CN116572608A - Copper-clad plate and preparation method thereof - Google Patents
Copper-clad plate and preparation method thereof Download PDFInfo
- Publication number
- CN116572608A CN116572608A CN202310534684.2A CN202310534684A CN116572608A CN 116572608 A CN116572608 A CN 116572608A CN 202310534684 A CN202310534684 A CN 202310534684A CN 116572608 A CN116572608 A CN 116572608A
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- CN
- China
- Prior art keywords
- copper
- heat
- insulating paper
- clad plate
- polytetrafluoroethylene
- Prior art date
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- Pending
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- 238000002360 preparation method Methods 0.000 title claims abstract description 24
- -1 polytetrafluoroethylene Polymers 0.000 claims abstract description 83
- 239000004810 polytetrafluoroethylene Substances 0.000 claims abstract description 80
- 229920001343 polytetrafluoroethylene Polymers 0.000 claims abstract description 80
- 239000000758 substrate Substances 0.000 claims abstract description 69
- 229920002635 polyurethane Polymers 0.000 claims abstract description 43
- 239000004814 polyurethane Substances 0.000 claims abstract description 43
- 230000001070 adhesive effect Effects 0.000 claims abstract description 42
- 239000000853 adhesive Substances 0.000 claims abstract description 41
- 239000006185 dispersion Substances 0.000 claims abstract description 39
- 239000012790 adhesive layer Substances 0.000 claims abstract description 36
- 239000011737 fluorine Substances 0.000 claims abstract description 36
- 229910052731 fluorine Inorganic materials 0.000 claims abstract description 36
- 239000002245 particle Substances 0.000 claims abstract description 36
- YCKRFDGAMUMZLT-UHFFFAOYSA-N Fluorine atom Chemical compound [F] YCKRFDGAMUMZLT-UHFFFAOYSA-N 0.000 claims abstract description 33
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 claims abstract description 32
- 239000000839 emulsion Substances 0.000 claims abstract description 28
- 239000011889 copper foil Substances 0.000 claims abstract description 24
- 238000007731 hot pressing Methods 0.000 claims abstract description 18
- 239000007788 liquid Substances 0.000 claims abstract description 11
- 239000011248 coating agent Substances 0.000 claims abstract description 6
- 238000000576 coating method Methods 0.000 claims abstract description 6
- 238000013329 compounding Methods 0.000 claims abstract description 5
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 42
- 229920005989 resin Polymers 0.000 claims description 25
- 239000011347 resin Substances 0.000 claims description 25
- 229910052582 BN Inorganic materials 0.000 claims description 24
- PZNSFCLAULLKQX-UHFFFAOYSA-N Boron nitride Chemical compound N#B PZNSFCLAULLKQX-UHFFFAOYSA-N 0.000 claims description 24
- 239000000919 ceramic Substances 0.000 claims description 21
- 239000000843 powder Substances 0.000 claims description 21
- 239000005543 nano-size silicon particle Substances 0.000 claims description 20
- 235000012239 silicon dioxide Nutrition 0.000 claims description 20
- 238000001035 drying Methods 0.000 claims description 19
- 229920003235 aromatic polyamide Polymers 0.000 claims description 10
- 238000002156 mixing Methods 0.000 claims description 10
- 229910052802 copper Inorganic materials 0.000 claims description 8
- 239000010949 copper Substances 0.000 claims description 8
- 239000011256 inorganic filler Substances 0.000 claims description 8
- 229910003475 inorganic filler Inorganic materials 0.000 claims description 8
- 238000009413 insulation Methods 0.000 claims description 7
- 239000010410 layer Substances 0.000 claims description 7
- 239000004760 aramid Substances 0.000 claims description 5
- 238000004519 manufacturing process Methods 0.000 claims description 5
- 239000004642 Polyimide Substances 0.000 claims description 4
- 238000000034 method Methods 0.000 claims description 4
- 229920001721 polyimide Polymers 0.000 claims description 4
- 229910052581 Si3N4 Inorganic materials 0.000 claims description 3
- PMHQVHHXPFUNSP-UHFFFAOYSA-M copper(1+);methylsulfanylmethane;bromide Chemical compound Br[Cu].CSC PMHQVHHXPFUNSP-UHFFFAOYSA-M 0.000 claims description 3
- 239000000395 magnesium oxide Substances 0.000 claims description 3
- CPLXHLVBOLITMK-UHFFFAOYSA-N magnesium oxide Inorganic materials [Mg]=O CPLXHLVBOLITMK-UHFFFAOYSA-N 0.000 claims description 3
- AXZKOIWUVFPNLO-UHFFFAOYSA-N magnesium;oxygen(2-) Chemical compound [O-2].[Mg+2] AXZKOIWUVFPNLO-UHFFFAOYSA-N 0.000 claims description 3
- TWNQGVIAIRXVLR-UHFFFAOYSA-N oxo(oxoalumanyloxy)alumane Chemical compound O=[Al]O[Al]=O TWNQGVIAIRXVLR-UHFFFAOYSA-N 0.000 claims description 3
- HBMJWWWQQXIZIP-UHFFFAOYSA-N silicon carbide Chemical compound [Si+]#[C-] HBMJWWWQQXIZIP-UHFFFAOYSA-N 0.000 claims description 3
- 229910010271 silicon carbide Inorganic materials 0.000 claims description 3
- HQVNEWCFYHHQES-UHFFFAOYSA-N silicon nitride Chemical compound N12[Si]34N5[Si]62N3[Si]51N64 HQVNEWCFYHHQES-UHFFFAOYSA-N 0.000 claims description 3
- 238000005470 impregnation Methods 0.000 claims 2
- ZMANZCXQSJIPKH-UHFFFAOYSA-N Triethylamine Chemical compound CCN(CC)CC ZMANZCXQSJIPKH-UHFFFAOYSA-N 0.000 description 27
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 18
- 238000006243 chemical reaction Methods 0.000 description 14
- 239000003795 chemical substances by application Substances 0.000 description 12
- 238000007598 dipping method Methods 0.000 description 12
- 239000011259 mixed solution Substances 0.000 description 10
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 10
- PTBDIHRZYDMNKB-UHFFFAOYSA-N 2,2-Bis(hydroxymethyl)propionic acid Chemical compound OCC(C)(CO)C(O)=O PTBDIHRZYDMNKB-UHFFFAOYSA-N 0.000 description 9
- PIICEJLVQHRZGT-UHFFFAOYSA-N Ethylenediamine Chemical compound NCCN PIICEJLVQHRZGT-UHFFFAOYSA-N 0.000 description 9
- 239000005058 Isophorone diisocyanate Substances 0.000 description 9
- 229920001730 Moisture cure polyurethane Polymers 0.000 description 9
- UKLDJPRMSDWDSL-UHFFFAOYSA-L [dibutyl(dodecanoyloxy)stannyl] dodecanoate Chemical compound CCCCCCCCCCCC(=O)O[Sn](CCCC)(CCCC)OC(=O)CCCCCCCCCCC UKLDJPRMSDWDSL-UHFFFAOYSA-L 0.000 description 9
- 239000008367 deionised water Substances 0.000 description 9
- 229910021641 deionized water Inorganic materials 0.000 description 9
- 239000012975 dibutyltin dilaurate Substances 0.000 description 9
- NIMLQBUJDJZYEJ-UHFFFAOYSA-N isophorone diisocyanate Chemical compound CC1(C)CC(N=C=O)CC(C)(CN=C=O)C1 NIMLQBUJDJZYEJ-UHFFFAOYSA-N 0.000 description 9
- 238000006386 neutralization reaction Methods 0.000 description 9
- 229920000728 polyester Polymers 0.000 description 8
- QQQSFSZALRVCSZ-UHFFFAOYSA-N triethoxysilane Chemical compound CCO[SiH](OCC)OCC QQQSFSZALRVCSZ-UHFFFAOYSA-N 0.000 description 8
- 239000000126 substance Substances 0.000 description 7
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 6
- 230000009286 beneficial effect Effects 0.000 description 4
- 230000005540 biological transmission Effects 0.000 description 4
- 238000012986 modification Methods 0.000 description 4
- 230000004048 modification Effects 0.000 description 4
- 239000003607 modifier Substances 0.000 description 4
- 125000001153 fluoro group Chemical group F* 0.000 description 3
- 230000001965 increasing effect Effects 0.000 description 3
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 2
- 230000008878 coupling Effects 0.000 description 2
- 238000010168 coupling process Methods 0.000 description 2
- 238000005859 coupling reaction Methods 0.000 description 2
- 125000005442 diisocyanate group Chemical group 0.000 description 2
- 150000002009 diols Chemical class 0.000 description 2
- 230000003670 easy-to-clean Effects 0.000 description 2
- 230000002708 enhancing effect Effects 0.000 description 2
- 239000000945 filler Substances 0.000 description 2
- 239000003292 glue Substances 0.000 description 2
- 239000003960 organic solvent Substances 0.000 description 2
- 238000002791 soaking Methods 0.000 description 2
- QQGISFDJEJMKIL-JAIQZWGSSA-N (5z)-5-[[3-(hydroxymethyl)thiophen-2-yl]methylidene]-10-methoxy-2,2,4-trimethyl-1h-chromeno[3,4-f]quinolin-9-ol Chemical compound C1=CC=2NC(C)(C)C=C(C)C=2C2=C1C=1C(OC)=C(O)C=CC=1O\C2=C/C=1SC=CC=1CO QQGISFDJEJMKIL-JAIQZWGSSA-N 0.000 description 1
- LBTSNEJGMVFUEW-UHFFFAOYSA-N 2,2,3,3,4,4,5,5,6,8,8,8-dodecafluorooctoxy-dimethoxy-propylsilane Chemical compound FC(C(C(C(C(F)(F)CO[Si](OC)(OC)CCC)(F)F)(F)F)(F)F)CC(F)(F)F LBTSNEJGMVFUEW-UHFFFAOYSA-N 0.000 description 1
- JVYDLYGCSIHCMR-UHFFFAOYSA-N 2,2-bis(hydroxymethyl)butanoic acid Chemical compound CCC(CO)(CO)C(O)=O JVYDLYGCSIHCMR-UHFFFAOYSA-N 0.000 description 1
- UPMLOUAZCHDJJD-UHFFFAOYSA-N 4,4'-Diphenylmethane Diisocyanate Chemical compound C1=CC(N=C=O)=CC=C1CC1=CC=C(N=C=O)C=C1 UPMLOUAZCHDJJD-UHFFFAOYSA-N 0.000 description 1
- 239000005057 Hexamethylene diisocyanate Substances 0.000 description 1
- KXBFLNPZHXDQLV-UHFFFAOYSA-N [cyclohexyl(diisocyanato)methyl]cyclohexane Chemical compound C1CCCCC1C(N=C=O)(N=C=O)C1CCCCC1 KXBFLNPZHXDQLV-UHFFFAOYSA-N 0.000 description 1
- 230000032683 aging Effects 0.000 description 1
- 238000004891 communication Methods 0.000 description 1
- 230000007423 decrease Effects 0.000 description 1
- 238000001125 extrusion Methods 0.000 description 1
- RRAMGCGOFNQTLD-UHFFFAOYSA-N hexamethylene diisocyanate Chemical compound O=C=NCCCCCCN=C=O RRAMGCGOFNQTLD-UHFFFAOYSA-N 0.000 description 1
- 239000012535 impurity Substances 0.000 description 1
- DRRZZMBHJXLZRS-UHFFFAOYSA-N n-[3-[dimethoxy(methyl)silyl]propyl]cyclohexanamine Chemical compound CO[Si](C)(OC)CCCNC1CCCCC1 DRRZZMBHJXLZRS-UHFFFAOYSA-N 0.000 description 1
- 239000011368 organic material Substances 0.000 description 1
- 229920001610 polycaprolactone Polymers 0.000 description 1
- 239000004632 polycaprolactone Substances 0.000 description 1
- 229920000515 polycarbonate Polymers 0.000 description 1
- 239000004417 polycarbonate Substances 0.000 description 1
- 229920001451 polypropylene glycol Polymers 0.000 description 1
- 229920001296 polysiloxane Polymers 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
- 239000000377 silicon dioxide Substances 0.000 description 1
- 238000005507 spraying Methods 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
- 229920001169 thermoplastic Polymers 0.000 description 1
- 239000004416 thermosoftening plastic Substances 0.000 description 1
- DVKJHBMWWAPEIU-UHFFFAOYSA-N toluene 2,4-diisocyanate Chemical compound CC1=CC=C(N=C=O)C=C1N=C=O DVKJHBMWWAPEIU-UHFFFAOYSA-N 0.000 description 1
Classifications
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B7/00—Layered products characterised by the relation between layers; Layered products characterised by the relative orientation of features between layers, or by the relative values of a measurable parameter between layers, i.e. products comprising layers having different physical, chemical or physicochemical properties; Layered products characterised by the interconnection of layers
- B32B7/04—Interconnection of layers
- B32B7/12—Interconnection of layers using interposed adhesives or interposed materials with bonding properties
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B15/00—Layered products comprising a layer of metal
- B32B15/04—Layered products comprising a layer of metal comprising metal as the main or only constituent of a layer, which is next to another layer of the same or of a different material
- B32B15/08—Layered products comprising a layer of metal comprising metal as the main or only constituent of a layer, which is next to another layer of the same or of a different material of synthetic resin
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B15/00—Layered products comprising a layer of metal
- B32B15/14—Layered products comprising a layer of metal next to a fibrous or filamentary layer
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B15/00—Layered products comprising a layer of metal
- B32B15/20—Layered products comprising a layer of metal comprising aluminium or copper
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B27/00—Layered products comprising a layer of synthetic resin
- B32B27/28—Layered products comprising a layer of synthetic resin comprising synthetic resins not wholly covered by any one of the sub-groups B32B27/30 - B32B27/42
- B32B27/281—Layered products comprising a layer of synthetic resin comprising synthetic resins not wholly covered by any one of the sub-groups B32B27/30 - B32B27/42 comprising polyimides
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B37/00—Methods or apparatus for laminating, e.g. by curing or by ultrasonic bonding
- B32B37/06—Methods or apparatus for laminating, e.g. by curing or by ultrasonic bonding characterised by the heating method
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B37/00—Methods or apparatus for laminating, e.g. by curing or by ultrasonic bonding
- B32B37/10—Methods or apparatus for laminating, e.g. by curing or by ultrasonic bonding characterised by the pressing technique, e.g. using action of vacuum or fluid pressure
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B5/00—Layered products characterised by the non- homogeneity or physical structure, i.e. comprising a fibrous, filamentary, particulate or foam layer; Layered products characterised by having a layer differing constitutionally or physically in different parts
- B32B5/02—Layered products characterised by the non- homogeneity or physical structure, i.e. comprising a fibrous, filamentary, particulate or foam layer; Layered products characterised by having a layer differing constitutionally or physically in different parts characterised by structural features of a fibrous or filamentary layer
-
- 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
-
- 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
- C09J175/00—Adhesives based on polyureas or polyurethanes; Adhesives based on derivatives of such polymers
- C09J175/04—Polyurethanes
- C09J175/06—Polyurethanes from polyesters
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B2260/00—Layered product comprising an impregnated, embedded, or bonded layer wherein the layer comprises an impregnation, embedding, or binder material
- B32B2260/02—Composition of the impregnated, bonded or embedded layer
- B32B2260/021—Fibrous or filamentary layer
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B2260/00—Layered product comprising an impregnated, embedded, or bonded layer wherein the layer comprises an impregnation, embedding, or binder material
- B32B2260/04—Impregnation, embedding, or binder material
- B32B2260/046—Synthetic resin
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B2262/00—Composition or structural features of fibres which form a fibrous or filamentary layer or are present as additives
- B32B2262/02—Synthetic macromolecular fibres
- B32B2262/0261—Polyamide fibres
- B32B2262/0269—Aromatic polyamide fibres
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K3/00—Use of inorganic substances as compounding ingredients
- C08K3/38—Boron-containing compounds
- C08K2003/382—Boron-containing compounds and nitrogen
- C08K2003/385—Binary compounds of nitrogen with boron
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
- Y02E60/10—Energy storage using batteries
Abstract
The invention discloses a copper-clad plate and a preparation method thereof, and relates to the technical field of copper-clad plates, so as to enhance the peeling strength, the thermal conductivity and the dimensional thermal stability of the copper-clad plate. The preparation method comprises the steps of immersing insulating paper in polytetrafluoroethylene dispersion liquid to form an insulating paper substrate, wherein the polytetrafluoroethylene dispersion liquid contains polytetrafluoroethylene and first heat conducting particles; compounding the fluorine modified aqueous polyurethane emulsion with second heat conducting particles to form a heat conducting adhesive; forming a heat-conducting adhesive layer on one or both sides of the insulating paper substrate; and (3) coating at least one roughened copper foil on the corresponding heat-conducting adhesive layer, and hot-pressing to form the copper-clad plate.
Description
Technical Field
The invention relates to the technical field of copper-clad plates, in particular to a copper-clad plate and a preparation method thereof
Background
Polytetrafluoroethylene is a novel thermoplastic organic material, and can realize high-frequency and high-speed transmission on the premise of ensuring higher reliability. Polytetrafluoroethylene has excellent chemical stability, extremely strong high and low temperature resistance, outstanding non-tackiness, self-lubricity, aging resistance, high insulation, flame retardance, and excellent dielectric properties, and has small dielectric constant and dielectric loss and small variation in a high frequency range, and has a dielectric loss tangent of only 0.0002 and an increase of only 0.001 even at 110 GHz. Therefore, polytetrafluoroethylene is widely used in the manufacturing industries of communication equipment, computers, automotive electronics, household appliances, and the like.
However, polytetrafluoroethylene has a high linear expansion coefficient, a low thermal conductivity, is easy to cold flow and has softer mechanical properties. At the same time, polytetrafluoroethylene has very low surface energy and is not easy to adhere to any substance. Therefore, the prior polytetrafluoroethylene copper-clad plate has the problems of low peeling strength, poor thermal conductivity and poor dimensional thermal stability.
Disclosure of Invention
The invention aims to provide a copper-clad plate and a preparation method thereof, which are used for enhancing the peeling strength, the heat conductivity and the dimensional heat stability of the copper-clad plate.
In order to achieve the above object, the present invention provides a method for preparing a copper-clad plate, including:
immersing insulating paper in polytetrafluoroethylene dispersion liquid to form an insulating paper substrate, wherein the polytetrafluoroethylene dispersion liquid contains polytetrafluoroethylene and first heat conducting particles;
compounding the fluorine modified aqueous polyurethane emulsion with second heat conducting particles to form a heat conducting adhesive;
forming a heat-conducting adhesive layer on one or both sides of the insulating paper substrate;
and coating at least one roughened copper foil on the corresponding heat-conducting adhesive layer, and hot-pressing to form the copper-clad plate.
Compared with the prior art, in the preparation method of the copper-clad plate, the insulating paper is immersed in the polytetrafluoroethylene dispersion liquid to form the insulating paper substrate, wherein the polytetrafluoroethylene dispersion liquid contains polytetrafluoroethylene and first heat conducting particles. Compared with the disordered molecular chain inside the polytetrafluoroethylene, when the polytetrafluoroethylene modified by the first heat conducting particles carries out heat transfer, phonons can effectively and orderly move along a heat conducting path constructed by the heat conducting particles, the phonon mean free path is larger, heat transfer is facilitated, heat conducting capacity and heat radiating capacity of an insulating paper substrate are improved, and therefore the copper-clad plate with high heat conductivity and high dimensional heat stability is facilitated to be prepared.
And then, compounding the fluorine modified aqueous polyurethane emulsion with second heat conducting particles to obtain the heat conducting adhesive. In this process, the second thermally conductive particles may be in sufficient contact with the fluorine-modified aqueous polyurethane emulsion. And finally, forming a heat-conducting adhesive layer on one or two sides of the insulating paper substrate, covering at least one roughened copper foil on the corresponding heat-conducting adhesive layer, and hot-pressing to obtain the copper-clad plate. Because the cohesive substance contained in the heat-conducting adhesive is fluorine modified waterborne polyurethane, the prepared heat-conducting adhesive has higher compatibility to the interface of the insulating paper substrate. The heat-conducting adhesive is used as a connecting phase between the insulating paper substrate and the copper foil, so that the connectivity between the insulating paper substrate and the copper foil can be enhanced, and the peeling strength of the copper-clad plate can be enhanced.
In addition, the aqueous polyurethane adhesive is convenient to operate, easy to clean residual glue, free of organic solvents, low in VOC content and low in smell, and is more environment-friendly.
The second aspect of the invention also provides a copper-clad plate, which is prepared by the preparation method of the copper-clad plate, and comprises the following steps:
the insulation paper comprises an insulation paper base plate, an adhesive layer and a copper foil layer which are sequentially laminated together, wherein the insulation paper base plate contains polytetrafluoroethylene resin, first heat conducting particles and inorganic filler, and the adhesive layer contains second heat conducting particles and fluorine modified waterborne polyurethane.
Compared with the prior art, the beneficial effects of the copper-clad plate provided by the invention are the same as those of the preparation method of the copper-clad plate in the first aspect, and the description is omitted here.
Drawings
The accompanying drawings, which are included to provide a further understanding of the invention and are incorporated in and constitute a part of this specification, illustrate embodiments of the invention and together with the description serve to explain the invention and do not constitute a limitation on the invention. In the drawings:
fig. 1 shows a preparation flow chart of the copper-clad plate provided in the present embodiment.
Detailed Description
In order to make the technical problems, technical schemes and beneficial effects to be solved more clear, the invention is further described in detail below with reference to the accompanying drawings and embodiments. It should be understood that the specific embodiments described herein are for purposes of illustration only and are not intended to limit the scope of the invention.
Furthermore, the terms "first," "second," and the like, are used for descriptive purposes only and are not to be construed as indicating or implying a relative importance or implicitly indicating the number of technical features indicated. Thus, a feature defining "a first" or "a second" may explicitly or implicitly include one or more such feature. In the description of the present invention, the meaning of "a plurality" is two or more, unless explicitly defined otherwise. The meaning of "a number" is one or more than one unless specifically defined otherwise.
At present, the linear expansion coefficient of polytetrafluoroethylene is large, the heat conductivity coefficient is low, cold flow is easy, and the mechanical property is softer. At the same time, polytetrafluoroethylene has very low surface energy and is not easy to adhere to any substance. Therefore, the prior polytetrafluoroethylene copper-clad plate has the problems of low peeling strength, poor thermal conductivity and poor dimensional thermal stability.
Aiming at the problems, the preparation method of the copper-clad plate provided by the embodiment of the invention is used for enhancing the peeling strength, the thermal conductivity and the dimensional thermal stability of the copper-clad plate. Fig. 1 shows a preparation flow chart of a copper-clad plate provided by an embodiment of the invention. As shown in fig. 1, the preparation method of the copper-clad plate comprises the following steps:
step 101: the insulating paper is immersed in the polytetrafluoroethylene dispersion to form an insulating paper substrate.
Illustratively, immersing the insulating paper in the polytetrafluoroethylene dispersion, forming the insulating paper substrate includes: and immersing the insulating paper in polytetrafluoroethylene dispersion liquid, and forming the insulating paper substrate in a drying mode, wherein the polytetrafluoroethylene dispersion liquid is prepared by blending polytetrafluoroethylene resin emulsion, first heat conducting particles and inorganic filler. Specifically, the first heat conductive particles used in the embodiments of the present invention include at least one of aluminum oxide, magnesium oxide, aluminum nitride, boron nitride, silicon nitride, and silicon carbide. The inorganic filler used in the embodiments of the present invention includes nano silica and ceramic powder. The insulating paper used in the embodiment of the invention comprises at least one of meta-aramid paper, para-aramid paper and polyimide paper.
In order to prepare the polytetrafluoroethylene dispersion in the embodiment of the invention, the mass ratio of polytetrafluoroethylene resin, first heat-conducting particles, nano silicon dioxide and ceramic powder is controlled to be (70-100): (10-40) the following (5-10): (5-10). Subsequently, the insulating paper is immersed in the polytetrafluoroethylene dispersion a plurality of times, and the insulating paper substrate is formed after drying. The times of soaking are two times, and the time of each soaking is 3-5 min. When the insulating paper is immersed in the polytetrafluoroethylene dispersion for 3-5 min for the first time, the insulating paper is taken out and placed in an oven and dried for 5-10 min at the temperature of 100-110 ℃, then the insulating paper is immersed in the polytetrafluoroethylene dispersion for 3-5 min for the second time, the insulating paper is taken out and placed in the oven and dried at the temperature of 200-250 ℃ to form the insulating paper substrate. The insulating paper impregnated with the polytetrafluoroethylene dispersion may be dried and then hot-pressed. Specifically, the dried insulating paper is hot-pressed for 30-180 min at 220-280 ℃ under 5-15 MPa, so that gas impurities in the insulating paper can be discharged in time, and the impregnated polytetrafluoroethylene dispersion liquid can be better contacted with the insulating paper. Meanwhile, as the insulating paper substrate contains the first heat conducting particles, the insulating paper substrate has better heat conducting performance, so that when the ambient temperature rises, the insulating paper substrate can transmit heat, thereby improving the thermal stability of the copper-clad plate, reducing the occurrence probability of deformation of the insulating paper substrate along with the rise of the temperature, and improving the dimensional stability of the insulating paper substrate. And secondly, the ceramic powder and the nano silicon dioxide filler contained in the insulating paper substrate have extremely low thermal expansion coefficients, and the overall strength of the insulating paper substrate can be improved, so that the thermal stability of the insulating paper substrate is further improved, and the strength of the insulating paper with the insulating paper substrate is enhanced.
Step 102: and compounding the fluorine modified aqueous polyurethane emulsion with the second heat conducting particles to form the heat conducting adhesive.
Illustratively, the second thermally conductive particles used in embodiments of the present invention include at least one of aluminum oxide, magnesium oxide, aluminum nitride, boron nitride, silicon nitride, and silicon carbide. In order to ensure the adhesive performance of the heat-conducting adhesive, the curing agent is added after the fluorine-modified waterborne polyurethane emulsion and the second heat-conducting particles are compounded, so that the mass ratio of the second heat-conducting particles to the fluorine-modified waterborne polyurethane to the curing agent is controlled to be (10-40): (60-90): (0.03-0.06). In this step, the second heat conductive particles may be sufficiently contacted with the fluorine-modified aqueous polyurethane emulsion.
The following is a preparation method of fluorine modified aqueous polyurethane emulsion: 15 to 35 parts of diisocyanate, 60 to 70 parts of dehydrated dihydric alcohol, 8 to 10 parts of acetone, 4 to 5 parts of hydrophilic agent and 0.06 to 0.1 part of dibutyltin dilaurate are mixed for reaction to obtain a mixed solution; adding 5-30 parts of excessive fluorine coupling modifier into the mixed solution for continuous reaction to obtain fluorine modified waterborne polyurethane prepolymer; adding 6-7 parts of triethylamine into the prepolymer for neutralization reaction, and then adding 140-250 parts of deionized water and 0.6-3.6 parts of ethylenediamine to obtain fluorine modified waterborne polyurethane emulsion. Wherein, the fluorine coupling modifier used in the embodiment of the invention comprises at least one of poly (trifluoropropyl methyl siloxane), dodecafluoroheptyl propyl methyl dimethoxy silane and dodecafluoroheptyl propyl trimethoxy silane. The diisocyanate used in the embodiments of the present invention includes at least one of isophorone diisocyanate, toluene diisocyanate, diphenylmethane diisocyanate, dicyclohexylmethane diisocyanate, and hexamethylene diisocyanate. The dihydric alcohol used in the embodiment of the invention comprises at least one of polycaprolactone diol, polycarbonate dihydric alcohol, polybutylene adipate, polypropylene glycol and polysiloxane diol. The hydrophilic agent used in the embodiment of the present invention includes at least one of dimethylolpropionic acid and dimethylolbutyric acid.
Step 103: a heat conductive adhesive layer is formed on one or both sides of the insulating paper substrate.
The manner of forming the heat-conductive adhesive layer on one or both sides of the insulating paper substrate may be, for example, blade coating, spray coating or slot extrusion, and the heat-conductive adhesive may be present in an amount of 10g/m 2 ～30g/m 2 。
Because the cohesive substance contained in the heat-conducting adhesive is fluorine modified waterborne polyurethane, the interface between the prepared heat-conducting adhesive and the insulating paper substrate has higher compatibility. In addition, the aqueous polyurethane adhesive is convenient to operate, easy to clean residual glue, free of organic solvents, low in VOC content and low in smell, and is more environment-friendly.
Step 104: and (3) coating at least one roughened copper foil on the corresponding heat-conducting adhesive layer, and hot-pressing to obtain the copper-clad plate.
Illustratively, after the roughened copper foil is coated on the heat-conductive adhesive layer, it may be hot-pressed at 220-260 ℃ for 30-180 min under 1-30 MPa.
Because the cohesive substance contained in the heat-conducting adhesive is fluorine modified waterborne polyurethane, the prepared heat-conducting adhesive has higher compatibility with the interface between the insulating paper substrates. The heat-conducting adhesive is used as a connecting phase between the insulating paper substrate and the copper foil, so that the connectivity between the insulating paper substrate and the copper foil can be enhanced, and the peeling strength of the copper-clad plate can be enhanced.
The embodiment of the invention also provides a copper-clad plate, which is prepared by the preparation method of the copper-clad plate, and comprises the following steps:
the insulation paper substrate, the bonding layer and the copper foil layer are sequentially laminated together, the insulation paper substrate comprises polytetrafluoroethylene resin, first heat conducting particles and inorganic filler, and the bonding layer comprises second heat conducting particles and fluorine modified waterborne polyurethane.
The insulating paper substrate in the copper-clad plate contains the first heat conducting particles, polytetrafluoroethylene resin and inorganic filler, so that when the insulating paper substrate carries out heat transmission, phonons can efficiently and orderly move along a heat conducting path constructed by the heat conducting particles, the average free path of the phonons is larger, the heat transmission is facilitated, the heat conducting capacity and the heat radiating capacity of the insulating paper substrate are improved, and the copper-clad plate with high heat stability is facilitated to be prepared. In addition, the adhesive layer contains second heat-conducting particles and fluorine-modified waterborne polyurethane, wherein, because the adhesive substance contained in the heat-conducting adhesive is fluorine-modified waterborne polyurethane, the compatibility of the adhesive layer and the insulating paper substrate is higher, so that the insulating paper substrate containing polytetrafluoroethylene resin can be firmly adhered with the copper foil layer through the adhesive layer containing fluorine-modified waterborne polyurethane, thereby improving the peeling strength of the copper-clad plate; the second heat conducting particles contained in the bonding layer can further improve the heat conducting performance and the heat stability of the copper-clad plate.
The invention is further illustrated below with reference to examples.
In order to investigate the influence of the polytetrafluoroethylene dispersion ratio on the heat conductivity, dielectric constant and peel strength of the obtained copper-clad laminate, the following examples were used.
Example 1
The preparation method of the copper-clad plate provided by the embodiment of the invention comprises the following steps:
first, preparing an insulating paper substrate: and (3) blending polytetrafluoroethylene resin with boron nitride, nano silicon dioxide and ceramic powder to obtain polytetrafluoroethylene dispersion. Then dipping meta-aramid paper in polytetrafluoroethylene dispersion for 3min, taking out, drying in an oven at 110 ℃ for 5min, dipping for 5min again, and drying at 200 ℃ to form the insulating paper substrate.
Wherein the mass ratio of the polytetrafluoroethylene resin to the boron nitride to the nano silicon dioxide to the ceramic powder is 80:10:10:10 in sequence.
Secondly, preparing a heat-conducting adhesive: 60 parts of dehydrated polyester diol-1000, 8 parts of acetone, 4 parts of dimethylolpropionic acid, 17 parts of isophorone diisocyanate and 0.07 part of dibutyltin dilaurate are mixed for reaction to obtain a mixed solution. Then 7.3 parts of heptadecafluoro-sunflower-base triethoxysilane is added for continuous reaction, and the fluorine modified waterborne polyurethane prepolymer is obtained. Then, 6 parts of triethylamine was added to the prepolymer for neutralization, and then 142 parts of deionized water and 0.6 part of ethylenediamine were added to obtain a fluorine-modified aqueous polyurethane emulsion. Finally, adding 10 parts of boron nitride and 0.03 part of curing agent into the fluorine modified waterborne polyurethane emulsion, and uniformly dispersing to obtain the heat-conducting adhesive.
Thirdly, preparing a copper-clad plate: forming a heat-conductive adhesive layer at one surface of the insulating paper substrate to form 10g/m 2 And then the roughened copper foil is covered on the heat-conducting adhesive layer, and the copper-clad plate is obtained by hot-pressing for 60min under the conditions of 220 ℃ and 5 MPa.
Table 1 shows that the copper clad laminate prepared in the first embodiment of the present invention is a performance parameter.
Example two
The preparation method of the copper-clad plate provided by the embodiment of the invention comprises the following steps:
first, preparing an insulating paper substrate: and (3) blending polytetrafluoroethylene resin with boron nitride, nano silicon dioxide and ceramic powder to obtain polytetrafluoroethylene dispersion. Then dipping meta-aramid paper in polytetrafluoroethylene dispersion for 3min, taking out, drying in an oven at 110 ℃ for 5min, dipping for 5min again, and drying at 200 ℃ to form the insulating paper substrate.
Wherein the mass ratio of the polytetrafluoroethylene resin to the boron nitride to the nano silicon dioxide to the ceramic powder is 80:20:10:10 in sequence.
Secondly, preparing a heat-conducting adhesive: 60 parts of dehydrated polyester diol-1000, 8 parts of acetone, 4 parts of dimethylolpropionic acid, 17 parts of isophorone diisocyanate and 0.07 part of dibutyltin dilaurate are mixed for reaction to obtain a mixed solution. Then 7.3 parts of heptadecafluoro-sunflower-base triethoxysilane is added for continuous reaction, and the fluorine modified waterborne polyurethane prepolymer is obtained. Then, 6 parts of triethylamine was added to the prepolymer for neutralization, and then 142 parts of deionized water and 0.6 part of ethylenediamine were added to obtain a fluorine-modified aqueous polyurethane emulsion. Finally, adding 10 parts of boron nitride and 0.03 part of curing agent into the fluorine modified waterborne polyurethane emulsion, and uniformly dispersing to obtain the heat-conducting adhesive.
Thirdly, preparing a copper-clad plate: forming a heat-conductive adhesive layer at one surface of the insulating paper substrate to form 10g/m 2 And then the roughened copper foil is covered on the heat-conducting adhesive layer, and the copper-clad plate is obtained by hot-pressing for 60min under the conditions of 220 ℃ and 5 MPa.
Table 1 shows that the copper clad laminate prepared in the second embodiment of the present invention is a performance parameter.
Example III
The preparation method of the copper-clad plate provided by the embodiment of the invention comprises the following steps:
first, preparing an insulating paper substrate: and (3) blending polytetrafluoroethylene resin with boron nitride, nano silicon dioxide and ceramic powder to obtain polytetrafluoroethylene dispersion. Then dipping meta-aramid paper in polytetrafluoroethylene dispersion for 3min, taking out, drying in an oven at 110 ℃ for 5min, dipping for 5min again, and drying at 200 ℃ to form the insulating paper substrate.
Wherein the mass ratio of the polytetrafluoroethylene resin to the boron nitride to the nano silicon dioxide to the ceramic powder is 80:40:10:10 in sequence.
Secondly, preparing a heat-conducting adhesive: 60 parts of dehydrated polyester diol-1000, 8 parts of acetone, 4 parts of dimethylolpropionic acid, 17 parts of isophorone diisocyanate and 0.07 part of dibutyltin dilaurate are mixed for reaction to obtain a mixed solution. Then 7.3 parts of heptadecafluoro-sunflower-base triethoxysilane is added for continuous reaction, and the fluorine modified waterborne polyurethane prepolymer is obtained. Then, 6 parts of triethylamine was added to the prepolymer for neutralization, and then 142 parts of deionized water and 0.6 part of ethylenediamine were added to obtain a fluorine-modified aqueous polyurethane emulsion. Finally, adding 10 parts of boron nitride and 0.03 part of curing agent into the fluorine modified waterborne polyurethane emulsion, and uniformly dispersing to obtain the heat-conducting adhesive.
Thirdly, preparing a copper-clad plate: forming a heat-conductive adhesive layer at one surface of the insulating paper substrate to form 10g/m 2 And then the roughened copper foil is covered on the heat-conducting adhesive layer, and the copper-clad plate is obtained by hot-pressing for 60min under the conditions of 220 ℃ and 5 MPa.
Table 1 shows the performance parameters of the copper clad laminate prepared in example three of the present invention.
TABLE 1
| Numbering device | Thermal conductivity (W/m.k) | Dielectric constant (10 GHz) | Peel strength (N/mm) |
| Example 1 | 11 | 2.21 | 1.63 |
| Example two | 12 | 2.26 | 1.66 |
| Example III | 15 | 2.30 | 1.67 |
From the above, the peel strength parameters of the copper-clad plates prepared in examples one to three are not much different, which shows that the proportion of each component of the polytetrafluoroethylene dispersion has little influence on the peel strength of the copper-clad plate. The heat conductivity and the dielectric constant of the copper-clad plate prepared in the first to third embodiments tend to increase along with the increase of the boron nitride proportion of the heat conducting particles, which shows that increasing the boron nitride proportion is beneficial to forming a connected heat conducting passage in the solidified polytetrafluoroethylene, so that the heat is transmitted more efficiently; the addition of fillers generally results in an increase in dielectric constant.
In order to investigate the influence of the addition amount of the fluorine modifier in the adhesive on the heat conductivity, dielectric constant and peel strength of the obtained copper clad laminate, the following examples were used.
Example IV
The preparation method of the copper-clad plate provided by the embodiment of the invention comprises the following steps:
first, preparing an insulating paper substrate: and (3) blending polytetrafluoroethylene resin with alumina, nano silicon dioxide and ceramic powder to obtain polytetrafluoroethylene dispersion. Then dipping para-aramid paper in polytetrafluoroethylene dispersion for 5min, taking out, drying for 5min at 110 ℃ in an oven, dipping for 5min again, drying at 200 ℃ and hot-pressing for 30min at 280 ℃ under 5MPa to form the insulating paper substrate.
Wherein the mass ratio of the polytetrafluoroethylene resin to the alumina to the nano silicon dioxide to the ceramic powder is 80:40:10:10 in sequence.
Secondly, preparing a heat-conducting adhesive: 60 parts of dehydrated polyester diol-1000, 8 parts of acetone, 4 parts of dimethylolpropionic acid, 25 parts of isophorone diisocyanate and 0.08 part of dibutyltin dilaurate are mixed for reaction to obtain a mixed solution. Then 15 parts of heptadecafluoro-sunflower-based triethoxysilane is added for continuous reaction, and the fluorine modified waterborne polyurethane prepolymer is obtained. Then adding 6 parts of triethylamine to the prepolymer for neutralization reaction, and then adding 168 parts of deionized water and 2.4 parts of ethylenediamine to obtain the fluorine-modified waterborne polyurethane emulsion. Finally, adding 10 parts of boron nitride and 0.05 part of curing agent into the fluorine modified waterborne polyurethane emulsion, and uniformly dispersing to obtain the heat-conducting adhesive.
Thirdly, preparing a copper-clad plate: forming a heat-conductive adhesive layer at one surface of the insulating paper substrate to form 10g/m 2 And then the roughened copper foil is covered on the heat-conducting adhesive layer, and the copper-clad plate is obtained by hot-pressing for 60min under the conditions of the temperature of 240 ℃ and the pressure of 5 MPa.
Table 2 shows the performance parameters of the copper clad laminate prepared in example four of the present invention.
Example five
The preparation method of the copper-clad plate provided by the embodiment of the invention comprises the following steps:
first, preparing an insulating paper substrate: and (3) blending polytetrafluoroethylene resin with alumina, nano silicon dioxide and ceramic powder to obtain polytetrafluoroethylene dispersion. Then dipping para-aramid paper in polytetrafluoroethylene dispersion for 5min, taking out, drying for 5min at 110 ℃ in an oven, dipping for 5min again, drying at 200 ℃ and hot-pressing for 30min at 15MPa and 270 ℃ to form the insulating paper substrate.
Wherein the mass ratio of the polytetrafluoroethylene resin to the alumina to the nano silicon dioxide to the ceramic powder is 80:40:10:10 in sequence.
Secondly, preparing a heat-conducting adhesive: 60 parts of dehydrated polyester diol-1000, 8 parts of acetone, 4 parts of dimethylolpropionic acid, 30 parts of isophorone diisocyanate and 0.09 part of dibutyltin dilaurate are mixed and reacted to obtain a mixed solution. Then adding 24.2 parts of heptadecafluoro-sunflower-base triethoxysilane to continue the reaction to obtain the fluorine modified waterborne polyurethane prepolymer. Then adding 6 parts of triethylamine into the prepolymer for neutralization reaction, and then adding 190 parts of deionized water and 3 parts of ethylenediamine to obtain the fluorine-modified waterborne polyurethane emulsion. Finally, adding 10 parts of boron nitride and 0.05 part of curing agent into the fluorine modified waterborne polyurethane emulsion, and uniformly dispersing to obtain the heat-conducting adhesive.
Thirdly, preparing a copper-clad plate: forming a heat-conductive adhesive layer at one surface of the insulating paper substrate to form 10g/m 2 And then the roughened copper foil is covered on the heat-conducting adhesive layer, and the copper-clad plate is obtained by hot-pressing for 60min under the conditions of the temperature of 240 ℃ and the pressure of 5 MPa.
Table 2 shows the performance parameters of the copper clad laminate prepared in example five of the present invention.
Example six
The preparation method of the copper-clad plate provided by the embodiment of the invention comprises the following steps:
first, preparing an insulating paper substrate: and (3) blending polytetrafluoroethylene resin with alumina, nano silicon dioxide and ceramic powder to obtain polytetrafluoroethylene dispersion. Then dipping para-aramid paper in polytetrafluoroethylene dispersion for 5min, taking out, drying for 5min at 110 ℃ in an oven, dipping for 5min again, drying at 200 ℃ and hot-pressing for 30min at 280 ℃ under 5MPa to form the insulating paper substrate.
Wherein the mass ratio of the polytetrafluoroethylene resin to the alumina to the nano silicon dioxide to the ceramic powder is 80:40:10:10 in sequence.
Secondly, preparing a heat-conducting adhesive: 60 parts of dehydrated polyester diol-1000, 8 parts of acetone, 4 parts of dimethylolpropionic acid, 34 parts of isophorone diisocyanate and 0.1 part of dibutyltin dilaurate are mixed and reacted to obtain a mixed solution. Then adding 32 parts of seventeen fluoro-sunflower-base triethoxysilane to continue the reaction to obtain the fluorine modified waterborne polyurethane prepolymer. Then, 6 parts of triethylamine was added to the prepolymer for neutralization, and then 210 parts of deionized water and 3.6 parts of ethylenediamine were added to obtain a fluorine-modified aqueous polyurethane emulsion. Finally, adding 10 parts of boron nitride and 0.05 part of curing agent into the fluorine modified waterborne polyurethane emulsion, and uniformly dispersing to obtain the heat-conducting adhesive.
Thirdly, preparing a copper-clad plate: forming a heat-conductive adhesive layer at one surface of the insulating paper substrate to form 10g/m 2 Then the roughened copper foil is covered on the heat-conducting adhesive layer, and hot-pressed for 60min under the conditions of 240 ℃ and 5MPa to obtain the copper-clad plate。
Table 2 shows the performance parameters of the copper-clad laminate prepared in example six of the present invention.
TABLE 2
| Numbering device | Thermal conductivity (W/m.k) | Dielectric constant (10 GHz) | Peel strength (N/mm) |
| Example IV | 15 | 2.3 | 1.72 |
| Example five | 15 | 2.29 | 1.76 |
| Example six | 16 | 2.27 | 1.93 |
From the above, with the increase of the amount of the fluorine modifier, the thermal conductivity of the copper-clad plate is improved, the dielectric constant is very small, and the peel strength is gradually increased. The fluorine modified waterborne polyurethane has the advantages that when the fluorine modified waterborne polyurethane is used as an adhesive layer, the affinity with the insulating paper substrate is increased, meanwhile, the polyurethane has good adhesive property and heat resistance, and the copper foil and the insulating paper substrate can be firmly spliced together, so that the separation problem caused by the difference of thermal expansion coefficients of the copper foil and the insulating paper substrate at high temperature is effectively solved.
In order to investigate the influence of the amount of the heat conductive adhesive used on the heat conductivity, dielectric constant and peel strength of the obtained copper clad laminate, the following examples were used.
Example seven
The preparation method of the copper-clad plate provided by the embodiment of the invention comprises the following steps:
first, preparing an insulating paper substrate: and (3) blending polytetrafluoroethylene resin with boron nitride, nano silicon dioxide and ceramic powder to obtain polytetrafluoroethylene dispersion. Then, the polyimide paper is immersed in polytetrafluoroethylene dispersion for 5min, taken out, dried in an oven at 110 ℃ for 5min, immersed for 5min again, and dried at 200 ℃ to form the insulating paper substrate.
Wherein the mass ratio of the polytetrafluoroethylene resin to the boron nitride to the nano silicon dioxide to the ceramic powder is 80:40:10:10 in sequence.
Secondly, preparing a heat-conducting adhesive: 60 parts of dehydrated polyester diol-1000, 8 parts of acetone, 4 parts of dimethylolpropionic acid, 34 parts of isophorone diisocyanate and 0.1 part of dibutyltin dilaurate are mixed and reacted to obtain a mixed solution. Then adding 35 parts of seventeen fluoro-sunflower-based triethoxysilane to continue the reaction to obtain the fluorine modified waterborne polyurethane prepolymer. Then adding 6 parts of triethylamine to the prepolymer for neutralization reaction, and then adding 214 parts of deionized water and 3.6 parts of ethylenediamine to obtain the fluorine-modified waterborne polyurethane emulsion. Finally, adding 10 parts of boron nitride and 0.06 part of curing agent into the fluorine modified waterborne polyurethane emulsion, and uniformly dispersing to obtain the heat-conducting adhesive.
Thirdly, preparing a copper-clad plate: the heat-conducting adhesive layer is formed on two sides of the insulating paper substrate to form 20g/m 2 And then the roughened copper foil is covered on the corresponding heat-conducting adhesive layer, and the copper-clad plate is obtained by hot-pressing for 60min under the conditions of the temperature of 260 ℃ and the pressure of 5 MPa.
Table 3 shows the performance parameters of the copper-clad laminate prepared in example seven of the present invention.
Example eight
The preparation method of the copper-clad plate provided by the embodiment of the invention comprises the following steps:
first, preparing an insulating paper substrate: and (3) blending polytetrafluoroethylene resin with boron nitride, nano silicon dioxide and ceramic powder to obtain polytetrafluoroethylene dispersion. Then, the polyimide paper is immersed in polytetrafluoroethylene dispersion for 5min, taken out, dried in an oven at 110 ℃ for 5min, immersed for 5min again, and dried at 200 ℃ to form the insulating paper substrate.
Wherein the mass ratio of the polytetrafluoroethylene resin to the boron nitride to the nano silicon dioxide to the ceramic powder is 80:40:10:10 in sequence.
Secondly, preparing a heat-conducting adhesive: 60 parts of dehydrated polyester diol-1000, 8 parts of acetone, 4 parts of dimethylolpropionic acid, 34 parts of isophorone diisocyanate and 0.1 part of dibutyltin dilaurate are mixed and reacted to obtain a mixed solution. Then adding 35 parts of seventeen fluoro-sunflower-based triethoxysilane to continue the reaction to obtain the fluorine modified waterborne polyurethane prepolymer. Then adding 6 parts of triethylamine to the prepolymer for neutralization reaction, and then adding 214 parts of deionized water and 3.6 parts of ethylenediamine to obtain the fluorine-modified waterborne polyurethane emulsion. Finally, adding 10 parts of boron nitride and 0.06 part of curing agent into the fluorine modified waterborne polyurethane emulsion, and uniformly dispersing to obtain the heat-conducting adhesive.
Thirdly, preparing a copper-clad plate: forming a heat-conductive adhesive layer on both sides of the insulating paper substrate to form 30g/m 2 And then the roughened copper foil is covered on the corresponding heat-conducting adhesive layer, and the copper-clad plate is obtained by hot-pressing for 60min under the conditions of the temperature of 260 ℃ and the pressure of 5 MPa.
Table 3 shows that the copper-clad laminate prepared in example eight of the present invention is a performance parameter.
TABLE 3 Table 3
| Numbering device | Thermal conductivity (W/m.k) | Dielectric constant (10 GHz) | Peel strength (N/mm) |
| Example seven | 16 | 2.30 | 1.99 |
| Example eight | 15 | 2.33 | 2.08 |
From the above, as the coating amount of the heat-conductive adhesive increases, the peel strength and dielectric constant of the copper-clad plate increase, and the thermal conductivity decreases. The water polyurethane in the heat-conducting adhesive has larger occupation, low heat conductivity and large use amount in the heat-conducting adhesive, so that the density of the boron nitride heat-conducting channel is reduced to a certain extent in practice, and the heat is not beneficial to heat transmission.
The foregoing is merely a specific embodiment of the invention, and it will be apparent that various modifications and combinations thereof can be made without departing from the spirit and scope of the invention. Accordingly, the specification and drawings are merely exemplary illustrations of the present invention as defined in the appended claims and are considered to cover any and all modifications, variations, combinations, or equivalents that fall within the scope of the invention. It will be apparent to those skilled in the art that various modifications and variations can be made to the present invention without departing from the spirit or scope of the invention. Thus, it is intended that the present invention cover the modifications and variations of this invention provided they come within the scope of the appended claims and their equivalents. Any person skilled in the art can easily think of changes or substitutions within the technical scope of the present disclosure, and the present disclosure is intended to be covered by the present disclosure. Therefore, the protection scope of the present invention shall be subject to the protection scope of the claims.
Claims (10)
1. The preparation method of the copper-clad plate is characterized by comprising the following steps of:
immersing insulating paper in polytetrafluoroethylene dispersion liquid to form an insulating paper substrate, wherein the polytetrafluoroethylene dispersion liquid contains polytetrafluoroethylene and first heat conducting particles;
compounding the fluorine modified aqueous polyurethane emulsion with second heat conducting particles to form a heat conducting adhesive;
forming a heat-conducting adhesive layer on one or both sides of the insulating paper substrate;
and coating at least one roughened copper foil on the corresponding heat-conducting adhesive layer, and hot-pressing to form the copper-clad plate.
2. The method for producing a copper-clad plate according to claim 1, wherein the insulating paper is immersed in a polytetrafluoroethylene dispersion to obtain an insulating paper substrate, comprising:
the insulating paper is immersed in the polytetrafluoroethylene dispersion, and the insulating paper substrate is formed by drying.
3. The method of producing a copper-clad plate according to claim 1, wherein the polytetrafluoroethylene dispersion is obtained by blending polytetrafluoroethylene resin emulsion, first heat conductive particles and inorganic filler.
4. The method for producing a copper-clad plate according to claim 2, wherein the number of times of impregnation and drying is two, the time of each impregnation is 3 to 5 minutes, the temperature of the first drying is 100 to 110 ℃, the temperature of the second drying is 200 to 250 ℃, and the time of each drying is 5 to 10 minutes.
5. The method for producing a copper clad laminate according to claim 1, wherein the hot pressing temperature is 220 to 260 ℃, the hot pressing pressure is 1 to 30MPa, and the hot pressing time is 30 to 180 minutes.
6. The method of producing a copper-clad laminate according to claim 1, wherein the insulating paper comprises at least one of meta-aramid paper, para-aramid paper and polyimide paper.
7. A copper-clad laminate produced by the production method of a copper-clad laminate according to any one of claims 1 to 6, characterized by comprising: the insulation paper substrate comprises polytetrafluoroethylene resin, first heat conducting particles and inorganic filler, an adhesive layer and a copper foil layer which are sequentially laminated together, wherein the adhesive layer comprises second heat conducting particles and fluorine modified waterborne polyurethane.
8. The copper-clad laminate according to claim 7, wherein the second heat conductive particles and the first heat conductive particles comprise at least one of aluminum oxide, magnesium oxide, aluminum nitride, boron nitride, silicon nitride, and silicon carbide.
9. The copper-clad plate according to claim 7, wherein the inorganic filler comprises nano silicon dioxide and ceramic powder, and the mass ratio of the polytetrafluoroethylene resin to the first heat conducting particles to the nano silicon dioxide to the ceramic powder is (70-100): (10-40) the following (5-10): (5-10).
10. The copper-clad plate according to claim 7, wherein the mass ratio of the second heat conductive particles to the fluorine-modified waterborne polyurethane is (10 to 40): (60-90).
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Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN106476390A (en) * | 2017-01-03 | 2017-03-08 | 山东金宝科创股份有限公司 | A kind of preparation method of paper-based copper-coated board |
| CN109082944A (en) * | 2018-09-30 | 2018-12-25 | 深圳昊天龙邦复合材料有限公司 | Novel aramid fiber paper-based copper-coated board and preparation method thereof |
| CN109651995A (en) * | 2018-12-04 | 2019-04-19 | 顺德职业技术学院 | One-component flame-retarded heat-conducting fluorine silicon modified polyurethane hot melt adhesive and preparation method thereof |
| US20200165501A1 (en) * | 2018-11-28 | 2020-05-28 | Nan Ya Plastics Corporation | Fluorocarbon resin composition and prepreg and copper foil substrate using the same |
| CN114311884A (en) * | 2021-12-15 | 2022-04-12 | 山东金宝电子股份有限公司 | Radiation-resistant anti-aging copper-clad laminate and preparation method thereof |
-
2023
- 2023-05-10 CN CN202310534684.2A patent/CN116572608A/en active Pending
Patent Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN106476390A (en) * | 2017-01-03 | 2017-03-08 | 山东金宝科创股份有限公司 | A kind of preparation method of paper-based copper-coated board |
| CN109082944A (en) * | 2018-09-30 | 2018-12-25 | 深圳昊天龙邦复合材料有限公司 | Novel aramid fiber paper-based copper-coated board and preparation method thereof |
| US20200165501A1 (en) * | 2018-11-28 | 2020-05-28 | Nan Ya Plastics Corporation | Fluorocarbon resin composition and prepreg and copper foil substrate using the same |
| CN109651995A (en) * | 2018-12-04 | 2019-04-19 | 顺德职业技术学院 | One-component flame-retarded heat-conducting fluorine silicon modified polyurethane hot melt adhesive and preparation method thereof |
| CN114311884A (en) * | 2021-12-15 | 2022-04-12 | 山东金宝电子股份有限公司 | Radiation-resistant anti-aging copper-clad laminate and preparation method thereof |
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