CN110996536B - Carrier copper foil and preparation method and application thereof - Google Patents
Carrier copper foil and preparation method and application thereof Download PDFInfo
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- CN110996536B CN110996536B CN201911359477.8A CN201911359477A CN110996536B CN 110996536 B CN110996536 B CN 110996536B CN 201911359477 A CN201911359477 A CN 201911359477A CN 110996536 B CN110996536 B CN 110996536B
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- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 title claims abstract description 158
- 239000011889 copper foil Substances 0.000 title claims abstract description 145
- 238000002360 preparation method Methods 0.000 title claims abstract description 26
- 238000000034 method Methods 0.000 claims abstract description 34
- 238000004519 manufacturing process Methods 0.000 claims abstract description 14
- 239000010410 layer Substances 0.000 claims description 91
- 239000000853 adhesive Substances 0.000 claims description 39
- 230000001070 adhesive effect Effects 0.000 claims description 26
- 239000011888 foil Substances 0.000 claims description 19
- 239000011248 coating agent Substances 0.000 claims description 11
- 238000000576 coating method Methods 0.000 claims description 11
- 238000004381 surface treatment Methods 0.000 claims description 9
- 239000012790 adhesive layer Substances 0.000 claims description 8
- 229920001971 elastomer Polymers 0.000 claims description 8
- 238000007747 plating Methods 0.000 claims description 8
- 238000001035 drying Methods 0.000 claims description 7
- 229910052751 metal Inorganic materials 0.000 claims description 6
- 239000002184 metal Substances 0.000 claims description 6
- 229920000058 polyacrylate Polymers 0.000 claims description 6
- -1 polybutylene terephthalate Polymers 0.000 claims description 5
- 238000005096 rolling process Methods 0.000 claims description 5
- 238000004804 winding Methods 0.000 claims description 5
- 239000004819 Drying adhesive Substances 0.000 claims description 4
- BLRPTPMANUNPDV-UHFFFAOYSA-N Silane Chemical compound [SiH4] BLRPTPMANUNPDV-UHFFFAOYSA-N 0.000 claims description 4
- 229920000139 polyethylene terephthalate Polymers 0.000 claims description 4
- 239000005020 polyethylene terephthalate Substances 0.000 claims description 4
- 229910000077 silane Inorganic materials 0.000 claims description 4
- 238000003475 lamination Methods 0.000 claims description 3
- 229920001707 polybutylene terephthalate Polymers 0.000 claims description 3
- 229920001721 polyimide Polymers 0.000 claims description 3
- 238000007788 roughening Methods 0.000 claims description 3
- 229920006290 polyethylene naphthalate film Polymers 0.000 claims description 2
- 229920001296 polysiloxane Polymers 0.000 claims 1
- 230000008569 process Effects 0.000 abstract description 9
- 238000010924 continuous production Methods 0.000 abstract description 4
- 238000010030 laminating Methods 0.000 description 17
- 239000003292 glue Substances 0.000 description 14
- 239000011347 resin Substances 0.000 description 14
- 229920005989 resin Polymers 0.000 description 14
- 229910052802 copper Inorganic materials 0.000 description 13
- 239000010949 copper Substances 0.000 description 13
- 239000003795 chemical substances by application Substances 0.000 description 10
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 9
- 239000007787 solid Substances 0.000 description 9
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 8
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 8
- 238000009713 electroplating Methods 0.000 description 8
- 230000003746 surface roughness Effects 0.000 description 8
- ZWEHNKRNPOVVGH-UHFFFAOYSA-N 2-Butanone Chemical compound CCC(C)=O ZWEHNKRNPOVVGH-UHFFFAOYSA-N 0.000 description 6
- 239000000654 additive Substances 0.000 description 6
- 230000000996 additive effect Effects 0.000 description 6
- 239000006087 Silane Coupling Agent Substances 0.000 description 5
- 230000000052 comparative effect Effects 0.000 description 5
- 238000011161 development Methods 0.000 description 5
- 239000000126 substance Substances 0.000 description 5
- VYZAMTAEIAYCRO-UHFFFAOYSA-N Chromium Chemical compound [Cr] VYZAMTAEIAYCRO-UHFFFAOYSA-N 0.000 description 4
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 description 4
- 239000004820 Pressure-sensitive adhesive Substances 0.000 description 4
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 description 4
- 229910052804 chromium Inorganic materials 0.000 description 4
- 239000011651 chromium Substances 0.000 description 4
- JHIVVAPYMSGYDF-UHFFFAOYSA-N cyclohexanone Chemical compound O=C1CCCCC1 JHIVVAPYMSGYDF-UHFFFAOYSA-N 0.000 description 4
- 229910052759 nickel Inorganic materials 0.000 description 4
- 239000003960 organic solvent Substances 0.000 description 4
- 229920002379 silicone rubber Polymers 0.000 description 4
- 239000004945 silicone rubber Substances 0.000 description 4
- 239000002904 solvent Substances 0.000 description 4
- 238000003756 stirring Methods 0.000 description 4
- 239000011701 zinc Substances 0.000 description 4
- 229910052725 zinc Inorganic materials 0.000 description 4
- 229920002799 BoPET Polymers 0.000 description 3
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 3
- 239000004593 Epoxy Substances 0.000 description 3
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 3
- 229910052799 carbon Inorganic materials 0.000 description 3
- 239000003431 cross linking reagent Substances 0.000 description 3
- 238000009776 industrial production Methods 0.000 description 3
- 239000012948 isocyanate Substances 0.000 description 3
- 150000002513 isocyanates Chemical class 0.000 description 3
- 239000000203 mixture Substances 0.000 description 3
- 229920003207 poly(ethylene-2,6-naphthalate) Polymers 0.000 description 3
- 239000011112 polyethylene naphthalate Substances 0.000 description 3
- 229910052710 silicon Inorganic materials 0.000 description 3
- 239000010703 silicon Substances 0.000 description 3
- 239000004094 surface-active agent Substances 0.000 description 3
- 238000012360 testing method Methods 0.000 description 3
- 239000004925 Acrylic resin Substances 0.000 description 2
- 239000004342 Benzoyl peroxide Substances 0.000 description 2
- OMPJBNCRMGITSC-UHFFFAOYSA-N Benzoylperoxide Chemical compound C=1C=CC=CC=1C(=O)OOC(=O)C1=CC=CC=C1 OMPJBNCRMGITSC-UHFFFAOYSA-N 0.000 description 2
- 239000004695 Polyether sulfone Substances 0.000 description 2
- 235000019400 benzoyl peroxide Nutrition 0.000 description 2
- 230000032798 delamination Effects 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- 239000000463 material Substances 0.000 description 2
- 230000003647 oxidation Effects 0.000 description 2
- 238000007254 oxidation reaction Methods 0.000 description 2
- 239000004014 plasticizer Substances 0.000 description 2
- 229920006393 polyether sulfone Polymers 0.000 description 2
- 238000003825 pressing Methods 0.000 description 2
- 239000002994 raw material Substances 0.000 description 2
- OZAIFHULBGXAKX-UHFFFAOYSA-N 2-(2-cyanopropan-2-yldiazenyl)-2-methylpropanenitrile Chemical compound N#CC(C)(C)N=NC(C)(C)C#N OZAIFHULBGXAKX-UHFFFAOYSA-N 0.000 description 1
- 241000282320 Panthera leo Species 0.000 description 1
- 239000004734 Polyphenylene sulfide Substances 0.000 description 1
- WNLRTRBMVRJNCN-UHFFFAOYSA-L adipate(2-) Chemical compound [O-]C(=O)CCCCC([O-])=O WNLRTRBMVRJNCN-UHFFFAOYSA-L 0.000 description 1
- 230000002411 adverse Effects 0.000 description 1
- 239000012752 auxiliary agent Substances 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 238000004132 cross linking Methods 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 239000003822 epoxy resin Substances 0.000 description 1
- 238000005530 etching Methods 0.000 description 1
- 238000007731 hot pressing Methods 0.000 description 1
- 230000008676 import Effects 0.000 description 1
- 239000011810 insulating material Substances 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 238000010297 mechanical methods and process Methods 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 239000002736 nonionic surfactant Substances 0.000 description 1
- 238000011056 performance test Methods 0.000 description 1
- 150000003071 polychlorinated biphenyls Chemical class 0.000 description 1
- 229920000647 polyepoxide Polymers 0.000 description 1
- 239000009719 polyimide resin Substances 0.000 description 1
- 229920000069 polyphenylene sulfide Polymers 0.000 description 1
- 125000002924 primary amino group Chemical group [H]N([H])* 0.000 description 1
- 238000012545 processing Methods 0.000 description 1
- BWJUFXUULUEGMA-UHFFFAOYSA-N propan-2-yl propan-2-yloxycarbonyloxy carbonate Chemical compound CC(C)OC(=O)OOC(=O)OC(C)C BWJUFXUULUEGMA-UHFFFAOYSA-N 0.000 description 1
- 230000000630 rising effect Effects 0.000 description 1
- 229940116351 sebacate Drugs 0.000 description 1
- CXMXRPHRNRROMY-UHFFFAOYSA-L sebacate(2-) Chemical compound [O-]C(=O)CCCCCCCCC([O-])=O CXMXRPHRNRROMY-UHFFFAOYSA-L 0.000 description 1
- 238000007711 solidification Methods 0.000 description 1
- 230000008023 solidification Effects 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
- KDYFGRWQOYBRFD-UHFFFAOYSA-L succinate(2-) Chemical compound [O-]C(=O)CCC([O-])=O KDYFGRWQOYBRFD-UHFFFAOYSA-L 0.000 description 1
- 150000003900 succinic acid esters Chemical class 0.000 description 1
- 125000000391 vinyl group Chemical group [H]C([*])=C([H])[H] 0.000 description 1
- 229920002554 vinyl polymer Polymers 0.000 description 1
- 239000002699 waste material Substances 0.000 description 1
- 230000037303 wrinkles Effects 0.000 description 1
Classifications
-
- 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
- H05K3/025—Processes for manufacturing precursors of printed circuits, i.e. copper-clad substrates by transfer of thin metal foil formed on a temporary carrier, e.g. peel-apart copper
-
- 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
Landscapes
- Engineering & Computer Science (AREA)
- Manufacturing & Machinery (AREA)
- Microelectronics & Electronic Packaging (AREA)
- Laminated Bodies (AREA)
Abstract
The invention provides a carrier copper foil, a preparation method and application thereof, comprising an electrolytic copper foil and a carrier layer arranged on one side of the electrolytic copper foil; wherein the thickness of the electrolytic copper foil is 3-9 mu m. The carrier copper foil provided by the invention can effectively avoid the problems of wrinkling, tearing, folding and the like of the ultrathin copper foil in the production, transportation and use processes, can realize continuous production in a roll-to-roll mode, and is suitable for large-area popularization; meanwhile, the carrier layer is easy to peel, and after the carrier layer is peeled off, the copper foil layer is not damaged, and no carrier layer remains; meanwhile, the preparation method provided by the invention is simple and easy to operate.
Description
Technical Field
The invention belongs to the technical field of copper-clad plates, and relates to a carrier copper foil, a preparation method and application thereof.
Background
In recent years, the electrolytic copper foil industry in China develops rapidly, and as a main raw material of a Printed Circuit Board (PCB), the development of the electrolytic copper foil is followed with the development of PCB technology, and the PCB is continuously improved along with the daily change of electronic products, and the electronic products are developed in the directions of low cost, high reliability, high stability and multifunction at present, so that higher requirements for updating the performance and variety of the electrolytic copper foil are provided, and the electrolytic copper foil has a brand-new development trend, and the thickness of the electrolytic copper foil is developed in the directions of thinness and ultra-thinness.
Copper foil having a thickness of 12 μm or less is generally called ultra-thin copper foil, and the copper foil becomes thinner and thinner, so that it becomes more difficult to prepare and is easily wrinkled and torn during transportation. At present, the production of ultra-thin copper foil in industry mostly adopts metal carrier foil with a certain thickness as cathode, and copper is electrodeposited on the cathode; then, the plated ultrathin copper foil and the cathode carrier foil are pressed on an insulating material plate together through hot pressing, solidification and pressing, and then the metal carrier foil used as the cathode is stripped and removed by a chemical or mechanical method; such an ultra-thin copper foil electrodeposited on a metal carrier is called a carrier ultra-thin copper foil. The preparation technology of the carrier ultrathin copper foil is mainly mastered in the hands of China such as Japan, the United states and the like, the price and the price are expensive, domestic demands are all solved by import, and the problem that a carrier layer is difficult to strip exists.
CN108349208A discloses a method for producing a copper foil with carrier, a copper foil with resin, and a printed circuit board, the copper foil with carrier comprising: a support composed of at least 1 resin selected from polyethylene naphthalate resin (PEN), polyether sulfone resin (PES), polyimide resin, and polyphenylene sulfide resin; a silicon layer provided on the carrier and mainly containing silicon; a carbon layer provided on the silicon layer and mainly containing carbon; and an extremely thin copper layer arranged on the carbon layer, the carrier obtained by the patent has excellent peeling strength, is difficult to peel off the carrier, causes complex subsequent treatment, does not relate to the surface treatment process of the extremely thin copper layer, and does not disclose whether the carrier layer can meet the requirement of extremely thin normal surface treatment, so that the copper foil which is not subjected to surface treatment is difficult to meet the circuit manufacturing requirement of a printed circuit board. CN108277509a discloses a copper foil with carrier, comprising, in order, a carrier, a release layer, an extremely thin copper layer, and an optional resin layer, wherein the average value of Rz on the surface of the extremely thin copper layer is 1.5 μm or less and the standard deviation of Rz is 0.1 μm or less as measured by a contact roughness meter according to JISB 0601-1982; the copper foil with the carrier provided by the patent is suitable for forming fine spacing, has higher in-plane uniformity of surface roughness and possibly improves the yield, but on one hand, the preparation method is complex, and is not suitable for industrial production, and on the other hand, one side of the copper foil with the carrier is provided with a resin layer, so that the application of the copper foil with the carrier is limited.
With the development of multilayering, thinning, high density and high speed of PCBs, the electrolytic copper foil is developed towards ultrathin, low-profile, high-strength, high-ductility and other high-quality and high-performance copper foils, and the development of mass production of copper foils with the thickness of less than 12 μm has great practical value and has great significance for improving the competitiveness of enterprises.
Disclosure of Invention
The invention aims to provide a carrier copper foil and a preparation method and application thereof. The carrier copper foil provided by the invention can effectively avoid the problems of wrinkling, tearing, folding and the like of the ultrathin copper foil in the production, transportation and use processes, can realize roll-to-roll continuous production, and is suitable for large-area popularization; meanwhile, the carrier layer is easy to peel, and after the carrier layer is peeled off, the copper foil layer is not damaged, and no carrier layer remains; meanwhile, the preparation method provided by the invention is simple and easy to operate.
To achieve the purpose, the invention adopts the following technical scheme:
in a first aspect, the present invention provides a carrier copper foil comprising an electrolytic copper foil and a carrier layer disposed on one side of the electrolytic copper foil;
wherein the electrolytic copper foil has a thickness of 3 to 9 μm, for example, 3.5 μm, 4 μm, 4.5 μm, 5 μm, 5.5 μm, 6 μm, 6.5 μm, 7 μm, 7.5 μm, 8 μm, 8.5 μm, etc.
According to the invention, the carrier layer is arranged on one side of the ultrathin electrolytic copper foil, so that the problems of wrinkling, tearing, folding and the like of the ultrathin copper foil in the production, transportation and use processes can be effectively avoided.
When the thickness of the ultrathin electrolytic copper foil is more than 9 mu m, the ultrathin electrolytic copper foil has better rigidity, and the problems of wrinkling, folding, tearing and the like generally do not occur in the production, transportation and use process, and the material waste is caused by arranging the carrier layer; when the thickness of the ultra-thin electrolytic copper foil is 3 μm or less, defects such as pinholes occur, and it is difficult to use the ultra-thin electrolytic copper foil for producing copper-clad plates.
In the present invention, the carrier layer includes a base film and a pressure-sensitive adhesive layer, which is located between the base film and the electrolytic copper foil.
In the present invention, the thickness of the base film is 50 to 100 μm, for example, 55 μm, 60 μm, 65 μm, 70 μm, 75 μm, 80 μm, 85 μm, 90 μm, 95 μm, etc.
Preferably, the base film is selected from a polybutylene terephthalate film (PBT film), a polyethylene naphthalate film (PEN film), a polyethylene terephthalate film (PET film) or a polyimide film (PI film), and further preferably a PI film having superior temperature resistance and dimensional stability.
In the present invention, if the thickness of the base film is too thin, the rigidity is insufficient, and it is difficult to improve the operability of the ultra-thin electrolytic copper foil; if the base film is too thick, the base film is too hard, and after the electrolytic copper foil is attached, larger stress is easily generated in winding, so that delamination is caused.
In the present invention, the thickness of the pressure-sensitive adhesive layer is 5 to 10 μm, for example, 6 μm, 7 μm, 8 μm, 9 μm, etc.
In the invention, if the thickness of the adhesive layer is too thick, the adhesive residue is easy to be caused when the carrier layer is peeled off in the later period; if the thickness of the adhesive layer is too thin, the adhesive is not enough in viscosity, and the phenomena of layering, folding and the like are easy to occur, so that the operation is not easy.
In the present invention, the peel strength of the support layer to the room temperature receiving state of the electrolytic copper foil is 0.05 to 0.3N/25 mm, for example, 0.1N/25 mm, 0.15N/25 mm, 0.2N/25 mm, 0.25N/25 mm, etc.
In the invention, the peel strength of the carrier layer and the electrolytic copper foil in the room temperature receiving state is 0.05-0.3N/25 mm, and when the carrier copper foil is treated at high temperature, the wettability is improved due to the flowing of the adhesive, and the peel strength between the carrier layer and the electrolytic copper foil is increased to different degrees.
Preferably, the carrier copper foil has a peel strength from the electrolytic copper foil of 0.2 to 0.5N/25 mm, such as 0.25N/25 mm, 0.3N/25 mm, 0.35N/25 mm, 0.4N/25 mm, 0.45N/25 mm, etc., after the carrier copper foil has been treated at 200 ℃ for 5 h; and no residual glue is left on the surface of the electrolytic copper foil after the carrier layer is stripped.
If the peeling strength of the receiving state is too low at room temperature, layering and wrinkling are easy to occur in the production, transportation and use processes; if the peeling strength after high temperature treatment is too high, after the copper-clad plate is manufactured by lamination, the carrier layer is difficult to peel, and residual glue is easy to generate on the surface of the copper foil.
The adhesive has excellent strippability, heat resistance, chemical resistance and pollution resistance, and can not damage the copper foil layer or remain after stripping the carrier layer.
Preferably, the self-adhesive is selected from polyacrylate self-adhesive or organosilicon self-adhesive.
In the invention, the polyacrylate self-adhesive comprises 100 parts by weight of polyacrylate, 5-10 parts by weight of curing agent, 8-10 parts by weight of viscosity reducing additive and an appropriate amount of organic solvent, wherein the solid content is controlled to be 10-20wt%, such as 12-wt%, 14-wt%, 15-wt%, 16-wt%, 18-wt% and the like.
The adhesive layer is thinner, so the solid content of the adhesive is not too high, otherwise, the adhesive is difficult to coat, the operation time of the adhesive is too short, the adhesive is easy to gel, and the adhesive is not suitable for mass production; if the solid content is too low, the viscosity of the glue is small, and the glue tends to sag during coating, so that the coating appearance is poor.
The polyacrylate may be selected from SG-790, SG-280TEA, AS200X, AS X, japanese lion king company, etc. of Nagase Chemtex company.
The curing agent 5-10 parts by weight may be 6 parts by weight, 7 parts by weight, 8 parts by weight, 9 parts by weight, etc. The curing agent may be an isocyanate curing agent or an epoxy curing agent, and the isocyanate curing agent may be any one or a combination of at least two selected from N3390, N3800 or HDT-100 of bayer company; the epoxy curing agent may be selected from ERISYS GA-240 manufactured by CVC company in the United states and/or NPPN-431A70 manufactured by south Asia company in Taiwan.
8-10 parts by weight of the viscosity reducing additive can be 8.5 parts by weight, 9 parts by weight, 9.5 parts by weight and the like. The viscosity reducing additive is indispensable in the formula of the polyacrylate self-adhesive, can reduce the viscosity of the self-adhesive, is easy to peel, can prevent the self-adhesive from rising greatly after high-temperature treatment, and can reduce the crosslinking density of the self-adhesive and easily cause residual adhesive due to excessive consumption of the viscosity reducing additive; the viscosity reducing additive is insufficient in dosage, so that the viscosity of the non-setting adhesive is too high, the viscosity is easily increased greatly after high-temperature treatment, and the non-setting adhesive is not easy to peel; the viscosity reducing additive can be selected from a plasticizer and/or a surfactant, wherein the plasticizer can be any one or a combination of at least two of succinate, adipate or sebacate; the surfactant is a nonionic surfactant, and specifically, may be selected from any one or a combination of at least two of OP-10, AE-09 or TX-10.
The organic solvent may be selected from butanone, acetone, cyclohexanone, toluene orN,N'-any one or a combination of at least two of dimethylformamide.
The organosilicon non-setting adhesive comprises 100 parts by weight of silicone rubber, 15-25 parts by weight of MQ resin, 5-10 parts by weight of cross-linking agent and a proper amount of organic solvent, and the solid content is controlled to be 10-20wt%, such as 12 wt%, 14 wt%, 15 wt%, 16 wt%, 18 wt% and the like.
The solid content of the adhesive is not too high due to the thinner coating glue layer, otherwise, the adhesive is difficult to coat, the operation time of the glue is too short, the glue is easy to gel, and the mass production is not suitable; if the solid content is too low, the viscosity of the glue is small, and the glue tends to sag during coating, so that the coating appearance is poor.
The silicone rubber may be selected from DY-107 and/or DY-V110-2 of Shandong Dayi chemical Co., ltd.
The MQ resin 15-25 parts by weight may be 17 parts by weight, 18 parts by weight, 19 parts by weight, 20 parts by weight, 22 parts by weight, 24 parts by weight, etc. The M/Q value of the MQ resin is 0.6-1.0, such as 0.7, 0.8, 0.9 and the like, is oil-soluble resin, has better compatibility with silicone rubber, can increase cohesive strength of the self-adhesive, and can adjust the stripping force of the self-adhesive, and particularly, can be one or a combination of at least two of DY-MQ101, DY-MQ102 or DY-VMQ101 of Shandong Dayike chemical industry Co.
The crosslinking agent 5-10 parts by weight may be 6 parts by weight, 7 parts by weight, 8 parts by weight, 9 parts by weight, etc. The cross-linking agent is any one or the combination of at least two of azodiisobutyronitrile, benzoyl peroxide or diisopropyl peroxydicarbonate.
The organic solvent may be selected from butanone, acetone, cyclohexanone, toluene orN,N'-dimethylformamide, or a combination of any one or at least two thereof.
Preferably, a side of the electrolytic copper foil remote from the carrier layer is surface-treated.
The surface of the electrolytic copper foil far away from the carrier layer is subjected to surface treatment, so that the heat resistance, oxidation resistance, etching resistance and peeling strength of the copper foil can be improved.
Preferably, the surface treatment method includes sequentially roughening treatment, electroplating of a dissimilar metal, and silane treatment.
The roughening treatment is to form copper nodules on the surface of the copper foil by an electroplating method and solidify the copper nodules so as to increase the surface roughness of the copper foil, so that the specific surface area of the copper foil can be increased, the binding force between the copper foil and resin is improved, and the roughness Rz of the treated surface of the copper foil is less than or equal to 2 mu m; the different metal plating is nickel plating, zinc plating and chromium plating, and the thickness of each plating is less than or equal to 200 and nm; the silane treatment is to adopt a silane coupling agent with the concentration of 5-10 wt percent to the surface of the copper foilThe method comprises the steps of treating to improve the peeling strength and oxidation resistance of the copper foil, wherein the structural general formula of a silane coupling agent used for silane treatment is Y- (CH) 2 ) n -SiX 3 Wherein n is an integer from 0 to 3, such as 0, 1, 2, 3, etc.; three X are each independently selected from-OCH 3 or-OCH 2 CH 3 The method comprises the steps of carrying out a first treatment on the surface of the Y is one of amino, epoxy or vinyl.
The surface treatment process is carried out in a wet process, so that the carrier layer and the electrolytic copper foil must have good bonding force and chemical resistance so as to avoid the problems of delamination between the carrier layer and the copper foil, leakage of chemical liquid and the like.
In a second aspect, the present invention provides a method for preparing the carrier copper foil according to the first aspect, the method comprising the steps of:
and (3) attaching the carrier layer to the electrolytic copper foil in a roll-to-roll rolling manner to obtain the carrier green foil.
Wherein the bonding temperature is 50-60deg.C, such as 51deg.C, 52 deg.C, 53 deg.C, 54 deg.C, 55 deg.C, 56 deg.C, 57 deg.C, 58 deg.C, 59 deg.C, etc., and the pressure is 0.1-0.3 MPa, such as 0.15 MPa, 0.2 MPa, 0.25 MPa, etc.
The invention can realize the preparation of the rolled carrier copper foil by using a rolling laminating mode, has simple preparation method and continuous process, and can be suitable for industrial production.
In the invention, if the bonding temperature is too low, the bonding between the carrier layer and the copper foil is not firm, and if the bonding temperature is too high, the copper foil is easy to generate bad phenomena such as scale marks, discounting and the like; if the bonding pressure is too low, the bonding between the carrier layer and the copper foil is not firm, and if the bonding pressure is too high, the copper foil is easy to fold.
Preferably, the preparation method comprises the steps of attaching the carrier layer to the electrolytic copper foil on the surface of the cathode roller through a rubber pressing roller, stripping and winding to obtain the carrier green foil.
Preferably, the preparation method further comprises the step of carrying out surface treatment on one side, away from the carrier layer, of the carrier green foil after lamination, so as to obtain the carrier copper foil.
Preferably, the preparation method of the carrier layer comprises the following steps:
and (3) coating the adhesive on the surface of the base film, and drying and curing to obtain the carrier layer.
Preferably, the preparation method of the non-drying adhesive comprises the steps of dissolving, mixing and stirring resin, curing agent and other auxiliary agents uniformly by using a solvent to prepare the non-drying adhesive.
Preferably, the surface of the base film is coated with a non-setting adhesive.
Preferably, the temperature of the drying (or pre-curing) is 100-160 ℃, e.g. 110 ℃, 120 ℃, 130 ℃, 140 ℃, 150 ℃, etc., for a period of 5-10 min, e.g. 6 min, 7 min, 8 min, 9 min, etc.
Preferably, the curing temperature is 50-80 ℃, e.g. 60 ℃, 70 ℃, etc., for a period of time of 48-96 h, e.g. 50 h, 52 h, 55 h, 58 h, 60 h, 65 h, 70 h, 75 h, 80 h, 85 h, 90 h, etc.
In a third aspect, the present invention provides an application of the carrier copper foil according to the first aspect in a copper-clad plate.
Compared with the prior art, the invention has the following beneficial effects:
(1) According to the invention, the carrier layer is arranged on one side of the ultrathin electrolytic copper foil, so that the problems of wrinkling, tearing, folding and the like of the ultrathin copper foil in the production, transportation and use processes can be effectively avoided;
(2) The carrier layer of the carrier copper foil provided by the invention is easy to peel, and after the carrier layer is peeled, the copper foil layer is not damaged, and no carrier layer remains;
(3) The invention can realize the preparation of the rolled carrier copper foil by using a rolling laminating mode, has simple preparation method and continuous process, and can be suitable for industrial production.
Detailed Description
The technical scheme of the invention is further described by the following specific embodiments. It will be apparent to those skilled in the art that the examples are merely to aid in understanding the invention and are not to be construed as a specific limitation thereof.
Example 1
A carrier copper foil is prepared by the following steps:
(1) Preparation of the support layer
Preparing a non-setting adhesive: polyacrylate resin SG-790 100 weight parts, isocyanate curing agent N3390 weight parts and succinic acid ester 10 weight parts, butanone is used as a solvent, the solid content is controlled to be 20wt percent, and stirring is carried out to uniformly mix the materials for standby;
and (3) coating a layer of the non-setting adhesive on the surface of the 50 mu m PI film, controlling the thickness of the non-setting adhesive layer to be 5 mu m, drying and pre-curing for 5 min at 100 ℃, and curing for 48 hours at 60 ℃ to obtain the PI-based carrier layer.
(2) Preparation of Carrier copper foil
Adopting a foil producing machine to produce ultrathin electrolytic copper foil, arranging a rubber laminating roller on one side of a cathode roller, laminating the PI-based carrier layer in the step (1) with the electrolytic copper foil with the surface of the cathode roller being 9 mu m through the rubber laminating roller, wherein the laminating temperature is 50 ℃, the laminating pressure is 0.1 MPa, and rolling to obtain carrier raw foil;
forming copper nodules on the surface of a copper foil by an electroplating method through a carrier raw foil and solidifying the copper nodules to increase the surface roughness of the copper foil, wherein the surface roughness Rz is 2 mu m; sequentially electroplating a plating layer of 200 nm nickel, 200 nm zinc and 180 nm chromium; finally, treating for 30 min by using a silane coupling agent KH171 with the concentration of 10 wt%, thus obtaining the carrier copper foil.
Examples 2 to 4
The difference from example 1 is that the bonding temperature in step (2) was controlled to 60 ℃ (example 2), 45 ℃ (example 3), 65 ℃ (example 4).
Examples 5 to 7
The difference from example 1 is that the bonding pressure in the control step (2) was 0.3 MPa (example 5), 0.05 MPa (example 6) and 0.4 MPa (example 7).
Examples 8 to 10
The difference from example 1 is that the thickness of the pressure-sensitive adhesive layer in step (1) was controlled to be 10 μm (example 8), 2 μm (example 9), 15 μm (example 10).
Examples 11 to 13
The difference from example 1 is that the PI film in step (1) has a thickness of 100 μm (example 11), 40 μm (example 12), 110 μm (example 13).
Example 14
A carrier copper foil is prepared by the following steps:
(1) Preparation of the support layer
Preparing a non-setting adhesive: 100 parts by weight of polyacrylic resin SG-280TEA, 10 parts by weight of epoxy resin curing agent ERISYS GA-240 and 8 parts by weight of surfactant OP-10, and using acetone as a solvent, controlling the solid content to be 20wt%, and stirring to uniformly mix the components for later use.
And (3) taking a 75-mu m PI film, coating a layer of the non-setting adhesive on the surface of the PI film, controlling the thickness of the non-setting adhesive layer to be 7 mu m, drying and pre-curing for 10 min at 120 ℃, and curing for 72 hours at 75 ℃ to finally obtain the PI-based carrier layer.
(2) Preparation of Carrier copper foil
Adopting a foil producing machine to produce ultrathin electrolytic copper foil, arranging a rubber laminating roller on one side of a cathode roller, laminating the PI-based carrier layer in the step (1) with the 6 mu m electrolytic copper foil on the surface of the cathode roller through the rubber laminating roller, and obtaining the carrier raw foil by winding at the laminating temperature of 60 ℃ and the laminating pressure of 0.2 MPa;
forming copper nodules on the surface of a copper foil by an electroplating method through a carrier raw foil and solidifying the copper nodules to increase the surface roughness of the copper foil, wherein the surface roughness Rz is 2 mu m; sequentially electroplating a chromium coating with the thickness of 100 nm nickel, 150 nm zinc and 200 nm; finally, treating for 40 min by using a silane coupling agent KH560 with the concentration of 5 wt%, thus obtaining the carrier copper foil.
Example 15
A preparation method of a carrier copper foil comprises the following steps:
(1) Preparation of the support layer
The adhesive is prepared from (by weight parts) silicone rubber DY-107 100, MQ resin DY-VMQ101 20, benzoyl peroxide 5, toluene as solvent, and stirring to obtain a mixture with solid content of 15-wt%.
And (3) taking a PET film with the thickness of 100 mu m, coating a layer of the non-setting adhesive on the surface of the PET film, controlling the thickness of the non-setting adhesive layer to be 10 mu m, drying and pre-curing for 7 min at 160 ℃, and curing for 96 hours at 80 ℃ to finally obtain the PET-based carrier layer.
(2) Preparation of Carrier copper foil
Adopting a foil producing machine to produce ultrathin electrolytic copper foil, arranging a rubber laminating roller on one side of a cathode roller, laminating the PET-based carrier layer in the step (1) with the electrolytic copper foil with the thickness of 3 mu m on the surface of the cathode roller through the rubber laminating roller, and obtaining the carrier raw foil by winding at the laminating temperature of 55 ℃ and the laminating pressure of 0.3 MPa;
forming copper nodules on the surface of a copper foil by an electroplating method through a carrier raw foil and solidifying to increase the surface roughness of the copper foil, wherein the surface roughness Rz is 0.8 mu m; sequentially electroplating a plating layer of 200 nm nickel, 120 nm zinc and 200 nm chromium; finally, treating for 25 min by using a silane coupling agent KH550 with the concentration of 10 wt%, thus obtaining the carrier copper foil.
Comparative example 1
The rolled copper foil provided in this comparative example does not include a carrier layer, i.e., the rolled copper foil provided in this comparative example is an ultrathin electrolytic copper foil having a thickness of 9 μm produced in step (2) of example 1 using a foil producing machine.
Performance testing
The carrier copper foil provided in examples 1-15 and comparative example 1 was subjected to performance testing by the following method:
(1) Peel strength: the peel strength of the carrier layer and the electrolytic copper foil after 5 hours of treatment at room temperature and 200 ℃ is tested according to the GB/T2792-1998 method;
(2) Copper foil operability: observing whether the copper foil has the adverse phenomena of scale patterns, folds, discounts, tearing and the like after being attached to the carrier layer (carrier copper foil), wherein:
class a: no phenomena of scale marks, wrinkles, folds and tearing;
b level: has scale patterns, folds and folds, and has no tearing phenomenon;
c level: has tearing phenomenon.
(3) Whether residual glue exists: after the carrier copper foil is placed in a 200 ℃ environment for 5 hours for treatment, the carrier layer is peeled off to observe whether residual glue exists on the surface of the copper foil, wherein:
stage I: no residual glue exists;
stage II: slight residual glue exists;
class III: has large area and serious residual glue.
The test results are shown in Table 1:
TABLE 1
The embodiment and the performance test show that the carrier copper foil provided by the invention is easy to peel, the copper foil layer is not damaged after the carrier layer is peeled off, the carrier layer is not remained, the peel strength of the carrier layer and the electrolytic copper foil in a room temperature receiving state is in the range of 0.02-0.35N/25 mm, and the peel strength of the carrier layer and the electrolytic copper foil is in the range of 0.14-0.55N/25 mm after the carrier layer and the electrolytic copper foil are treated at 200 ℃ for 5 h; when the peel strength of the support layer and the electrolytic copper foil in the room temperature receiving state is in the range of 0.05 to 0.3N/25 mm in the preferred case of the present invention, the peel strength of the support layer and the electrolytic copper foil is in the range of 0.2 to 0.5N/25 mm after 5 h of treatment at 200 ℃. Meanwhile, no residual adhesive exists after stripping, and the copper foil has good operability.
As is clear from the comparison between example 1 and examples 5 to 7, the bonding temperature of the present invention is preferably 50 to 60℃and the pressure is preferably 0.1 to 0.3 MPa, and the carrier copper foil prepared at this time has a high workability. As is clear from a comparison of example 1 and examples 8 to 13, the thickness of the pressure-sensitive adhesive layer in the carrier layer of the present invention is preferably 5 to 10. Mu.m, and the thickness of the base film is preferably 50 to 100. Mu.m, and the carrier copper foil prepared at this time is strong in operability and free from residual adhesive after peeling.
As is clear from example 1 and comparative example 1, the ultra-thin electrolytic copper foil without the carrier layer has a tearing phenomenon, has poor operability, and is difficult to meet the processing application requirements of the copper-clad plate.
The applicant states that the carrier copper foil of the present invention, and the method of preparing the same and the use thereof are described by way of the above examples, but the present invention is not limited to the above detailed methods, i.e., it is not meant that the present invention must be practiced by relying on the above detailed methods. It should be apparent to those skilled in the art that any modification of the present invention, equivalent substitution of raw materials for the product of the present invention, addition of auxiliary components, selection of specific modes, etc., falls within the scope of the present invention and the scope of disclosure.
Claims (11)
1. The preparation method of the carrier copper foil is characterized by comprising the following steps of:
attaching the carrier layer to the electrolytic copper foil in a roll-to-roll rolling manner to obtain a carrier green foil;
wherein the bonding temperature is 50-60 ℃ and the pressure is 0.1-0.3 MPa;
the carrier layer comprises a base film and a non-drying adhesive layer, and the non-drying adhesive layer is positioned between the base film and the electrolytic copper foil;
the thickness of the base film is 50-100 mu m;
the thickness of the non-setting adhesive layer is 5-10 mu m;
the carrier copper foil comprises an electrolytic copper foil and a carrier layer arranged on one side of the electrolytic copper foil;
wherein the thickness of the electrolytic copper foil is 3-9 mu m;
the peel strength of the carrier layer and the electrolytic copper foil after 5 hours of treatment at room temperature and 200 ℃ is tested according to the GB/T2792-1998 method;
the peel strength of the carrier layer and the electrolytic copper foil in the room temperature receiving state is 0.05-0.3N/25 mm;
after the carrier copper foil is treated at 200 ℃ for 5 h, the peel strength of the carrier layer and the electrolytic copper foil is 0.2-0.5N/25 mm.
2. The method according to claim 1, wherein the base film is selected from a polybutylene terephthalate film, a polyethylene naphthalate film, a polyethylene terephthalate film, and a polyimide film.
3. The method of claim 1, wherein the self-adhesive of the self-adhesive layer is selected from the group consisting of polyacrylate self-adhesive and silicone self-adhesive.
4. The method of claim 1, wherein a side of the electrolytic copper foil remote from the carrier layer is surface-treated.
5. The method according to claim 4, wherein the surface treatment method comprises sequentially roughening treatment, plating a dissimilar metal, and silane treatment.
6. The method according to claim 1, wherein the method comprises adhering the carrier layer to an electrolytic copper foil on the surface of a cathode roller by a rubber lamination roller, peeling and winding to obtain the carrier green foil.
7. The method according to claim 1, further comprising subjecting a side of the carrier foil remote from the carrier layer to surface treatment after bonding to obtain the carrier copper foil.
8. The method of manufacturing according to claim 1, wherein the method of manufacturing the carrier layer comprises:
and (3) coating the adhesive on the surface of the base film, and drying and curing to obtain the carrier layer.
9. The method according to claim 8, wherein the drying is carried out at a temperature of 100 to 160 ℃ for a time of 5 to 10 min.
10. The method of claim 8, wherein the curing is performed at a temperature of 50-80 ℃ for a time of 48-96 h.
11. Use of the carrier copper foil prepared by the preparation method according to any one of claims 1 to 10 in copper-clad laminate.
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| US20050158574A1 (en) * | 2003-11-11 | 2005-07-21 | Furukawa Circuit Foil Co., Ltd. | Ultra-thin copper foil with carrier and printed wiring board using ultra-thin copper foil with carrier |
| KR20070038407A (en) * | 2005-10-05 | 2007-04-10 | 스미또모 가가꾸 가부시끼가이샤 | Flexible wiring board and its manufacturing method |
| CN202573178U (en) * | 2012-04-01 | 2012-12-05 | 松扬电子材料(昆山)有限公司 | Composite double-faced copper foil base plate |
| CN108277513A (en) * | 2013-06-13 | 2018-07-13 | Jx日矿日石金属株式会社 | The copper foil of appendix body, the manufacturing method of copper-cover laminated plate, printed circuit board, e-machine and printed circuit board |
| CN204442830U (en) * | 2015-03-11 | 2015-07-01 | 松扬电子材料(昆山)有限公司 | For the black polyamide copper clad laminate of flexible circuit board |
| JP6236120B2 (en) * | 2015-06-24 | 2017-11-22 | Ｊｘ金属株式会社 | Copper foil with carrier, laminate, laminate production method, printed wiring board production method, and electronic device production method |
| JP6190500B2 (en) * | 2015-08-06 | 2017-08-30 | Ｊｘ金属株式会社 | Copper foil with carrier, laminate, printed wiring board manufacturing method and electronic device manufacturing method |
| JP7102691B2 (en) * | 2016-09-05 | 2022-07-20 | 荒川化学工業株式会社 | Copper-clad laminate for flexible printed wiring board and flexible printed wiring board |
| CN209462709U (en) * | 2018-12-10 | 2019-10-01 | 广州方邦电子股份有限公司 | A kind of substrate and wiring board with carrier |
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