019-04-16 | 厦门韦尔通科技有限公司 | A kind of resistance to fire-retardant adhesive and preparation method thereof |
| CN112442202B (en) * | 2019-09-04 | 2022-10-18 | 广东生益科技股份有限公司 | Interlayer bonding sheet for multilayer board and preparation method and application thereof |
| CN112538184B (en) * | 2019-09-04 | 2022-10-18 | 广东生益科技股份有限公司 | Interlayer bonding sheet for multilayer board and preparation method and application thereof |
| CN111849003B (en) * | 2020-08-06 | 2021-01-19 | 广东创辉鑫材科技股份有限公司 | Preparation method of rubber sheet for filling holes in slotted holes of metal substrate |
| CN114369428B (en) * | 2021-11-05 | 2023-08-11 | 常州中英科技股份有限公司 | Bonding sheet with low thermal expansion coefficient for high-frequency copper-clad plate |
| CN114369239A (en) * | 2021-11-05 | 2022-04-19 | 常州中英科技股份有限公司 | Non-fiber-reinforced low-thermal-expansion fluorine-containing resin-based high-frequency copper-clad plate and preparation method thereof |
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| US6495244B1 (en) * | 2000-09-07 | 2002-12-17 | Oak-Mitsui, Inc. | Manufacturing fire retardant circuit boards without the use of fire retardant resin additives |
| CN1380812A (en) * | 2002-02-07 | 2002-11-20 | 泰州市旺灵绝缘材料厂 | Composite medium copper-covered aluiminium base plate and its production method |
| DE602006021155D1 (en) * | 2005-02-03 | 2011-05-19 | Asahi Kasei Chemicals Corp | RESIN COMPOSITION FOR ELECTRONIC AND ELECTRICAL COMPONENTS OF HIGH FREQUENCY APPLICATIONS AND SHAPED PRODUCT THEREOF |
| CN200941382Y (en) * | 2006-08-31 | 2007-08-29 | 焦作市恒元电子材料有限公司 | High heat transferring metal-base copper coated board |
| CN106142754A (en) * | 2016-07-06 | 2016-11-23 | 武汉联恒电子材料有限公司 | A kind of high-frequency circuit base material of resin combination and manufacture thereof |
| CN106113802B (en) * | 2016-08-16 | 2018-04-13 | 中国电子科技集团公司第三十八研究所 | A kind of preparation method for the microwave copper-clad plate for reducing Z axis thermal coefficient of expansion |
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