CN114644846A - Fluorine-containing polymer emulsion copper-clad plate and preparation method thereof - Google Patents
Fluorine-containing polymer emulsion copper-clad plate and preparation method thereof Download PDFInfo
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- CN114644846A CN114644846A CN202011492971.4A CN202011492971A CN114644846A CN 114644846 A CN114644846 A CN 114644846A CN 202011492971 A CN202011492971 A CN 202011492971A CN 114644846 A CN114644846 A CN 114644846A
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- 229920000642 polymer Polymers 0.000 title claims abstract description 49
- 229910052731 fluorine Inorganic materials 0.000 title claims abstract description 47
- YCKRFDGAMUMZLT-UHFFFAOYSA-N Fluorine atom Chemical compound [F] YCKRFDGAMUMZLT-UHFFFAOYSA-N 0.000 title claims abstract description 45
- 239000011737 fluorine Substances 0.000 title claims abstract description 45
- 239000000839 emulsion Substances 0.000 title claims abstract description 44
- 238000002360 preparation method Methods 0.000 title description 6
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 claims abstract description 37
- 229910052802 copper Inorganic materials 0.000 claims abstract description 36
- 239000010949 copper Substances 0.000 claims abstract description 36
- 239000002105 nanoparticle Substances 0.000 claims abstract description 34
- 238000000034 method Methods 0.000 claims abstract description 31
- 239000002994 raw material Substances 0.000 claims abstract description 28
- 239000002002 slurry Substances 0.000 claims abstract description 28
- 239000011248 coating agent Substances 0.000 claims abstract description 26
- 238000000576 coating method Methods 0.000 claims abstract description 26
- 239000002131 composite material Substances 0.000 claims abstract description 24
- 238000002156 mixing Methods 0.000 claims abstract description 24
- 239000000203 mixture Substances 0.000 claims abstract description 21
- 239000002086 nanomaterial Substances 0.000 claims abstract description 19
- 239000006185 dispersion Substances 0.000 claims abstract description 18
- 238000001035 drying Methods 0.000 claims abstract description 17
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 17
- 239000003945 anionic surfactant Substances 0.000 claims abstract description 15
- 239000002736 nonionic surfactant Substances 0.000 claims abstract description 15
- 230000001678 irradiating effect Effects 0.000 claims abstract description 9
- 239000007788 liquid Substances 0.000 claims abstract description 9
- MCMNRKCIXSYSNV-UHFFFAOYSA-N ZrO2 Inorganic materials O=[Zr]=O MCMNRKCIXSYSNV-UHFFFAOYSA-N 0.000 claims abstract description 8
- 229910052681 coesite Inorganic materials 0.000 claims abstract description 8
- 229910052906 cristobalite Inorganic materials 0.000 claims abstract description 8
- 239000000377 silicon dioxide Substances 0.000 claims abstract description 8
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N silicon dioxide Inorganic materials O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims abstract description 8
- 229910052682 stishovite Inorganic materials 0.000 claims abstract description 8
- 229910052905 tridymite Inorganic materials 0.000 claims abstract description 8
- VTYYLEPIZMXCLO-UHFFFAOYSA-L calcium carbonate Substances [Ca+2].[O-]C([O-])=O VTYYLEPIZMXCLO-UHFFFAOYSA-L 0.000 claims abstract description 6
- 229910000019 calcium carbonate Inorganic materials 0.000 claims abstract description 6
- 230000000977 initiatory effect Effects 0.000 claims abstract description 6
- 229920002313 fluoropolymer Polymers 0.000 claims description 47
- 239000004811 fluoropolymer Substances 0.000 claims description 47
- 229920001343 polytetrafluoroethylene Polymers 0.000 claims description 14
- 239000004810 polytetrafluoroethylene Substances 0.000 claims description 14
- 239000000853 adhesive Substances 0.000 claims description 11
- 230000001070 adhesive effect Effects 0.000 claims description 11
- 239000003431 cross linking reagent Substances 0.000 claims description 11
- 239000004812 Fluorinated ethylene propylene Substances 0.000 claims description 8
- 239000003795 chemical substances by application Substances 0.000 claims description 7
- 239000002270 dispersing agent Substances 0.000 claims description 7
- 239000003349 gelling agent Substances 0.000 claims description 7
- 238000004519 manufacturing process Methods 0.000 claims description 7
- 239000004014 plasticizer Substances 0.000 claims description 7
- 239000002562 thickening agent Substances 0.000 claims description 7
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 claims description 6
- 229910052593 corundum Inorganic materials 0.000 claims description 6
- 229910001845 yogo sapphire Inorganic materials 0.000 claims description 6
- 230000003712 anti-aging effect Effects 0.000 claims description 5
- 238000006243 chemical reaction Methods 0.000 claims description 5
- 239000008367 deionised water Substances 0.000 claims description 5
- 229910021641 deionized water Inorganic materials 0.000 claims description 5
- 238000003825 pressing Methods 0.000 claims description 4
- 239000012528 membrane Substances 0.000 claims description 2
- 239000004813 Perfluoroalkoxy alkane Substances 0.000 claims 1
- QUAMTGJKVDWJEQ-UHFFFAOYSA-N octabenzone Chemical compound OC1=CC(OCCCCCCCC)=CC=C1C(=O)C1=CC=CC=C1 QUAMTGJKVDWJEQ-UHFFFAOYSA-N 0.000 description 10
- BJQHLKABXJIVAM-UHFFFAOYSA-N bis(2-ethylhexyl) phthalate Chemical compound CCCCC(CC)COC(=O)C1=CC=CC=C1C(=O)OCC(CC)CCCC BJQHLKABXJIVAM-UHFFFAOYSA-N 0.000 description 8
- 239000000463 material Substances 0.000 description 8
- 238000000016 photochemical curing Methods 0.000 description 8
- 229920000058 polyacrylate Polymers 0.000 description 8
- 239000004094 surface-active agent Substances 0.000 description 8
- -1 Polytetrafluoroethylene Polymers 0.000 description 7
- 229920009441 perflouroethylene propylene Polymers 0.000 description 7
- 238000001029 thermal curing Methods 0.000 description 7
- 238000012360 testing method Methods 0.000 description 6
- 238000005406 washing Methods 0.000 description 5
- RLWTYSCBQDVDRW-UHFFFAOYSA-N 2,2-bis(propanoyloxymethyl)butyl propanoate Chemical group CCC(=O)OCC(CC)(COC(=O)CC)COC(=O)CC RLWTYSCBQDVDRW-UHFFFAOYSA-N 0.000 description 4
- 229920001817 Agar Polymers 0.000 description 4
- QGZKDVFQNNGYKY-UHFFFAOYSA-O Ammonium Chemical compound [NH4+] QGZKDVFQNNGYKY-UHFFFAOYSA-O 0.000 description 4
- DPXJVFZANSGRMM-UHFFFAOYSA-N acetic acid;2,3,4,5,6-pentahydroxyhexanal;sodium Chemical compound [Na].CC(O)=O.OCC(O)C(O)C(O)C(O)C=O DPXJVFZANSGRMM-UHFFFAOYSA-N 0.000 description 4
- 239000001768 carboxy methyl cellulose Substances 0.000 description 4
- 238000001723 curing Methods 0.000 description 4
- 230000008569 process Effects 0.000 description 4
- 235000019812 sodium carboxymethyl cellulose Nutrition 0.000 description 4
- 229920001027 sodium carboxymethylcellulose Polymers 0.000 description 4
- 238000003756 stirring Methods 0.000 description 4
- 239000008272 agar Substances 0.000 description 3
- 239000004744 fabric Substances 0.000 description 3
- 239000003365 glass fiber Substances 0.000 description 3
- 125000004435 hydrogen atom Chemical group [H]* 0.000 description 3
- 239000002245 particle Substances 0.000 description 3
- 150000003839 salts Chemical class 0.000 description 3
- 239000000243 solution Substances 0.000 description 3
- 239000000126 substance Substances 0.000 description 3
- 239000000758 substrate Substances 0.000 description 3
- KWOLFJPFCHCOCG-UHFFFAOYSA-N Acetophenone Chemical compound CC(=O)C1=CC=CC=C1 KWOLFJPFCHCOCG-UHFFFAOYSA-N 0.000 description 2
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 2
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 2
- 229910052783 alkali metal Inorganic materials 0.000 description 2
- 150000001340 alkali metals Chemical class 0.000 description 2
- 239000007864 aqueous solution Substances 0.000 description 2
- 239000002585 base Substances 0.000 description 2
- 229910052799 carbon Inorganic materials 0.000 description 2
- 125000002843 carboxylic acid group Chemical group 0.000 description 2
- 238000004891 communication Methods 0.000 description 2
- 230000000052 comparative effect Effects 0.000 description 2
- 238000007796 conventional method Methods 0.000 description 2
- 239000003995 emulsifying agent Substances 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- 238000001027 hydrothermal synthesis Methods 0.000 description 2
- 239000011159 matrix material Substances 0.000 description 2
- 238000002715 modification method Methods 0.000 description 2
- ZSQCNVWYBBKUHS-UHFFFAOYSA-N (2,3-dimethylphenyl)-phenylmethanone Chemical compound CC1=CC=CC(C(=O)C=2C=CC=CC=2)=C1C ZSQCNVWYBBKUHS-UHFFFAOYSA-N 0.000 description 1
- 241000070928 Calligonum comosum Species 0.000 description 1
- 229920001774 Perfluoroether Polymers 0.000 description 1
- 229920004890 Triton X-100 Polymers 0.000 description 1
- 238000010521 absorption reaction Methods 0.000 description 1
- 238000005452 bending Methods 0.000 description 1
- 238000003763 carbonization Methods 0.000 description 1
- 239000000919 ceramic Substances 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 239000011889 copper foil Substances 0.000 description 1
- 125000004122 cyclic group Chemical group 0.000 description 1
- 125000005594 diketone group Chemical group 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- HQQADJVZYDDRJT-UHFFFAOYSA-N ethene;prop-1-ene Chemical group C=C.CC=C HQQADJVZYDDRJT-UHFFFAOYSA-N 0.000 description 1
- 238000001914 filtration Methods 0.000 description 1
- 125000001153 fluoro group Chemical group F* 0.000 description 1
- 125000003709 fluoroalkyl group Chemical group 0.000 description 1
- 239000008187 granular material Substances 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 238000005098 hot rolling Methods 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- 230000006872 improvement Effects 0.000 description 1
- 150000002484 inorganic compounds Chemical class 0.000 description 1
- 229910010272 inorganic material Inorganic materials 0.000 description 1
- 238000009413 insulation Methods 0.000 description 1
- 125000005647 linker group Chemical group 0.000 description 1
- 238000005259 measurement Methods 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 239000004745 nonwoven fabric Substances 0.000 description 1
- 125000004430 oxygen atom Chemical group O* 0.000 description 1
- 239000010702 perfluoropolyether Substances 0.000 description 1
- ONJQDTZCDSESIW-UHFFFAOYSA-N polidocanol Chemical compound CCCCCCCCCCCCOCCOCCOCCOCCOCCOCCOCCOCCOCCO ONJQDTZCDSESIW-UHFFFAOYSA-N 0.000 description 1
- 239000002952 polymeric resin Substances 0.000 description 1
- 238000006116 polymerization reaction Methods 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 239000011347 resin Substances 0.000 description 1
- 229920005989 resin Polymers 0.000 description 1
- 238000009774 resonance method Methods 0.000 description 1
- 238000005245 sintering Methods 0.000 description 1
- 238000004513 sizing Methods 0.000 description 1
- 238000002791 soaking Methods 0.000 description 1
- 239000007858 starting material Substances 0.000 description 1
- 229920003002 synthetic resin Polymers 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
- C09D4/00—Coating compositions, e.g. paints, varnishes or lacquers, based on organic non-macromolecular compounds having at least one polymerisable carbon-to-carbon unsaturated bond ; Coating compositions, based on monomers of macromolecular compounds of groups C09D183/00 - C09D183/16
- C09D4/06—Organic non-macromolecular compounds having at least one polymerisable carbon-to-carbon unsaturated bond in combination with a macromolecular compound other than an unsaturated polymer of groups C09D159/00 - C09D187/00
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
- C09D7/00—Features of coating compositions, not provided for in group C09D5/00; Processes for incorporating ingredients in coating compositions
- C09D7/40—Additives
- C09D7/60—Additives non-macromolecular
- C09D7/61—Additives non-macromolecular inorganic
- C09D7/62—Additives non-macromolecular inorganic modified by treatment with other compounds
-
- 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
- H05K1/05—Insulated conductive substrates, e.g. insulated metal substrate
- H05K1/053—Insulated conductive substrates, e.g. insulated metal substrate the metal substrate being covered by an inorganic insulating layer
-
- 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
Abstract
The fluorine-containing polymer emulsion copper-clad plate comprises a surface copper layer and one or more fluorine-containing polymer layers superposed on the copper layer, and is prepared by the following method: (1) mixing a fluorine-containing polymer emulsion and a surface-modified inorganic nano material dispersion liquid in a weight ratio of 3: 1-1: 1 to obtain a slurry, wherein the content of an anionic surfactant in the polymer emulsion is 800-2500ppm by weight, the content of a nonionic surfactant in the polymer emulsion is 4-8% by weight, and the surface-modified inorganic nano material Al is2O3Nanoparticles, ZrO2Nanoparticles, SiO2Nanoparticles, CaCO3Nanoparticles or mixtures thereof; (2) mixing 20-40% of the slurry, an effective initiating amount of a photoinitiator and the balance of water by weight to prepare a raw material; (3) and uniformly coating the raw materials on the surface of a copper plate, compacting a coating film and the copper plate by a compacting device, repeatedly coating and compacting to obtain a composite film, and drying and irradiating by ultraviolet light to obtain the fluorine-containing polymer copper-clad plate.
Description
Technical Field
The invention relates to a preparation method of a copper-clad plate containing a fluorine-containing polymer emulsion. The copper-clad plate prepared by the method has improved dielectric loss factor.
Background
The copper-clad plate is widely applied to the fields of mobile phones, computers, vending machines, communication base stations, satellites, wearable equipment, unmanned vehicles, unmanned aerial vehicles, intelligent robots and the like, and is one of key basic materials in electronic communication and information industries. For printed circuit boards in such applications, reducing losses at high frequencies is a key issue.
The fluorine-containing resin represented by Polytetrafluoroethylene (PTFE) has various excellent performances such as low dielectric constant, low dielectric loss, high thermal stability, chemical stability and the like which are incomparable with other polymer resins, and is an ideal copper-clad plate base material. The fluorine-containing polymer copper-clad plate has low loss characteristic, and is the best choice as a substrate of a millimeter wave band printed circuit board. The printed circuit board has a very low loss tangent and therefore very low dielectric loss. Therefore, the fluorine-containing polymer copper-clad plate technology is a core technology for preparing the low-loss printed circuit board.
In general, a low dielectric loss fluoropolymer such as Polytetrafluoroethylene (PTFE), meltable Polytetrafluoroethylene (PFA) and fluorinated ethylene propylene copolymer (FEP) has excellent dielectric, chemical and thermal properties, a small water absorption rate, a wide range of applications, and a small change in dielectric constant and dielectric dissipation factor even at high frequencies, so that the low dielectric loss fluoropolymer is used for the production of high frequency substrate materials.
The prior art proposes that fluorine-containing high polymer composite other materials, such as ceramics, glass fiber cloth and non-woven fabrics, are used for producing high-frequency copper-clad circuit boards. For example:
CN102173172B discloses a preparation method of a polytetrafluoroethylene copper-clad plate, which uses polytetrafluoroethylene emulsion and perfluoroalkoxy concentrated dispersion liquid to impregnate glass fiber cloth. Soaking the treated glass fiber cloth in different fluorine-containing polymers, drying at different temperatures, and curing in a three-section heating drying tunnel at 350-400 ℃. Finally obtaining the dielectric loss factor of 7 multiplied by 10-4The copper clad laminate has surface insulation resistance 1015, bending strength 140MPa and peeling strength 3 kN/m.
CN102350825B discloses a process method for preparing fluorine-containing high polymer high-frequency circuit board material by a hydrothermal method, which comprises the steps of uniformly mixing PTFE, FEP and PFA, adding salt, adding a molecular guide agent and a molecular weight regulator, uniformly mixing, adding the mixture into a reaction kettle to perform hydrothermal reaction to complete secondary polymerization of high molecules, obtaining a substance of high molecule coated dielectric inorganic compound nanoparticles, filtering, washing, drying, removing end groups, sintering at 380 ℃ of 320 plus materials for 10-48 hour, and hot rolling at 200-280 ℃ to form a thin plate with the thickness of 0.1-3 mm, and finally obtaining the high-frequency circuit board material with different dielectric constants.
Although the prior art provides a plurality of methods for manufacturing the fluorine-containing polymer copper-clad plate, the dielectric loss factor of the copper-clad plate product prepared by the method has room for improvement.
Disclosure of Invention
The invention aims to provide a fluorine-containing polymer copper-clad plate which has an improved dielectric loss factor.
The invention also aims to provide a manufacturing method of the fluorine-containing polymer copper-clad plate.
Therefore, one aspect of the present invention provides a fluoropolymer copper-clad plate, which comprises a surface copper layer and one or more fluoropolymer layers laminated on the copper layer, wherein the fluoropolymer copper-clad plate is prepared by the following steps:
(1) mixing 30-60 wt% of fluorine-containing polymer emulsion and 10-30 wt% of inorganic nano material dispersion liquid in a weight ratio of 3: 1-1: 1 to obtain slurry, wherein the content of anionic surfactant in the polymer emulsion is 800-2500ppm by weight, and the content of nonionic surfactant in the polymer emulsion is 4-8% by weight;
(2) mixing 20-40% of the slurry, 0.05-0.2% of a cross-linking agent, an effective initiating amount of a photoinitiator and water by weight to prepare a raw material;
(3) and uniformly coating the raw materials on the surface of a copper plate, compacting a coating film and the copper plate through a pressing device to obtain a composite film, and drying and irradiating by ultraviolet light to obtain the fluorine-containing polymer copper-clad plate.
Another aspect of the present invention provides a method for manufacturing a fluoropolymer copper-clad plate, wherein the fluoropolymer copper-clad plate comprises a surface copper layer and one or more fluoropolymer layers laminated on the copper layer, and the method comprises:
(1) mixing 30-60 wt% of fluorine-containing polymer emulsion slurry and 10-30 wt% of inorganic nano material dispersion liquid in a weight ratio of 3: 1-1: 1 to obtain slurry, wherein the polymer emulsion contains 800-2500ppm of anionic surfactant and 4-8% of nonionic surfactant by weight;
(2) mixing 20-40% of the slurry, 0.05-0.2% of a cross-linking agent, 0.3-1% of a photoinitiator and water by weight to prepare a raw material;
(3) and uniformly coating the raw materials on the surface of a copper plate, compacting a coating film and the copper plate by a pressing device to obtain a composite film, and drying and irradiating by ultraviolet light for 3-5 minutes to obtain the fluorine-containing polymer copper-clad plate.
The invention also relates to application of ultraviolet curing in preparation of the fluorine-containing polymer copper-clad plate.
Detailed Description
The inventors of the present invention studied how to further improve the performance, such as dielectric loss factor, of the fluoropolymer copper-clad plate prepared by the prior art method, and found that the dielectric loss of the prepared fluoropolymer copper-clad plate can be advantageously improved if photo-curing is used instead of thermal curing used in the prior art, and the present invention was completed on the basis of this finding.
Therefore, the invention provides a fluoropolymer copper-clad plate which comprises a surface copper layer and one or more fluoropolymer layers laminated on the copper layer.
The structure of the fluoropolymer copper-clad plate of the present invention is not particularly limited and may be a conventional structure known in the art, for example, it comprises a surface copper layer and one or more fluoropolymer layers laminated on the copper layer.
The fluoropolymer suitable for forming the fluoropolymer copper-clad layer of the present invention is not particularly limited and may be a conventional fluoropolymer known in the art. In one embodiment of the invention, the fluoropolymer is selected from a mixture of one or more of PTFE, FEP, PFA.
The manufacturing method of the fluorine-containing polymer copper-clad plate comprises the following steps:
(1) mixing 30-60 wt% of fluorine-containing polymer emulsion and 10-30 wt% of inorganic nano material dispersion liquid in a weight ratio of 3: 1-1: 1 to obtain slurry, wherein the content of anionic surfactant in the polymer emulsion is 800-2500ppm by weight, and the content of nonionic surfactant in the polymer emulsion is 4-8% by weight.
In one embodiment of the present invention, the inorganic nanomaterial is selected from Al2O3Nanoparticles, ZrO2Nanoparticles, SiO2Nanoparticles, CaCO3Nanoparticles or a mixture of two or more thereof.
The fluoropolymer emulsion suitable for use in the process of the present invention is not particularly limited and may be conventional fluoropolymer emulsions known in the art. In one embodiment of the invention, the fluoropolymer emulsion is an emulsion of a fluoropolymer selected from a mixture of one or more of PTFE, FEP, PFA.
In one embodiment of the invention, the fluoropolymer emulsion has an emulsion concentration of 30 to 60 wt%, preferably 35 to 55 wt%, more preferably 40 to 50 wt%, and preferably 42 to 48 wt%.
In one example of the invention, the fluoropolymer emulsion is commercially available, for example, from shanghai friendship new rich material ltd as FR302W (PTFE emulsion), FR305W, FR463W (FEP emulsion).
The fluoropolymer emulsions suitable for use in the process of the present invention contain an anionic surfactant and a nonionic surfactant. Suitable anionic surfactants and nonionic surfactants are not particularly limited and may be conventional anionic surfactants and nonionic surfactants known in the art.
In the method of the present invention, the anionic surfactant and the nonionic surfactant may be anionic surfactant and nonionic surfactant carried by commercially available fluoropolymer emulsion or inorganic nanomaterial dispersion, or added during mixing to prepare slurry.
In one embodiment of the invention, the anionic surfactant is a fluorinated surfactant, for example, which may be selected from:
(a) a perfluoropolyether having the following general formula (I) or (II):
CF3-(OCF)mO-CF2-X (I)
wherein m is an integer of 1 to 6;
x represents a carboxylic acid group or a salt thereof;
CF3-O-(CF2)3-(OCF(CF3)-CF2)zOLY (II)
wherein z is an integer from 0 to 3;
l represents a group selected from-CF (CF)3)-，-CF2-and-CF2CF2-a divalent linking group; and
y represents a carboxylic acid group or a salt thereof;
(b) a cyclic fluorochemical compound having the general formula:
wherein, X'1And X'2Each, the same or different from each other, is independently selected from H, F and C1-6(per) fluoroalkyl, optionally containing one or more catenated or non-linked radicalsCatenated oxygen atoms;
RFis a divalent fluorinated C1-3A bridging group;
(c) a fluorine-containing emulsifier selected from the group consisting of:
A2O3SCF2(CF2OCF(CF3))n-1COOA、CF3CF2(CF2OCF(CF3))n-1COOA、H3COOCF2(CF2OCF(CF3))n-1COOA, or a mixture of two or more thereof;
in the formula: n is 1 to 4,
a is a hydrogen atom, an alkali metal or NH4；
(d) A fluorine-containing emulsifier represented by the following general formula:
XCF2CF2(O)mCF2CF2OCF2COOA
wherein X is a hydrogen atom or a fluorine atom, A is a hydrogen atom, an alkali metal or NH4，
m is an integer of 0 to 1;
or a combination of two or more of the foregoing fluorinated surfactants.
In one embodiment of the invention, non-limiting examples of nonionic surfactants suitable for use in the methods of the invention are, for example: triton X100, GENAPOL X080, NP10, or a combination of two or more thereof.
In one embodiment of the present invention, the concentration of the anionic surfactant in the fluoropolymer emulsion of the present invention is 800-2500ppm by weight, preferably 850-2300ppm by weight, more preferably 900-2100ppm by weight, preferably 950-1900ppm by weight, preferably 980-1700ppm by weight, preferably 1000-1500ppm by weight.
In one embodiment of the invention, the nonionic surfactant is present in the fluoropolymer emulsion of the invention at a concentration of 4 to 8%, preferably 4.3 to 7.7%, more preferably 4.5 to 7.5%, preferably 4.8 to 7.2%, most preferably 5 to 7%, and most preferably 5.3 to 6.6% by weight.
The inorganic nanomaterial dispersion liquid suitable for use in the method of the present invention is not particularly limited, and may be one commonly used in the artA conventional inorganic nanomaterial dispersion. In one embodiment of the present invention, the inorganic nanomaterial is selected from Al2O3Nanoparticles, ZrO2Nanoparticles, SiO2Nanoparticles, CaCO3Nanoparticles or mixtures thereof.
In one embodiment of the present invention, the nanoparticle in the nano-dispersion has a particle size D90 of less than 100 nm, preferably less than 95 nm, and more preferably less than 90 nm.
In one embodiment of the present invention, the inorganic nanoparticles may be modified with fluorosurfactants to provide better dispersion in the polymer matrix. The modification method of the fluorosurfactant to be used is not particularly limited, and may be a conventional method known in the art as long as a stable nanoparticle dispersion can be formed and the inorganic nanoparticles can be uniformly dispersed in the polymer matrix.
In one embodiment of the invention, the inorganic nanoparticles are selected from Al stabilized by modification with fluorosurfactants2O3Nanoparticles, ZrO2Nanoparticles, SiO2Nanoparticles, CaCO3Nanoparticles or a mixture thereof.
In one embodiment of the invention, the surface modification method comprises the steps of mixing the fluorine-containing surfactant and the nanoparticles according to the mass ratio of 1:400-600, stirring the mixture in an aqueous solution at the temperature of 2-6 ℃ for 20-40 hours, and then washing and drying the mixture.
The fluorosurfactant suitable for modifying the nanoparticles is not particularly limited and can be a conventional fluorosurfactant known in the art, such as the fluorinated surfactants mentioned above as anionic surfactants.
In one embodiment of the present invention, the inorganic nanomaterial dispersion has a concentration of 10 to 30% by weight, preferably 12 to 28% by weight, more preferably 14 to 26% by weight, preferably 15 to 24% by weight, and preferably 18 to 22% by weight.
The method comprises the following steps of mixing the fluorine-containing polymer emulsion and the inorganic nano material dispersion liquid in a weight ratio of 3: 1-1: 1, preferably 2.8: 1-1.2: 1, preferably in a weight ratio of 2.5: 1-1.5: 1, preferably in a weight ratio of 2.2: 1-1.8: 1 to obtain a slurry.
(2) Mixing 20-40% of the slurry, 0.05-0.2% of a cross-linking agent, an initiating effective amount of a photoinitiator and water by weight to prepare a raw material;
the amount of the slurry used in preparing the raw material is 20 to 40% by weight, preferably 25 to 35% by weight, more preferably 28 to 32% by weight.
The photoinitiator suitable for use in the method of the present invention is not particularly limited and may be a conventional photoinitiator known in the art, and may be used in an amount effective for initiation. In one embodiment of the invention, the photoinitiator is selected from one or more of tolidine, alkyl ketone, diketone or acetyl benzene. In one embodiment of the present invention, the photoinitiator is used in an amount of 0.3 to 1%, preferably 0.5 to 0.8%, more preferably 0.6 to 0.7%, based on the total weight of the starting materials.
In formulating the raw materials, the crosslinking agent is used in an amount of 0.05 to 0.2%, preferably 0.08 to 0.18%, more preferably 0.10 to 0.16%, preferably 0.12 to 0.14% by weight.
The crosslinking agent to be used is not particularly limited and may be a conventional crosslinking agent known in the art. In one embodiment of the invention, the cross-linking agent is selected from trimethylolpropane tripropionate.
Other components can be optionally added when the raw materials are prepared so as to more easily prepare the fluorine-containing polymer copper-clad plate. The other components are selected, for example, from adhesives, dispersants, gelling agents, plasticizers, anti-aging agents, thickeners, or mixtures thereof.
In one embodiment of the invention, the feedstock contains 3-6%, preferably 3.5-5.5%, more preferably 4-5% by weight of the adhesive. The adhesive to be used is not particularly limited, and may be a conventional adhesive known in the art. In one embodiment of the present invention, the adhesive comprises a polyacrylate aqueous adhesive.
In one embodiment of the invention, the feedstock contains 0.2 to 0.5%, preferably 0.25 to 0.45%, more preferably 0.3 to 0.4% by weight of dispersant. The dispersant to be used is not particularly limited and may be a conventional dispersant known in the art. In one embodiment of the invention, the dispersant comprises ammonium polyacrylate.
In one embodiment of the invention, the feedstock contains 0.2 to 0.5%, preferably 0.25 to 0.45%, more preferably 0.3 to 0.4% by weight of gelling agent. The gelling agent to be used is not particularly limited and may be a conventional gelling agent known in the art. In one example of the present invention, the gelling agent comprises agar.
In one embodiment of the invention, the feedstock contains 0.05 to 0.2%, preferably 0.08 to 0.18%, more preferably 0.1 to 0.15% by weight of a plasticizer. The plasticizer to be used is not particularly limited and may be a conventional plasticizer known in the art. In one embodiment of the invention, the plasticizer comprises di (2-ethylhexyl) phthalate.
In one embodiment of the invention, the feedstock contains 0.05 to 0.2%, preferably 0.08 to 0.18%, more preferably 0.10 to 0.15% by weight of the anti-aging agent. The suitable age resisters are not particularly limited and may be conventional ones known in the art. In one embodiment of the present invention, the anti-aging agent comprises 2-hydroxy-4-n-octoxybenzophenone.
In one embodiment of the invention, the feedstock contains 0.1 to 0.5%, preferably 0.15 to 0.45%, more preferably 0.2 to 0.4% by weight of a thickener. The thickener to be used is not particularly limited and may be a conventional thickener known in the art. In one embodiment of the invention, the thickening agent comprises sodium carboxymethyl cellulose.
(3) And uniformly coating the raw materials on the surface of a copper plate, compacting a coating film and the copper plate through a pressing device to obtain a composite film, and drying and irradiating by ultraviolet light to obtain the fluorine-containing polymer copper-clad plate.
The method for coating the raw material on the surface of the copper plate to obtain the composite film is not particularly limited and may be a conventional method known in the art, for example, the raw material may be coated on a copper foil, dried at 50 to 70 c and pressed, and the above operation may be repeated until a fluoropolymer layer of a desired thickness is obtained. And then drying the obtained composite membrane at 50-70 ℃ for 10-60 minutes.
The process of the invention comprises the step of photocuring the resulting composite film, for example by irradiation with ultraviolet light. The time of the ultraviolet light irradiation is not particularly limited, and a person of ordinary skill in the art can easily determine an appropriate ultraviolet light irradiation time depending on the details of the light source, the photoinitiator, and the like. In one embodiment of the invention, the composite film is irradiated with ultraviolet light for 3-5 minutes, preferably 3.5-4.5 minutes, more preferably 3.8-4.2 minutes, to obtain the final fluoropolymer copper-clad plate.
The ultraviolet light source for irradiation to be used is not particularly limited, and may be any of those known in the art for photocuring.
The present inventors have found, through studies on the prior art, that the dielectric loss of the product can be advantageously improved by using a photo-curing method instead of a thermal curing method. The applicant speculates that the possible reason for this effect is that the temperature conditions for thermal curing of the fluoropolymer copper-clad plate in the prior art are too severe, so that the surfactant in the raw material is more or less carbonized, and the conductive carbon particles formed by carbonization affect the dielectric properties of the prepared fluoropolymer copper-clad plate, thus making the fluoropolymer copper-clad plate difficult to be used in some fields with high requirements, such as the manufacture of high-frequency substrates. The inventor finds out from the above research that if photo curing is used instead of thermal curing, carbon conductive particles generated by thermal curing are advantageously avoided, thereby improving the dielectric properties of the fluoropolymer copper-clad plate.
Examples
The technical solution of the present invention is further described below by specific examples. The following examples are further illustrative of the present invention and do not limit the scope of the present invention.
Preparation of test specimens
The fluoropolymer feedstock is coated onto a release liner, dried, compacted and the above steps are repeated, and after thermal or light curing, the release liner is removed to provide the fluoropolymer sheet for testing.
Measurement of dielectric constant
Dielectric properties (dielectric constant/dielectric loss) of the cured fluoropolymer the dielectric properties at 10GHz were tested using the split cylinder resonance method (SPDR).
Example 1
(1) Adding fluorine-containing surfactant C2F5-OCFO-CF2-COONH4With Al2O3Mixing the nano materials according to the mass ratio of 1:500, stirring the mixture in a water solution at 4 ℃ for 24 hours, washing and drying the mixture to obtain surface-modified nano particles for later use.
(2) And preparing the fluorine-containing polymer emulsion slurry. Using a PTFE emulsion (FR302W, available from Shanghai Huayi Sanai-Rich materials Co., Ltd., 60 wt%) containing 4% of a nonionic surfactant TMN, and the above surface-modified Al2O3The nanodispersion (20 wt%) was stirred thoroughly to give a slurry with a weight ratio of emulsion to dispersion of 3: 1.
(3) Taking the following raw materials according to the mass percentage, mixing 20% of the slurry, 3% of polyacrylate water-based adhesive, 0.2% of ammonium polyacrylate, 0.2% of agaropectin, 0.05% of di (2-ethylhexyl) phthalate, 0.05% of 2-hydroxy-4-n-octoxybenzophenone, 0.05% of trimethylolpropane tripropionate, 0.1% of sodium carboxymethylcellulose, 0.3% of xylophenone and the balance of deionized water to prepare the raw materials for later use.
(4) Uniformly coating the raw materials on the surface of a copper plate, compacting a coating film and the copper plate by a compacting device, repeatedly coating and compacting to obtain a composite film, then drying the composite film at 50 ℃ for 30 minutes, and irradiating the dried composite film by using an ultraviolet light reaction instrument for 3 minutes to obtain a fluorine-containing polymer copper-clad product.
Test specimens were prepared in the above-described manner and the dielectric constants thereof were measured, with the results shown in Table 1.
Example 2
(1) Adding fluorine-containing surfactant C2F5-OCFO-CF2-COONH4And ZrO2Mixing the nano materials according to the mass ratio of 1:500, stirring the mixture in aqueous solution at 4 ℃ for 24 hours, washing and drying the mixture to obtain surface-modified nano particlesThe granules are ready for use.
(2) And preparing the fluorine-containing polymer emulsion slurry. FEP emulsion (type FR463, 50% concentration, available from Shanghai Huayi Sanai-Rich materials Co., Ltd.) with TMN nonionic surfactant content of 5% is mixed with the above-mentioned surface-modified ZrO2The nanodispersion (18 wt%) was stirred thoroughly to give a slurry with a weight ratio of emulsion to dispersion of 2: 1.
(3) The raw materials are taken according to the mass percentage, 40 percent of the sizing agent, 5 percent of polyacrylate water-based adhesive, 0.4 percent of ammonium polyacrylate, 0.5 percent of agar, 0.2 percent of di (2-ethylhexyl) phthalate, 0.2 percent of 2-hydroxy-4-n-octoxy benzophenone, 0.2 percent of trimethylolpropane tripropionate, 0.5 percent of sodium carboxymethylcellulose, 1 percent of alkyl ketone and the balance of deionized water are mixed to prepare the raw materials for standby.
(4) The method comprises the steps of uniformly coating the raw materials on the surface of a copper plate, compacting a coating film and the copper plate through a compacting device, repeatedly coating and compacting to obtain a composite film, drying the composite film at 70 ℃ for 30 minutes, and irradiating the dried composite film for 3 minutes by using an ultraviolet light reaction instrument.
Test specimens were prepared in the above-described manner and the dielectric constants thereof were measured, with the results shown in Table 1.
Example 3
(1) Adding fluorine-containing surfactant C2F5-OCFO-CF2-COONH4With SiO2Mixing the nano materials according to the mass ratio of 1:500, stirring the mixture in a water solution at 4 ℃ for 24 hours, washing and drying the mixture to obtain surface-modified nano particles for later use.
(2) And preparing the fluorine-containing polymer emulsion slurry. Using a fluorine-containing anionic surfactant (C)2F5-OCFO-CF2-COONH4) PFA emulsion (type FR305, 50% strength, from Sanai Rich materials Co., Ltd., Shanghai) with a content of 800ppm and the above surface-modified SiO2The nanodispersion (18 wt) was stirred thoroughly to give a slurry with a weight ratio of emulsion to dispersion of 1: 1.
(2) Taking 30% of slurry, 4% of polyacrylate water-based adhesive, 0.3% of ammonium polyacrylate, 0.4% of agar, 0.1% of di (2-ethylhexyl) phthalate, 0.1% of 2-hydroxy-4-n-octoxybenzophenone, 0.1% of trimethylolpropane tripropionate, 0.3% of sodium carboxymethylcellulose, 1% of acetyl benzene and the balance of deionized water according to mass percentage, mixing and preparing the raw materials for later use.
(3) The method comprises the steps of uniformly coating the raw materials on the surface of a copper plate, compacting a coating film and the copper plate through a compacting device, repeatedly coating and compacting to obtain a composite film, drying the composite film at 70 ℃ for 60 minutes, and irradiating the dried composite film for 5 minutes by using an ultraviolet light reaction instrument.
Test specimens were prepared in the above-described manner, and the dielectric constants thereof were measured, with the results shown in Table 1.
Comparative example 1
The procedure of example 1 was repeated, but without adding 0.05% of photoinitiator 2-hydroxy-4-n-octyloxybenzophenone, the raw materials were uniformly coated on the surface of a copper plate, the coating film and the copper plate were compacted by a compacting device, the coating and compacting were repeated to obtain a composite film, and then the composite film was dried at 370 ℃ for 6 hours.
The dielectric constant of the fluoropolymer film after thermal curing was tested as described above and the results are shown in table 1.
TABLE 1
| Curing method | Dielectric constant | Dielectric loss | |
| Example 1 | Photo-curing | 6.0 | 1.8×10-3 |
| Example 2 | Photocuring | 3.8 | 1.0×10-3 |
| Example 3 | Photocuring | 14 | 5.8×10-3 |
| Comparative example 1 | Thermal curing at 370 DEG C | 6.0 | 2.4×10-3 |
As can be seen from the above test results, the inventors of the present invention have found a method for further improving the dielectric properties of a fluoropolymer copper-clad plate based on the study on the prior art, so that the resulting product can be advantageously used in, for example, high frequency fields.
Claims (10)
1. A fluorine-containing polymer copper-clad plate comprises a surface copper layer and one or more fluorine-containing polymer layers superposed on the copper layer, wherein the fluorine-containing polymer copper-clad plate is prepared by the following method:
(1) mixing 30-60 wt% of fluorine-containing polymer emulsion and 10-30 wt% of inorganic nano material dispersion liquid in a weight ratio of 3: 1-1: 1 to obtain slurry, wherein the content of anionic surfactant in the polymer emulsion is 800-2500ppm by weight, and the content of nonionic surfactant in the polymer emulsion is 4-8% by weight;
(2) mixing 20-40% of the slurry, 0.05-0.2% of a cross-linking agent, an initiating effective amount of a photoinitiator and water by weight to prepare a raw material;
(3) and uniformly coating the raw materials on the surface of a copper plate, compacting a coating film and the copper plate through a pressing device to obtain a composite film, and drying and irradiating by ultraviolet light to obtain the fluorine-containing polymer copper-clad plate.
2. The fluorine-containing polymer copper-clad plate according to claim 1, wherein the raw materials are prepared by mixing, by weight, 20-40% of the slurry, 3-6% of an adhesive, 0.2-0.5% of a dispersant, 0.2-0.5% of a gelling agent, 0.05-0.2% of a plasticizer, 0.05-0.2% of an anti-aging agent, 0.08-0.18% of a cross-linking agent, 0.1-0.5% of a thickening agent, 0.3-1% of a photoinitiator and deionized water.
3. The fluoropolymer copper-clad plate according to claim 1 or 2, wherein the composite film is irradiated for 3-5 minutes by an ultraviolet light reaction instrument.
4. The copper-clad plate containing fluoropolymer according to claim 1 or 2, wherein the fluoropolymer is selected from PTFE, FEP, PFA or a mixture thereof.
5. The fluoropolymer copper-clad plate according to claim 1 or 2, wherein the inorganic nano-material is selected from Al2O3Nanoparticles, ZrO2Nanoparticles, SiO2Nanoparticles, CaCO3Nanoparticles or mixtures thereof.
6. A method for manufacturing a fluoropolymer copper-clad plate, wherein the fluoropolymer copper-clad plate comprises a surface copper layer and one or more fluoropolymer layers laminated on the copper layer, and the method comprises the following steps:
(1) mixing 30-60 wt% of fluorine-containing polymer emulsion slurry and 10-30 wt% of inorganic nano material dispersion liquid in a weight ratio of 3: 1-1: 1 to obtain slurry, wherein the polymer emulsion contains 800-2500ppm of anionic surfactant and 4-8% of nonionic surfactant by weight;
(2) mixing 20-40% of the slurry, 0.05-0.2% of a cross-linking agent, an initiating effective amount of a photoinitiator and water by weight to prepare a raw material;
(3) and uniformly coating the raw materials on the surface of a copper plate, compacting a coating film and the copper plate by a compacting device, repeatedly coating and compacting to obtain a composite film, and drying and irradiating by ultraviolet light to obtain the fluorine-containing polymer copper-clad plate.
7. The method of claim 6, wherein the slurry is prepared by mixing, by weight, 20 to 40% of the slurry, 3 to 6% of the adhesive, 0.2 to 0.5% of the dispersant, 0.2 to 0.5% of the gelling agent, 0.05 to 0.2% of the plasticizer, 0.05 to 0.2% of the anti-aging agent, 0.08 to 0.18% of the crosslinking agent, 0.1 to 0.5% of the thickener, 0.3 to 1% of the photoinitiator, and deionized water.
8. A method according to claim 6 or 7, wherein the composite membrane is irradiated with UV light for 3 to 5 minutes.
9. The method of claim 6 or 7, wherein the fluoropolymer is selected from PTFE, FEP, PFA, or mixtures thereof.
10. The method of claim 6 or 7, wherein the inorganic nanomaterial is selected from Al2O3Nanoparticles, ZrO2Nanoparticles, SiO2Nanoparticles, CaCO3Nanoparticles or mixtures thereof.
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| WO2024007535A1 (en) * | 2022-07-05 | 2024-01-11 | 广东生益科技股份有限公司 | Fluorine-containing resin copper-clad laminate and multi-layer circuit board |
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