CN112029236A - Photocuring 3D printing resin, preparation method and application thereof, and 3D printing product - Google Patents
Photocuring 3D printing resin, preparation method and application thereof, and 3D printing product Download PDFInfo
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- CN112029236A CN112029236A CN202010786021.6A CN202010786021A CN112029236A CN 112029236 A CN112029236 A CN 112029236A CN 202010786021 A CN202010786021 A CN 202010786021A CN 112029236 A CN112029236 A CN 112029236A
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- resin
- printing
- photocuring
- laser
- metal compound
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- 239000011347 resin Substances 0.000 title claims abstract description 163
- 229920005989 resin Polymers 0.000 title claims abstract description 163
- 238000000016 photochemical curing Methods 0.000 title claims abstract description 77
- 238000010146 3D printing Methods 0.000 title claims abstract description 69
- 238000002360 preparation method Methods 0.000 title claims abstract description 28
- 150000002736 metal compounds Chemical class 0.000 claims abstract description 39
- 238000004519 manufacturing process Methods 0.000 claims abstract description 37
- 239000000463 material Substances 0.000 claims abstract description 30
- 238000002156 mixing Methods 0.000 claims abstract description 28
- 239000002270 dispersing agent Substances 0.000 claims abstract description 22
- 239000000203 mixture Substances 0.000 claims abstract description 20
- 239000000843 powder Substances 0.000 claims abstract description 20
- 239000002518 antifoaming agent Substances 0.000 claims abstract description 18
- 239000003085 diluting agent Substances 0.000 claims abstract description 18
- 239000002994 raw material Substances 0.000 claims abstract description 17
- 230000004913 activation Effects 0.000 claims abstract description 15
- 238000010438 heat treatment Methods 0.000 claims abstract description 11
- 238000000498 ball milling Methods 0.000 claims abstract description 10
- 238000000465 moulding Methods 0.000 claims abstract description 8
- 238000001035 drying Methods 0.000 claims abstract description 7
- 239000000047 product Substances 0.000 claims description 38
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 claims description 24
- 238000007639 printing Methods 0.000 claims description 21
- 150000003254 radicals Chemical class 0.000 claims description 20
- 238000003756 stirring Methods 0.000 claims description 15
- 238000000034 method Methods 0.000 claims description 13
- 229910000147 aluminium phosphate Inorganic materials 0.000 claims description 12
- 125000002091 cationic group Chemical group 0.000 claims description 12
- LLHKCFNBLRBOGN-UHFFFAOYSA-N propylene glycol methyl ether acetate Chemical compound COCC(C)OC(C)=O LLHKCFNBLRBOGN-UHFFFAOYSA-N 0.000 claims description 9
- 238000001723 curing Methods 0.000 claims description 8
- 239000013067 intermediate product Substances 0.000 claims description 8
- 239000012952 cationic photoinitiator Substances 0.000 claims description 6
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical group CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 claims description 6
- 229920000728 polyester Polymers 0.000 claims description 6
- 229910052751 metal Inorganic materials 0.000 claims description 5
- 239000002184 metal Substances 0.000 claims description 5
- DKPFZGUDAPQIHT-UHFFFAOYSA-N Butyl acetate Natural products CCCCOC(C)=O DKPFZGUDAPQIHT-UHFFFAOYSA-N 0.000 claims description 4
- FUZZWVXGSFPDMH-UHFFFAOYSA-N hexanoic acid Chemical compound CCCCCC(O)=O FUZZWVXGSFPDMH-UHFFFAOYSA-N 0.000 claims description 4
- GXDVEXJTVGRLNW-UHFFFAOYSA-N [Cr].[Cu] Chemical compound [Cr].[Cu] GXDVEXJTVGRLNW-UHFFFAOYSA-N 0.000 claims description 3
- 238000000151 deposition Methods 0.000 claims description 3
- 229910052596 spinel Inorganic materials 0.000 claims description 3
- 239000011029 spinel Substances 0.000 claims description 3
- JJLJMEJHUUYSSY-UHFFFAOYSA-L Copper hydroxide Chemical compound [OH-].[OH-].[Cu+2] JJLJMEJHUUYSSY-UHFFFAOYSA-L 0.000 claims description 2
- 239000005750 Copper hydroxide Substances 0.000 claims description 2
- 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
- XXLJGBGJDROPKW-UHFFFAOYSA-N antimony;oxotin Chemical compound [Sb].[Sn]=O XXLJGBGJDROPKW-UHFFFAOYSA-N 0.000 claims description 2
- 229910001956 copper hydroxide Inorganic materials 0.000 claims description 2
- 229910000431 copper oxide Inorganic materials 0.000 claims description 2
- 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 2
- 239000002904 solvent 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
- 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 1
- 239000000126 substance Substances 0.000 abstract description 28
- 238000007747 plating Methods 0.000 abstract description 24
- 238000004891 communication Methods 0.000 abstract description 3
- 238000004108 freeze drying Methods 0.000 abstract description 3
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 10
- 229910052802 copper Inorganic materials 0.000 description 10
- 239000010949 copper Substances 0.000 description 10
- 239000007787 solid Substances 0.000 description 10
- MCMNRKCIXSYSNV-UHFFFAOYSA-N Zirconium dioxide Chemical compound O=[Zr]=O MCMNRKCIXSYSNV-UHFFFAOYSA-N 0.000 description 8
- 238000005516 engineering process Methods 0.000 description 8
- 230000000694 effects Effects 0.000 description 7
- -1 vinyl ether compound Chemical class 0.000 description 7
- KCTAWXVAICEBSD-UHFFFAOYSA-N prop-2-enoyloxy prop-2-eneperoxoate Chemical group C=CC(=O)OOOC(=O)C=C KCTAWXVAICEBSD-UHFFFAOYSA-N 0.000 description 6
- HHLFWLYXYJOTON-UHFFFAOYSA-N glyoxylic acid Chemical compound OC(=O)C=O HHLFWLYXYJOTON-UHFFFAOYSA-N 0.000 description 5
- 239000010410 layer Substances 0.000 description 5
- 239000007788 liquid Substances 0.000 description 5
- 239000000243 solution Substances 0.000 description 5
- IISBACLAFKSPIT-UHFFFAOYSA-N bisphenol A Chemical compound C=1C=C(O)C=CC=1C(C)(C)C1=CC=C(O)C=C1 IISBACLAFKSPIT-UHFFFAOYSA-N 0.000 description 4
- 239000000919 ceramic Substances 0.000 description 4
- 238000011982 device technology Methods 0.000 description 4
- 239000002356 single layer Substances 0.000 description 4
- 238000012360 testing method Methods 0.000 description 4
- UNMJLQGKEDTEKJ-UHFFFAOYSA-N (3-ethyloxetan-3-yl)methanol Chemical compound CCC1(CO)COC1 UNMJLQGKEDTEKJ-UHFFFAOYSA-N 0.000 description 3
- 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 description 3
- YIKSHDNOAYSSPX-UHFFFAOYSA-N 1-propan-2-ylthioxanthen-9-one Chemical compound S1C2=CC=CC=C2C(=O)C2=C1C=CC=C2C(C)C YIKSHDNOAYSSPX-UHFFFAOYSA-N 0.000 description 3
- JUXZNIDKDPLYBY-UHFFFAOYSA-N 3-ethyl-3-(phenoxymethyl)oxetane Chemical compound C=1C=CC=CC=1OCC1(CC)COC1 JUXZNIDKDPLYBY-UHFFFAOYSA-N 0.000 description 3
- 239000000654 additive Substances 0.000 description 3
- 230000000996 additive effect Effects 0.000 description 3
- 150000001768 cations Chemical class 0.000 description 3
- ISAOCJYIOMOJEB-UHFFFAOYSA-N desyl alcohol Natural products C=1C=CC=CC=1C(O)C(=O)C1=CC=CC=C1 ISAOCJYIOMOJEB-UHFFFAOYSA-N 0.000 description 3
- 238000001746 injection moulding Methods 0.000 description 3
- 239000003960 organic solvent Substances 0.000 description 3
- FSDNTQSJGHSJBG-UHFFFAOYSA-N piperidine-4-carbonitrile Chemical compound N#CC1CCNCC1 FSDNTQSJGHSJBG-UHFFFAOYSA-N 0.000 description 3
- 239000000758 substrate Substances 0.000 description 3
- UBRWOYCTUYUNTR-UHFFFAOYSA-N 7-oxabicyclo[4.1.0]heptan-4-yl formate Chemical compound C1C(OC=O)CCC2OC21 UBRWOYCTUYUNTR-UHFFFAOYSA-N 0.000 description 2
- LCGLNKUTAGEVQW-UHFFFAOYSA-N Dimethyl ether Chemical compound COC LCGLNKUTAGEVQW-UHFFFAOYSA-N 0.000 description 2
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 2
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 description 2
- 244000028419 Styrax benzoin Species 0.000 description 2
- 235000000126 Styrax benzoin Nutrition 0.000 description 2
- 235000008411 Sumatra benzointree Nutrition 0.000 description 2
- 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 description 2
- RAOSIAYCXKBGFE-UHFFFAOYSA-K [Cu+3].[O-]P([O-])([O-])=O Chemical compound [Cu+3].[O-]P([O-])([O-])=O RAOSIAYCXKBGFE-UHFFFAOYSA-K 0.000 description 2
- 230000009286 beneficial effect Effects 0.000 description 2
- 229960002130 benzoin Drugs 0.000 description 2
- 230000005540 biological transmission Effects 0.000 description 2
- DJUWPHRCMMMSCV-UHFFFAOYSA-N bis(7-oxabicyclo[4.1.0]heptan-4-ylmethyl) hexanedioate Chemical compound C1CC2OC2CC1COC(=O)CCCCC(=O)OCC1CC2OC2CC1 DJUWPHRCMMMSCV-UHFFFAOYSA-N 0.000 description 2
- 239000003153 chemical reaction reagent Substances 0.000 description 2
- 238000010586 diagram Methods 0.000 description 2
- WCMHCPWEQCWRSR-UHFFFAOYSA-J dicopper;hydroxide;phosphate Chemical compound [OH-].[Cu+2].[Cu+2].[O-]P([O-])([O-])=O WCMHCPWEQCWRSR-UHFFFAOYSA-J 0.000 description 2
- 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 description 2
- 235000019382 gum benzoic Nutrition 0.000 description 2
- 229910000765 intermetallic Inorganic materials 0.000 description 2
- 238000007146 photocatalysis Methods 0.000 description 2
- 230000001699 photocatalysis Effects 0.000 description 2
- 239000002244 precipitate Substances 0.000 description 2
- 238000012545 processing Methods 0.000 description 2
- 238000000926 separation method Methods 0.000 description 2
- 125000005409 triarylsulfonium group Chemical group 0.000 description 2
- 229960000834 vinyl ether Drugs 0.000 description 2
- CYIGRWUIQAVBFG-UHFFFAOYSA-N 1,2-bis(2-ethenoxyethoxy)ethane Chemical compound C=COCCOCCOCCOC=C CYIGRWUIQAVBFG-UHFFFAOYSA-N 0.000 description 1
- UHFFVFAKEGKNAQ-UHFFFAOYSA-N 2-benzyl-2-(dimethylamino)-1-(4-morpholin-4-ylphenyl)butan-1-one Chemical compound C=1C=C(N2CCOCC2)C=CC=1C(=O)C(CC)(N(C)C)CC1=CC=CC=C1 UHFFVFAKEGKNAQ-UHFFFAOYSA-N 0.000 description 1
- LWRBVKNFOYUCNP-UHFFFAOYSA-N 2-methyl-1-(4-methylsulfanylphenyl)-2-morpholin-4-ylpropan-1-one Chemical compound C1=CC(SC)=CC=C1C(=O)C(C)(C)N1CCOCC1 LWRBVKNFOYUCNP-UHFFFAOYSA-N 0.000 description 1
- NIXOWILDQLNWCW-UHFFFAOYSA-M Acrylate Chemical compound [O-]C(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-M 0.000 description 1
- QYKIQEUNHZKYBP-UHFFFAOYSA-N Vinyl ether Chemical compound C=COC=C QYKIQEUNHZKYBP-UHFFFAOYSA-N 0.000 description 1
- 150000008062 acetophenones Chemical class 0.000 description 1
- 239000004844 aliphatic epoxy resin Substances 0.000 description 1
- 238000010923 batch production Methods 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 239000003054 catalyst Substances 0.000 description 1
- 238000006555 catalytic reaction Methods 0.000 description 1
- 238000006243 chemical reaction Methods 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 230000001112 coagulating effect Effects 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
- 238000004132 cross linking Methods 0.000 description 1
- 238000005520 cutting process Methods 0.000 description 1
- 230000032798 delamination Effects 0.000 description 1
- 230000008021 deposition Effects 0.000 description 1
- 125000005520 diaryliodonium group Chemical group 0.000 description 1
- MTHSVFCYNBDYFN-UHFFFAOYSA-N diethylene glycol Chemical compound OCCOCCO MTHSVFCYNBDYFN-UHFFFAOYSA-N 0.000 description 1
- 125000000118 dimethyl group Chemical group [H]C([H])([H])* 0.000 description 1
- 238000009826 distribution Methods 0.000 description 1
- 238000009713 electroplating Methods 0.000 description 1
- 238000005530 etching Methods 0.000 description 1
- 229940052303 ethers for general anesthesia Drugs 0.000 description 1
- 239000006260 foam Substances 0.000 description 1
- 239000012949 free radical photoinitiator Substances 0.000 description 1
- 238000000227 grinding Methods 0.000 description 1
- 230000005764 inhibitory process Effects 0.000 description 1
- 230000010354 integration Effects 0.000 description 1
- 239000011817 metal compound particle Substances 0.000 description 1
- 239000000178 monomer Substances 0.000 description 1
- 239000004570 mortar (masonry) Substances 0.000 description 1
- 239000002245 particle Substances 0.000 description 1
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N phenol group Chemical group C1(=CC=CC=C1)O ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 description 1
- 239000004033 plastic Substances 0.000 description 1
- 229920003023 plastic Polymers 0.000 description 1
- 238000006116 polymerization reaction Methods 0.000 description 1
- 238000011417 postcuring Methods 0.000 description 1
- 238000006479 redox reaction Methods 0.000 description 1
- 229920002545 silicone oil Polymers 0.000 description 1
- 239000007858 starting material Substances 0.000 description 1
- 238000003860 storage Methods 0.000 description 1
- YRHRIQCWCFGUEQ-UHFFFAOYSA-N thioxanthen-9-one Chemical compound C1=CC=C2C(=O)C3=CC=CC=C3SC2=C1 YRHRIQCWCFGUEQ-UHFFFAOYSA-N 0.000 description 1
- 238000012546 transfer Methods 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 1
Images
Classifications
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L63/00—Compositions of epoxy resins; Compositions of derivatives of epoxy resins
-
- 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
-
- 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
- B33Y80/00—Products made by additive manufacturing
-
- 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
- C08F283/10—Macromolecular compounds obtained by polymerising monomers on to polymers provided for in subclass C08G on to polymers containing more than one epoxy radical per molecule
-
- 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
- C08F283/10—Macromolecular compounds obtained by polymerising monomers on to polymers provided for in subclass C08G on to polymers containing more than one epoxy radical per molecule
- C08F283/105—Macromolecular compounds obtained by polymerising monomers on to polymers provided for in subclass C08G on to polymers containing more than one epoxy radical per molecule on to unsaturated polymers containing more than one epoxy radical per molecule
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- H—ELECTRICITY
- H05—ELECTRIC TECHNIQUES NOT OTHERWISE PROVIDED FOR
- H05K—PRINTED CIRCUITS; CASINGS OR CONSTRUCTIONAL DETAILS OF ELECTRIC APPARATUS; MANUFACTURE OF ASSEMBLAGES OF ELECTRICAL COMPONENTS
- H05K1/00—Printed circuits
- H05K1/02—Details
- H05K1/03—Use of materials for the substrate
- H05K1/0313—Organic insulating material
- H05K1/0353—Organic insulating material consisting of two or more materials, e.g. two or more polymers, polymer + filler, + reinforcement
- H05K1/0373—Organic insulating material consisting of two or more materials, e.g. two or more polymers, polymer + filler, + reinforcement containing additives, e.g. fillers
-
- 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
- H05K3/10—Apparatus or processes for manufacturing printed circuits in which conductive material is applied to the insulating support in such a manner as to form the desired conductive pattern
- H05K3/105—Apparatus or processes for manufacturing printed circuits in which conductive material is applied to the insulating support in such a manner as to form the desired conductive pattern by conversion of non-conductive material on or in the support into conductive material, e.g. by using an energy beam
-
- 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
- C08K2003/2248—Oxides; Hydroxides of metals of copper
-
- 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
- C08K3/32—Phosphorus-containing compounds
- C08K2003/321—Phosphates
- C08K2003/328—Phosphates of heavy metals
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L2205/00—Polymer mixtures characterised by other features
- C08L2205/02—Polymer mixtures characterised by other features containing two or more polymers of the same C08L -group
-
- 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
- H05K2201/00—Indexing scheme relating to printed circuits covered by H05K1/00
- H05K2201/01—Dielectrics
- H05K2201/0137—Materials
Abstract
The invention discloses a photocuring 3D printing resin, a preparation method and application thereof, and a 3D printing product, wherein resin raw materials comprise a photocuring resin prepolymer, a photoinitiator, an active diluent, a dispersant, a defoaming agent and a laser-activatable metal compound; the preparation method comprises the steps of heating and mixing the prepolymer and the photoinitiator, adding the diluent and uniformly mixing to obtain a resin base material; carrying out ball milling treatment on the laser-activatable metal compound, and then carrying out freeze drying or drying treatment to obtain dry powder; and fully mixing the metal compound powder with a dispersing agent, a defoaming agent and a resin base material, and placing the mixture in a vacuum kettle for defoaming treatment to finally obtain a resin finished product. The resin prepared by the invention can be subjected to laser activation selective chemical plating after photocuring and molding to manufacture a two-dimensional/three-dimensional electronic circuit, and can be applied to the fields of aerospace, automobile industry, microwave communication devices, artware manufacturing and the like.
Description
Technical Field
The invention relates to a resin, a preparation method and application thereof, in particular to a 3D printing resin, a preparation method and application thereof.
Background
Most current electronic circuit products rely primarily on printed circuit board technology (PCB) for manufacturing. The printed circuit board not only provides support for the electronic components, but also is a carrier for the conductive interconnection of the electronic components. The manufacturing process of the printed circuit board mainly comprises the following steps: cutting, copper deposition, pattern transfer, pattern electroplating, film stripping, etching, green oil, molding and the like, and the process is mature and suitable for batch production. But PCB manufacturing technology processes are many, production cycle is long, and input cost is higher. With the technological progress, many industries put forward higher requirements on the performance of electronic products, for example, in the fields of communication engineering, aviation and aerospace engineering, etc., customized electronic circuit products with complex three-dimensional structures, such as 5G conformal antennas, three-dimensional circuit boards, etc., need to be manufactured quickly, economically and efficiently, so as to improve the performance of the products, reduce the overall weight, improve the integration level and reduce the size of the products. However, the conventional printed circuit board manufacturing technology can only manufacture a two-dimensional planar circuit board, and it is difficult to satisfy the above requirements.
The molding interconnection device technology (MID) can manufacture a three-dimensional circuit on the surface of a part formed by injection molding and realize the interconnection of electronic components, but the molding interconnection device based on the injection molding process needs expensive injection molding equipment and a precision mold, and the three-dimensional structure of a plastic part is greatly limited due to the restriction of taking the part by a separation mold; in addition, the process needs to open a die, has large early investment and long production period, is only suitable for mass production and is not beneficial to manufacturing customized products. Therefore, a substitute process with high precision, low cost, high production speed and capability of manufacturing a complex three-dimensional electronic circuit structure is urgently needed, and the key of the new process lies in the preparation of novel materials.
Disclosure of Invention
The purpose of the invention is as follows: one of the purposes of the invention is to provide a photocuring 3D printing resin which is used for manufacturing electronic circuits, and solves the problems that the conventional printed circuit board manufacturing technology (PCB) can not manufacture customized three-dimensional electronic circuits, and the limitation that the molding interconnection device technology (MID) equipment is expensive and is not suitable for small and medium-scale customized production; the second purpose of the invention is to provide a preparation method of the photocuring 3D printing resin; the invention also aims to provide application of the 3D printing resin; the fourth purpose of the invention is to provide a 3D printing product.
The technical scheme is as follows: the invention provides a photocuring 3D printing resin which comprises the following raw material components in parts by weight:
in the photocuring 3D printing resin for preparing electronic circuits, the photocuring resin base material is a hybrid photocuring resin formed by doping free radical photocuring system photocuring resin and cation photocuring resin, and the resin has the advantages of both the free radical photocuring resin and the cation photocuring resin, namely high curing speed, moisture resistance, small curing system shrinkage and capability of post-curing under dark conditions; the laser activation type metal compound is added into the light-cured resin base material, so that the chemical property of the laser activation type metal compound can be endowed to the light-cured resin material, namely, a light-cured resin printed piece can generate simple substance copper in the chemical copper plating solution under the irradiation of near infrared light. Wherein the light-cured resin prepolymer is a light-cured resin main body; the active diluent has the auxiliary functions of improving the flow and adjusting the viscosity; the photoinitiator is a substance capable of absorbing certain energy in an ultraviolet light area, and generates free radicals or cations to initiate the crosslinking polymerization reaction of the photocuring resin prepolymer and the reactive diluent to generate a high molecular substance, so that the photocuring resin curing process is completed; the laser-activatable metal compound is a substance which can generate simple substance copper in chemical copper plating solution after absorbing light energy in a near infrared region and then generating oxidation-reduction reaction; the dispersing agent is a reagent which can disperse the laser activated metal compound in the light-cured resin and can prevent the laser activated metal compound particles from settling and coagulating; the defoaming agent is an agent that can reduce the surface tension of the photocurable resin and prevent the formation of foam.
The laser-activatable metal compound is selected from at least one of copper hydroxy 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 (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 defoaming agent is n-hexane, naphtha or a mixture of naphtha and 1-methoxy-2-propanol acetate (marked as a mixture C), and the mass ratio of the naphtha to the 1-methoxy-2-propanol acetate in the mixture C is 10-30: 1. Wherein, the defoaming agent is preferably selected from n-hexane.
The cationic light-cured resin prepolymer is aliphatic epoxy resin, and can be one of bis ((3, 4-epoxycyclohexyl) methyl) adipate and 3, 4-epoxycyclohexyl formate.
The cationic photoinitiator is selected from diaryl iodonium salt and triaryl sulfonium salt.
The cationic light-cured resin reactive diluent is a vinyl ether compound or an oxetane compound, and is selected from one of triethylene glycol divinyl ether (DVE-3), 3-ethyl-3-Phenoxymethyloxetane (POX) and 3-ethyl-3-hydroxymethyl oxetane (EHMO).
The free radical type photo-curing resin prepolymer is epoxy acrylate, and is selected from bisphenol A type epoxy acrylate, phenolic aldehyde type epoxy acrylate and hydrogenated epoxy acrylate.
The free radical photoinitiator refers to benzoin ethers, acetophenones, acylphosphine oxides, thioxanthone and derivatives thereof, and is selected from one of benzoin dimethyl ether, 2-benzyl-2-dimethylamino-1- (4-morpholinylphenyl) butanone-1 (Irgacure 369), 2-methyl-1- (4-methylmercaptophenyl) -2-morpholineacetone-1 (Irgacure 907), 2, 4, 6-trimethylbenzoyl-diphenylphosphine oxide (TPO) and Isopropyl Thioxanthone (ITX).
The free radical type light-cured resin reactive diluent refers to acrylate monomers and is selected from one of tripropylene glycol diacrylate (TPGDA), trimethylolpropane triacrylate (TMPTA) and dipropylene glycol diacrylate (DPGDA).
Preferably, the printing layer thickness of the light-cured 3D printing resin is less than or equal to 70 mu m.
The invention also provides a preparation method of the photocuring 3D printing resin, which comprises the following steps:
(1) mixing the cationic photocuring resin prepolymer and the cationic photoinitiator in proportion, heating and stirring, and then adding a cationic photocuring resin reactive diluent to obtain an intermediate product A;
(2) mixing the free radical type photo-curing resin prepolymer and the free radical type photoinitiator in proportion, heating and stirring, and then adding a free radical type photo-curing resin reactive diluent to obtain an intermediate product B;
(3) uniformly mixing the intermediate product A and the intermediate product B in a dark place to obtain a photocuring resin base material;
(4) mixing a laser-activatable metal compound with a solvent, carrying out ball milling treatment, and drying to obtain metal compound powder;
(5) and mixing the metal compound powder with the light-cured resin base material, the dispersing agent and the defoaming agent, putting the mixed product into a vacuum kettle, and defoaming in a dark place to obtain the light-cured resin.
Specifically, the steps include:
(1) uniformly mixing the cationic light-cured resin prepolymer and the cationic photoinitiator according to a certain proportion, and heating and stirring;
(2) uniformly mixing a cationic light-cured resin reactive diluent with the product obtained in the step (1) according to a certain proportion;
(3) uniformly mixing the free radical type light-cured resin prepolymer and the free radical type photoinitiator according to a certain proportion, and heating and stirring;
(4) uniformly mixing a free radical type light-cured resin reactive diluent with the product obtained in the step (3) according to a certain proportion;
(5) uniformly mixing the products obtained in the steps (2) and (4) in a certain proportion in a dark place to obtain a photocuring resin base material;
(6) ball-milling the laser-activatable metal compound powder in a ball mill by using an organic solvent or water as a medium;
(7) carrying out freeze drying or heating drying treatment on the product mixed with the solid and the liquid in the step (6) to obtain dry metal compound powder;
(8) mixing a certain amount of the metal compound powder in the step (7) with the photocuring resin base material, the dispersing agent and the defoaming agent in the step (5), and fully mixing in a ball mill;
(9) and (4) placing the product obtained in the step (8) into a vacuum kettle, and defoaming in a dark place to obtain the photocuring additive manufacturing material for manufacturing the electronic circuit.
The invention provides application of the photocuring 3D printing resin in electronic circuit manufacturing.
The invention provides a 3D printing product which is prepared by adopting the photocuring 3D printing resin.
Preferably, the preparation method of the product comprises the steps of carrying out 3D printing photocuring forming on the photocuring 3D printing resin, adopting laser selective activation treatment, and depositing metal at the activated position to obtain the product.
Preferably, the curing light source adopts an ultraviolet laser with the wavelength of 405nm, and the laser activation adopts an infrared light source with the wavelength of 1064 nm.
The key technical links of the photocuring 3D printing resin are in the components and proportion, and the laser-activatable metal compound, the corresponding dispersing agent and the defoaming agent are added into the photocuring resin base material, so that the purpose that the surface of a photocuring resin printing piece can be metalized after laser activation is achieved; the material prepared by the technical scheme can be used for light-cured 3D printing equipment such as SLA, DLP and LCD.
The photocuring 3D printing resin comprises a photocuring resin prepolymer, a photoinitiator, an active diluent, a dispersing agent, a defoaming agent and a laser-activatable metal compound, and is prepared by heating and mixing the prepolymer and the photoinitiator, adding the diluent and uniformly mixing to obtain a resin base material; carrying out ball milling treatment on the laser-activatable metal compound, and then carrying out freeze drying or drying treatment to obtain dry powder; and fully mixing the metal compound powder with a dispersing agent, a defoaming agent and a resin base material, and placing the mixture in a vacuum kettle for defoaming treatment to finally obtain a resin finished product. The resin prepared by the invention can be subjected to laser activation selective chemical plating after photocuring and molding to manufacture a two-dimensional/three-dimensional electronic circuit, and can be applied to the fields of aerospace, automobile industry, microwave communication devices, artware manufacturing and the like.
The proportion of the light-cured resin is set based on the consideration of physical and chemical properties of the light-cured resin, so that the effects of high curing speed, moderate viscosity, small shrinkage rate of a curing system and the like are realized; when the mass fraction of the laser activated metal compound is less than 4%, the photocuring resin printed piece is difficult to activate under infrared laser so as to be difficult to plate; when the mass fraction is more than 8%, the content thereof is high, which may cause the inhibition of ultraviolet light propagation during the photocuring printing process to reduce the ultraviolet light propagation distance, and ultimately affect the photocuring printing layer thickness.
The key technical links in the preparation method of the photocuring 3D printing resin are ball-milling treatment of the laser-activatable metal compound, mixing of the laser-activatable metal compound and the photocuring resin base material and post-treatment, so that the properties and functions of the photocuring resin material are completely changed, and the photocuring 3D printing resin with excellent performance is finally obtained.
The invention applies the light-cured resin to the electronic circuit manufacturing method in a breakthrough manner, namely the light-cured 3D printing resin for manufacturing the electronic circuit, which can be used for a light-cured 3D printer, is prepared by the invention. The resin can be cured by a photocuring 3D printing process to form a three-dimensional electronic circuit substrate, and a circuit pattern can be formed on the substrate by a selective chemical plating process after laser activation, so that three-dimensional conductive interconnection of electronic components is realized, and a customized electronic circuit product with high precision, low cost and a complex three-dimensional structure is rapidly manufactured. Whereas the conventional electronic circuit manufacturing method is the printed circuit board manufacturing technology (PCB), the molded interconnect device technology (MID) has appeared in recent years, but both of them do not manufacture the electronic circuit using the photo-curable resin. Compared with the two technologies, the resin prepared by the invention has low price, can quickly manufacture customized electronic circuit products with high precision, low cost and complex three-dimensional structures, and does not need to rely on expensive equipment and dies.
Compared with the prior art, the invention has the following beneficial effects:
(1) the novel photocuring 3D printing resin comprises a chemical plating catalyst which can be activated by laser, and after photocuring 3D printing forming, selective activation can be carried out on the surface of the resin by laser, so that metal is selectively deposited in a chemical plating process to obtain a circuit pattern, and three-dimensional conductive interconnection of electronic components is realized, and thus, customized electronic circuit products with high precision, low cost and complex three-dimensional structures are quickly manufactured, and the novel photocuring 3D printing resin has obvious advantages compared with a printed circuit board manufacturing technology (PCB) and a molding interconnection device technology (MID);
(2) the activation of the surface of the resin after photocuring can be realized by using low-power (0.1W) near-infrared laser, the requirement on processing equipment is low, and the production cost is reduced;
(3) the resin can be stably stored for a long time after being prepared, and the metal compound powder is not easy to settle and delaminate, so that the material failure is avoided;
(4) the resin has moderate viscosity, good light transmission and curing effects and good leveling property, does not cause the metal compound powder to be rapidly settled, has good printability and is suitable for most SLA, DLP and LCD photocuring 3D printing equipment in the market;
(5) the resin has common raw materials, simple processing technology, can be prepared by using conventional equipment and has strong operability.
Drawings
Fig. 1 is a schematic flow diagram of the preparation of a photocurable 3D printing resin of the present invention;
FIG. 2 is a viscosity test comparison curve;
FIG. 3 is a print thickness test contrast curve;
FIG. 4 is photograph one of a printed matter in example 6;
FIG. 5 is photograph II of a printed matter in example 6;
FIG. 6 is a photograph of a printed material in example 7;
FIG. 7 is an SEM photograph of a print of example 1;
FIG. 8 is an SEM photograph of a print of example 8;
FIG. 9 is a photograph of a print of example 13;
FIG. 10 is a photograph of a print of example 14;
FIG. 11 is a photograph of a printed matter of example 15;
FIG. 12 is a photograph of the front surface of the circuit board in example 16;
FIG. 13 is a photograph of the back of the circuit board in example 16;
fig. 14 is an overall photograph of the key fob of example 16.
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.
Example 1:
the photocuring 3D printing resin in the embodiment comprises the following raw materials in parts by weight:
the preparation method of the photocurable 3D printing resin in this example is as follows:
(1) 100g of cationic photocurable resin prepolymer bis ((3, 4-epoxycyclohexyl) methyl) adipate and 8g of cationic photoinitiator triarylsulfonium salt are mechanically stirred at 50 ℃ for 60 minutes;
(2) mechanically stirring 50g of cationic light-cured resin reactive diluent 3-ethyl-3-hydroxymethyl oxetane and the product in the step (1) at 50 ℃ for 20 minutes;
(3) mechanically stirring 24g of free radical type light-cured resin prepolymer bisphenol A epoxy acrylate and 3g of free radical type photoinitiator 2, 4, 6-trimethylbenzoyl-diphenylphosphine oxide at 50 ℃ for 60 minutes;
(4) mechanically stirring 15g of a free radical type light-cured resin reactive diluent, namely tripropylene glycol diacrylate, and the product in the step (3) at the temperature of 50 ℃ for 20 minutes;
(5) mixing the products obtained in the steps (2) and (3) and mechanically stirring to obtain 200g of a light-cured resin base material;
(6) 80g of basic copper phosphate powder with near infrared photocatalysis characteristic is ball-milled for 30 minutes in a ball mill with a medium of 70ml of ethanol and zirconia ceramic balls with the diameter of 4mm at the rotating speed of 500 rpm; since the carrying capacity of the laser-activatable metal compound cannot be too small at one time of ball milling, 80g of the laser-activatable metal compound is milled at one time, and 10g of the laser-activatable metal compound is taken out in the subsequent steps.
(7) Heating and drying the product mixed with the solid and the liquid in the step (6) at 80 ℃ until the organic solvent is completely evaporated;
(8) mixing 10g of the solid in the step (7) with 190g of the photocurable resin base material, 1g of the dispersing agent and 0.4g of the defoaming agent in the step (5), and ball-milling the mixture in a ball mill containing zirconia ceramic balls with the diameter of 6mm at the rotation speed of 200rpm for 60 minutes;
(9) and (4) placing the product obtained in the step (8) into a vacuum kettle, and defoaming for 1 hour in a dark place to obtain the photocuring additive manufacturing material for manufacturing the electronic circuit after treatment.
Example 2:
the preparation method of the photocuring 3D printing resin in the embodiment comprises the following steps:
(1) mechanically stirring 60g of cationic photocurable resin prepolymer 3, 4-epoxycyclohexyl formate and 4g of cationic photoinitiator diaryl sulfonium salt at 50 ℃ for 60 minutes;
(2) mechanically stirring 28g of cationic light-cured resin reactive diluent 3-ethyl-3-phenoxymethyloxetane and the product in the step (1) at the temperature of 50 ℃ for 20 minutes;
(3) mechanically stirring 66g of free radical type light-cured resin prepolymer phenolic epoxy acrylate and 4g of free radical type photoinitiator isopropyl thioxanthone for 60 minutes at the temperature of 50 ℃;
(4) mechanically stirring 38g of free radical type light-cured resin reactive diluent dipropylene glycol diacrylate and the product in (3) at 50 ℃ for 20 minutes;
(5) mixing the products in the steps (2) and (3) and mechanically stirring to obtain 200g of a light-cured resin base material;
(6) ball-milling 60g of copper-chromium spinel powder with near infrared photocatalysis characteristic in a ball mill with a medium of 80ml of isopropanol and zirconia ceramic balls with the diameter of 4mm at the rotating speed of 500rpm for 40 minutes;
(7) heating and drying the product mixed with the solid and the liquid in the step (6) at 80 ℃ until the organic solvent is completely evaporated;
(8) putting 12g of the solid in the step (7) into a mortar, grinding until hardening disappears, mixing the ground solid with 190g of the light-cured resin base material in the step (5), 1.2g of a dispersing agent (a mixture of phosphoric acid polyester and phosphoric acid, the mass ratio of the two is 45: 1) and 0.4g of a defoaming agent (a mixture of naphtha and 1-methoxy-2-propanol acetate, the mass ratio of the two is 20: 1), and ball-milling the mixture in a ball mill containing zirconia ceramic balls with the diameter of 6mm at the rotating speed of 200rpm for 120 minutes;
(9) and (3) placing the product in the step (8) into a vacuum kettle, and defoaming for 1 hour in a dark place to obtain the photocuring additive manufacturing material for manufacturing electronic circuits.
Example 3:
the photocuring 3D printing resin in the embodiment comprises the following raw material components in parts by weight:
the preparation method of the photocurable 3D printing resin of this example is the same as that of example 1.
Example 4:
the photocuring 3D printing resin in the embodiment comprises the following raw material components in parts by weight:
the preparation method of the photocurable 3D printing resin of this example is the same as that of example 1.
Example 5:
the photocuring 3D printing resin in the embodiment comprises the following raw material components in parts by weight:
the preparation method of the photocurable 3D printing resin of this example is the same as that of example 1.
The resins prepared in examples 1 to 5 were tested by a rotary viscometer, and the printing temperature of the photocurable resin was set at 30 ℃, and it was found that the viscosities of the photocurable resin base material and the modified resin doped with the metal compound powder were relatively close, as shown in fig. 2, the viscosity of the photocurable resin base material was 608mPa · s, and the viscosity of the modified resin doped with the metal compound powder was 728mPa · s; the viscosity of the two is moderate, so that the leveling property of the light-cured resin in a printing tank is not influenced, and the metal compound powder in the light-cured resin is not settled too fast due to too low viscosity.
The resin was subjected to a printing test using an SLA photocuring 3D printer with a wavelength of 405nm, as shown in fig. 3, and the maximum single-layer printing thickness of the photocured resin substrate was 280 micrometers, and the maximum single-layer printing thickness of the modified resin incorporating the metal compound powder was 70 micrometers.
Example 6:
the raw materials of the photocuring 3D printing resin in the embodiment are the same except for the laser-activatable metal compound in different parts by weight; wherein the parts by weight of the copper hydroxide phosphate are 3 parts and 9 parts respectively, and the preparation method is the same as that of example 1, and the prepared resin can not be well applied to the manufacture of electronic circuits.
When the copper hydroxide phosphate is 3 parts, the laser activation is found in the preparation process to partially catalyze the laser-activatable metal compound into the chemical plating metal attachment sites, but the chemical plating cannot be completed in the chemical copper plating solution, as shown in figure 4.
When the weight portion of the basic copper phosphate is 9, too much laser-activatable metal compound is catalyzed into chemical plating metal attachment sites by laser activation, and solid particles generated by chemical plating reaction can be splashed on the surface of a 3D printed piece by catalysis in the laser activation, so that the effect of excessive plating is caused, as shown in figure 5, and chemical plating solution is polluted, so that the chemical plating of a product fails, and the chemical plating solution fails.
Example 7:
the raw materials of the photocurable 3D printing resin in this example were not added with a dispersant, and the remaining components were the same as in example 1, and the preparation method was similar to example 1, except for the preparation steps related to the addition of the dispersant.
As shown in fig. 6, the arrows indicate the printing direction, the printing direction is from left to right, and the leftmost side is the first printing layer; it is evident that the printed portion on the right side is darker in color than the printed portion on the left side, indicating that the laser activatable metallic compound failed to print due to delamination of the precipitates during printing, and that the powder did not flow with the resin due to the precipitates, and the printed portion on the right side in the figure did not have the laser activatable metallic compound.
The distribution of the laser-activatable metal compound in the solid printed matter printed with the resin in this embodiment was not uniform. The resin prepared by the embodiment greatly reduces the effective storage time of the photocuring 3D printing resin, and causes the solid-liquid separation phenomenon between the laser-activatable metal compound in the resin and the resin.
Example 8:
the raw materials of the photocurable 3D printing resin in this example were not added with a defoaming agent, and the remaining components were the same as in example 1, and the preparation method was similar to example 1, and accordingly the preparation steps related to the addition of a defoaming agent were removed.
When the resin is used for printing to obtain a photocured printed matter, SEM observation is performed on the photocured printed matter, and the photocured printed matter is compared with the printed matter of the example 1, as shown in fig. 7 and 8, SEM pictures of the surfaces of the solid photocured printed matters of the example 1 and the example show that the printed matter of the example has poor surface compactness. Therefore, if no dispersant is added to the resin raw material components, the compactness of the liquid photocurable 3D printing resin is reduced, and at the same time, the compactness of the solid photocurable 3D print is reduced.
Example 9:
the raw materials of the photocuring 3D printing resin in the embodiment have different contents of the dispersant, the rest components are the same as those in the embodiment 1, and the preparation method is the same as that in the embodiment 1; wherein, the dispersant is respectively 0.3 weight part and 1.5 weight part. When the dispersant was 0.3 parts by weight, the printing effect of the resin prepared was the same as that of example 7; when the dispersant is 1.5 parts by weight, the single-layer print thickness of the resin is more than 70 μm.
Example 10:
in the raw materials of the photocurable 3D printing resin in this example, the defoaming agent was 0.5 parts by weight, and the rest of the components were the same as in example 1, and the preparation method was the same as in example 1. The single-layer printing thickness prepared by the embodiment is more than 70 μm, and the effect of a printed product is poor.
Example 11:
in the raw materials of the photocuring 3D printing resin in the present embodiment, the type of the dispersant is changed to PEG2000, the types and the parts by weight of the rest of the raw materials are the same as those in embodiment 1, and the preparation method is the same as that in embodiment 1.
The thickness of the resin printing layer prepared by the embodiment is more than 70 μm, and the effect of the printing piece subjected to 3D printing by using the resin of the embodiment is the same as that of the embodiment 7.
Example 12:
the raw materials of the photocuring 3D printing resin in this example are the same as those in example 1 except that the type of the defoaming agent is changed to dimethyl silicone oil, and the preparation method is the same as that in example 1.
The thickness of the resin printing layer prepared in the embodiment is 60-70 μm, and the effect of the printing piece subjected to 3D printing by using the resin of the embodiment is the same as that of embodiment 8.
Example 13:
the embodiment provides a first application example of the photocuring 3D printing resin.
The 3D printing resin prepared in example 1 was printed using an SLA photocuring 3D printer with a wavelength of 405nm using an Nd: YAG laser with wavelength of 1064nm and power of 0.1W, and chemical plating by glyoxylate electroless copper plating to obtain a planar transmission line and a resonant ring structure for measuring electromagnetic properties of the material, as shown in FIG. 9.
Example 14:
this embodiment provides a second application example of the photo-curable 3D printing resin according to the present invention.
The 3D printing resin prepared by the invention is printed by an SLA photocuring 3D printer with the wavelength of 405nm, and the Nd: YAG laser with wavelength of 1064nm and power of 0.1W, and performing chemical plating by adopting glyoxylate chemical copper plating process to obtain the quadrifilar helix antenna, as shown in FIG. 10.
Example 15:
this embodiment provides a third application example of the photo-curable 3D printing resin according to the present invention.
The 3D printing resin prepared by the invention is printed by an SLA photocuring 3D printer with the wavelength of 405nm, and the Nd: YAG laser with wavelength of 1064nm and power of 0.1W, and chemical plating by glyoxylic acid electroless copper plating to obtain a three-dimensional fine 555 stroboscopic circuit with wire width of 100 μm, which can be connected with a USB port, as shown in FIG. 11.
Example 16:
the present embodiment provides an application example of a 3D printing resin using photocuring of the present invention.
The 3D printing resin prepared by the invention is printed by an SLA photocuring 3D printer with the wavelength of 405nm, and the Nd: YAG laser with wavelength of 1064nm and power of 0.1W, and performing chemical plating by glyoxylate chemical copper plating process to obtain the mutual inductance circuit-key ring test pencil, wherein the front surface of the working circuit board is shown in figure 12, the back surface of the working circuit board is shown in figure 13, and the whole key ring diagram is shown in figure 14.
Claims (10)
1. The photocuring 3D printing resin is characterized by comprising the following raw materials in parts by weight:
2. the photocurable 3D printing resin of claim 1, wherein: the laser-activatable metal compound is at least one of hydroxyl copper phosphate, copper chromium spinel, copper acetylacetonate, copper hydroxide, copper oxide, tin antimony oxide and tin oxide.
3. The photocurable 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: 1, and the mass ratio of the 1-methoxy-2-propanol acetate to the butyl acetate is 8-10: 1.
4. The photocurable 3D printing resin of claim 1, wherein: the defoaming agent is n-hexane, naphtha or a mixture of naphtha and 1-methoxy-2-propanol acetate, and the mass ratio of the naphtha to the 1-methoxy-2-propanol acetate in the mixture is 10-30: 1.
5. The photocurable 3D printing resin of claim 1, wherein: the thickness of the printing layer of the resin is less than or equal to 70 mu m.
6. The method for preparing a photocurable 3D printing resin according to claim 1, characterized by comprising the steps of:
(1) mixing the cationic photocuring resin prepolymer and the cationic photoinitiator in proportion, heating and stirring, and then adding a cationic photocuring resin reactive diluent to obtain an intermediate product A;
(2) mixing the free radical type photo-curing resin prepolymer and the free radical type photoinitiator in proportion, heating and stirring, and then adding a free radical type photo-curing resin reactive diluent to obtain an intermediate product B;
(3) uniformly mixing the intermediate product A and the intermediate product B in a dark place to obtain a photocuring resin base material;
(4) mixing a laser-activatable metal compound with a solvent, carrying out ball milling treatment, and drying to obtain metal compound powder;
(5) and mixing the metal compound powder with the light-cured resin base material, the dispersing agent and the defoaming agent, putting the mixed product into a vacuum kettle, and defoaming in a dark place to obtain the light-cured resin.
7. Use of a photocurable 3D printing resin according to any one of claims 1-5 in the manufacture of electronic circuits.
8. The utility model provides a 3D prints product which characterized in that: the product is made using the photocurable 3D printing resin of claim 1.
9. The 3D printed product according to claim 8, wherein the preparation method comprises 3D printing and photocuring molding of the resin, and depositing metal at the activated position by adopting laser selective activation treatment.
10. The 3D printed product according to claim 8, wherein: the curing light source adopts ultraviolet laser with the wavelength of 405nm, and the laser activation adopts an infrared light source with the wavelength of 1064 nm.
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| CN112739029A (en) * | 2021-01-08 | 2021-04-30 | 深圳市溪猫网络科技有限公司 | Manufacturing method and control method for manufacturing 3D circuit board based on photocuring |
| CN113136011A (en) * | 2021-05-13 | 2021-07-20 | 东南大学 | 3D printing resin for manufacturing low-loss antenna and application thereof |
| CN114956793A (en) * | 2022-06-01 | 2022-08-30 | 东南大学 | Ceramic slurry for 3D printing ceramic electronic circuit, preparation technology thereof and mixed additive manufacturing method |
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