CN106590452A - Adhesive sheet for copper-clad laminate - Google Patents
Adhesive sheet for copper-clad laminate Download PDFInfo
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- CN106590452A CN106590452A CN201611051432.0A CN201611051432A CN106590452A CN 106590452 A CN106590452 A CN 106590452A CN 201611051432 A CN201611051432 A CN 201611051432A CN 106590452 A CN106590452 A CN 106590452A
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- copper
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- clad plate
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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
-
- 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
- C09J11/00—Features of adhesives not provided for in group C09J9/00, e.g. additives
- C09J11/02—Non-macromolecular additives
- C09J11/04—Non-macromolecular additives inorganic
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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
- 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
-
- 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
- C09J11/00—Features of adhesives not provided for in group C09J9/00, e.g. additives
- C09J11/08—Macromolecular additives
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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
- 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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- 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
- 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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- 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
- 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
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- 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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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L2205/00—Polymer mixtures characterised by other features
- C08L2205/03—Polymer mixtures characterised by other features containing three or more polymers in a blend
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L2205/00—Polymer mixtures characterised by other features
- C08L2205/03—Polymer mixtures characterised by other features containing three or more polymers in a blend
- C08L2205/035—Polymer mixtures characterised by other features containing three or more polymers in a blend containing four or more polymers in a blend
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- 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
- C09J2425/00—Presence of styrenic polymer
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- 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
- C09J2427/00—Presence of halogenated polymer
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- C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
- C09J2471/00—Presence of polyether
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Abstract
The invention belongs to the field of communication materials, and in particular relates to an adhesive sheet for a copper-clad laminate. The adhesive sheet with a controllable area, a smooth surface, a uniform easy-to-control thickness and suitable toughness and viscosity is prepared by mixing uniformly resin, an inorganic filler and an auxiliary agent, then hot pressing, sintering, turning, and the like. According to actual application scenes, various types of composite adhesive sheets are prepared by selecting of the suitable resin and inorganic filler, and prepregs with various polymer matrixes, different dielectric properties and different surface structures can be well composited. In particular, due to the use of glass fiber and other reinforcing materials, the dielectric properties of the adhesive sheet can be adjusted to a large extent, and the practicability and universality of the adhesive sheet can be effectively enhanced. In the invention, the adhesive sheets and the prepregs are well compatible and strong in adhesion, and a prepared multilayer board has good thermal and mechanical performances, high stability and low hygroscopicity, and can meet comprehensive performance requirements of different communication fields on the copper-clad laminate.
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 electron trade is in the high speed development stage, is just progressively becoming one of pillar industry of various countries.As
The copper-clad plate of one of information electronic industries critical material, has been widely used in communication base station, satellite, navigation positioning system, automatically
The fields such as vending machine, computer, mobile phone.Prepreg as copper-clad plate one of basic component units, 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 various
Polymer matrix, different dielectric properties, the prepreg of different surfaces structure are compound to together, to realize the polynary of copper-clad plate performance
Change, work that can be simultaneously normal in multiple frequency ranges, stable.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 are reported using the bonding sheet of commercialization（As gathered
The compound Kapton series membranes of acid imide-fluorine material）For manufacturing high performance copper-clad plate.However, commercialization bonding sheet composition
It is fixed, can use range it is little and expensive.Chinese patent CN101885900A, CN102794949B, CN103731980A,
CN105898984A, CN101880441A and CN102558861B etc. there is provided various bonding sheet for copper-clad plate preparation method,
But have that the dielectric properties adjustable extent of bonding sheet is narrower, solidification process is complicated, technique is difficult to control to and causes production difficulty to increase
Greatly, and due to being related to the use of various 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 that the present invention is provided, its concrete preparation process is：Weigh resin, inorganic filler and help
Agent, after agitated mix homogeneously, then Jing hot pressed sinterings-turning process prepares bonding sheet；The thickness of the bonding sheet is
0.005~5mm。
Inventor has found that bonding sheet for copper-clad plate prepares it and all refer to glass-fiber-fabric or glass fibre etc. in prior art
The use of reinforcing material, or do bonding sheet using curable system；The former causes because of reinforcing material itself dielectric constant height
The dielectric properties adjustable extent of bonding sheet significantly narrows；The latter's solidification process complexity, technique are difficult to control to and cause production difficult
Degree increase.
By after resin, inorganic filler and auxiliary agent mix homogeneously, the technique such as Jing hot pressed sinterings-turning can quickly connect the present invention
Controllable area, surfacing, the thickness uniformly suitable bonding sheet of easily-controllable, toughness and viscosity has been prepared continuously.According to reality
Application scenarios, the present invention has prepared all kinds of compoiste adhering pieces by selecting suitable resin and inorganic filler, realizes
It is good compound between multiple polymers base, different dielectric properties, the prepreg of different surfaces structure.Especially because being not used
The reinforcing materials such as glass fibre, greatly improve the adjustable scope of bonding sheet dielectric properties, effectively enhance the reality of bonding sheet
With property and universality.In the present invention, the compatibility is good between bonding sheet and prepreg, cohesive force is strong, preparation-obtained multilamellar
Plate heat-mechanical performance is good, stable high, hygroscopicity is low, can meet different communication field and every combination property of copper-clad plate is required.
Operating process of the present invention is simple, universality is strong, preparation condition is gentle, low production cost, be easy to mass and scale
Metaplasia is produced, with the basic and wide application prospect of good industrialized production.
The multi-layer sheet that bonding sheet of the present invention is obtained after pressing with prepreg processes at high temperature 5min, is repeated 5 times not
Generation foaming, 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) reach V1 or V0,288oIt is resistance to dip solderability more than 20 times under C, 288 after pressure cooker steaming and decoctingoUnder C it is resistance to dip solderability still above
20 times.
In the present invention, described resin is fluorine resin（As politef (PTFE), perfluoroethylene-propylene (FEP,
F46), tetrafluoroethylene-perfluoro alkoxy vinyl ethers copolymer (PFA) etc.）, polyolefin（Such as polypropylene, polybutadiene, polyphenyl
Ethylene etc.）, it is polyamide, polyimides, polyether-ketone, polyether-ether-ketone, Merlon, 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 mixture of one or more in derivant.
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, Pulvis Talci, 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 the mixing of one or more 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 ester idol
Connection agent（Such as DN-27, DN-37）With the mixture of one or more in sulfonyl azide coupling agent and its derivant, its consumption
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, sodium metaborate, Firebrake ZB）, molybdenum stannum flame retardant（Such as zinc, oxidation
Molybdenum etc.）, one or more in antimony oxide and its derivant of mixture；Its consumption 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) propanoic acid] pentaerythritol ester, hexanediol [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- diacetyls adipyl two etc.）, one or more in ZnS, ZnO and MgO
Mixture；Its consumption is 0 ~ 3wt% of resin.
In the present invention, described releasing agent is fatty acid（Such as stearic acid, Palmic acid, lauric acid）, soap（As firmly
Fat acid calcium, zinc stearate etc.）, fatty acid ester（Such as stearyl stearate, glycerol tristearate, the double stearates of tetramethylolmethane
Deng）, amide-type（Erucyl amide）, paraffin, glycerol, vaseline, silicone powder, silicone oil（Such as polydimethylsiloxane）, polyolefin
Wax（Such as Tissuemat E, polypropylene wax）, oxidized polyolefin waxes（Such as OPE, its chlorinated polypropylene wax）, Pulvis Talci,
The mixture of one or more in mica powder, potter's clay and clay and its derivant；Its consumption is 0 ~ 5wt% of resin.
In the present invention, described hot pressed sintering temperature is 120 ~ 430oC, pressure are 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。
Specific embodiment
A kind of bonding sheet for copper-clad plate and its preparation side that the present invention is provided 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 dioxide
（Just magnificent science and technology in Tianjin）With 1 part of KH550（Nanjing Shuguang Chemical General Plant）, after Jing homogenizer mix homogeneously,
360oC、120 kg/cm2After lower hot pressed sintering 24h, Jing turning obtains bonding sheet, its thickness about 0.095 ~ 0.105mm；Should
Multi-layer sheet is obtained after bonding sheet and PTFE plate high-temperature laminatings, subsequently 300o5min is processed under C, after being repeated 5 times, be can be observed many
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 titanium dioxide
（Just magnificent science and technology in Tianjin）With 2 parts of KH550（Nanjing Shuguang Chemical General Plant）, after Jing homogenizer mix homogeneously,
430oC、200 kg/cm2After lower hot pressed sintering 24h, Jing turning obtains bonding sheet, its thickness about 0.095 ~ 0.105mm；Should
Multi-layer sheet is obtained after bonding sheet and PTFE plate high-temperature laminatings, subsequently 300o5min is processed under C, after being repeated 5 times, be can be observed many
Laminate 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
Ethylene-tetrafluoroethylene copolymer (ETFE)（Du Pont Teflon Tefzel ETFE750）, 50 parts of titanium dioxide（Positive China in Tianjin
U.S. science and technology）, 30 parts of silicon dioxide（Xinyi Hong Run）With 1 part of KH550（Nanjing Shuguang Chemical General Plant）, the mixing of Jing homogenizers is
After even, 380oC、150 kg/cm2After lower hot pressed sintering 24h, Jing turning obtains bonding sheet, and its thickness about 0.0105 ~
0.115mm；Multi-layer sheet will be obtained after the bonding sheet and PTFE plate high-temperature laminatings, subsequently 300o5min is processed under C, is repeated 5 times
Afterwards, multi-layer sheet can be observed non-foaming, not stratified, 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 resin（Strange U.S. PA-717C）, 70 parts of aluminium oxidies
（Zibo perseverance nation）, 1 part of KH550（Nanjing Shuguang Chemical General Plant）, 0.8 part of antioxidant 225（Ciba refines）, 10 parts of bisphenol-As-bis-
（Diphenyl phosphoester）（The normal space chemical industry in Changzhou）With 0.5 part of zinc stearate（Plastic additive processing company limited is protected in Hebei celebrating）, Jing
After homogenizer mix homogeneously, 270oC、130 kg/cm2After lower hot pressed sintering 12h, then 350oC、150 kg/
cm2Lower hot pressed sintering 12h, the Jing turning with after obtains bonding sheet, its thickness about 0.010 ~ 0.110mm；By the bonding sheet two sides point
PTFE plates and polyphenylene oxide plate are not covered with, multi-layer sheet are obtained after high-temperature laminating, subsequently 240o5min is processed under C, after being repeated 5 times,
Multi-layer sheet can be observed non-foaming, bonding sheet is not stratified with PTFE plates and the compound place of polyphenylene oxide plate, and outward appearance, intensity and toughness
It is several unchanged.
Embodiment 5
By 40 parts of polyphenylene oxide resins（Husky Bick PPO640）, 70 parts of polystyrene（Strange U.S. PG-383）, 20 parts of silicon oxides（Xinyi is grand
Profit）, 20 parts of titanium oxides（Just magnificent science and technology in Tianjin）, 0.5 part of Silane coupling agent KH550（Nanjing Shuguang Chemical General Plant）, 1 part it is anti-
Oxygen agent 1010（Nanjing Milan chemical industry）, 1 part of Fischer-Tropsch wax（Nippon Seiro Co., Ltd. FT115）, 30 parts of aluminium hydroxide（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）Jing high-speed stirred mix homogeneously.Jing is high
After fast blender mix homogeneously, 220oC、110 kg/cm2After lower hot pressed sintering 16h, then 280oC、140 kg/cm2
Lower hot pressed sintering 8h, the Jing turning with after obtains bonding sheet, its thickness about 0.105 ~ 0.110mm；The bonding sheet two sides is covered respectively
Upper polyphenylene oxide plate, obtains multi-layer sheet, subsequently 160 after high-temperature laminatingo5min is processed under C, after being repeated 5 times, multilamellar can be observed
Plate 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 resin（It is strange beautiful
PA-717C）, 70 parts of aluminium oxidies（Zibo perseverance nation）, 1 part of KH550（Nanjing Shuguang Chemical General Plant）, 1 part of antioxidant 225（Ciba is smart
Change）, 6 parts of bisphenol-As-bis-（Diphenyl phosphoester）（The normal space chemical industry in Changzhou）With 0.5 part of zinc stearate（Hebei celebrating is protected plastic additive and is added
Work company limited）, after Jing homogenizer mix homogeneously, 260oC、130 kg/cm2After lower hot pressed sintering 16h, then
300oC、150 kg/cm2Lower hot pressed sintering 8h, the Jing turning with after obtains bonding sheet, its thickness about 0.095 ~ 0.105mm；This is glued
Sheeting two sides is covered with respectively polyphenylene oxide plate, multi-layer sheet is obtained after high-temperature laminating, subsequently 210o5min is processed under C, is repeated 5 times
Afterwards, multi-layer sheet can be observed non-foaming, not stratified, 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 U.S. PW-978B）, 20 parts of ABS resin（Strange U.S. PA-
717C）, 50 parts of aluminium oxidies（Zibo perseverance nation）, 10 parts of silicon oxides（Xinyi Hong Run）, 1 part of KH550（Nanjing Shuguang Chemical General Plant）、1
Part antioxidant 225（Ciba refines）, 5 parts of bisphenol-As-bis-（Diphenyl phosphoester）（The normal space chemical industry in Changzhou）, 10 parts of aluminium hydroxide（The Weihe River
Mill Far East rubber and plastic science and technology）With 0.5 part of zinc stearate（Plastic additive processing company limited is protected in Hebei celebrating）, the mixing of Jing homogenizers
After uniform, 220oC、120 kg/cm2After lower hot pressed sintering 16h, then 280oC、150 kg/cm2Lower hot pressed sintering 8h,
The Jing turning with after obtains bonding sheet, its thickness about 0.105 ~ 0.115mm；By the bonding sheet two sides be covered with respectively polyphenylene oxide plate and
FR-4 plates, obtain multi-layer sheet, subsequently 190 after high-temperature laminatingo5min is processed under C, after being repeated 5 times, multi-layer sheet can be observed not
Foaming, bonding sheet is not stratified with FR-4 plates and the compound place of polyphenylene oxide plate, and outward appearance, intensity and toughness are several unchanged.
Embodiment 8
Weigh 90 parts of polystyrene（Strange U.S. PG-383）, 20 parts of ASA resins（Strange U.S. PW-978B）, 10 parts of ABS resin（Strange U.S. 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
KH550（Nanjing Shuguang Chemical General Plant）, 50 parts of aluminium hydroxide（Weifang Far East rubber and plastic science and technology）With 0.5 part of zinc stearate（Celebrate in Hebei
Protect plastic additive processing company limited）, after Jing homogenizer mix homogeneously, 120oC、40 kg/cm2Lower hot pressed sintering
After 16h, then 180oC、100 kg/cm2Lower hot pressed sintering 8h, the Jing turning with after obtains bonding sheet, and its thickness about 0.105 ~
0.115mm；The bonding sheet two sides is covered with into respectively polyphenylene oxide plate, multi-layer sheet is obtained after high-temperature laminating, subsequently 120oProcess under C
5min, after being repeated 5 times, it is non-foaming to can be observed multi-layer sheet, and bonding sheet is not stratified with the compound place of polyphenylene oxide plate, and 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 U.S. PG-383）, 30 parts of ASA resins（It is strange beautiful
PW-978B）, 20 parts of silicon oxides（Xinyi Hong Run）, 20 parts of titanium oxides（Just magnificent science and technology in Tianjin）, 0.8 part of silane coupler
KH550（Nanjing Shuguang Chemical General Plant）, 1 part of antioxidant 1010（Nanjing Milan chemical industry）, 1 part of silicone powder（Triumphant outstanding high molecule plastic
Toughening material company limited）, 30 parts of aluminium hydroxide（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）Jing high-speed stirred mix homogeneously.After Jing homogenizer mix homogeneously, 190oC、130 kg/
cm2After lower hot pressed sintering 12h, then 260oC、150kg/cm2Lower hot pressed sintering 12h, the Jing turning with after obtains bonding sheet, its
Thickness about 0.110 ~ 0.115mm；The bonding sheet two sides is covered with into respectively polyphenylene oxide plate and FR-4 plates, multilamellar is obtained after high-temperature laminating
Plate, subsequently 170o5min is processed under C, after being repeated 5 times, it is non-foaming to can be observed multi-layer sheet, 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, PTFE plates Jing technique pressings in the same manner as in Example 1 are prepared into multi-layer sheet.
Comparative example 2
In the case of inapplicable bonding sheet, the technique pressing in the same manner as in Example 4 of PTFE plates and polyphenylene oxide plate Jing is prepared into
To multi-layer sheet.
Comparative example 3
In the case of inapplicable bonding sheet, polyphenylene oxide plate Jing technique pressings in the same manner as in Example 5 are prepared into multi-layer sheet.
Comparative example 4
In the case of inapplicable bonding sheet, technique pressing of the polyphenylene oxide plate with FR-4 plates Jing in the same manner as in Example 7 is prepared into
To 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 for thus preparing is good.Turning process is widely used, universality is strong.For different applications
Scene, the present invention selects 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.The compatibility is good between prepreg, cohesive force is strong, preparation-obtained multi-layer sheet
Heat-mechanical performance is good, stable high, hygroscopicity is low, can meet different communication field and every combination property of copper-clad plate is required.This
Outward, operating process of the present invention is simple, universality is strong, preparation condition is gentle, low production cost, be easy to mass and scale metaplasia
Produce, with the basic and wide application prospect of good industrialized production.
Note：More than it is eigenvalue；Z axis CTE is obtained by the TMA of IPC TM-650 2.4.24 Mettler 3000 tests.
Above example is not imposed any restrictions to the content of compositionss in the present invention.It is every according to the present invention technical spirit or
Any trickle amendment, equivalent variations and modification that compositionss composition or content are made to above example, still fall within the present invention
In the range of technical scheme.
Claims (10)
1. a kind of bonding sheet for copper-clad plate, it is characterised in that the concrete preparation process of bonding sheet for copper-clad plate is：Weigh resin, nothing
Machine filler and auxiliary agent, after agitated mix homogeneously, then Jing hot pressed sinterings-turning process and prepare bonding sheet；It is described viscous
The thickness of sheeting is 0.005 ~ 5mm.
2. bonding sheet for copper-clad plate as claimed in claim 1, it is characterised in that described resin be fluorine resin, polyolefin,
Polyamide, polyimides, polyether-ketone, polyether-ether-ketone, Merlon, polyarylether, poly arylidene thio-ester, polyether sulphone, polyaryl thioether sulfone,
PAEK, polyarylene sulfide ketone, polyethersulfone ketone, polyether sulphone nitrile, polyaryl thioether sulfone nitrile, polyphenylene quinoxaline, phenolic resin, ring
Oxygen tree fat, cyanate ester resin, polyester, polyformaldehyde, polyureas, polyurethane, acrylonitrile-styrene-acrylic ester copolymer, propylene
Nitrile-styrol copolymer, methacrylate-styrol copolymer, acrylonitrile-butadiene-styrene copolymer, ethylene-four
Fluoride copolymers, SEBS, styrene-butadiene-styrene, styrene-isoprene-styrene copolymer, benzene
Ethylene-polyolefin-styrol copolymer, SAN, butadiene-styrene rubber, nitrile rubber and cellulose and its spread out
The mixture of one or more in biology.
3. bonding sheet for copper-clad plate as claimed in claim 1, it is characterised in that 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, graphite oxide, fluorine
One kind or several mixture in graphite, Pulvis Talci, mica powder, Kaolin and clay；Described inorganic filler accounts for tree
0 ~ 85wt% of fat.
4. bonding sheet for copper-clad plate as claimed in claim 1, it is characterised in that described auxiliary agent is coupling agent, fire retardant, anti-
The mixture of one or more in oxygen agent and releasing agent.
5. bonding sheet for copper-clad plate as claimed in claim 4, 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
The mixture of one or more in nitrine coupling agent and its derivant, its consumption accounts for 0 ~ 5wt% of inorganic filler.
6. bonding sheet for copper-clad plate as claimed in claim 4, it is characterised in that described fire retardant is phosphorus flame retardant, nitrogen system
One kind in fire retardant, magnalium flame retardant, boron zinc flame retardant, molybdenum stannum flame retardant, antimony oxide and its derivant or
Various mixture；Its consumption is 0 ~ 50wt% of resin.
7. bonding sheet for copper-clad plate as claimed in claim 4, 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 of mixture；Its consumption is 0 ~ 3wt% of resin.
8. bonding sheet for copper-clad plate as claimed in claim 4, it is characterised in that described releasing agent is fatty acid, fatty acid
Salt, fatty acid ester, amide-type, paraffin, glycerol, vaseline, silicone powder, silicone oil, polyolefin-wax, oxidized polyolefin waxes, Pulvis Talci,
The mixture of one or more in mica powder, potter's clay and clay and its derivant；Its consumption is 0 ~ 5wt% of resin.
9. bonding sheet for copper-clad plate as claimed in claim 1, it is characterised in that described hot pressed sintering temperature is 120 ~ 430oC、
Pressure is 40 ~ 200kg/cm2, the time is 2 ~ 72h.
10. bonding sheet for copper-clad plate as claimed in claim 1, it is characterised in that described turning speed is 10 ~ 250m/min,
0.005 ~ 5mm/r of the amount of feeding, 0.005 ~ 5mm of cutting depth.
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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 |
| 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 |
| CN110733225A (en) * | 2018-10-19 | 2020-01-31 | 嘉兴学院 | Preparation method of high-thermal-conductivity high-toughness copper-clad plate |
| CN111849003A (en) * | 2020-08-06 | 2020-10-30 | 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 |
| CN112442202A (en) * | 2019-09-04 | 2021-03-05 | 广东生益科技股份有限公司 | Interlayer bonding sheet for multilayer board and preparation method and application thereof |
| CN112538184A (en) * | 2019-09-04 | 2021-03-23 | 广东生益科技股份有限公司 | Interlayer bonding sheet for multilayer board and preparation method and application thereof |
| 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 |
| CN114369428A (en) * | 2021-11-05 | 2022-04-19 | 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 |
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| CN112538184A (en) * | 2019-09-04 | 2021-03-23 | 广东生益科技股份有限公司 | Interlayer bonding sheet for multilayer board and preparation method and application thereof |
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| 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 |
| 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 |
| CN114369428A (en) * | 2021-11-05 | 2022-04-19 | 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 |
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