CN113136011A - 3D printing resin for manufacturing low-loss antenna and application thereof - Google Patents
3D printing resin for manufacturing low-loss antenna and application thereof Download PDFInfo
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- CN113136011A CN113136011A CN202110521335.8A CN202110521335A CN113136011A CN 113136011 A CN113136011 A CN 113136011A CN 202110521335 A CN202110521335 A CN 202110521335A CN 113136011 A CN113136011 A CN 113136011A
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- 239000011347 resin Substances 0.000 title claims abstract description 80
- 229920005989 resin Polymers 0.000 title claims abstract description 80
- 238000010146 3D printing Methods 0.000 title claims abstract description 43
- 238000004519 manufacturing process Methods 0.000 title claims abstract description 19
- 239000000463 material Substances 0.000 claims abstract description 39
- 239000000843 powder Substances 0.000 claims abstract description 21
- 229920000642 polymer Polymers 0.000 claims abstract description 13
- 230000004913 activation Effects 0.000 claims abstract description 11
- 238000002360 preparation method Methods 0.000 claims abstract description 10
- 239000002270 dispersing agent Substances 0.000 claims abstract description 8
- 238000011282 treatment Methods 0.000 claims abstract description 8
- 239000003085 diluting agent Substances 0.000 claims abstract description 7
- 150000002736 metal compounds Chemical class 0.000 claims abstract description 7
- 238000000016 photochemical curing Methods 0.000 claims description 41
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 claims description 28
- 239000004743 Polypropylene Substances 0.000 claims description 22
- 229920001155 polypropylene Polymers 0.000 claims description 22
- 238000003756 stirring Methods 0.000 claims description 20
- 238000001125 extrusion Methods 0.000 claims description 18
- 238000000034 method Methods 0.000 claims description 18
- 238000007639 printing Methods 0.000 claims description 17
- 238000002156 mixing Methods 0.000 claims description 15
- 229910000147 aluminium phosphate Inorganic materials 0.000 claims description 14
- 239000000203 mixture Substances 0.000 claims description 14
- 238000000465 moulding Methods 0.000 claims description 12
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 claims description 11
- 239000002202 Polyethylene glycol Substances 0.000 claims description 11
- 229910052802 copper Inorganic materials 0.000 claims description 11
- 239000010949 copper Substances 0.000 claims description 11
- 229920001223 polyethylene glycol Polymers 0.000 claims description 11
- -1 polypropylene Polymers 0.000 claims description 10
- 238000007747 plating Methods 0.000 claims description 9
- KUDUQBURMYMBIJ-UHFFFAOYSA-N 2-prop-2-enoyloxyethyl prop-2-enoate Chemical compound C=CC(=O)OCCOC(=O)C=C KUDUQBURMYMBIJ-UHFFFAOYSA-N 0.000 claims description 8
- 239000000126 substance Substances 0.000 claims description 8
- FIHBHSQYSYVZQE-UHFFFAOYSA-N 6-prop-2-enoyloxyhexyl prop-2-enoate Chemical compound C=CC(=O)OCCCCCCOC(=O)C=C FIHBHSQYSYVZQE-UHFFFAOYSA-N 0.000 claims description 7
- ZDHCZVWCTKTBRY-UHFFFAOYSA-N omega-Hydroxydodecanoic acid Natural products OCCCCCCCCCCCC(O)=O ZDHCZVWCTKTBRY-UHFFFAOYSA-N 0.000 claims description 7
- 239000003504 photosensitizing agent Substances 0.000 claims description 7
- 229920000728 polyester Polymers 0.000 claims description 7
- 239000002994 raw material Substances 0.000 claims description 7
- ZDQNWDNMNKSMHI-UHFFFAOYSA-N 1-[2-(2-prop-2-enoyloxypropoxy)propoxy]propan-2-yl prop-2-enoate Chemical compound C=CC(=O)OC(C)COC(C)COCC(C)OC(=O)C=C ZDQNWDNMNKSMHI-UHFFFAOYSA-N 0.000 claims description 6
- DKPFZGUDAPQIHT-UHFFFAOYSA-N Butyl acetate Natural products CCCCOC(C)=O DKPFZGUDAPQIHT-UHFFFAOYSA-N 0.000 claims description 6
- DAKWPKUUDNSNPN-UHFFFAOYSA-N Trimethylolpropane triacrylate Chemical compound C=CC(=O)OCC(CC)(COC(=O)C=C)COC(=O)C=C DAKWPKUUDNSNPN-UHFFFAOYSA-N 0.000 claims description 6
- FUZZWVXGSFPDMH-UHFFFAOYSA-N hexanoic acid Chemical compound CCCCCC(O)=O FUZZWVXGSFPDMH-UHFFFAOYSA-N 0.000 claims description 6
- 229910052751 metal Inorganic materials 0.000 claims description 6
- 239000002184 metal Substances 0.000 claims description 6
- FSDNTQSJGHSJBG-UHFFFAOYSA-N piperidine-4-carbonitrile Chemical compound N#CC1CCNCC1 FSDNTQSJGHSJBG-UHFFFAOYSA-N 0.000 claims description 6
- LLHKCFNBLRBOGN-UHFFFAOYSA-N propylene glycol methyl ether acetate Chemical compound COCC(C)OC(C)=O LLHKCFNBLRBOGN-UHFFFAOYSA-N 0.000 claims description 6
- 238000010586 diagram Methods 0.000 claims description 5
- 229910000570 Cupronickel Inorganic materials 0.000 claims description 4
- 239000004793 Polystyrene Substances 0.000 claims description 4
- ZBTDWLVGWJNPQM-UHFFFAOYSA-N [Ni].[Cu].[Au] Chemical compound [Ni].[Cu].[Au] ZBTDWLVGWJNPQM-UHFFFAOYSA-N 0.000 claims description 4
- 239000000654 additive Substances 0.000 claims description 4
- 230000000996 additive effect Effects 0.000 claims description 4
- YOCUPQPZWBBYIX-UHFFFAOYSA-N copper nickel Chemical compound [Ni].[Cu] YOCUPQPZWBBYIX-UHFFFAOYSA-N 0.000 claims description 4
- YCKOAAUKSGOOJH-UHFFFAOYSA-N copper silver Chemical compound [Cu].[Ag].[Ag] YCKOAAUKSGOOJH-UHFFFAOYSA-N 0.000 claims description 4
- 238000013532 laser treatment Methods 0.000 claims description 4
- 238000001465 metallisation Methods 0.000 claims description 4
- JJLJMEJHUUYSSY-UHFFFAOYSA-L Copper hydroxide Chemical compound [OH-].[OH-].[Cu+2] JJLJMEJHUUYSSY-UHFFFAOYSA-L 0.000 claims description 3
- 239000005750 Copper hydroxide Substances 0.000 claims description 3
- GXDVEXJTVGRLNW-UHFFFAOYSA-N [Cr].[Cu] Chemical compound [Cr].[Cu] GXDVEXJTVGRLNW-UHFFFAOYSA-N 0.000 claims description 3
- 229910001956 copper hydroxide Inorganic materials 0.000 claims description 3
- ZKXWKVVCCTZOLD-UHFFFAOYSA-N copper;4-hydroxypent-3-en-2-one Chemical compound [Cu].CC(O)=CC(C)=O.CC(O)=CC(C)=O ZKXWKVVCCTZOLD-UHFFFAOYSA-N 0.000 claims description 3
- 238000001723 curing Methods 0.000 claims description 3
- VFHVQBAGLAREND-UHFFFAOYSA-N diphenylphosphoryl-(2,4,6-trimethylphenyl)methanone Chemical compound CC1=CC(C)=CC(C)=C1C(=O)P(=O)(C=1C=CC=CC=1)C1=CC=CC=C1 VFHVQBAGLAREND-UHFFFAOYSA-N 0.000 claims description 3
- 238000011049 filling Methods 0.000 claims description 3
- 230000001678 irradiating effect Effects 0.000 claims description 3
- 229920002223 polystyrene Polymers 0.000 claims description 3
- 229910052596 spinel Inorganic materials 0.000 claims description 3
- 239000011029 spinel Substances 0.000 claims description 3
- 125000005409 triarylsulfonium group Chemical group 0.000 claims description 3
- QPLDLSVMHZLSFG-UHFFFAOYSA-N Copper oxide Chemical compound [Cu]=O QPLDLSVMHZLSFG-UHFFFAOYSA-N 0.000 claims description 2
- 239000005751 Copper oxide Substances 0.000 claims description 2
- YXHUUJPFJXLPQQ-UHFFFAOYSA-J P(=O)([O-])([O-])[O-].[OH-].[Cu+4] Chemical compound P(=O)([O-])([O-])[O-].[OH-].[Cu+4] YXHUUJPFJXLPQQ-UHFFFAOYSA-J 0.000 claims description 2
- XXLJGBGJDROPKW-UHFFFAOYSA-N antimony;oxotin Chemical compound [Sb].[Sn]=O XXLJGBGJDROPKW-UHFFFAOYSA-N 0.000 claims description 2
- 229910000431 copper oxide Inorganic materials 0.000 claims description 2
- 238000000151 deposition Methods 0.000 claims description 2
- 229920001684 low density polyethylene Polymers 0.000 claims description 2
- 239000004702 low-density polyethylene Substances 0.000 claims description 2
- XOLBLPGZBRYERU-UHFFFAOYSA-N tin dioxide Chemical compound O=[Sn]=O XOLBLPGZBRYERU-UHFFFAOYSA-N 0.000 claims description 2
- 229910001887 tin oxide Inorganic materials 0.000 claims description 2
- 238000003672 processing method Methods 0.000 abstract description 3
- 239000000758 substrate Substances 0.000 abstract description 2
- 239000003054 catalyst Substances 0.000 abstract 1
- 238000004891 communication Methods 0.000 abstract 1
- 238000005516 engineering process Methods 0.000 description 11
- 239000000243 solution Substances 0.000 description 7
- 239000007788 liquid Substances 0.000 description 5
- KCXVZYZYPLLWCC-UHFFFAOYSA-N EDTA Chemical compound OC(=O)CN(CC(O)=O)CCN(CC(O)=O)CC(O)=O KCXVZYZYPLLWCC-UHFFFAOYSA-N 0.000 description 4
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 4
- 230000005540 biological transmission Effects 0.000 description 4
- 229960001484 edetic acid Drugs 0.000 description 4
- HHLFWLYXYJOTON-UHFFFAOYSA-N glyoxylic acid Chemical compound OC(=O)C=O HHLFWLYXYJOTON-UHFFFAOYSA-N 0.000 description 4
- 238000012360 testing method Methods 0.000 description 4
- 238000004140 cleaning Methods 0.000 description 3
- JZCCFEFSEZPSOG-UHFFFAOYSA-L copper(II) sulfate pentahydrate Chemical compound O.O.O.O.O.[Cu+2].[O-]S([O-])(=O)=O JZCCFEFSEZPSOG-UHFFFAOYSA-L 0.000 description 3
- 239000003365 glass fiber Substances 0.000 description 3
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical class [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 description 2
- 229910000366 copper(II) sulfate Inorganic materials 0.000 description 2
- 239000011259 mixed solution Substances 0.000 description 2
- 238000002161 passivation Methods 0.000 description 2
- 235000011118 potassium hydroxide Nutrition 0.000 description 2
- ROFVEXUMMXZLPA-UHFFFAOYSA-N Bipyridyl Chemical compound N1=CC=CC=C1C1=CC=CC=N1 ROFVEXUMMXZLPA-UHFFFAOYSA-N 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- ZXTZSQTZPFDVIU-UHFFFAOYSA-L copper;hydroxy phosphate Chemical compound [Cu+2].OOP([O-])([O-])=O ZXTZSQTZPFDVIU-UHFFFAOYSA-L 0.000 description 1
- 238000001514 detection method Methods 0.000 description 1
- 239000012895 dilution Substances 0.000 description 1
- 238000010790 dilution Methods 0.000 description 1
- 238000007599 discharging Methods 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 238000005286 illumination Methods 0.000 description 1
- 238000001746 injection moulding Methods 0.000 description 1
- 239000002245 particle Substances 0.000 description 1
- 238000003825 pressing Methods 0.000 description 1
- 238000004904 shortening Methods 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 239000007858 starting material Substances 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 1
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F283/00—Macromolecular compounds obtained by polymerising monomers on to polymers provided for in subclass C08G
- C08F283/06—Macromolecular compounds obtained by polymerising monomers on to polymers provided for in subclass C08G on to polyethers, polyoxymethylenes or polyacetals
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B33—ADDITIVE MANUFACTURING TECHNOLOGY
- B33Y—ADDITIVE MANUFACTURING, i.e. MANUFACTURING OF THREE-DIMENSIONAL [3-D] OBJECTS BY ADDITIVE DEPOSITION, ADDITIVE AGGLOMERATION OR ADDITIVE LAYERING, e.g. BY 3-D PRINTING, STEREOLITHOGRAPHY OR SELECTIVE LASER SINTERING
- B33Y70/00—Materials specially adapted for additive manufacturing
- B33Y70/10—Composites of different types of material, e.g. mixtures of ceramics and polymers or mixtures of metals and biomaterials
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F2/00—Processes of polymerisation
- C08F2/46—Polymerisation initiated by wave energy or particle radiation
- C08F2/48—Polymerisation initiated by wave energy or particle radiation by ultraviolet or visible light
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F255/00—Macromolecular compounds obtained by polymerising monomers on to polymers of hydrocarbons as defined in group C08F10/00
- C08F255/02—Macromolecular compounds obtained by polymerising monomers on to polymers of hydrocarbons as defined in group C08F10/00 on to polymers of olefins having two or three carbon atoms
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K3/00—Use of inorganic substances as compounding ingredients
- C08K3/18—Oxygen-containing compounds, e.g. metal carbonyls
- C08K3/20—Oxides; Hydroxides
- C08K3/22—Oxides; Hydroxides of metals
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- Chemical & Material Sciences (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Organic Chemistry (AREA)
- Engineering & Computer Science (AREA)
- Ceramic Engineering (AREA)
- Civil Engineering (AREA)
- Composite Materials (AREA)
- Structural Engineering (AREA)
- Manufacturing & Machinery (AREA)
- Materials Engineering (AREA)
Abstract
The invention discloses a 3D printing resin for manufacturing a low-loss antenna and application thereof. The 3D printing material comprises a light-cured resin prepolymer, a photoinitiator, a reactive diluent, a dispersing agent, a laser-activatable metal compound and low-loss polymer powder. The preparation method comprises the following steps: preparing a light-cured resin base material; doping a low dielectric loss material; laser activatable catalyst doping; and (5) defoaming treatment. The processing method of the low-loss antenna comprises the following steps: firstly, constructing an antenna model by using a CAD tool; secondly, performing 3D printing on an antenna substrate by using the prepared light-cured resin material; thirdly, laser activation; fifthly, the antenna conducting circuit is metallized. The functional 3D printing material for manufacturing the low-loss antenna is obtained, the capability of 3D printing and manufacturing electronic circuit products is greatly improved, and the functional 3D printing material can be applied to the fields of aerospace, 5G communication, intelligent automobiles and the like.
Description
Technical Field
The invention relates to a functional 3D printing material for manufacturing a low-loss antenna, in particular to novel 3D printing resin and a process method.
Background
The arrival of the 5G era has enabled the transmission speed of signals to be greatly increased, which is much faster than that of 4G signals, and this has raised higher requirements for wireless electric devices, and antennas as important devices for radiating and receiving radio waves must ensure that the interference to signals is small, and also require that the dielectric constant of the materials used for the antennas is small and the loss to signals is low, so as to ensure that large data transmission is not interfered. At present, most of materials for preparing the low-loss antenna are high polymers with low loss angle and high strength mechanical property, and the method for preparing the low-loss antenna by using the high polymers mainly comprises the traditional processes of pressing, injection molding and the like. However, the traditional process can only prepare some antennas with simple and regular shapes, and the period is long, if the light curing molding (SLA) technology or the extrusion molding technology in the 3D printing technology is applied, polypropylene and photosensitive resin are fused, and the antennas are directly printed, the printing period is greatly shortened, the 3D printing technology is relatively simple to operate, the precision is high, no die is needed, and the process flow is simplified.
Disclosure of Invention
The purpose of the invention is as follows: one of the objectives of the present invention is to provide a novel antenna manufacturing method, which promotes the simplification of the antenna production process and the shortening of the period; the second purpose of the present invention is to provide a method for preparing a low-loss antenna raw material, which promotes polypropylene to be more widely applied to the manufacture of low-loss antennas; the invention also aims to provide an application scene of the 3D printing photocuring molding technology and the extrusion molding technology, and broadens the field covered by the 3D printing technology.
The invention aims to provide 3D printing photocuring resin using a doped low-loss material and application thereof, which are used for manufacturing a low-loss antenna by photocuring or extrusion molding 3D printing.
The technical scheme is as follows: a low-loss photo-curable 3D printing resin comprises the following raw materials in parts by weight:
the low-loss powder is one of polypropylene, polystyrene and low-density polyethylene, and the light-cured resin prepolymer is one of polyethylene glycol (PEG) and trimethylolpropane triacrylate (TMPTA).
The laser-activatable metal compound is one or two of hydroxyl copper phosphate, copper chromium spinel, copper acetylacetonate, copper hydroxide, copper oxide, tin antimony oxide and tin oxide.
The dispersing agent is a mixture of phosphoric acid polyester and phosphoric acid, or a mixture of 1-methoxy-2-propanol acetate and butyl acetate; wherein the mass ratio of the phosphoric acid polyester to the phosphoric acid is 40-60: the mass ratio of the 1, 1-methoxy-2-propanol acetate to the butyl acetate is 8-10: 1.
The photosensitizer is one of 2,4, 6-trimethylbenzoyl-diphenylphosphine oxide (TPO) and triarylsulfonium salt.
The active diluent is one of ethylene glycol diacrylate (HDDA), dipropylene glycol diacrylate (DPGDA) and tripropylene glycol diacrylate (TPGDA).
The preparation method of the photocuring 3D printing resin comprises the following steps:
(1) mixing the light-cured resin prepolymer and the reactive diluent in proportion at normal temperature and uniformly stirring to obtain a light-cured resin base material;
(2) adding a small amount of low-loss polymer powder into the light-cured resin base material for multiple times, and mixing and uniformly stirring at normal temperature to obtain low-loss light-cured resin;
(3) adding laser activatable (LDS) metal compound powder into low-loss light-cured resin, mixing and stirring uniformly at normal temperature to obtain the low-loss light-cured resin with laser activatable property;
(4) and adding the dispersing agent into the laser-activatable low-loss light-cured resin, and mixing and stirring uniformly at normal temperature.
(5) Adding a photosensitizer into the product obtained in the step (4) under the condition of keeping out of the sun, mixing at normal temperature and uniformly stirring;
(6) and (5) placing the product obtained in the step (5) into a vacuum defoaming machine, and defoaming for 10 minutes in a dark place to obtain the photocuring printing resin for the low-loss antenna.
The photocuring 3D printing resin is applied to preparation of a 3D printing antenna.
The preparation method of the 3D printing antenna comprises the steps of carrying out 3D printing photocuring forming and extrusion forming on resin, adopting laser selective activation treatment, and depositing metal at the activated position.
The preparation of the 3D printing antenna comprises the following steps:
(1) preparing low-loss light-cured resin;
(2) carrying out model modeling by utilizing a CAD tool;
(3) the resin in the step (1) is combined with the structure model in the step (2) to perform additive manufacturing, and the specific printing scheme is divided into two modes of extrusion molding and photocuring molding; the extrusion molding protocol was as follows: filling the light-cured resin doped with the low-loss polymer powder into an opaque metal dispensing needle cylinder in a dark place, slicing a model by using slicing software and converting the model into a G-code file capable of controlling an extrusion molding 3D printer so as to drive 3D printing to extrude and stack materials layer by layer, and irradiating the materials by using an ultraviolet light source to accelerate curing; sending the file to a photo-curing machine for printing; the photocuring molding scheme is as follows: and placing the photocuring resin doped with the low dielectric loss material into a photocuring printer resin tank, performing model slicing through slicing software to form projection pictures or light path information which can be identified by the photocuring 3D printer, and driving a photocuring light source to selectively cure the prepared 3D printing resin layer by layer.
(4) Laser activation: designing a circuit diagram, and carrying out selective laser treatment on the surface of the base structure printed in the step (3) to obtain an active surface;
(5) metallization of the circuit: and carrying out chemical plating treatment on the active surface of the antenna to form a required three-dimensional circuit on the surface of the antenna.
The three-dimensional circuit required in the antenna is a copper, copper nickel gold, copper nickel or copper silver circuit.
Has the advantages that:
(1) the novel 3D printing material prepared by the invention and composed of polypropylene and light-cured resin can be used in occasions requiring parts to have low loss characteristics. By applying the 3D printing technology, only a simple 3D model of the part is needed to be imported into the 3D printing software, and the parameters are adjusted, so that the complex low-loss part can be printed.
(2) The polypropylene has low cost, low loss factor and other performances superior to those of other high polymers, and the light-cured resin raw materials are common in the market, and the mixture of the polypropylene and the high-polymer is good in leveling property, stable in chemical state and low in dielectric constant, so that the polypropylene and the high-polymer can be used for preparing antennas and can completely surpass other materials.
(3) After the light-cured resin is mixed with PP powder according to a corresponding proportion, the light-cured technology or the direct-writing extrusion technology can be used for preparing the antenna, so that the period can be effectively shortened, the production flow can be simplified, and whether the new antenna design meets certain requirements or not can be quickly verified.
(4) The low-loss polymer powder is added into the light-cured resin, so that the loss angle of the light-cured resin is reduced, the high-frequency characteristic of the light-cured resin is improved, and the light-cured resin can be more effectively used in the preparation of low-loss antennas. Taking direct-writing printing doped 60% PP powder as an example, the loss angle of the original light-cured resin, the loss angle of PP, and the loss angle of the low-loss light-cured resin obtained by mixing the two can be obtained according to a transmission line test, and for the mass percentage of the used PP, the loss angle of the low-loss light-cured resin is reduced by 40% compared with the original light-cured resin.
Drawings
Fig. 1 is a schematic flow diagram of the preparation of a low loss photocurable resin for electronic circuit fabrication.
Fig. 2 is a schematic flow chart of a process for manufacturing a low-loss antenna by using a photo-curing molding technology.
Fig. 3 is a sample diagram of a manufactured low loss antenna.
Detailed Description
The present invention will be described in further detail with reference to examples.
The starting materials and reagents used in the following examples are all commercially available.
The photocuring 3D printing resin for preparing the electronic circuit comprises the following raw materials in parts by weight:
the light-cured resin prepolymer is selected from one of materials such as polyethylene glycol (PEG), trimethylolpropane triacrylate (TMPTA) and the like.
The active diluent is selected from one of materials such as ethylene glycol diacrylate (HDDA), dipropylene glycol diacrylate (DPGDA), tripropylene glycol diacrylate (TPGDA) and the like.
The low-loss polymer powder is made of one of polypropylene (PP), Polystyrene (PS) and the like.
The photosensitizer is selected from one of materials such as 2,4, 6-trimethylbenzoyl-diphenylphosphine oxide (TPO), triarylsulfonium salt and the like.
The laser-activatable metal compound is selected from one or two of copper hydroxy phosphate, copper chromium spinel, copper acetylacetonate and copper hydroxide.
The dispersing agent is a mixture of phosphoric acid polyester and phosphoric acid (marked as a mixture A) or a mixture of 1-methoxy-2-propanol acetate and butyl acetate (marked as a mixture B); wherein the mass ratio of the phosphoric acid polyester to the phosphoric acid in the mixture A is 40-60: 1; the mass ratio of the 1-methoxy-2-propanol acetate to the butyl acetate in the mixture B is 8-10: 1. The dispersant is preferably a mixture of phosphoric acid polyester and phosphoric acid.
The technical scheme of the invention is as follows: a low-loss antenna and a processing and manufacturing process of a material thereof are provided, the processing method of the low-loss antenna uses additive manufacturing, laser activation and chemical plating processes, and takes the photo-curing resin prepolymer as PEG, reactive diluent as HDDA, low-loss polymer powder as PP and photosensitizer as TPO as examples, and the complete process comprises the following steps:
in the first step, a PP-doped photocurable resin is manufactured. (1) Mixing PEG and HDDA according to the required weight ratio of 1 to 1, and stirring uniformly. (2) And adding the PP powder into the mixed solution of the PEG and the HDDA according to the required parts for a plurality of times in a small amount, and uniformly stirring. (3) LDS powder, TPO and a dispersing agent are added into the mixed solution according to the required parts, and a vacuum defoaming machine is used for stirring and defoaming. (4) And carrying out loss angle test on the prepared low-loss light-cured resin by using a transmission line method.
And secondly, modeling the model by utilizing a CAD tool.
And thirdly, using the PP-doped light-cured resin material for additive manufacturing. The specific printing scheme can be divided into two modes of extrusion molding and photocuring molding. The extrusion molding protocol was as follows: (1) and filling the PP-doped light-cured resin into an opaque metal dispensing syringe in a dark place. (2) And (3) slicing the model by using slicing software and converting the sliced model into a G-code file capable of controlling an extrusion molding 3D printer so as to drive the 3D printer to extrude and stack the materials layer by layer, wherein the materials are irradiated by an ultraviolet light source to be cured at an accelerated speed in the process. The photocuring molding scheme is as follows: (1) and (3) putting the PP-doped light-cured resin into a light-cured printer resin tank. (2) And performing model slicing through photocuring slicing software to form projection pictures or light path information which can be identified by the photocuring 3D printer, and driving a photocuring light source to selectively solidify the prepared 3D printing resin layer by layer. (3) And cleaning the surface of the printed product by using IPA solution.
And fourthly, laser activation. Designing a circuit diagram, and carrying out laser treatment on the part of the surface of the product needing electroless copper plating to obtain an active surface;
fifthly, metallization of the circuit is carried out. Carrying out chemical plating treatment on the active surface of the antenna to form a required three-dimensional circuit on the surface of the antenna; the three-dimensional circuit required in the antenna can be a copper, copper-nickel-gold, copper-nickel and copper-silver circuit.
Optionally, the low-loss substrate component powder comprises PP, PS. Preferably, the particle diameter of the powder is 5-10 um, and the molecular weight is 10^ 4-10 ^ 6. Preferably, PP is used with minimal loss.
Optionally, the laser used for surface activation is a glass fiber laser with a wavelength of 1064nm, and the laser processing frequency is 60KHz, the power is 0.1W-5.0W, and the speed is 2000mm/s-10000 mm/s.
Optionally, the laser used for surface activation is a glass fiber laser with a wavelength of 1064nm, and the laser processing frequency is 60KHz, the power is 0.1W-5.0W, and the speed is 2000mm/s-10000 mm/s.
Optionally, the three-dimensional circuit required in the antenna is copper, copper-nickel-gold, copper-nickel, or copper-silver.
Optionally, after the step of assembling, the shell finished product is tested and then packaged, wherein the testing includes functional testing and AOI detection.
Example 1:
the low-loss antenna material for photocuring 3D printing in the embodiment comprises the following raw materials in parts by weight:
the preparation method of the photocuring 3D printing low-loss antenna in the embodiment is as follows:
(1) mixing 70g of polyethylene glycol (PEG) and 70g of ethylene glycol diacrylate (HDDA) at normal temperature and uniformly stirring to obtain a photocuring resin base material;
(2) adding 50g of polypropylene (PP) powder into the product obtained in the step (1) for a plurality of times in a small amount, and stirring at high speed in a vacuum environment until mixing to obtain low-loss light-cured resin;
(3) and (3) adding 10g of laser activatable (LDS) metal compound powder into the product obtained in the step (2), and stirring at a high speed in a vacuum environment until the mixture is uniformly mixed to obtain the laser activatable low-loss photocuring resin.
(4) Adding 2g of photosensitizer (TPO) into the product in the step (3) under a light-proof condition, and stirring at a high speed under a vacuum light-proof environment until the mixture is uniformly mixed;
(5) and (3) placing the product obtained in the step (4) into a vacuum defoaming machine, and defoaming for 10 minutes in a dark place to obtain the photocuring molding resin for manufacturing the electronic circuit, wherein the pp content is about 25 percent, and the loss angle of the obtained low-loss photocuring resin is about 0.0023.
The 3D printing method used in this embodiment is photocuring molding: placing the prepared material into a resin tank of an SLA photocuring printer, performing model slicing through photocuring slicing software, and sending a file to a photocuring machine for printing, wherein the illumination intensity is 10.00mW/cm2The exposure time was 6.0000 s. After printing, the printed product is subjected to surface cleaning using an IPA solution.
The laser processing method comprises the steps of carrying out laser processing on a printed sample by using glass fiber laser with the wavelength of 1064nm, wherein the used laser scanner control software is Ezcad software, the used laser scanning area file is drawn by using the Cad software or directly using the Ezcad software, the laser processing frequency is 60KHz, the power is 0.1W-5.0W, and the speed is 2000mm/s-10000 mm/s.
Carrying out chemical plating on the sample subjected to laser treatment to metalize the circuit, wherein the specific solution component table and the process flow are as follows:
the related solvents added in the copper liquid and the contents thereof are as follows: 0.12mol/L (35g/L) EDTA (ethylene diamine tetraacetic acid), 0.15mol/L (14.8g/L) glyoxylic acid, 0.05mol/L (10.4g/L) copper sulfate pentahydrate, 5 mg/L2.2-bipyridine and a plurality of potassium hydroxides, wherein the pH of the copper liquid is 12.3 and 11.9, and the temperature of the copper liquid is 55 ℃.
(1) Dissolving EDTA in water, adding a proper amount of KOH, and stirring by using a magnetic stirrer until the solution is clear at the rotating speed of 900 r/s;
(2) adding blue vitriol into EDTA solution, stirring until the blue vitriol is completely dissolved, wherein the rotation speed is 900r/s, and the color of the solution is dark blue;
(3) adding 2, 2-bipyridine;
(4) glyoxylic acid was added and the pH adjusted to 12.5 and 13 before use.
(5) Heating to 65 ℃.
(6) Firstly, putting a model to be processed into copper liquid with pH value of 13, and transferring the model to the copper liquid with pH value of 12.5 for continuous plating after the laser-activated areas on the surface of the model are covered by a copper layer.
(7) And after the chemical plating is finished, cleaning the model, putting the model into a passivation solution for passivation, and finally drying the model.
And obtaining a low-loss antenna finished product through the treatment.
Example 2:
the low-loss antenna material in the embodiment comprises the following raw material components in parts by weight:
the material of the low loss antenna material of this example was prepared as in example 1, the only difference being that due to the high PP powder content, dilution with ethanol was required to help better mixing and stirring of the material, and due to the volatility of ethanol, its mass was not counted in the total mass of the material. The PP content of the material can reach 65%, and the loss angle of the obtained low-loss light-cured resin is about 0.0018. .
The 3D printing method used in this example is extrusion molding: the prepared material is filled into an opaque metal dispensing needle cylinder in a dark place, the diameter of a needle is 1.25mm, a model is sliced by FDM slicing software, the corresponding diameter of the needle is selected from the software, the thickness of a printing layer is 0.4/0.3mm, G-code in a slice file provided by the software is rewritten, the original printing head walking speed and blanking speed are deleted, the extrusion head is closed when the needle is lifted each time, the extrusion head is opened when wiring is started, the printing head walking speed is set to 3600mm/min, the slice file controls an air pump to perform direct writing printing, air pressure is adjusted in the printing process to enable the discharging speed to be appropriate, and an ultraviolet lamp is used for irradiating a 30-second printer baseplate area after printing is completed.
In this embodiment, the flow of the laser activation treatment and the chemical plating treatment for the circuit metallization of the 3D printed sample is the same as that in embodiment 1, so as to obtain a low-loss antenna product.
Claims (10)
1. The low-loss photocurable 3D printing resin is characterized by comprising the following raw materials in parts by weight:
the low-loss powder is one of polypropylene, polystyrene and low-density polyethylene, and the light-cured resin prepolymer is one of polyethylene glycol (PEG) and trimethylolpropane triacrylate (TMPTA).
2. The 3D printing resin of claim 1, wherein: the laser-activatable metal compound is one or two of hydroxyl copper phosphate, copper chromium spinel, copper acetylacetonate, copper hydroxide, copper oxide, tin antimony oxide and tin oxide.
3. The 3D printing resin of claim 1, wherein: the dispersing agent is a mixture of phosphoric acid polyester and phosphoric acid, or a mixture of 1-methoxy-2-propanol acetate and butyl acetate; wherein the mass ratio of the phosphoric acid polyester to the phosphoric acid is 40-60: the mass ratio of the 1, 1-methoxy-2-propanol acetate to the butyl acetate is 8-10: 1.
4. The 3D printing resin of claim 1, wherein: the photosensitizer is one of 2,4, 6-trimethylbenzoyl-diphenylphosphine oxide (TPO) and triarylsulfonium salt.
5. The 3D printing resin of claim 1, wherein: the active diluent is one of ethylene glycol diacrylate (HDDA), dipropylene glycol diacrylate (DPGDA) and tripropylene glycol diacrylate (TPGDA).
6. The method for preparing a photocurable 3D printing resin according to any one of claims 1 to 5, wherein: the method comprises the following steps:
(1) mixing the light-cured resin prepolymer and the reactive diluent in proportion at normal temperature and uniformly stirring to obtain a light-cured resin base material;
(2) adding a small amount of low-loss polymer powder into the light-cured resin base material for multiple times, and mixing and uniformly stirring at normal temperature to obtain low-loss light-cured resin;
(3) adding laser activatable (LDS) metal compound powder into low-loss light-cured resin, mixing and stirring uniformly at normal temperature to obtain the low-loss light-cured resin with laser activatable property;
(4) adding a dispersing agent into the laser-activatable low-loss photocureable resin, and mixing and stirring uniformly at normal temperature;
(5) adding a photosensitizer into the product obtained in the step (4) under the condition of keeping out of the sun, mixing at normal temperature and uniformly stirring;
(6) and (5) placing the product obtained in the step (5) into a vacuum defoaming machine, and defoaming for 10 minutes in a dark place to obtain the photocuring printing resin for the low-loss antenna.
7. Use of the photocurable 3D printing resin according to any one of claims 1 to 5 for the preparation of a 3D printed antenna.
8. The application of claim 7, wherein the 3D printed antenna is prepared by performing 3D printing photocuring molding and extrusion molding on resin, and depositing metal at the position of the activation processing by adopting laser selective activation processing.
9. Use according to claim 7, characterized in that the preparation of the 3D printed antenna comprises the following steps:
(1) preparing low-loss light-cured resin;
(2) carrying out model modeling by utilizing a CAD tool;
(3) the resin in the step (1) is combined with the structure model in the step (2) to perform additive manufacturing, and the specific printing scheme is divided into two modes of extrusion molding and photocuring molding; the extrusion molding protocol was as follows: filling the light-cured resin doped with the low-loss polymer powder into an opaque metal dispensing needle cylinder in a dark place, slicing a model by using slicing software and converting the model into a G-code file capable of controlling an extrusion molding 3D printer so as to drive 3D printing to extrude and stack materials layer by layer, and irradiating the materials by using an ultraviolet light source to accelerate curing; sending the file to a photo-curing machine for printing; the photocuring molding scheme is as follows: and placing the photocuring resin doped with the low dielectric loss material into a photocuring printer resin tank, performing model slicing through slicing software to form projection pictures or light path information which can be identified by the photocuring 3D printer, and driving a photocuring light source to selectively cure the prepared 3D printing resin layer by layer.
(4) Laser activation: designing a circuit diagram, and carrying out selective laser treatment on the surface of the base structure printed in the step (3) to obtain an active surface;
(5) metallization of the circuit: and carrying out chemical plating treatment on the active surface of the antenna to form a required three-dimensional circuit on the surface of the antenna.
10. Use according to claim 9, characterized in that: the three-dimensional circuit required in the antenna is a copper, copper nickel gold, copper nickel or copper silver circuit.
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Citations (3)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
WO2016200222A1 (en) * | 2015-06-10 | 2016-12-15 | (주)옵토라인 | Method for manufacturing electronic module having complex three-dimensional shape using 3d printing technology and manufacturing apparatus therefor |
CN111886659A (en) * | 2018-03-22 | 2020-11-03 | 罗杰斯公司 | Melt-processable thermoplastic composite material comprising a multimodal dielectric filler |
CN112029236A (en) * | 2020-08-06 | 2020-12-04 | 东南大学 | Photocuring 3D printing resin, preparation method and application thereof, and 3D printing product |
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Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
WO2016200222A1 (en) * | 2015-06-10 | 2016-12-15 | (주)옵토라인 | Method for manufacturing electronic module having complex three-dimensional shape using 3d printing technology and manufacturing apparatus therefor |
CN111886659A (en) * | 2018-03-22 | 2020-11-03 | 罗杰斯公司 | Melt-processable thermoplastic composite material comprising a multimodal dielectric filler |
CN112029236A (en) * | 2020-08-06 | 2020-12-04 | 东南大学 | Photocuring 3D printing resin, preparation method and application thereof, and 3D printing product |
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