CN106604535A - Thermal conductive non-plastic single-sided flexible copper clad laminate and the manufacturing method thereof - Google Patents
Thermal conductive non-plastic single-sided flexible copper clad laminate and the manufacturing method thereof Download PDFInfo
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- CN106604535A CN106604535A CN201611198973.6A CN201611198973A CN106604535A CN 106604535 A CN106604535 A CN 106604535A CN 201611198973 A CN201611198973 A CN 201611198973A CN 106604535 A CN106604535 A CN 106604535A
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- H—ELECTRICITY
- H05—ELECTRIC TECHNIQUES NOT OTHERWISE PROVIDED FOR
- H05K—PRINTED CIRCUITS; CASINGS OR CONSTRUCTIONAL DETAILS OF ELECTRIC APPARATUS; MANUFACTURE OF ASSEMBLAGES OF ELECTRICAL COMPONENTS
- H05K1/00—Printed circuits
- H05K1/02—Details
- H05K1/03—Use of materials for the substrate
- H05K1/0313—Organic insulating material
- H05K1/0353—Organic insulating material consisting of two or more materials, e.g. two or more polymers, polymer + filler, + reinforcement
- H05K1/036—Multilayers with layers of different types
-
- H—ELECTRICITY
- H05—ELECTRIC TECHNIQUES NOT OTHERWISE PROVIDED FOR
- H05K—PRINTED CIRCUITS; CASINGS OR CONSTRUCTIONAL DETAILS OF ELECTRIC APPARATUS; MANUFACTURE OF ASSEMBLAGES OF ELECTRICAL COMPONENTS
- H05K1/00—Printed circuits
- H05K1/02—Details
- H05K1/03—Use of materials for the substrate
- H05K1/0313—Organic insulating material
- H05K1/0353—Organic insulating material consisting of two or more materials, e.g. two or more polymers, polymer + filler, + reinforcement
- H05K1/0373—Organic insulating material consisting of two or more materials, e.g. two or more polymers, polymer + filler, + reinforcement containing additives, e.g. fillers
-
- H—ELECTRICITY
- H05—ELECTRIC TECHNIQUES NOT OTHERWISE PROVIDED FOR
- H05K—PRINTED CIRCUITS; CASINGS OR CONSTRUCTIONAL DETAILS OF ELECTRIC APPARATUS; MANUFACTURE OF ASSEMBLAGES OF ELECTRICAL COMPONENTS
- H05K3/00—Apparatus or processes for manufacturing printed circuits
- H05K3/02—Apparatus or processes for manufacturing printed circuits in which the conductive material is applied to the surface of the insulating support and is thereafter removed from such areas of the surface which are not intended for current conducting or shielding
- H05K3/022—Processes for manufacturing precursors of printed circuits, i.e. copper-clad substrates
-
- H—ELECTRICITY
- H05—ELECTRIC TECHNIQUES NOT OTHERWISE PROVIDED FOR
- H05K—PRINTED CIRCUITS; CASINGS OR CONSTRUCTIONAL DETAILS OF ELECTRIC APPARATUS; MANUFACTURE OF ASSEMBLAGES OF ELECTRICAL COMPONENTS
- H05K2201/00—Indexing scheme relating to printed circuits covered by H05K1/00
- H05K2201/02—Fillers; Particles; Fibers; Reinforcement materials
- H05K2201/0203—Fillers and particles
- H05K2201/0206—Materials
- H05K2201/0209—Inorganic, non-metallic particles
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- Engineering & Computer Science (AREA)
- Microelectronics & Electronic Packaging (AREA)
- Manufacturing & Machinery (AREA)
- Laminated Bodies (AREA)
Abstract
The invention discloses a thermal conductive non-plastic single-sided flexible copper clad laminate and the manufacturing method thereof. The thermal conductive non-plastic single-sided flexible copper clad laminate comprises the following elements attached and connected in sequence: a copper foil layer, a first polyamic acid resin layer and a second polyamic acid resin layer wherein the second polyamic acid resin layer contains an artificial graphite powder filler, and the thermal conductivity of the artificial graphite powder is 300 to 600 W / (M k). The method for producing the thermal conductive non-plastic single-sided flexible copper clad laminate includes the following steps: uniformly coating a layer of B-type polyamic acid resin containing artificial graphite powder on the surface of the first polyamic acid resin layer and obtaining the copper clad laminate after heat-treatment. In the copper clad laminate of the invention, the thermal conductive filler is self-made artificial graphite powder whose performance is stable, thermal conductivity is high, and production is convenient. All enable it for large scale production. Secondly, the thermal conductive single-sided flexible copper clad laminate has good dimensional stability, good heat resistance, and good mechanical and electrical characteristics. At the same time with good thermal conductivity and heat dissipation, it can meet the cooling needs of modern electronic equipment.
Description
Technical field
The invention belongs to flexibility coat copper plate technical field, more particularly to a kind of heat-conducting type without glue single-face flexibility copper-clad board and
Its manufacture method.
Background technology
Flexibility coat copper plate (FCCL) is the processing base material of flexible printed-circuit board (FPC), be widely used to national defense industry,
Electronics industry, auto industry, information industry field, such as Aero-Space, mobile phone, notebook computer, liquid crystal flat panel display, number
The various electronic equipments such as camera, automobile, sound equipment.With modern microelectronic technology high-speed develop, electronic equipment become it is light, thin, short,
Little and multi-functional, the density of loading member is increasing in electronic equipment, and power density is increasing, more and more so as to produce
Heat, heat forms aggregation in electronic equipment, if can not discharge in time will heat build-up produce high temperature, to electronic equipment
Stability, reliability, service life has a negative impact.Conventional flex copper-clad plate can not meet radiating requirements, therefore, have
Necessity improves its heat conduction, heat-sinking capability on the basis of conventional flex copper-clad plate, develops heat-conduction flexible copper-clad plate material.
At present flexible copper-clad panel material is divided into glue-type and gum-free.There is the adhesive layer in glue-type flexible copper-clad plate main
For modified epoxy or acrylic resin modified, adhesive layer is introduced after both resins, and the thermostability of material will be by shadow
Ring, it is impossible to reach the high thermal stability of polyimides, overall thermostability will be substantially reduced；Simultaneously the dimensional stability of material also can
It is affected, thermal coefficient of expansion (CTE) can be significantly raised.It is exactly thermosetting polyamides except Copper Foil in glue-free flexible copper-clad plate
Imines (one side) or TPI (two-sided), overall performance is excellent, therefore, glue-free flexible copper-clad plate becomes research and development
Emphasis and direction.
Patent CN201210291200.8 heat-conducting double-sided flexibility coat copper plate and preparation method thereof discloses following technology, heat conduction
Double side flexible copper coated board includes the first Copper Foil and the first heat conduction polyimide layer for being coated on the first Copper Foil, the first heat conduction
Heat conduction adhesive layer is coated with polyimide layer, heat conduction adhesive layer on covered the second Copper Foil, heat conduction adhesive layer and
The second heat conduction polyimide layer is additionally provided between second Copper Foil, the first heat conduction polyimide layer and the second heat conduction Zou imide layers
Include heat filling and additive.Heat filling is at least one in aluminium nitride, boron nitride, carborundum, aluminium oxide.Nitridation
The easy moisture absorption hydrolysis of aluminum generates aluminium hydroxide, interrupts thermal conducting path, causes thermal conductivity low；Boron nitride is expensive, addition
Amount is low, is unsuitable for large-scale production；The carbon and graphite that carborundum is produced in process of production is difficult to remove, and conductivity is high, affects base
Material insulating properties；Aluminium oxide heat conductivity itself is not high, and radiating effect improvement is undesirable.
The content of the invention
The first object of the present invention is to provide a kind of heat-conducting type without glue single-face flexibility copper-clad board；The second object of the present invention is
A kind of manufacture method of heat-conducting type without glue single-face flexibility copper-clad board is provided.
In order to realize above-mentioned first purpose, the present invention provides a kind of heat-conducting type without glue single-face flexibility copper-clad board, including successively
Copper foil layer, the first polyamic acid resin layer and the second polyamic acid resin layer being fitted and connected, in the second polyamic acid resin layer
Containing electrographite powder filler, the heat conductivity of the electrographite powder is 300～600W/ (mk).
In order to realize above-mentioned second purpose, the present invention provides a kind of making side of the heat-conducting type without glue single-face flexibility copper-clad board
Method, comprises the following steps：
Step 1, prepares electrographite powder；Organic polymer thin-film material with highly directional degree is added under an inert atmosphere
Pressure carbonization, and heated graphitization processing is obtained electrographite film, it is post-treated after obtain electrographite powder；
Preferably, in step 1, the organic polymer of the highly directional degree is polyimides, polyamide, polythiazole, poly-
One kind in benzoxazole；The thickness of organic polymer thin-film material is 10um～150um；Carbonization temperature is 900 DEG C～1500
℃；Graphitization temperature is 2500 DEG C～3200 DEG C；By the crushing of obtained electrographite film, sand milling, particle diameter distribution DN50 is obtained little
In 20um, electrographite powder of the DN90 less than 50um.
Step 2, prepares the A type polyamic acid resins without electrographite powder；Prepare the Type B containing the electrographite powder
Polyamic acid resin；
Preferably, the detailed process of step 2 is as follows：
The A type polyamic acid resins without electrographite powder are prepared, inorganic filler is added to into highly polar aprotic solvent
In, ultrasonic disperse 30 minutes, supersonic frequency 10KHz～50KHz, inorganic filler is in suspension in highly polar aprotic solvent；
Aromatic diamine monomer is dividedly in some parts in the suspension, 50～60 DEG C of bath temperature, 800～1500r/ of mixing speed
Min, stirs 1 hour, obtains solution mixture；Aromatic series tetracarboxylic dianhydride monomer is dividedly in some parts in the solution mixture, water
15～25 DEG C of bath temperature, 500～1000r/min of mixing speed in 10～12 hours response time, obtains A type polyamic acid resins；
Preferably, the inorganic filler is silicon dioxide, titanium dioxide, aluminium sesquioxide, hectorite, Pulvis Talci, covers de-
Soil, ZSM-5 molecular sieve, borosilicate it is therein one or more.
Preferably, during A type polyamic acid resins are prepared, it is 0.5 that inorganic filler accounts for the weight ratio of all reactants
～5%, it is 2～8% that aromatic diamine monomer accounts for the weight ratio of all reactants, and aromatic series tetracarboxylic dianhydride monomer accounts for all reactions
The weight ratio of thing is 10～18%, and it is 70～85% that highly polar aprotic solvent accounts for the weight ratio of all reactants.
The Type B polyamic acid resin containing electrographite powder is prepared, electrographite powder is added to highly polar non-proton molten
In agent, ultrasonic disperse 60 minutes, supersonic frequency 10KHz～50KHz, electrographite powder is in highly polar aprotic solvent in suspended
Liquid；Aromatic diamine monomer is dividedly in some parts in the suspension, 50～60 DEG C of bath temperature, mixing speed 800～
1500r/min, stirs 1 hour, obtains solution mixture；Aromatic series tetracarboxylic dianhydride monomer is dividedly in some parts into the solution mixture
In, 15～25 DEG C of 500～1000r/min of mixing speed of bath temperature in 10～12 hours response time, obtain Type B polyamic acid
Resin.
Preferably, the highly polar aprotic solvent be DMF, N, N dimethyl acetamide, N- methyl pyrroles
Pyrrolidone, dimethyl sulfoxide it is therein one or more.
Preferably, the aromatic diamine monomer is p-phenylenediamine, 4,4- diaminodiphenyl ethers, double [4- (4 amino of 2,2-
Phenoxy group) phenyl] propane, MDA, 4,4 pairs of (3 amino-benzene oxygen) benzophenone, double (the 4- aminobenzene oxygen of 1,3-
Base) benzene, 1,3- double [4- (3- amino-benzene oxygens) benzoyl] benzene, 3,3- dimethyl -4,4- MDAs, 4,4- bis-
Diaminodiphenylmethane it is therein one or more.
Preferably, aromatic series tetracarboxylic dianhydride be pyromellitic acid anhydride, 3,3,4,4- bibenzene tetracarboxylic dianhydrides, 3,3,4,4-
Benzophenone tetracarboxylic dianhydride (BTDA), 3,3,4,4 diphenyl ether tetraformic dianhydrides, 3,3,4,4- triphen bis ether tetracarboxylic acid dianhydrides one kind therein
Or it is several.
Preferably, during Type B polyamic acid resin is prepared, it is 5 that electrographite powder accounts for the weight ratio of all reactants
～15%, it is 1～6% that aromatic diamine monomer accounts for the weight ratio of all reactants, and aromatic series tetracarboxylic dianhydride monomer accounts for all anti-
The weight ratio for answering thing is 8～15%, and it is 75～85% that highly polar aprotic solvent accounts for the weight ratio of all reactants.
Step 3, A type polyamic acid glue even applications are obtained after copper foil surface, heat treatment to cover the first polyamide
The copper foil layer of acid resin layer；In one layer of Type B polyamic acid glue of the first polyamic acid resin layer surface even application, after heat treatment
Heat-conducting type is obtained without glue single-face flexibility copper-clad board.
Preferably, Copper Foil is the one kind in electrolytic copper foil and rolled copper foil；The thickness of copper foil layer is 1～70um；First gathers
The thickness of amic acid resin bed and the second polyamic acid resin layer is 1～60um.
Preferably, the detailed process of step 3 is as follows：By A type polyamic acid resin even applications in Copper Foil matsurface, in
Except solvent 20～60 minutes at 100～160 DEG C, then obtain in 280～360 DEG C of heat treatments 30～60 minutes under nitrogen protection
Cover the copper foil layer of the first polyamic acid resin layer；In one layer of Type B polyamic acid tree of the first polyamic acid resin layer even application
Fat, except solvent 10～30 minutes at 120～180 DEG C, then under nitrogen protection in 350～400 DEG C of heat treatments 60～90 minutes,
Heat-conducting type is obtained without glue single-face flexibility copper-clad board.
The invention has the beneficial effects as follows：
Heat-conducting type of the present invention is self-control electrographite powder without the heat filling in glue single-face flexibility copper-clad board, and chemical property is steady
Fixed, particle diameter distribution DN50 is less than 20um, and DN90 is less than 50um, heat conductivity at 300～600W/ (mk), in resin system
It is well dispersed, soilless sticking agglomeration problems, outward appearance is good after coating.Observe in the secure execution mode (sem, electrographite powder in the form of sheets, particle diameter distribution
Uniformly.Preparation method of the heat-conducting type of the present invention without glue single-face flexibility copper-clad board passes through to prepare A types, two kinds of polyamic acid resins of Type B,
It is obtained that there is good dimensional stability, thermostability, machinery and electricity without glue single-face flexibility copper-clad board using coating process twice
Gas characteristic, while with good heat conduction, thermal diffusivity, disclosure satisfy that the radiating requirements of modern electronic equipment.
Description of the drawings
Fig. 1 is the heat-conducting type of an embodiment of the present invention without glue single-face flexibility copper-clad board structure schematic diagram；
Fig. 2 schemes for SEM100 times of the natural graphite powder of an embodiment of the present invention；
Fig. 3 schemes for SEM300 times of the natural graphite powder of an embodiment of the present invention；
Fig. 4 schemes for SEM100 times of the electrographite powder of an embodiment of the present invention；
Fig. 5 schemes for SEM300 times of the electrographite powder of an embodiment of the present invention.
Specific embodiment
The embodiment that here is recorded is the specific specific embodiment of the present invention, for illustrating the design of the present invention,
It is explanatory and exemplary, should not be construed as the restriction to embodiment of the present invention and the scope of the invention.Except here record
Implement exception, those skilled in the art can also be based on the application claims and description disclosure of that using aobvious
Other technical schemes being clear to, these technical schemes include any obvious using making for the embodiment recorded to here
The technical scheme of substitutions and modifications.
Electrographite powder preparation process used by following examples is as follows：
Using the organic polymer thin-film material with highly directional degree, by carbonization of pressurizeing under an inert atmosphere, and Jing is high
Warm graphitization processing is obtained electrographite film, its space structure close to single crystal graphite, carbon atom SP2 hydridization in layer, in plane
Hexagonal network structure, interlayer is chained up layered structure by Van der Waals force, with good heat conductivility.Highly directional degree has
Machine high molecular film material is the Kapton of Jing biaxial tensiones, and thickness is 60um.Carbonization temperature is 1200 DEG C, graphitization
Temperature is 2800 DEG C.By the crushing of obtained electrographite film, sand milling, particle diameter distribution DN50 is obtained less than 20um, DN90 is less than
The electrographite powder of 50um, heat conductivity is 500W/ (mk).Native graphite heat conductivity is at 100-200W/ (mk).Will system
Standby electrographite powder is added in polyamic acid resin, it is found that artificial graphite powder is well dispersed in resin system, soilless sticking
Agglomeration problems, flat appearance after coating, without obvious granule.As shown in Figure 2-5, observe in the secure execution mode (sem, self-control electrographite powder is in piece
Shape, even particle size distribution, natural graphite powder is in granular form, and particle diameter distribution is uneven.
Embodiment 1
1st, A type polyamic acid resins are prepared
Weigh 10.9g particle diameters and be dissolved into 480g N in the silicon dioxide of 20nm, in N dimethyl acetyl amine solvent, ultrasound point
Dissipate 30 minutes, supersonic frequency 40KHz, solution is in suspension.Bath temperature rises to 50 DEG C, and 25.8g p-phenylenediamine is added at twice,
Every minor tick 20 minutes, it is subsequently disposable to add 5.3g 4,4- diaminodiphenyl ethers to stir 1 hour under 1200r/min.So
Afterwards bath temperature is down to into 25 DEG C, in seven times the addition bibenzene tetracarboxylic dianhydrides of 78.0g 3,3,4,4-, every minor tick 30 minutes,
Stir 10 hours under 800r/min, reaction obtains A type polyamic acid resins, froth breaking 24 hours, Ran Houyong under -0.1Mpa vacuum
PE winds film phonograph seal, is positioned under 5-10 DEG C of cryogenic conditions and preserves.
2nd, Type B polyamic acid resin is prepared
Weigh 46.3g particle diameter distributions DN50 and be dissolved into 492g N, N dimethyl acetyl amine solvent in the electrographite powder of 10um
In, ultrasonic disperse 60 minutes, supersonic frequency 40KHz, solution is in suspension.Bath temperature rises to 50 DEG C, and 24.0g is added at twice
P-phenylenediamine, every minor tick 20 minutes, subsequent disposable addition 10.1g 2, double [4- (4 amino-benzene oxygen) phenyl] propane of 2-,
Stir 1 hour under 1200r/min.Then bath temperature is down to into 25 DEG C, it is disposable to add the benzophenone four of 13.5g 3,3,4,4-
Formic acid dianhydride, is spaced 30 minutes, then adds the bibenzene tetracarboxylic dianhydrides of 60.3g 3,3,4,4- in five times, every minor tick 30 minutes,
Stir 10 hours under 800r/min, reaction obtains Type B polyamic acid resin, froth breaking 24 hours under -0.1Mpa vacuum, then
Film phonograph seal is wound with PE, is positioned under 5-10 DEG C of cryogenic conditions and is preserved.
3rd, heat-conducting type is prepared without glue single-face flexibility copper-clad board
The A types polyamic acid glue even application that reaction is obtained is coarse in electrolytic copper foil (in such as structural representation 1)
Face, copper thickness 12um, except solvent 30 minutes at 150 DEG C, under nitrogen protection, in 360 DEG C of heat treatments 30 minutes, carries out Asia
Amination, obtains Copper Foil+A type polyamic acid resins, A type polyamic acid resins (such as 2 in structural representation) thickness 8um.Then
One layer of Type B polyamic acid glue of even application on A type polyamic acid resins face, removes solvent 20 minutes, in nitrogen at 160 DEG C
Under protection, in 380 DEG C of heat treatments 60 minutes, imidization, Type B polyamic acid resin (such as 3 in structural representation Fig. 1) thickness are carried out
5um, obtains the heat conduction of Copper Foil+A type polyamic acid resins+Type B polyamic acid resin without glue single-face flexibility copper-clad board.In FIG,
Electrolytic copper foil 1, the first polyamic acid resin layer 2, the second polyamic acid resin layer 3.
Embodiment 2
1st, A type polyamic acid resins are prepared
Weigh 9.8g particle diameters and be dissolved into 492g N in the aluminium sesquioxide of 20nm, in N dimethyl acetyl amine solvent, ultrasound point
Dissipate 30 minutes, supersonic frequency 40KHz, solution is in suspension.Bath temperature rises to 50 DEG C, and 23.8g p-phenylenediamine is added at twice,
Every minor tick 20 minutes, it is subsequently disposable to add 3.8g 4,4- diaminodiphenyl ethers to stir 1 hour under 1200r/min.So
Afterwards bath temperature is down to into 25 DEG C, in seven times the addition bibenzene tetracarboxylic dianhydrides of 70.5g 3,3,4,4-, every minor tick 30 minutes,
Stir 10 hours under 800r/min, reaction obtains A type polyamic acid resins, froth breaking 24 hours, Ran Houyong under -0.1Mpa vacuum
PE winds film phonograph seal, is positioned under 5-10 DEG C of cryogenic conditions and preserves.
2nd, Type B polyamic acid resin is prepared
Weigh 51.4g particle diameter distributions DN50 and be dissolved into 480g N, N dimethyl acetyl amine solvent in the electrographite powder of 10um
In, ultrasonic disperse 60 minutes, supersonic frequency 40KHz, solution is in suspension.Bath temperature rises to 50 DEG C, and 25.8g is added at twice
P-phenylenediamine, every minor tick 20 minutes, subsequent disposable addition 13.3g 2, double [4- (4 amino-benzene oxygen) phenyl] propane of 2-,
Stir 1 hour under 1200r/min.Then bath temperature is down to into 25 DEG C, it is disposable to add the benzophenone four of 13.1g 3,3,4,4-
Formic acid dianhydride, is spaced 30 minutes, then adds the bibenzene tetracarboxylic dianhydrides of 67.8g 3,3,4,4- in seven times, every minor tick 30 minutes,
Stir 10 hours under 800r/min, reaction obtains Type B polyamic acid resin, froth breaking 24 hours under -0.1Mpa vacuum, then
Film phonograph seal is wound with PE, is positioned under 5-10 DEG C of cryogenic conditions and is preserved.
3rd, heat-conducting type is prepared without glue single-face flexibility copper-clad board
The A types polyamic acid glue even application for obtaining will be reacted in electrolytic copper foil (as 1 in structural representation) matsurface,
Copper thickness 18um, except solvent 30 minutes at 150 DEG C, under nitrogen protection, in 360 DEG C of heat treatments 30 minutes, carries out imines
Change, obtain Copper Foil+A type polyamic acid resins, A type polyamic acid resins (as 2 in structural representation), thickness 8um.Then in A
One layer of Type B polyamic acid glue of even application on type polyamic acid resin face, solvent is removed 20 minutes at 160 DEG C, then in nitrogen
Under protection, in 380 DEG C of heat treatments 60 minutes, imidization, Type B polyamic acid resin (as 3 in structural representation) thickness are carried out
5um, obtains the heat conduction of Copper Foil+A type polyamic acid resins+Type B polyamic acid resin without glue single-face flexibility copper-clad board.
Embodiment 3
1st, A type polyamic acid resins are prepared
Weigh 10.9g particle diameters and be dissolved into 480g N in the silicon dioxide of 20nm, in N dimethyl acetyl amine solvent, ultrasound point
Dissipate 30 minutes, supersonic frequency 40KHz, solution is in suspension.Bath temperature rises to 50 DEG C, and 29.0g p-phenylenediamine is added at twice,
Every minor tick 20 minutes, stirs 1 hour under 1200r/min.Then bath temperature is down to into 25 DEG C, 15.5g is added at twice
3,3,4,4- benzophenone tetracarboxylic dianhydride (BTDA)s, every minor tick 30 minutes, then the bibenzene tetracarboxylics of 64.6g 3,3,4,4- are added in five times
Dianhydride, every minor tick 30 minutes, stirs 10 hours under 800r/min, and reaction obtains A type polyamic acid resins, in -0.1Mpa
Froth breaking 24 hours under vacuum, then wind film phonograph seal with PE, are positioned under 5-10 DEG C of cryogenic conditions and preserve.
2nd, Type B polyamic acid resin is prepared
Weigh 46.3g particle diameter distributions DN50 and be dissolved into 492g N, N dimethyl acetyl amine solvent in the electrographite powder of 10um
In, ultrasonic disperse 60 minutes, supersonic frequency 40KHz, solution is in suspension.Bath temperature rises to 50 DEG C, and 25.5g is added at twice
P-phenylenediamine, every minor tick 20 minutes is subsequently disposable to add 5.3g 4,4- diaminodiphenyl ethers to stir 1 under 1200r/min
Hour.Then bath temperature is down to into 25 DEG C, the bibenzene tetracarboxylic dianhydrides of 77.2g 3,3,4,4- is added in seven times, per minor tick 30
Minute, to stir 10 hours under 800r/min, reaction obtains Type B polyamic acid resin, and froth breaking 24 is little under -0.1Mpa vacuum
When, then film phonograph seal is wound with PE, it is positioned under 5-10 DEG C of cryogenic conditions and preserves.
3rd, heat-conducting type is prepared without glue single-face flexibility copper-clad board
The A types polyamic acid glue even application for obtaining will be reacted in electrolytic copper foil (as 1 in structural representation) matsurface,
Copper thickness 12um, except solvent 60 minutes at 120 DEG C, under nitrogen protection, in 320 DEG C of heat treatments 60 minutes, carries out imines
Change, obtain Copper Foil+A type polyamic acid resins, A type polyamic acid resins (as 2 in structural representation) thickness 8um.Then in A types
One layer of Type B polyamic acid glue of even application on polyamic acid resin face, solvent is removed 30 minutes at 150 DEG C, in nitrogen protection
Under, in 360 DEG C of heat treatments 90 minutes, imidization being carried out, Type B polyamic acid resin (as 3 in structural representation) thickness 5um is obtained
Heat conduction to Copper Foil+A type polyamic acid resins+Type B polyamic acid resin is without glue single-face flexibility copper-clad board.
Embodiment 4
1st, A type polyamic acid resins are prepared
Weigh 9.8g particle diameters and be dissolved into 492g N in the aluminium sesquioxide of 20nm, in N dimethyl acetyl amine solvent, ultrasound point
Dissipate 30 minutes, supersonic frequency 40KHz, solution is in suspension.Bath temperature rises to 50 DEG C, and 26.1g p-phenylenediamine is added at twice,
Every minor tick 20 minutes, stirs 1 hour under 1200r/min.Then bath temperature is down to into 25 DEG C, 11.7g is added at twice
3,3,4,4- benzophenone tetracarboxylic dianhydride (BTDA)s, every minor tick 30 minutes, then the bibenzene tetracarboxylics of 60.4g 3,3,4,4- are added in five times
Dianhydride, every minor tick 30 minutes, stirs 10 hours under 800r/min, and reaction obtains A type polyamic acid resins, in -0.1Mpa
Froth breaking 24 hours under vacuum, then wind film phonograph seal with PE, are positioned under 5-10 DEG C of cryogenic conditions and preserve.
2nd, Type B polyamic acid resin is prepared
Weigh 51.4g particle diameter distributions DN50 and be dissolved into 480g N, N dimethyl acetyl amine solvent in the electrographite powder of 10um
In, ultrasonic disperse 60 minutes, supersonic frequency 40KHz, solution is in suspension.Bath temperature rises to 50 DEG C, and 27.6g is added at twice
P-phenylenediamine, every minor tick 20 minutes is subsequently disposable to add 7.0g 4,4- diaminodiphenyl ethers to stir 1 under 1200r/min
Hour.Then bath temperature is down to into 25 DEG C, the bibenzene tetracarboxylic dianhydrides of 85.4g 3,3,4,4- is added in seven times, per minor tick 30
Minute, to stir 10 hours under 800r/min, reaction obtains Type B polyamic acid resin, and froth breaking 24 is little under -0.1Mpa vacuum
When, then film phonograph seal is wound with PE, it is positioned under 5-10 DEG C of cryogenic conditions and preserves.
3rd, heat-conducting type is prepared without glue single-face flexibility copper-clad board
The A types polyamic acid glue even application for obtaining will be reacted in electrolytic copper foil (as 1 in structural representation) matsurface,
Copper thickness 18um, except solvent 60 minutes at 120 DEG C, under nitrogen protection, in 320 DEG C of heat treatments 60 minutes, carries out imines
Change, obtain Copper Foil+A type polyamic acid resins, A type polyamic acid resins (as 2 in structural representation) thickness 8um.Then in A types
One layer of Type B polyamic acid glue of even application on polyamic acid resin face, solvent is removed 30 minutes at 150 DEG C, in nitrogen protection
Under, in 360 DEG C of heat treatments 90 minutes, imidization being carried out, Type B polyamic acid resin (as 3 in structural representation) thickness 5um is obtained
Heat conduction to Copper Foil+A type polyamic acid resins+Type B polyamic acid resin is without glue single-face flexibility copper-clad board.
Embodiment 5
1st, A type polyamic acid resins are prepared
Weigh 10.9g particle diameters and be dissolved into 480g N in the silicon dioxide of 20nm, in N dimethyl acetyl amine solvent, ultrasound point
Dissipate 30 minutes, supersonic frequency 40KHz, solution is in suspension.Bath temperature rises to 50 DEG C, and 24.3g p-phenylenediamine is added at twice,
Every minor tick 20 minutes, it is subsequently disposable to add 10.2g2, double [4- (4 amino-benzene oxygen) phenyl] propane of 2-, in 1200r/min
Lower stirring 1 hour.Then bath temperature is down to into 25 DEG C, the benzophenone tetracarboxylic dianhydride (BTDA)s of 12.1g 3,3,4,4- is added at twice,
Every minor tick 30 minutes, then the bibenzene tetracarboxylic dianhydrides of 62.5g 3,3,4,4- are added in five times, every minor tick 30 minutes,
Stir 10 hours under 800r/min, reaction obtains A type polyamic acid resins, froth breaking 24 hours, Ran Houyong under -0.1Mpa vacuum
PE winds film phonograph seal, is positioned under 5-10 DEG C of cryogenic conditions and preserves.
2nd, Type B polyamic acid resin is prepared
Weigh 46.3g particle diameter distributions DN50 and be dissolved into 492g N, N dimethyl acetyl amine solvent in the electrographite powder of 10um
In, ultrasonic disperse 60 minutes, supersonic frequency 40KHz, solution is in suspension.Bath temperature rises to 50 DEG C, and 23.6g is added at twice
P-phenylenediamine, every minor tick 20 minutes is subsequently disposable to add 7.7g 4,4- diaminodiphenyl ethers to stir 1 under 1200r/min
Hour.Then bath temperature is down to into 25 DEG C, it is disposable to add the benzophenone tetracarboxylic dianhydride (BTDA)s of 12.4g 3,3,4,4-, it is spaced 30 points
Clock, then the bibenzene tetracarboxylic dianhydrides of 64.3g 3,3,4,4- are added in five times, every minor tick 30 minutes stirs 10 under 800r/min
Hour, reaction obtains Type B polyamic acid resin, froth breaking 24 hours under -0.1Mpa vacuum, then winds film phonograph seal with PE, puts
It is placed under 5-10 DEG C of cryogenic conditions and preserves.
3rd, heat-conducting type is prepared without glue single-face flexibility copper-clad board
The A types polyamic acid glue even application for obtaining will be reacted in electrolytic copper foil (as 1 in structural representation) matsurface,
Copper thickness 12um, except solvent 60 minutes at 130 DEG C, under nitrogen protection, in 300 DEG C of heat treatments 60 minutes, carries out imines
Change, obtain Copper Foil+A type polyamic acid resins, A type polyamic acid resins (as 2 in structural representation) thickness 8um.Then in A types
One layer of Type B polyamic acid glue of even application on polyamic acid resin face, solvent is removed 30 minutes at 130 DEG C, in nitrogen protection
Under, in 380 DEG C of heat treatments 60 minutes, imidization being carried out, Type B polyamic acid resin (as 3 in structural representation) thickness 5um is obtained
Heat conduction to Copper Foil+A type polyamic acid resins+Type B polyamic acid resin is without glue single-face flexibility copper-clad board.
Comparative example 1
The vast grace green wood tradition of Yuntianhua is without glue single-face flexibility copper-clad board.Marque：Y-FSE1312, polyimide film
13um, Copper Foil is 12um electrolytic copper foils.
Comparative example 2
The vast grace green wood tradition of Yuntianhua is without glue single-face flexibility copper-clad board.Marque：Y-FSE1318, polyimide film
13um, Copper Foil is 18um electrolytic copper foils.
The performance comparison of the embodiment of the present invention and comparative example such as table 1, table 2.
Table 1
With the rising of testing electronic element power, the temperature of electronic component is just stepped up.Can be with by correction data
It was found that：The heat conduction of the present invention is (more same without glue single-face flexibility copper-clad board than conventional without glue single-face flexibility copper-clad board (same model Copper Foil)
Model Copper Foil) test temperature it is lower, radiating effect is more preferable.
Table 2
Performance test standard is as follows：
Heat conductivity：ASTM E1461
Polyamic acid resin dimensional stability：IPC-TM-650 2.2.4
FCCL peel strengths：IPC-TM-650 2.4.9
Polyamic acid resin sheet resistance：IPC-TM-650 2.4.3.1
Polyamic acid resin volume resistance：IPC-TM-650 2.5.17
Resistance to weldering, solderable (300 DEG C, 10Sec, 3 times)：IPC-TM-650 2.4.13
The heat-conducting type of the present invention is higher without glue single-face flexibility copper-clad board heat conductivity than routine without glue single-face flexibility copper-clad board,
Dimensional stability, peel strength, surface resistivity, specific insulation, resistance to weldering/solderability reach and judge to mark without glue one side product
It is accurate.
Each technical characteristic of above-mentioned disclosure is not limited to disclosed and further feature combination, and those skilled in the art are also
Can according to the purpose of invention carry out between each technical characteristic other combination, to realize that the purpose of the present invention is defined.
Claims (12)
1. a kind of heat-conducting type is without glue single-face flexibility copper-clad board, including the copper foil layer being fitted and connected successively, the first polyamic acid resin
Layer and the second polyamic acid resin layer, it is characterised in that the second polyamic acid resin layer is contained within electrographite powder filler, described
The heat conductivity of electrographite powder is 300～600W/ (mk).
2. manufacture method of the heat-conducting type described in claim 1 without glue single-face flexibility copper-clad board, it is characterised in that the method include with
Lower step：
Step 1, prepares electrographite powder；Organic polymer thin-film material with highly directional degree is pressurizeed under an inert atmosphere charcoal
Change, and heated graphitization processing is obtained electrographite film, it is post-treated after obtain electrographite powder；
Step 2, prepares the A type polyamic acid resins without electrographite powder；Prepare the Type B polyamides containing the electrographite powder
Amino acid resin；
Step 3, A type polyamic acid glue even applications are obtained after copper foil surface, heat treatment to cover the first polyamic acid tree
The copper foil layer of lipid layer；In one layer of Type B polyamic acid glue of the first polyamic acid resin layer surface even application, obtain after heat treatment
Heat-conducting type is without glue single-face flexibility copper-clad board.
3. manufacture method of the heat-conducting type according to claim 2 without glue single-face flexibility copper-clad board, it is characterised in that in step
In 1, the organic polymer of the highly directional degree is the one kind in polyimides, polyamide, polythiazole, polybenzoxazole；It is organic
The thickness of high molecular film material is 10um～150um；Carbonization temperature is 900 DEG C～1500 DEG C；Graphitization temperature is 2500 DEG C
～3200 DEG C；By the crushing of obtained electrographite film, sand milling, particle diameter distribution DN50 is obtained less than 20um, DN90 is less than 50um's
Electrographite powder.
4. manufacture method of the heat-conducting type according to claim 3 without glue single-face flexibility copper-clad board, it is characterised in that step 2
Detailed process it is as follows：
The A type polyamic acid resins without electrographite powder are prepared, inorganic filler is added in highly polar aprotic solvent, surpassed
Sound disperses 30 minutes, supersonic frequency 10KHz～50KHz, and inorganic filler is in suspension in highly polar aprotic solvent；By fragrance
Race's diamine monomer is dividedly in some parts in the suspension, 50～60 DEG C of bath temperature, 800～1500r/min of mixing speed, stirring
1 hour, obtain solution mixture；Aromatic series tetracarboxylic dianhydride monomer is dividedly in some parts in the solution mixture, bath temperature 15
～25 DEG C, 500～1000r/min of mixing speed in 10～12 hours response time, obtains A type polyamic acid resins；
The Type B polyamic acid resin containing electrographite powder is prepared, electrographite powder is added in highly polar aprotic solvent,
Ultrasonic disperse 60 minutes, supersonic frequency 10KHz～50KHz, electrographite powder is in suspension in highly polar aprotic solvent；Will
Aromatic diamine monomer is dividedly in some parts in the suspension, 50～60 DEG C of bath temperature, 800～1500r/min of mixing speed,
Stirring 1 hour, obtains solution mixture；Aromatic series tetracarboxylic dianhydride monomer is dividedly in some parts in the solution mixture, water-bath temperature
15～25 DEG C of 500～1000r/min of mixing speed of degree, in 10～12 hours response time, obtain Type B polyamic acid resin.
5. manufacture method of the heat-conducting type according to claim 4 without glue single-face flexibility copper-clad board, it is characterised in that the nothing
Machine filler is silicon dioxide, titanium dioxide, aluminium sesquioxide, hectorite, Pulvis Talci, montmorillonite, ZSM-5 molecular sieve, borosilicic acid
Salt it is therein one or more.
6. manufacture method of the heat-conducting type according to claim 4 without glue single-face flexibility copper-clad board, it is characterised in that described strong
Polar non-solute is DMF, N, and N dimethyl acetamide, N-Methyl pyrrolidone, dimethyl sulfoxide are wherein
One or more.
7. manufacture method of the heat-conducting type according to claim 4 without glue single-face flexibility copper-clad board, it is characterised in that the virtue
Fragrant race's diamine monomer is p-phenylenediamine, 4,4- diaminodiphenyl ethers, 2,2- double [4- (4 amino-benzene oxygen) phenyl] propane, diaminos
Base diphenyl-methane, 4,4 pairs of (3 amino-benzene oxygen) benzophenone, double (4- amino-benzene oxygens) benzene of 1,3-, double [4- (the 3- amino of 1,3-
Phenoxy group) benzoyl] benzene, 3,3- dimethyl -4,4- MDAs, 4,4- MDAs one kind therein
Or it is several.
8. manufacture method of the heat-conducting type according to claim 4 without glue single-face flexibility copper-clad board, it is characterised in that the virtue
Fragrant race's tetracarboxylic dianhydride be pyromellitic acid anhydride, 3,3,4,4- bibenzene tetracarboxylic dianhydrides, 3,3,4,4- benzophenone tetracarboxylic dianhydride (BTDA)s,
3,3,4,4 diphenyl ether tetraformic dianhydrides, 3,3,4,4- triphen bis ether tetracarboxylic acid dianhydrides it is therein one or more.
9. manufacture method of the heat-conducting type according to any one of claim 4-8 without glue single-face flexibility copper-clad board, its feature exists
During A type polyamic acid resins are prepared, it is 0.5～5% that inorganic filler accounts for the weight ratio of all reactants, aromatic series
It is 2～8% that diamine monomer accounts for the weight ratio of all reactants, and aromatic series tetracarboxylic dianhydride monomer accounts for the weight ratio of all reactants and is
10～18%, it is 70～85% that highly polar aprotic solvent accounts for the weight ratio of all reactants.
10. manufacture method of the heat-conducting type according to any one of claim 4-8 without glue single-face flexibility copper-clad board, its feature exists
During Type B polyamic acid resin is prepared, it is 5～15% that electrographite powder accounts for the weight ratio of all reactants, aromatic series
It is 1～6% that diamine monomer accounts for the weight ratio of all reactants, and aromatic series tetracarboxylic dianhydride monomer accounts for the weight ratio of all reactants and is
8～15%, it is 75～85% that highly polar aprotic solvent accounts for the weight ratio of all reactants.
11. manufacture methods of the heat-conducting type according to claim 2 without glue single-face flexibility copper-clad board, it is characterised in that Copper Foil
For the one kind in electrolytic copper foil and rolled copper foil；The thickness of copper foil layer is 1～70um；First polyamic acid resin layer and second gathers
The thickness of amic acid resin bed is 1～60um.
12. manufacture methods of the heat-conducting type according to claim 2 without glue single-face flexibility copper-clad board, it is characterised in that step 3
Detailed process it is as follows：By A type polyamic acid resin even applications in Copper Foil matsurface, at 100～160 DEG C except solvent 20～
60 minutes, then obtain covering the first polyamic acid resin layer in 280～360 DEG C of heat treatments 30～60 minutes under nitrogen protection
Copper foil layer；In first one layer of Type B polyamic acid resin of polyamic acid resin layer even application, solvent is removed at 120～180 DEG C
10～30 minutes, then obtain heat-conducting type flexible without glue one side in 350～400 DEG C of heat treatments 60～90 minutes under nitrogen protection
Copper-clad plate.
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| CN108893048A (en) * | 2018-07-19 | 2018-11-27 | 宁波信幸隆密封制品有限公司 | A kind of composite material and its preparation process |
| CN109246928A (en) * | 2018-09-27 | 2019-01-18 | 常州市武进三维电子有限公司 | The production technology of the flexible wires wiring board of new-energy automobile |
| CN110167324A (en) * | 2019-06-21 | 2019-08-23 | Oppo广东移动通信有限公司 | Housing unit and preparation method thereof and electronic equipment |
| CN114679837A (en) * | 2020-12-24 | 2022-06-28 | 广东生益科技股份有限公司 | Black glue-free flexible copper-clad plate and preparation method and application thereof |
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| CN108893048A (en) * | 2018-07-19 | 2018-11-27 | 宁波信幸隆密封制品有限公司 | A kind of composite material and its preparation process |
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| CN110167324A (en) * | 2019-06-21 | 2019-08-23 | Oppo广东移动通信有限公司 | Housing unit and preparation method thereof and electronic equipment |
| CN114679837A (en) * | 2020-12-24 | 2022-06-28 | 广东生益科技股份有限公司 | Black glue-free flexible copper-clad plate and preparation method and application thereof |
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