CN115846646A - Modified PET flexible circuit board, preparation method and application thereof - Google Patents
Modified PET flexible circuit board, preparation method and application thereof Download PDFInfo
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- CN115846646A CN115846646A CN202211578315.5A CN202211578315A CN115846646A CN 115846646 A CN115846646 A CN 115846646A CN 202211578315 A CN202211578315 A CN 202211578315A CN 115846646 A CN115846646 A CN 115846646A
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- China
- Prior art keywords
- modified pet
- plating
- flexible circuit
- circuit board
- film
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- 238000002360 preparation method Methods 0.000 title claims abstract description 17
- 229920002799 BoPET Polymers 0.000 claims abstract description 56
- 238000007747 plating Methods 0.000 claims abstract description 53
- 229920000139 polyethylene terephthalate Polymers 0.000 claims abstract description 33
- 238000000034 method Methods 0.000 claims abstract description 27
- 238000011282 treatment Methods 0.000 claims abstract description 25
- 238000001465 metallisation Methods 0.000 claims abstract description 19
- 238000005516 engineering process Methods 0.000 claims abstract description 7
- 238000004891 communication Methods 0.000 claims abstract description 6
- 229910017052 cobalt Inorganic materials 0.000 claims description 54
- 239000010941 cobalt Substances 0.000 claims description 54
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 claims description 54
- 239000000843 powder Substances 0.000 claims description 19
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 claims description 17
- 229910052802 copper Inorganic materials 0.000 claims description 17
- 239000010949 copper Substances 0.000 claims description 17
- 229910052751 metal Inorganic materials 0.000 claims description 17
- 239000002184 metal Substances 0.000 claims description 17
- 238000002156 mixing Methods 0.000 claims description 17
- 238000012545 processing Methods 0.000 claims description 14
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims description 12
- 239000003963 antioxidant agent Substances 0.000 claims description 12
- 229910044991 metal oxide Inorganic materials 0.000 claims description 12
- 150000004706 metal oxides Chemical class 0.000 claims description 12
- 239000003607 modifier Substances 0.000 claims description 11
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- 238000000576 coating method Methods 0.000 claims description 10
- 238000001035 drying Methods 0.000 claims description 10
- 239000000203 mixture Substances 0.000 claims description 10
- 239000002245 particle Substances 0.000 claims description 10
- WSFSSNUMVMOOMR-UHFFFAOYSA-N Formaldehyde Chemical compound O=C WSFSSNUMVMOOMR-UHFFFAOYSA-N 0.000 claims description 9
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 9
- 230000003078 antioxidant effect Effects 0.000 claims description 9
- 229920005989 resin Polymers 0.000 claims description 9
- 239000011347 resin Substances 0.000 claims description 9
- -1 salt compounds Chemical class 0.000 claims description 8
- 229920001971 elastomer Polymers 0.000 claims description 7
- 229920000642 polymer Polymers 0.000 claims description 7
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 claims description 6
- 239000012752 auxiliary agent Substances 0.000 claims description 6
- 239000008139 complexing agent Substances 0.000 claims description 6
- 238000009998 heat setting Methods 0.000 claims description 6
- 230000003381 solubilizing effect Effects 0.000 claims description 6
- 229920001169 thermoplastic Polymers 0.000 claims description 6
- 239000004416 thermosoftening plastic Substances 0.000 claims description 6
- 238000001125 extrusion Methods 0.000 claims description 5
- 238000010791 quenching Methods 0.000 claims description 5
- 230000000171 quenching effect Effects 0.000 claims description 5
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- 230000003213 activating effect Effects 0.000 claims description 4
- 230000004913 activation Effects 0.000 claims description 4
- 239000007795 chemical reaction product Substances 0.000 claims description 4
- 229910000365 copper sulfate Inorganic materials 0.000 claims description 4
- ARUVKPQLZAKDPS-UHFFFAOYSA-L copper(II) sulfate Chemical compound [Cu+2].[O-][S+2]([O-])([O-])[O-] ARUVKPQLZAKDPS-UHFFFAOYSA-L 0.000 claims description 4
- 239000012760 heat stabilizer Substances 0.000 claims description 4
- IWDCLRJOBJJRNH-UHFFFAOYSA-N p-cresol Chemical compound CC1=CC=C(O)C=C1 IWDCLRJOBJJRNH-UHFFFAOYSA-N 0.000 claims description 4
- VYZAMTAEIAYCRO-UHFFFAOYSA-N Chromium Chemical compound [Cr] VYZAMTAEIAYCRO-UHFFFAOYSA-N 0.000 claims description 3
- KCXVZYZYPLLWCC-UHFFFAOYSA-N EDTA Chemical group OC(=O)CN(CC(O)=O)CCN(CC(O)=O)CC(O)=O KCXVZYZYPLLWCC-UHFFFAOYSA-N 0.000 claims description 3
- BQCADISMDOOEFD-UHFFFAOYSA-N Silver Chemical compound [Ag] BQCADISMDOOEFD-UHFFFAOYSA-N 0.000 claims description 3
- ATJFFYVFTNAWJD-UHFFFAOYSA-N Tin Chemical compound [Sn] ATJFFYVFTNAWJD-UHFFFAOYSA-N 0.000 claims description 3
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- 229910052793 cadmium Inorganic materials 0.000 claims description 3
- BDOSMKKIYDKNTQ-UHFFFAOYSA-N cadmium atom Chemical compound [Cd] BDOSMKKIYDKNTQ-UHFFFAOYSA-N 0.000 claims description 3
- 239000003795 chemical substances by application Substances 0.000 claims description 3
- 229910052804 chromium Inorganic materials 0.000 claims description 3
- 239000011651 chromium Substances 0.000 claims description 3
- 238000001816 cooling Methods 0.000 claims description 3
- 239000000110 cooling liquid Substances 0.000 claims description 3
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- 238000000151 deposition Methods 0.000 claims description 3
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- 239000000806 elastomer Substances 0.000 claims description 3
- 238000011049 filling Methods 0.000 claims description 3
- PCHJSUWPFVWCPO-UHFFFAOYSA-N gold Chemical compound [Au] PCHJSUWPFVWCPO-UHFFFAOYSA-N 0.000 claims description 3
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- 239000010931 gold Substances 0.000 claims description 3
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- 229910052759 nickel Inorganic materials 0.000 claims description 3
- 238000005121 nitriding Methods 0.000 claims description 3
- LJCNRYVRMXRIQR-OLXYHTOASA-L potassium sodium L-tartrate Chemical compound [Na+].[K+].[O-]C(=O)[C@H](O)[C@@H](O)C([O-])=O LJCNRYVRMXRIQR-OLXYHTOASA-L 0.000 claims description 3
- 229910052709 silver Inorganic materials 0.000 claims description 3
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- 238000005496 tempering Methods 0.000 claims description 3
- 229910052718 tin Inorganic materials 0.000 claims description 3
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- 239000006096 absorbing agent Substances 0.000 claims description 2
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- OXDOANYFRLHSML-UHFFFAOYSA-N dimethoxyphosphorylbenzene Chemical compound COP(=O)(OC)C1=CC=CC=C1 OXDOANYFRLHSML-UHFFFAOYSA-N 0.000 claims description 2
- 229910052719 titanium Inorganic materials 0.000 claims description 2
- WVLBCYQITXONBZ-UHFFFAOYSA-N trimethyl phosphate Chemical compound COP(=O)(OC)OC WVLBCYQITXONBZ-UHFFFAOYSA-N 0.000 claims description 2
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N Phenol Chemical class OC1=CC=CC=C1 ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 claims 3
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- 229920001296 polysiloxane Polymers 0.000 claims 2
- HVLLSGMXQDNUAL-UHFFFAOYSA-N triphenyl phosphite Chemical compound C=1C=CC=CC=1OP(OC=1C=CC=CC=1)OC1=CC=CC=C1 HVLLSGMXQDNUAL-UHFFFAOYSA-N 0.000 claims 2
- 229910019142 PO4 Inorganic materials 0.000 claims 1
- 125000000687 hydroquinonyl group Chemical class C1(O)=C(C=C(O)C=C1)* 0.000 claims 1
- NBIIXXVUZAFLBC-UHFFFAOYSA-K phosphate Chemical compound [O-]P([O-])([O-])=O NBIIXXVUZAFLBC-UHFFFAOYSA-K 0.000 claims 1
- 239000010452 phosphate Substances 0.000 claims 1
- UEZVMMHDMIWARA-UHFFFAOYSA-M phosphonate Chemical compound [O-]P(=O)=O UEZVMMHDMIWARA-UHFFFAOYSA-M 0.000 claims 1
- 239000000853 adhesive Substances 0.000 abstract description 5
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- VBICKXHEKHSIBG-UHFFFAOYSA-N 1-monostearoylglycerol Chemical compound CCCCCCCCCCCCCCCCCC(=O)OCC(O)CO VBICKXHEKHSIBG-UHFFFAOYSA-N 0.000 description 2
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- HJIAMFHSAAEUKR-UHFFFAOYSA-N (2-hydroxyphenyl)-phenylmethanone Chemical compound OC1=CC=CC=C1C(=O)C1=CC=CC=C1 HJIAMFHSAAEUKR-UHFFFAOYSA-N 0.000 description 1
- XCPFSALHURPPJE-UHFFFAOYSA-N (3,5-ditert-butyl-4-hydroxyphenyl) propanoate Chemical compound CCC(=O)OC1=CC(C(C)(C)C)=C(O)C(C(C)(C)C)=C1 XCPFSALHURPPJE-UHFFFAOYSA-N 0.000 description 1
- WYTZZXDRDKSJID-UHFFFAOYSA-N (3-aminopropyl)triethoxysilane Chemical compound CCO[Si](OCC)(OCC)CCCN WYTZZXDRDKSJID-UHFFFAOYSA-N 0.000 description 1
- 150000005208 1,4-dihydroxybenzenes Chemical class 0.000 description 1
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- DMSSTTLDFWKBSX-UHFFFAOYSA-N 1h-1,2,3-benzotriazin-4-one Chemical compound C1=CC=C2C(=O)N=NNC2=C1 DMSSTTLDFWKBSX-UHFFFAOYSA-N 0.000 description 1
- JMTMSDXUXJISAY-UHFFFAOYSA-N 2H-benzotriazol-4-ol Chemical compound OC1=CC=CC2=C1N=NN2 JMTMSDXUXJISAY-UHFFFAOYSA-N 0.000 description 1
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- OCKWAZCWKSMKNC-UHFFFAOYSA-N [3-octadecanoyloxy-2,2-bis(octadecanoyloxymethyl)propyl] octadecanoate Chemical compound CCCCCCCCCCCCCCCCCC(=O)OCC(COC(=O)CCCCCCCCCCCCCCCCC)(COC(=O)CCCCCCCCCCCCCCCCC)COC(=O)CCCCCCCCCCCCCCCCC OCKWAZCWKSMKNC-UHFFFAOYSA-N 0.000 description 1
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- GVGUFUZHNYFZLC-UHFFFAOYSA-N dodecyl benzenesulfonate;sodium Chemical compound [Na].CCCCCCCCCCCCOS(=O)(=O)C1=CC=CC=C1 GVGUFUZHNYFZLC-UHFFFAOYSA-N 0.000 description 1
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Landscapes
- Chemically Coating (AREA)
Abstract
The invention provides a modified PET flexible circuit board, a preparation method and application thereof, wherein the modified PET flexible circuit board comprises a modified PET film layer and a metallization layer, and the metallization layer is arranged on one side of the modified PET film layer; the thickness of the metallization layer is 5-20 microns; the thickness of the modified PET film is 60-150 microns. The metalized plating layer finally obtained by the modified PET film prepared by the invention has uniform thickness, fine crystallization and good adhesive force, and can realize fine circuits below 100 um. The method has wide application prospect in the aspects of communication equipment such as notebook computers, portable computers, mobile phone antennas and the like, medical treatment, radio Frequency Identification (RFID) technology, new energy automobile battery composite bus bar sensors and other weak current circuits.
Description
Technical Field
The invention relates to the field of modified PET flexible circuit boards, in particular to a modified PET flexible circuit board, a preparation method and application thereof.
Background
The flexible printed circuit board, called 'soft board' for short, is commonly called FPC in the industry, is a printed circuit board made of flexible insulating base materials, and has many advantages which are not possessed by hard printed circuit boards. For example, it can be freely bent, rolled, folded. The FPC can be used for greatly reducing the volume of electronic products, and is suitable for the development of the electronic products in the directions of high density, miniaturization and high reliability. Therefore, the FPC is widely applied to the fields or products of aerospace, military, mobile communication, laptop computers, computer peripherals, PDAs, digital cameras and the like.
At present, the preparation process of the flexible circuit board mainly comprises the steps of material fine mixing and drying, film preparation, vacuum metallization, photosensitive printing, development, etching and the like; preparing a layer of metallized (Al and the like) film not more than 2 microns on the surface of the film in a mode of vacuum plating of low-melting-point alloy, and thickening the film to the required thickness through aqueous solution plating; and then coating a UV photosensitive resist on the metallized film, realizing circuit pattern transfer in 365-410nm ultraviolet light environment by using a photosensitive mask, and obtaining a circuit through development and etching. The preparation process is the circuit manufacturing of semi-additive (full metallization) and semi-subtractive (regional metal removal), the process period is correspondingly increased, and a plurality of working procedures are required to complete the processing. Therefore, a method for manufacturing a flexible circuit board with a simple manufacturing process is continued.
Disclosure of Invention
In view of the complex process flow of the prior art, the invention aims to provide a modified PET flexible circuit, a preparation method and application thereof.
In order to achieve the purpose, the invention provides the following technical scheme: a modified PET flexible circuit board comprises a modified PET film layer and a metallization layer, wherein the metallization layer is arranged on one side of the modified PET film layer; the thickness of the metallization layer is 5-20 microns; the thickness of the modified PET film is 60-150 microns.
The modified PET film layer comprises the following components in percentage by weight:
further, the toner is selected from one or more of nanoscale metal powder, nanoscale vacancy type metal mixed oxide and single metal oxide; the toner is selected from one or more of nano metal powder, nano vacancy type metal mixed oxide, single metal oxide or salt compounds thereof; for example: copper salt, basic copper phosphate, copper sulfate, cuprous thiocyanate, etc.; the preferred weight percentage of toner is 5 to 9%;
further, the nanoscale metal powder has a particle size of 1.5 microns or less, such as aluminum metal particles; the nano-scale vacancy type metal mixed oxide is at least one of cobalt green and cobalt blue, and preferably comprises the following components: the particle size of the cobalt green is 0.5-0.8 micron, and the particle size of the cobalt blue is 0.8-1.5 micron; the particle size of the nano-scale vacancy type metal mixed oxide is 20-500nm; the single metal oxide is CuO or Co 2 O 3 (ii) a The particle size of the thermoplastic PET resin is 15-40 micrometers; the grain size of the antioxidant is 0.8-1.5 microns;
further, the solubilizing polymer is at least one of organic silicon or mixture of organic silicon and common rubber elastomer;
the introduction of metal oxide in the toner can cause the thermal degradation of polymer materials in the processing process to reduce the mechanical property, and the dispersion of metal oxide filler is uneven to cause poor performance; in addition, the increase of the metal oxide filler leads to the decrease of the system mixability and fluidity, leading to a series of problems in processing. The invention selects rubber solubilizing polymer, firstly coats metal oxide, and simultaneously utilizes the good fluidity of the metal oxide to relieve the stress effect in the system and play a balance role, the toner types comprise rubber toughening agent, and the total amount of the solubilizing polymer is in a preferred range: 1 to 3 percent.
The toughening agent has excellent compatibility with resin, excellent thermal stability and aging resistance, good moldability and processing fluidity and can obviously improve the toughness of products, such as Glycidyl Methacrylate (GMA) and acrylate bifunctional ethylene elastomers. Methyl methacrylate-butadiene-styrene terpolymer (MBS), EMBS, organic silicon graft polymer and the like, and an active toughening agent can be selected, wherein the molecular chain of the active toughening agent contains active groups capable of reacting with matrix resin, and the active groups can form a network structure and increase a part of flexible chains, so that the impact resistance of the composite material is improved. The amount of the toughening agent is 2-5wt%, namely 20-50 g of the toughening agent is added into 1 kg of raw materials, and the raw materials can be preferably premixed or directly blended for use. Meanwhile, in order to solve the dispersion problem among the powder filler, the toughening agent, other additives and the like, an organic solvent can be added, and after the mixing is finished, the solvent is removed by vacuum, wherein the selectable solvents comprise: esters, benzenes, alkane compounds, etc., in an amount of 1-10 wt%.
Further, the surface modifier is at least one of organic silicon and organic titanium modifiers; in order to further improve the dispersion problem of inorganic and metal oxides in the system, a surface modifier is required to be added, and the surface modifier is a coupling agent system. The class includes silane coupling agents, available in the general formula: ROO (4-n) Ti (OX-R' Y) n (n =2,3); wherein RO-is a hydrolyzable short-chain alkoxy group; OX-can be carboxyl, alkoxy, sulfonic group, phosphorus group, etc. The silane coupling agent may be vinyltriethoxysilane, vinyltrimethoxysilane, vinyltris (beta-methoxyethoxy) silane, gamma-aminopropyltriethoxysilane, gamma- (2, 3-glycidoxy) propyltrimethoxysilane, gamma- (methacryloyloxy) propyltrimethoxysilane, N- (beta-aminoethyl) -gamma-aminopropylmethyldimethoxysilane, N- (beta-aminoethyl) -gamma-aminopropyltrimethoxysilane, and titanate coupling agents. In the preparation process of the modified PET film, the surface modifier can be added in a solvent mixing mode or a direct blending mode; in order to improve the dispersibility, the surface modifier is preferably added in a proportion of 1 to 1.5wt% by coating treatment.
Further, the antioxidant is at least one of alkylated monophenols or polyphenols, alkylated reaction products of polyphenols with dienes, butylated reaction products of p-cresol or dicyclopentadiene, alkylated hydroquinones, hydroxylated thiodiphenyl ethers, alkylidene-bisphenols, benzyl compounds, such as pentaerythritol tetrakis [ beta- (3, 5-di-tert-butyl-4-hydroxyphenyl) propionate ]; esters of B- (3, 5-di-tert-butyl-4-hydroxyphenyl) monopropionic acid with monohydric or polyhydric alcohols; esters of B- (5-tert-butyl-4-hydroxy-3-methylphenyl) monopropionic acid with monohydric or polyhydric alcohols; esters of thioalkyl or thioaryl compounds such as distearylthio tombstone propionate, dilaurylthio propionate, ditridecylthiodipropionate, octadecyl-3-mono (3, 5-di-tert-butyl-4-hydroxyphenyl) propionate, pentaerythrityl-mono-tetrakis [3- (3, 5-di-tert-butyl-4-hydroxyphenyl) propionate and the like; amides of B- (3, 5-di-tert-butyl-4-hydroxyphenyl) monopropionic acid, and the like, or combinations comprising at least one of the foregoing antioxidants. Antioxidants are generally used in amounts of 0.01 to 0.5 parts by weight, based on 100 parts by weight of the total composition, preferably comprising S, N, and the like, antioxidants having a molecular weight greater than 150, excluding any filler; the preferred weight percentage of the antioxidant is 0.1-0.5%.
Further, the other auxiliary agents are one or more of antistatic agents, release agents and ultraviolet absorbers;
the antistatic agent is at least one of glycerol monostearate, stearyl sodium sulfonate and sodium dodecyl benzene sulfonate; the release agent is at least one of metal stearate, stearyl stearate, pentaerythritol tetrastearate, montan wax and paraffin; the ultraviolet absorbent is at least one of hydroxybenzophenone, hydroxybenzotriazole and hydroxybenzotriazine.
In the processing process of the modified PET film, the thickness uniformity, the dispersion performance and the material selectivity line processing performance of the line are determined by the dispersion uniformity of the toner in the material, so that other additives are required to be introduced; in addition, due to the fact that a part of thermoplastic resin can be subjected to molecular chain breakage under the heating state of the high-valence Mixed Metal Oxide (MMO), the final mechanical property of the material is influenced; therefore, proper auxiliaries are required to be introduced to inhibit the thermal degradation and the improvement of toughness of the system, so that sufficient mechanical properties are ensured to be maintained in the processes of film forming and subsequent use; other auxiliary agents, the adding proportion of which is controlled within 2 percent.
Further, the modified PET film may further include a heat stabilizer, which may further increase the heat stability of the modified PET film, and is generally used in an amount of 0.01 to 0.5 parts by weight, based on 100 parts by weight of the total composition, excluding any filler. The heat stabilizer is at least one of organophosphorus compounds, such as triphenyl organophosphite, phosphonic acid esters such as dimethylphenyl phosphonate, and the like, and phosphoric acid esters such as trimethyl phosphate.
The modified film of the present invention comprises a thermoplastic resin, wherein the thermoplastic resin is selected from PET resins, preferably a powder raw material. Meanwhile, in consideration of basic requirements of the film stretching process on flexibility, stretchability and the like of materials, the method comprehensively considers factors such as the activity of a catalyst of a toner mixture, the final plating time, the adhesive force of a metalized plating layer and the like under the condition of reducing the total amount of solid toner as much as possible, and optimizes the particle size of the materials, the formula of the materials and the like by combining the past experience on the basis of modification of materials such as PC, LCP and the like.
Further, the preparation method of the modified PET film layer comprises the following steps:
s1, fine mixing and coating the toner, namely performing fine mixing and coating on 5-9% of the toner, 1-3% of the solubilizing polymer, 2-5% of the toughening agent, 1-1.5% of the surface modifier and 0.5-1.8% of other auxiliary agents for 1-2 hours;
s2, vacuum drying, namely drying the powder obtained after the treatment in the S1, wherein the drying temperature is 40-50 ℃, the vacuum degree is less than 130Pa, the constant temperature fluctuation degree is +/-1 ℃, and the drying time is as follows: 20-30mins;
s3, premixing before extrusion: finely mixing the powder obtained after the S2 treatment with 84.5-90.4 wt% of thermoplastic PET resin and 0.1-0.5 wt% of antioxidant, and finely mixing the mixture for 0.5-1 hour by adopting high-pressure hot air with the pressure of 0.05-0.1MPa and the temperature of 70-100 ℃;
s4, extruding the mixture into a film by using 38CrMoAl nitriding tempering double screws with D/L value of more than or equal to 25 to form a film machine, extruding the powder treated in the step S3 into an amorphous film by using a T-shaped die in an extruder at the temperature of 280 ℃, quenching the amorphous film by using a cooling drum or cooling liquid to keep the amorphous film in an amorphous state, preheating the amorphous film to 85-90 ℃, and stretching the amorphous film by about 3 times along the longitudinal direction of the extension of the film plane at the temperature; the transverse stretching preheating temperature is 95-100 ℃, the stretching temperature is 100-120 ℃, the stretching ratio is 2.0-3.0, and the heat setting temperature is 230-240 ℃; the longitudinally and transversely stretched film is subjected to heat setting to eliminate film deformation generated by stretching, so that a PET film with better heat stability is prepared; the preferred PET film thickness is 60-150 microns.
The inorganic toner coating treatment is more beneficial to the dispersion of a system, is particularly suitable for preparing high-concentration master batches, and can be mixed with thermoplastic PET resin in any proportion for use. The selected inorganic materials can be mechanically and physically ground into powders. The molding sample of the modified PET film prepared by the invention can obtain good fluidity at the thickness of 1.0mm (+ -10%), and meanwhile, the product has the indexes of qualified mechanical property, dimensional stability, certain flame retardance and the like.
Adding nano-micron level toner into PET colloidal particles to obtain PET modified powder which is uniformly mixed and can be activated and metallized after laser ablation; obtaining a modified PET film by adopting an extrusion film forming mode; activating and roughening the surface of the modified PET film prepared by the modified material by using a plane laser device with a CCD positioning and galvanometer system, and performing V-ion treatment
A plating layer and a circuit with fine crystals are obtained in a series of fine plating systems, and the problems that the existing flexible circuit board manufacturing process is complex in flow, the metal selectivity of a circuit layer is limited, the pollution is large and the like are solved.
The second purpose of the invention is to provide a preparation method of the modified PET flexible circuit board, which comprises the following steps:
step 1, activating and roughening the surface of the modified PET film by adopting laser, wherein general laser processing parameters in the laser-induced activation method are as follows: filling the space: <50 μm, scanning frequency: 50-80 khz, scan speed 2000-3500 mm/s, power 6-8 w, laser wavelength: 1064nm;
step 2, metallization treatment: and (3) carrying out chemical plating treatment on the modified PET film subjected to the laser treatment in the step (1), wherein the plating starting time is 25-35 minutes, and the deposition rate of a pre-plating section is 3-5 microns/hour.
Further, the chemical plating is at least one of copper plating, gold plating, nickel plating, silver plating, zinc plating, tin plating, chromium plating and cadmium plating; the copper plating system used in the chemical plating and copper plating treatment consists of the following components: 150-200 parts of copper complexing agent, 20-40 parts of copper sulfate, 2-5 parts of methanol, 25-30 parts of sodium hydroxide, 12-18 parts of formaldehyde and 700-1000 parts of deionized water; wherein, the copper complexing agent is EDTA and sodium potassium tartrate according to the weight ratio of 1: 1.
The amount of methanol is well balanced, but does not lead to other side reactions such as coarse crystals and surface oxidation.
The third purpose of the present invention is to provide an application of the modified flexible circuit board or the modified PET flexible circuit board prepared by the preparation method, wherein the application of the modified PET flexible circuit refers to an application in communication equipment, medical treatment, radio frequency identification technology, and automobile weak current lines.
The invention provides a modified PET film capable of being used in a laser direct imaging method, wherein the basic formula of the modified PET film comprises thermoplastic resin, laser direct imaging toner, a solubilizer, a surface treatment agent, a toughening agent, an antioxidant and the like. The resulting product retains both the mechanical properties of the base thermoplastic resin and good processability. The invention solves the problem of uneven components of the existing material caused by injection molding and other reasons, and the metalized plating layer obtained by the invention has uniform thickness, fine crystallization and good adhesive force and can realize fine lines below 100 um. The method has wide application prospect in the aspects of communication equipment such as notebook computers, portable computers, mobile phone antennas and the like, medical treatment, radio Frequency Identification (RFID) technology, automobile and other weak current circuits.
Has the advantages that:
1. the modified PET film obtained by the invention has good dispersibility, excellent mechanical property and chemical plating property, good chemical plating property and film processing formability, and solves the problems of non-collinear processing of film forming and metallization and long manufacturing process in the existing RFID manufacturing process;
2. the method takes a modified PET film as a substrate layer, carries out computer processing on processing graphics and line data, directly carries out activation and surface roughening treatment on the surface of the modified PET film by combining 365um-1064um planar laser with a CCD positioning and vibrating mirror system, and then metallizes the film in a specified plating solution system (a plating layer requires fine and compact crystallization and has certain ductility), thus obtaining the required graphics line in an activated and roughened area.
3. The process capacity in the current market is limited by a vacuum link, two processes of printing and developing are added, and the pollution link is increased; compared with the prior process flow, the material is finely mixed and dried- > film preparation- > vacuum metallization- > photosensitive printing- > development- > etching; the process flow of the invention comprises the steps of material fine mixing and drying- > film preparation- > laser treatment- > metallization; the invention has simple processing technology, and can realize the mass production of continuous roll-To-roll (R To R) by combining with horizontal plating equipment; the electroless plating can be performed without limitation to copper, gold, nickel, silver, zinc, tin, chromium, cadmium, and the like. The invention reduces three procedures of UV photosensitive resist coating, photosensitive mask + exposure process, development and the like. The environmental requirement is reduced, the environmental pollution is reduced, and the overall cost is reduced.
4. The metalized plating layer finally obtained by the modified PET film prepared by the invention has uniform thickness, fine crystallization and good adhesive force, and can realize fine circuits below 100 um. The method has wide application prospect in the aspects of communication equipment such as notebook computers, portable computers, mobile phone antennas and the like, medical treatment, radio frequency identification technology (RFID), new energy automobile battery composite bus bars and other weak current circuits.
Detailed Description
In order to make the objects, technical solutions and effects of the present invention clearer and clearer, the present invention is described in further detail below. It should be understood that the specific embodiments described herein are merely illustrative of the invention and are not intended to limit the invention.
Example 1
A modified PET flexible circuit board comprises a modified PET film layer and a metallization layer, wherein the metallization layer is arranged on one side of the modified PET film layer; the thickness of the metallization layer is 10 microns; the modified PET film had a thickness of 70 microns.
Example 2
The modified PET film layer as described in example 1 consists of the following components in weight percent:
wherein, the toner is cobalt green and cobalt blue, the mass ratio of cobalt green to cobalt blue is 4.
Example 3
The modified PET film layer as described in example 1 consists of the following components in weight percent:
wherein, the toner is cobalt green and cobalt blue, the mass ratio of cobalt green to cobalt blue is 4.
Example 4
The modified PET film layer as described in example 1 consists of the following components in weight percent:
wherein, the toner is cobalt green and cobalt blue, the mass ratio of cobalt green to cobalt blue is 4.
Example 5
The modified PET film layer as described in example 1 consists of the following components in weight percent:
wherein, the toner is cobalt green and cobalt blue, the mass ratio of cobalt green to cobalt blue is 4.
Example 6
The modified PET film layer as described in example 1 consists of the following components in weight percent:
wherein, the toner is cobalt green and cobalt blue, the mass ratio of cobalt green to cobalt blue is 4.
Example 7
The modified PET film layer as described in example 1 consisted of the following components in weight percent:
wherein, the toner is cobalt green and cobalt blue, the mass ratio of cobalt green to cobalt blue is 4.
Example 8
The modified PET film layer as described in example 1 consists of the following components in weight percent:
wherein, the toner is cobalt green and cobalt blue, the mass ratio of cobalt green to cobalt blue is 4.
Example 9
The modified PET film layer as described in example 1 consists of the following components in weight percent:
wherein, the toner is cobalt green and cobalt blue, the mass ratio of cobalt green to cobalt blue is 4.
Example 10
The modified PET film layer as described in example 1 consists of the following components in weight percent:
wherein, the toner is cobalt green and cobalt blue, the mass ratio of cobalt green to cobalt blue is 4.
Example 11
The modified PET film layer as described in example 1 consists of the following components in weight percent:
wherein, the toner is cobalt green and cobalt blue, the mass ratio of cobalt green to cobalt blue is 4.
Example 12
The modified PET film layer as described in example 1 consists of the following components in weight percent:
wherein, the toner is cobalt green and cobalt blue, the mass ratio of cobalt green to cobalt blue is 4.
Example 13
The modified PET film layer as described in example 1 consisted of the following components in weight percent:
wherein, the toner is cobalt green and cobalt blue, the mass ratio of cobalt green to cobalt blue is 4.
Example 14
The method for preparing the modified PET film layer in example 1, using the components of examples 2-12, includes the following steps:
s1, fine mixing and coating the toner, namely performing fine mixing and coating on the toner, the solubilized polymer, the toughening agent, the surface modifier and other auxiliary agents for 1 hour according to the weight percentage;
s2, vacuum drying, namely drying the powder obtained after the treatment of the S1, wherein the drying temperature is 40 ℃, the vacuum degree is less than 130Pa, the constant temperature fluctuation degree is +/-1 ℃, and the drying time is as follows: 20mins;
s3, premixing before extrusion: finely mixing the powder obtained after the S2 treatment with thermoplastic PET resin and an antioxidant according to the weight percentage, and finely mixing for 1 hour by adopting high-pressure hot air with the pressure of 0.1 MPa;
s4, extruding the mixture into a film by using 38CrMoAl double-screw extrusion film forming machine subjected to nitriding quenching and tempering, wherein the D/L value is more than or equal to 25, extruding the powder treated in the step S3 into an amorphous film by using a T-shaped die in an extruder at the temperature of 280 ℃, quenching the amorphous film by using a cooling drum or cooling liquid to keep the amorphous state, preheating the amorphous film to 85 ℃, and stretching the amorphous film by 3 times along the extension direction of the film plane at the temperature so that the amorphous film can be oriented to improve the crystallinity to reach a higher temperature: the transverse stretching preheating temperature is 95 ℃, the stretching temperature is 110 ℃, the stretching ratio is 3.0, and the heat setting temperature is 240 ℃; and (3) performing heat setting on the longitudinally and transversely stretched film to eliminate film deformation generated by stretching, and preparing the PET film with better heat stability.
Example 15
The preparation method of the modified PET flexible circuit board in embodiment 1 includes the following steps:
step 1, activating and roughening the surface of the modified PET film by adopting laser
The general laser processing parameters in the laser-induced activation method are as follows: filling the space: <50 μm, scanning frequency: 70 khz, scan speed: 2500 mm/sec, power: 7 w, laser wavelength: 1064nm;
step 2, metallization treatment: and (3) carrying out chemical plating treatment on the modified PET film subjected to the laser treatment in the step (1), wherein the plating starting time is 30 minutes, and the deposition rate of a pre-plating section is 4 microns/h.
The chemical plating is copper plating; the copper plating system used in the chemical plating and copper plating treatment consists of the following components: 180 parts of copper complexing agent, 30 parts of copper sulfate, 3 parts of methanol, 28 parts of sodium hydroxide, 15 parts of formaldehyde and 800 parts of deionized water; wherein, the copper complexing agent is EDTA and sodium potassium tartrate according to the weight ratio of 1: 1.
The properties of the copper wiring layers were tested using the components of examples 2-13, the film layer preparation method of example 14, the modified PET flexible circuit board preparation method of example 15 using standard ASTM D3359. The results are reported in table 1.
TABLE 1
As can be seen from table 1, the modified PET film prepared by using the components of the present invention has excellent tensile strength, elastic modulus, and adhesion, and can be used in a laser direct patterning method, and the modified PET film can maintain the mechanical properties of the base thermoplastic resin and maintain good processability. The invention solves the problem of uneven components of the existing material caused by injection molding and other reasons, and the metalized plating layer obtained by the invention has uniform thickness, fine crystallization and good adhesive force and can realize fine lines below 100 um. The method has wide application prospect in the aspects of communication equipment such as notebook computers, portable computers, mobile phone antennas and the like, medical treatment, radio Frequency Identification (RFID) technology, automobile and other weak current circuits.
The above description is only for the preferred embodiment of the present invention, and it should be noted that any modification, equivalent replacement, improvement, etc. made by those skilled in the art without departing from the principle of the present invention shall be included in the protection scope of the present invention.
Claims (10)
1. A modified PET flexible circuit board is characterized by comprising a modified PET film layer and a metallization layer, wherein the metallization layer is arranged on one side of the modified PET film layer; the thickness of the metallization layer is 5-20 microns; the thickness of the modified PET film is 60-150 microns.
2. The modified PET flexible circuit board of claim 1, wherein the modified PET film layer consists of the following components in percentage by weight:
3. the modified PET flexible circuit board of claim 1, wherein the toner is selected from one or more of a nano-scale metal powder, a nano-scale vacancy type metal mixed oxide, a single metal oxide; the toner is selected from one or more of nanoscale metal powder, nanoscale vacancy type metal mixed oxide, single metal oxide or salt compounds thereof.
4. The modified PET flexible circuit board of claim 2, wherein the nanoscale metal powder particle size is 1.5 microns or less; the nano-scale vacancy type metal mixed oxide is at least one of cobalt green and cobalt blue; the particle size of the nano-scale vacancy type metal mixed oxide is 20-500nm; what is neededThe single metal oxide is CuO or Co 2 O 3 (ii) a The particle size of the thermoplastic PET resin is 15-40 micrometers; the grain diameter of the antioxidant is 0.8-1.5 microns.
5. The modified PET flexible circuit board of claim 2, wherein the solubilizing polymer is at least one of silicones or a mixture of silicones and common rubber elastomers; the surface modifier is at least one of organic silicon and organic titanium modifiers; the antioxidant is at least one of alkylated monophenol or polyhydric phenol, alkylated reaction product of polyhydric phenol and diene, butylated reaction product of p-cresol or dicyclopentadiene, alkylated hydroquinone, hydroxylated thiodiphenyl ether, alkylidene-bisphenol and benzyl compound; the other auxiliary agents are one or more of antistatic agents, release agents and ultraviolet absorbers.
6. The modified PET flexible circuit board of claim 2, wherein the modified PET film further comprises a heat stabilizer in an amount of 0.01 to 0.5 parts by weight, based on 100 parts by weight of the total composition; the heat stabilizer is at least one of triphenyl phosphite, phosphonate such as dimethyl phenyl phosphonate and the like, and phosphate such as trimethyl phosphate.
7. The modified PET flexible circuit board of claim 1, wherein the preparation method of the modified PET film layer comprises the following steps:
s1, fine mixing and coating the toner, namely performing fine mixing and coating on 5-9% of the toner, 1-3% of the solubilizing polymer, 2-5% of the toughening agent, 1-1.5% of the surface modifier and 0.5-1.8% of other auxiliary agents for 1-2 hours;
s2, vacuum drying, namely drying the powder obtained after the treatment in the S1, wherein the drying temperature is 40-50 ℃, the vacuum degree is less than 130Pa, the constant temperature fluctuation degree is +/-1 ℃, and the drying time is as follows: 20-30mins;
s3, premixing before extrusion: finely mixing the powder obtained after the S2 treatment with 84.5-90.4 wt% of thermoplastic PET resin and 0.1-0.5 wt% of antioxidant, and finely mixing for 0.5-1 hour at a high pressure of 0.05-0.1MPa and a temperature of 70-100 ℃;
s4, extruding the mixture into a film, namely selecting a 38CrMoAl nitriding quenching and tempering double-screw extruder with the D/L value of more than or equal to 25 to extrude a film forming machine, extruding the powder treated in the step S3 into an amorphous film through a T-shaped die in the extruder at the temperature of 280 ℃, quenching the amorphous film through a cooling drum or cooling liquid to keep the amorphous film in an amorphous state, preheating the amorphous film to 85-90 ℃, and longitudinally stretching the amorphous film by about 3 times along the extension direction of the plane of the film at the temperature; transversely stretching at the preheating temperature of 95-100 ℃, the stretching temperature of 100-120 ℃, the stretching ratio of 2.0-3.0 and the heat setting temperature of 230-240 ℃; and (3) performing heat setting on the longitudinally and transversely stretched film to eliminate film deformation generated by stretching, and preparing the PET film with better heat stability.
8. The method for preparing the modified PET flexible circuit board according to claim 1, comprising the steps of:
step 1, activating and roughening the surface of the modified PET film by adopting laser
The laser processing parameters in the laser induced activation method are as follows: filling the space: <50 μm, scanning frequency: 50-80 khz, scan speed 2000-3500 mm/s, power 6-8 w, laser wavelength: 1064nm;
step 2, metallization treatment: and (3) carrying out chemical plating treatment on the modified PET film subjected to the laser treatment in the step (1), wherein the plating starting time is 25-35 minutes, and the deposition rate of a pre-plating section is 3-5 microns/hour.
9. The method for preparing a modified PET flexible circuit board according to claim 8,
the chemical plating is at least one of copper plating, gold plating, nickel plating, silver plating, zinc plating, tin plating, chromium plating and cadmium plating; the copper plating system used in the chemical plating and copper plating treatment consists of the following components: 150-200 parts of copper complexing agent, 20-40 parts of copper sulfate, 2-5 parts of methanol, 25-30 parts of sodium hydroxide, 12-18 parts of formaldehyde and 700-1000 parts of deionized water; wherein, the copper complexing agent is EDTA and sodium potassium tartrate according to the weight ratio of 1: 1.
10. The modified flexible circuit board as claimed in claims 1 to 7 or the modified PET flexible circuit board prepared by the preparation method as claimed in claims 8 to 9, wherein the application of the modified PET flexible circuit is in the fields of communication equipment, medical treatment, radio frequency identification technology and automobile weak current circuits.
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