CN104562115A - Black hole liquid for printed circuit board and preparation method of black hole liquid - Google Patents
Black hole liquid for printed circuit board and preparation method of black hole liquid Download PDFInfo
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- CN104562115A CN104562115A CN201410317526.2A CN201410317526A CN104562115A CN 104562115 A CN104562115 A CN 104562115A CN 201410317526 A CN201410317526 A CN 201410317526A CN 104562115 A CN104562115 A CN 104562115A
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- hole liquid
- blank hole
- soluble polymer
- liquid
- water soluble
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- 239000007788 liquid Substances 0.000 title claims abstract description 93
- 238000002360 preparation method Methods 0.000 title abstract description 10
- 239000002245 particle Substances 0.000 claims abstract description 54
- 239000006185 dispersion Substances 0.000 claims abstract description 38
- 229920003169 water-soluble polymer Polymers 0.000 claims abstract description 37
- 239000004094 surface-active agent Substances 0.000 claims abstract description 32
- 239000002904 solvent Substances 0.000 claims abstract description 22
- 238000003756 stirring Methods 0.000 claims abstract description 13
- 238000000227 grinding Methods 0.000 claims abstract description 5
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 70
- 239000010439 graphite Substances 0.000 claims description 65
- 229910002804 graphite Inorganic materials 0.000 claims description 65
- 238000000034 method Methods 0.000 claims description 32
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 31
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 claims description 21
- 239000013530 defoamer Substances 0.000 claims description 14
- 239000003960 organic solvent Substances 0.000 claims description 14
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 14
- 239000001768 carboxy methyl cellulose Substances 0.000 claims description 12
- -1 Polyoxyethylene Polymers 0.000 claims description 10
- 239000000203 mixture Substances 0.000 claims description 10
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 claims description 9
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 9
- SECXISVLQFMRJM-UHFFFAOYSA-N N-Methylpyrrolidone Chemical compound CN1CCCC1=O SECXISVLQFMRJM-UHFFFAOYSA-N 0.000 claims description 7
- 229920003171 Poly (ethylene oxide) Polymers 0.000 claims description 7
- 239000002736 nonionic surfactant Substances 0.000 claims description 7
- KFZMGEQAYNKOFK-UHFFFAOYSA-N isopropyl alcohol Natural products CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 claims description 6
- IXPNQXFRVYWDDI-UHFFFAOYSA-N 1-methyl-2,4-dioxo-1,3-diazinane-5-carboximidamide Chemical compound CN1CC(C(N)=N)C(=O)NC1=O IXPNQXFRVYWDDI-UHFFFAOYSA-N 0.000 claims description 5
- 239000002202 Polyethylene glycol Substances 0.000 claims description 5
- 239000004372 Polyvinyl alcohol Substances 0.000 claims description 5
- 229920001223 polyethylene glycol Polymers 0.000 claims description 5
- 229920002451 polyvinyl alcohol Polymers 0.000 claims description 5
- 229920000036 polyvinylpyrrolidone Polymers 0.000 claims description 5
- 235000013855 polyvinylpyrrolidone Nutrition 0.000 claims description 5
- 239000001267 polyvinylpyrrolidone Substances 0.000 claims description 5
- 239000011734 sodium Substances 0.000 claims description 5
- 239000000661 sodium alginate Substances 0.000 claims description 5
- 235000010413 sodium alginate Nutrition 0.000 claims description 5
- 229940005550 sodium alginate Drugs 0.000 claims description 5
- STCOOQWBFONSKY-UHFFFAOYSA-N tributyl phosphate Chemical compound CCCCOP(=O)(OCCCC)OCCCC STCOOQWBFONSKY-UHFFFAOYSA-N 0.000 claims description 5
- 241001272567 Hominoidea Species 0.000 claims description 3
- 229920001219 Polysorbate 40 Polymers 0.000 claims description 3
- 229920001214 Polysorbate 60 Polymers 0.000 claims description 3
- DPXJVFZANSGRMM-UHFFFAOYSA-N acetic acid;2,3,4,5,6-pentahydroxyhexanal;sodium Chemical compound [Na].CC(O)=O.OCC(O)C(O)C(O)C(O)C=O DPXJVFZANSGRMM-UHFFFAOYSA-N 0.000 claims description 3
- 239000008367 deionised water Substances 0.000 claims description 3
- 229910021641 deionized water Inorganic materials 0.000 claims description 3
- 229940008099 dimethicone Drugs 0.000 claims description 3
- 239000004205 dimethyl polysiloxane Substances 0.000 claims description 3
- 235000013870 dimethyl polysiloxane Nutrition 0.000 claims description 3
- RBNPOMFGQQGHHO-UHFFFAOYSA-N glyceric acid Chemical compound OCC(O)C(O)=O RBNPOMFGQQGHHO-UHFFFAOYSA-N 0.000 claims description 3
- 125000001449 isopropyl group Chemical group [H]C([H])([H])C([H])(*)C([H])([H])[H] 0.000 claims description 3
- 229920000435 poly(dimethylsiloxane) Polymers 0.000 claims description 3
- 229920001495 poly(sodium acrylate) polymer Polymers 0.000 claims description 3
- 235000010482 polyoxyethylene sorbitan monooleate Nutrition 0.000 claims description 3
- 235000010483 polyoxyethylene sorbitan monopalmitate Nutrition 0.000 claims description 3
- 239000000249 polyoxyethylene sorbitan monopalmitate Substances 0.000 claims description 3
- 235000010989 polyoxyethylene sorbitan monostearate Nutrition 0.000 claims description 3
- 239000001818 polyoxyethylene sorbitan monostearate Substances 0.000 claims description 3
- 229940101027 polysorbate 40 Drugs 0.000 claims description 3
- 229940113124 polysorbate 60 Drugs 0.000 claims description 3
- 229920000053 polysorbate 80 Polymers 0.000 claims description 3
- 235000019812 sodium carboxymethyl cellulose Nutrition 0.000 claims description 3
- 229920001027 sodium carboxymethylcellulose Polymers 0.000 claims description 3
- NNMHYFLPFNGQFZ-UHFFFAOYSA-M sodium polyacrylate Chemical compound [Na+].[O-]C(=O)C=C NNMHYFLPFNGQFZ-UHFFFAOYSA-M 0.000 claims description 3
- 229920001477 hydrophilic polymer Polymers 0.000 abstract description 10
- 229920000642 polymer Polymers 0.000 abstract description 4
- 239000011159 matrix material Substances 0.000 abstract 3
- 239000000126 substance Substances 0.000 abstract 2
- 239000006229 carbon black Substances 0.000 description 15
- 230000008569 process Effects 0.000 description 13
- 230000006641 stabilisation Effects 0.000 description 11
- 238000011105 stabilization Methods 0.000 description 11
- 229920002134 Carboxymethyl cellulose Polymers 0.000 description 9
- 235000010948 carboxy methyl cellulose Nutrition 0.000 description 9
- 239000008112 carboxymethyl-cellulose Substances 0.000 description 9
- 239000011248 coating agent Substances 0.000 description 9
- 238000000576 coating method Methods 0.000 description 9
- 239000000725 suspension Substances 0.000 description 9
- 239000002270 dispersing agent Substances 0.000 description 8
- 238000005516 engineering process Methods 0.000 description 8
- 230000004048 modification Effects 0.000 description 7
- 238000012986 modification Methods 0.000 description 7
- 238000007747 plating Methods 0.000 description 6
- 239000000243 solution Substances 0.000 description 6
- 239000000758 substrate Substances 0.000 description 6
- 238000000498 ball milling Methods 0.000 description 5
- 229910052799 carbon Inorganic materials 0.000 description 5
- 230000000052 comparative effect Effects 0.000 description 5
- 238000009713 electroplating Methods 0.000 description 5
- 230000010148 water-pollination Effects 0.000 description 5
- 239000008346 aqueous phase Substances 0.000 description 4
- 239000007864 aqueous solution Substances 0.000 description 4
- 230000006698 induction Effects 0.000 description 4
- 238000004519 manufacturing process Methods 0.000 description 4
- 238000001465 metallisation Methods 0.000 description 4
- 238000012360 testing method Methods 0.000 description 4
- WSFSSNUMVMOOMR-UHFFFAOYSA-N Formaldehyde Chemical compound O=C WSFSSNUMVMOOMR-UHFFFAOYSA-N 0.000 description 3
- 230000000694 effects Effects 0.000 description 3
- 230000000284 resting effect Effects 0.000 description 3
- 230000001070 adhesive effect Effects 0.000 description 2
- 230000008859 change Effects 0.000 description 2
- 239000002131 composite material Substances 0.000 description 2
- 238000000151 deposition Methods 0.000 description 2
- 238000003795 desorption Methods 0.000 description 2
- 239000008187 granular material Substances 0.000 description 2
- 239000010410 layer Substances 0.000 description 2
- 229920002521 macromolecule Polymers 0.000 description 2
- 239000003094 microcapsule Substances 0.000 description 2
- 238000005191 phase separation Methods 0.000 description 2
- 238000011160 research Methods 0.000 description 2
- 238000005728 strengthening Methods 0.000 description 2
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 1
- MYMOFIZGZYHOMD-UHFFFAOYSA-N Dioxygen Chemical compound O=O MYMOFIZGZYHOMD-UHFFFAOYSA-N 0.000 description 1
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 description 1
- 239000005977 Ethylene Substances 0.000 description 1
- 238000010521 absorption reaction Methods 0.000 description 1
- 238000004220 aggregation Methods 0.000 description 1
- 230000002776 aggregation Effects 0.000 description 1
- 238000000149 argon plasma sintering Methods 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000033228 biological regulation Effects 0.000 description 1
- 230000000711 cancerogenic effect Effects 0.000 description 1
- 231100000315 carcinogenic Toxicity 0.000 description 1
- 239000003638 chemical reducing agent Substances 0.000 description 1
- 238000005253 cladding Methods 0.000 description 1
- 238000005345 coagulation Methods 0.000 description 1
- 230000015271 coagulation Effects 0.000 description 1
- 238000004891 communication Methods 0.000 description 1
- 238000011109 contamination Methods 0.000 description 1
- 239000011889 copper foil Substances 0.000 description 1
- 239000013078 crystal Substances 0.000 description 1
- 230000007812 deficiency Effects 0.000 description 1
- 238000003912 environmental pollution Methods 0.000 description 1
- 238000011049 filling Methods 0.000 description 1
- 239000012535 impurity Substances 0.000 description 1
- 239000011229 interlayer Substances 0.000 description 1
- 150000002500 ions Chemical class 0.000 description 1
- 238000012423 maintenance Methods 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 238000012703 microemulsion polymerization Methods 0.000 description 1
- 239000000615 nonconductor Substances 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 239000012071 phase Substances 0.000 description 1
- 230000000704 physical effect Effects 0.000 description 1
- 238000006116 polymerization reaction Methods 0.000 description 1
- 229920000136 polysorbate Polymers 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 230000009467 reduction Effects 0.000 description 1
- 230000015227 regulation of liquid surface tension Effects 0.000 description 1
- 238000004062 sedimentation Methods 0.000 description 1
- 238000003860 storage Methods 0.000 description 1
- 238000004065 wastewater treatment Methods 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
- C25D—PROCESSES FOR THE ELECTROLYTIC OR ELECTROPHORETIC PRODUCTION OF COATINGS; ELECTROFORMING; APPARATUS THEREFOR
- C25D5/00—Electroplating characterised by the process; Pretreatment or after-treatment of workpieces
- C25D5/54—Electroplating of non-metallic surfaces
-
- 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
- H05K3/40—Forming printed elements for providing electric connections to or between printed circuits
- H05K3/42—Plated through-holes or plated via connections
- H05K3/423—Plated through-holes or plated via connections characterised by electroplating method
-
- 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
- H05K2203/00—Indexing scheme relating to apparatus or processes for manufacturing printed circuits covered by H05K3/00
- H05K2203/07—Treatments involving liquids, e.g. plating, rinsing
- H05K2203/0779—Treatments involving liquids, e.g. plating, rinsing characterised by the specific liquids involved
- H05K2203/0783—Using solvent, e.g. for cleaning; Regulating solvent content of pastes or coatings for adjusting the viscosity
Abstract
The invention discloses a black hole liquid for a printed circuit board and a preparation method of the black hole liquid. The black hole liquid comprises a conductive matrix, a surfactant, a water-soluble polymer, a poor solvent corresponding to the water-soluble polymer, a basic substance and a dispersing medium. The preparation method of the black hole liquid comprises the following steps of adding the conductive matrix and the surfactant into the dispersing medium, grinding, adding the water-soluble polymer, vigorously stirring, adding the poor solvent corresponding to the water-soluble polymer and finally adding the basic substance to form the black hole liquid. According to the black hole liquid for the printed circuit board, by adding the water-soluble polymer and the poor solvent corresponding to the water-soluble polymer into the black hole liquid, the black hole liquid containing conductive matrix coated with the hydrophilic polymer is formed and by use of the steric hindrance and electrostatic repulsive force of a long chain polymer on the surfaces of particles, the dispersion stability of the black hole liquid is greatly enhanced.
Description
Technical field
The present invention relates to the manufacture field of printed circuit board, particularly relate to and a kind ofly make blank hole liquid of printed circuit board Direct Electroplating and preparation method thereof.
Background technology
Along with continuous portability, the miniaturization of communication electronic device, the integrated level of the printed circuit board of employing is more and more higher.The wiring of printed circuit board plate face is more and more closeer, and the associated aperture of playing interlayer conduction effect and footpath are deeply than more and more less, and this just proposes requirements at the higher level to the hole metallization process of printed circuit board.Existing hole metallization printed-circuit board manufacturing technology, first adopts chemical-copper-plating process, and the non-conductor hole wall surface of through hole is metallized, and then electro-coppering thickeies.Although this manufacturing process can successfully manufacturing hole metallization printed board, but chemical-copper-plating process Problems existing wherein has: (1) complex process, is difficult to operation and maintenance; (2) technological process is long, water consumption is large, waste water treatment is difficult; (3) adopt formaldehyde to make reducing agent, not only endanger biological environment, and have carcinogenic danger.Based on chemical-copper-plating process Problems existing, people are devoted to the research of the directly electroplating technology cancelling chemical-copper-plating process always, and one of wherein comparatively ripe technique is the directly electroplating technology utilizing carbon black suspension---black holes technology.
Black holes technology is using carbon black or graphite is independent or jointly as conductive matrices, make dispersion suspension liquid, hole is carried out to the method for conductive treatment.Compared with chemical-copper-plating process, black holes technology has the advantages such as work simplification, non-environmental-pollution, cost reduction, and the core of its technique is formula and the performance of blank hole liquid.The blank hole liquid (as: Chinese patent CN1733980A, US Patent No. 5015339, US5389270 and US P4724005A etc.) that current PCB Hole Metallization directly electroplating technology adopts, be take water as decentralized medium, carbon black/graphite particle suspension that is conductive matrices, because the hydrophily of carbon black/graphite is poor, cause suspension unstable, very easily there is coagulation, have a strong impact on the serviceability of blank hole liquid.In order to improve the stability of dispersion liquid, normally adopt the method for adding dispersant (low molecular weight surfactant activity and/or high molecular surfactant), because the dispersant added is adsorbed on carbon black/graphite surface by physical action, there is the balance of absorption and desorption, and the desorption of dispersant can cause, and carbon black/graphite particle reassembles during storage, sedimentation, the problem of carbon black/graphite suspension stability fundamentally can not be solved.
Summary of the invention
For solving the problem, the invention provides a kind of blank hole liquid for printed circuit board and preparation method thereof, by the method at conductive matrices Surface coating hydrophilic polymer, utilize the sterically hindered and electrostatic repulsion of conductive matrices surface long-chain polymer, greatly strengthen the dispersion stabilization of blank hole liquid.
For achieving the above object, the present invention by the following technical solutions:
The invention discloses a kind of blank hole liquid for printed circuit board, comprise the poor solvent of conductive matrices, surfactant, water soluble polymer and correspondence thereof, alkaline matter and decentralized medium.
Preferably, the poor solvent of described water soluble polymer and correspondence thereof comprises: sodium carboxymethylcellulose (CMC) // ethanol, Sodium Polyacrylate (PA-Na) // ethanol or acetone, polyvinyl alcohol (PVA) // isopropyl alcohol or acetone or ethylene glycol, polyvinylpyrrolidone (PVP) // acetone, sodium alginate (SA-Na) // ethanol.
Preferably, described surfactant comprises non-ionic surface active agent, and described non-ionic surface active agent comprises Determination of Polyoxyethylene Non-ionic Surfactants and polyvalent alcohol type non-ionic surface active agent.
Preferably, described Determination of Polyoxyethylene Non-ionic Surfactants comprises one or more the mixture in polyethylene glycol (PEG), AEO (paregal O), APES (OP-10), NPE (TX-10); Described polyvalent alcohol type non-ionic surface active agent comprises one or more the mixture in Tween 80, polysorbate60, polysorbate40, polysorbas20.
Preferably, described conductive matrices comprises graphite particle; Described alkaline matter comprises NaOH, KOH, NH
4one or more mixture in OH; Described decentralized medium comprises deionized water.
Preferably, described blank hole liquid also comprises organic solvent, and described organic solvent comprises 1-METHYLPYRROLIDONE (NMP).
Preferably, described blank hole liquid also comprises defoamer, and described defoamer comprises one or more the mixture in dimethicone, tributyl phosphate (TBP), polyoxyethylene glycerol ether.
Preferably, described blank hole liquid also comprises inorganic bond, and described inorganic bond comprises Na
2siO
3, K
2siO
3in one or both mixture.
Preferably, the parts by weight ratio of each component of described blank hole liquid is: described conductive matrices is 2-5 part; Described surfactant is 0.8-1.2 part; The poor solvent of described water soluble polymer and correspondence thereof is respectively 1-2 part and 15-25 part; Described alkaline matter is 2-4 part; Described decentralized medium is 50-70 part.
Preferably, described blank hole liquid also comprises parts by weight ratio and is: the organic solvent of 8-12 part, the defoamer of 0.4-1.0 part, the inorganic bond of 0.5-1.5 part.
Preferably, the pH value of described blank hole liquid is 9-13.
The invention also discloses a kind of method preparing blank hole liquid as above, comprise the following steps successively: S1: described conducting medium and described surfactant are joined in described decentralized medium, grinds, form uniform dispersion liquid A; S2: add described water soluble polymer in described dispersion liquid A, adds the poor solvent of the described correspondence of water soluble polymer after stirring, form dispersion liquid B; S3: add alkaline matter in described dispersion liquid B, stirs and forms described blank hole liquid.
Preferably, also comprise before grinding in step S1 and organic solvent, defoamer are joined in described decentralized medium; Also comprise before step S3 stirs and add inorganic bond in described dispersion liquid B.
Preferably, the time of carrying out in step S1 grinding is 5-7h.
Preferably, after adding described water soluble polymer in step S2 in described dispersion liquid A, after stirring 20-40min, add the poor solvent of the described correspondence of water soluble polymer again.
The present invention's beneficial effect compared with prior art comprises: blank hole liquid for printed circuit board of the present invention and preparation method thereof, by adding the poor solvent of water soluble polymer and correspondence thereof in blank hole liquid, water soluble polymer is under the induction of the poor solvent of its correspondence, be separate out core with conductive matrices, condense at aqueous phase, aqueous high molecular chain is only attached to conductive matrices surface by physics bonding force, be coated on around conductive matrices, form the blank hole liquid of the coated conductive matrices of hydrophilic polymer, utilize the sterically hindered of particle surface long-chain polymer and electrostatic repulsion, greatly strengthen the dispersion stabilization of blank hole liquid.
In preferred version: the conductive matrices in blank hole liquid formula comprises graphite particle; Surfactant comprises Determination of Polyoxyethylene Non-ionic Surfactants and polyvalent alcohol type non-ionic surface active agent, both composite uses, for the hydrophily process before the coated water soluble polymer of Graphite particle surfaces, improve the tack of graphite particle and the dispersion stabilization of blank hole liquid.More preferably, organic solvent, defoamer and inorganic bond is also comprised in blank hole liquid formula, wherein organic solvent is used for the hydrophily process before the coated water soluble polymer of Graphite particle surfaces, and is conducive to strengthening the compatibility between graphite particle and non-ionic surface active agent; The interpolation of defoamer ensures that printed circuit board obtains uniform conductive substrates graphite linings, thus prevents printed circuit board to occur the phenomenon of local without coating; Inorganic bond is for improving the adhesive property between graphite particle and insulating substrate.
Embodiment
Below in conjunction with preferred embodiment the invention will be further described.
Embodiments of the invention provide a kind of blank hole liquid for printed circuit board, comprise the poor solvent of conductive matrices, surfactant, water soluble polymer and correspondence thereof, alkaline matter and decentralized medium, preferably also comprise organic solvent, defoamer and inorganic bond.
Wherein conductive matrices comprises graphite particle, and compared to carbon black particle, because graphite has thin type sheet crystal structure, electronic energy shifts at two dimensional surface, so can give aperture and the better conductivity of deep hole on hole wall after film forming, also makes conductive layer become thinner.The average grain diameter of the graphite particle in the present embodiment should be less than 2 μm, is advisable, is more preferably and is less than 0.7 μm to be less than 1 μm; If graphite particle average grain diameter is greater than 2 μm, then can reduce its conductivity, also can reduce the tack between coated metal and insulating substrate; The content of graphite particle in suspension lower than 6wt%, should be preferably 2-5wt%; If carbon particle content is higher than 6wt%, then can cause coating and the tack between insulating substrate and Copper Foil bad, and if carbon particle content lower than 1wt%, then can be too low due to carbon particle density, be difficult to the basalis obtaining sufficient conductivity, and then local can be produced without coating phenomenon.
Surfactant comprises non-ionic surface active agent, non-ionic surface active agent comprises Determination of Polyoxyethylene Non-ionic Surfactants and polyvalent alcohol type non-ionic surface active agent, and wherein Determination of Polyoxyethylene Non-ionic Surfactants comprises polyethylene glycol (PEG), AEO (paregal O), APES (OP-10) and NPE (TX-10) etc.; Polyvalent alcohol type non-ionic surface active agent is TWEEN Series, as: Tween 80, polysorbate60, polysorbate40 and polysorbas20 etc.Oxygen ethylene type and the composite use of polyvalent alcohol type non-ionic surface active agent, for the hydrophily process before the coated water soluble polymer of graphite particle, improve the tack of carbon particle and the stability of blank hole liquid.
The poor solvent of water soluble polymer and correspondence thereof is respectively: sodium carboxymethylcellulose (CMC) // ethanol, Sodium Polyacrylate (PA-Na) // ethanol or acetone, polyvinyl alcohol (PVA) // isopropyl alcohol or acetone or ethylene glycol, polyvinylpyrrolidone (PVP) // acetone, sodium alginate (SA-Na) // ethanol.Its effect is: water soluble polymer is under the induction of poor solvent, be separate out core with graphite particle, condense at aqueous phase, aqueous high molecular chain is tightly attached to Graphite particle surfaces by physics bonding force, be coated on around graphite particle, form the graphite particle dispersion liquid that hydrophilic polymer is coated, thus significantly improve the dispersion stabilization of blank hole liquid.
Alkaline matter comprises NaOH, KOH, NH
4oH etc., be wherein good with KOH, in order to regulate the pH value of blank hole liquid to 9-13, refer to for 10-12 is good with pH, ensure that dispersion stabilization and the Graphite particle surfaces of blank hole liquid are electronegative, promote that graphite particle is adsorbed in hole wall surface positively charged after adjustment, form complete graphite cover layer.
Decentralized medium comprises deionized water (DI water), mainly considers cost and be easy to plating behaviour ashamed, and it is not containing impurity such as Ca, I, F of containing in usual water, to reduce contamination and the interference of foreign ion in electroplating work procedure.
Organic solvent comprises 1-METHYLPYRROLIDONE (NMP), for the hydrophily process before the coated water soluble polymer of graphite particle, is conducive to strengthening the compatibility between graphite particle and non-ionic surface active agent.
Defoamer comprises dimethicone, tributyl phosphate (TBP), polyoxyethylene glycerol ether etc., ensures to obtain uniform conductive substrates graphite linings, prevents local without coating phenomenon.
Inorganic bond comprises Na
2siO
3, K
2siO
3deng, be intended to improve the adhesive property between carbon particle and insulating substrate.
Each ratio of components parts by weight are preferably above: graphite particle: 2-5 part; Polyoxyethylene-type // polyvalent alcohol type non-ionic surface active agent: 0.6-0.8 part // 0.2-0.4 part; The poor solvent of water soluble polymer // correspondence: 1-2 part // 15-25 part; Alkaline matter: 2-4 part; Organic solvent: 8-12 part; Defoamer: 0.4-1.0 part; Inorganic bond: 0.5-1.5 part.
Another embodiment of the present invention additionally provides a kind of preparation method of the blank hole liquid for printed circuit board, comprises the following steps successively:
S1: join in decentralized medium by conductive matrices, surfactant, ball milling 5-7h in ball mill, form uniform dispersion liquid A;
S2: add water soluble polymer in dispersion liquid A, vigorous stirring 20-40min, then the poor solvent of water soluble polymer is added, induction water soluble polymer condenses at aqueous phase, be separate out core with graphite particle, tightly be coated on around graphite particle, form the dispersion liquid B of the coated graphite particle of hydrophilic polymer;
S3: add alkaline matter in dispersion liquid B, stirring and allocating blank hole liquid to pH value is 9-13.
In a preferred embodiment, also comprise before ball milling in step S1 organic solvent, defoamer are joined in decentralized medium; Also comprise before stirring in step S3 and add inorganic bond in dispersion liquid B.
In the embodiment be more preferably, the water soluble polymer added in dispersion liquid A in step S2 adds with the aqueous solution form of the water soluble polymer of 5wt%, and the mass fraction of the water wherein in this solution counts in decentralized medium.
Below in conjunction with specific embodiment, technical scheme of the present invention is described further.
Each component and the content thereof of the blank hole liquid of embodiment one to embodiment five are as shown in table 1:
The blank hole liquid raw materials formula of table 1 embodiment one to embodiment five and proportioning
Each embodiment prepares blank hole liquid step following (for embodiment one) above:
S1: by the DI water of 4g graphite, 0.7gPEG, 0.3g polysorbate60,10gNMP, 0.6gTBP and 25g, ball milling 6h in ball mill, obtains uniform graphite dispersing solution;
S2: in the graphite dispersing solution obtained in S1, the CMC aqueous solution being added dropwise to the 5wt% of the 30ml prepared in advance (wherein comprises CMC in this CMC aqueous solution and is about 1.5g, DI water is about 30g), vigorous stirring 30min simultaneously, then the poor solvent ethanol 20g of CMC is dripped, induction CMC condenses at aqueous phase, be separate out core with graphite particle, CMC strand is attached to Graphite particle surfaces by physics bonding force, be coated on around graphite particle, form the dispersion liquid of the coated graphite particle of hydrophilic polymer;
S3: in the dispersion liquid of the graphite particle that the hydrophilic polymer obtained in S2 is coated, add 1gNa
2siO
3with 3g NH
4oH, is uniformly mixed and allocates dispersion pH value to 10-12, forms blank hole liquid.
Comparative example:
Adopt the method for directly adding dispersant to prepare blank hole liquid, same embodiment 1 of filling a prescription, be the poor solvent ethanol of not adding water soluble macromolecule CMC, preparation process is as follows:
S1: by 0.7gPEG, 0.3g polysorbate60,1.5gCMC, 10gNMP, 0.6gTBP and 1gNa
2siO
3be dissolved in NH
4the OH aqueous solution (NH
4oH:3g; DI water: 20g), form continuous phase, then add 4g graphite, this dense suspension is dropped into ball milling 6h in ball mill, obtains uniform graphite dispersing solution;
S2: add 35gDI water again in the graphite dense suspension that the ball milling obtained in S1 is crossed, be uniformly mixed, be diluted to the black holes initial concentration of regulation.
The dispersion stabilization test result of each embodiment and comparative example gained graphite suspension above:
In blank hole liquid, the average grain diameter of graphite particle is with the situation of change of resting period, the aggregation extent (i.e. dispersion stabilization) of graphite particle can be reflected, average grain diameter increases more in time, and illustrate that graphite particle clustering phenomena is more serious, the dispersion stabilization in water is poorer.Adopt light scattering particle size analyzer test graphite average particle size, contrast the hydrophilic macromolecule coating modification (embodiment one to embodiment five) of graphite particle and the dispersion effect directly adding dispersant method (comparative example) with this, test result is as shown in table 2 below:
The test result of table 2 embodiment one to embodiment five and comparative example
From table 2, the stability of the blank hole liquid (graphite dispersion liquid system) adopting water soluble polymer coating modification to obtain in embodiment one to embodiment five is far above the blank hole liquid (graphite dispersing solution) directly adding dispersant in comparative example, graphite particle particle diameter in embodiment one to embodiment five is very micro-with the prolongation change of resting period, even if after depositing 4 months, average grain diameter also only increases to from initial about 200nm and is no more than 250nm (growth rate < 25%@4months), still instructions for use can be met, absolutely prove and be coated on Graphite particle surfaces, the water soluble polymer be under condensed state can stop the gathering of graphite particle effectively, thus substantially increase the dispersion stabilization of blank hole liquid, and adopt the dispersion stabilization directly adding the blank hole liquid that dispersant method obtains poor, its graphite particle particle diameter is larger with the prolongation increase degree of resting period, after depositing 4 months, average grain diameter increases above 1700nm (growth rate > 790%@4months) from initial about 200nm, can not meet instructions for use again.
Embodiments of the invention overcome the deficiencies in the prior art, provide a kind of ratio directly to add the more stable blank hole liquid of dispersant method (carbon black/graphite suspension system).By the method (phase separation method is coated) at the coated hydrophilic polymer of carbon black/Graphite particle surfaces, form carbon black/graphite microcapsule granule that hydrophilic polymer is coated, utilize the sterically hindered of particle surface long-chain polymer and electrostatic repulsion, greatly can strengthen the dispersion stabilization of blank hole liquid.With the hydrophilically modified method of other carbon black/graphite, as: oxidation modification, graft modification etc. are compared, the kind of coating modification and carbon black/graphite has nothing to do, and especially phase separation method coating modification can avoid complicated polymerization reaction, has stronger operability than micro-emulsion polymerization cladding process.Therefore, the preparation of carbon black/graphite microcapsule granule that hydrophilic polymer is coated may be the trend of the hydrophilically modified research of carbon black/graphite.
Above content is in conjunction with concrete preferred implementation further description made for the present invention, can not assert that specific embodiment of the invention is confined to these explanations.For those skilled in the art, without departing from the inventive concept of the premise, some equivalent to substitute or obvious modification can also be made, and performance or purposes identical, all should be considered as belonging to protection scope of the present invention.
Claims (15)
1. for a blank hole liquid for printed circuit board, it is characterized in that, comprise the poor solvent of conductive matrices, surfactant, water soluble polymer and correspondence thereof, alkaline matter and decentralized medium.
2. blank hole liquid as claimed in claim 1, it is characterized in that, the poor solvent of described water soluble polymer and correspondence thereof comprises: sodium carboxymethylcellulose // ethanol, Sodium Polyacrylate // ethanol or acetone, polyvinyl alcohol // isopropyl alcohol or acetone or ethylene glycol, polyvinylpyrrolidone // acetone, sodium alginate // ethanol.
3. blank hole liquid as claimed in claim 1, it is characterized in that, described surfactant comprises non-ionic surface active agent, and described non-ionic surface active agent comprises Determination of Polyoxyethylene Non-ionic Surfactants and polyvalent alcohol type non-ionic surface active agent.
4. blank hole liquid as claimed in claim 3, it is characterized in that, described Determination of Polyoxyethylene Non-ionic Surfactants comprises one or more the mixture in polyethylene glycol, AEO, APES, NPE; Described polyvalent alcohol type non-ionic surface active agent comprises one or more the mixture in Tween 80, polysorbate60, polysorbate40, polysorbas20.
5. blank hole liquid as claimed in claim 1, it is characterized in that, described conductive matrices comprises graphite particle; Described alkaline matter comprises NaOH, KOH, NH
4one or more mixture in OH; Described decentralized medium comprises deionized water.
6. blank hole liquid as claimed in claim 1, it is characterized in that, also comprise organic solvent, described organic solvent comprises 1-METHYLPYRROLIDONE.
7. blank hole liquid as claimed in claim 1, it is characterized in that, also comprise defoamer, described defoamer comprises one or more the mixture in dimethicone, tributyl phosphate, polyoxyethylene glycerol ether.
8. blank hole liquid as claimed in claim 1, it is characterized in that, also comprise inorganic bond, described inorganic bond comprises Na
2siO
3, K
2siO
3in one or both mixture.
9. blank hole liquid as claimed in claim 1, it is characterized in that, the parts by weight ratio of each component of described blank hole liquid is: described conductive matrices is 2-5 part; Described surfactant is 0.8-1.2 part; The poor solvent of described water soluble polymer and correspondence thereof is respectively 1-2 part and 15-25 part; Described alkaline matter is 2-4 part; Described decentralized medium is 50-70 part.
10. blank hole liquid as claimed in claim 9, it is characterized in that, described blank hole liquid also comprises parts by weight ratio and is: the organic solvent of 8-12 part, the defoamer of 0.4-1.0 part, the inorganic bond of 0.5-1.5 part.
11. blank hole liquids as described in any one of claim 1 to 10, it is characterized in that, the pH value of described blank hole liquid is 9-13.
12. 1 kinds of methods preparing the blank hole liquid described in any one of claim 1 to 5, is characterized in that, comprise the following steps successively:
S1: described conducting medium and described surfactant are joined in described decentralized medium, grind, forms uniform dispersion liquid A;
S2: add described water soluble polymer in described dispersion liquid A, adds the poor solvent of the described correspondence of water soluble polymer after stirring, form dispersion liquid B;
S3: add alkaline matter in described dispersion liquid B, stirs and forms described blank hole liquid.
13. methods as claimed in claim 12, is characterized in that, also comprise and join in described decentralized medium by organic solvent, defoamer in step S1 before grinding; Also comprise before step S3 stirs and add inorganic bond in described dispersion liquid B.
14. methods as described in claim 12 or 13, it is characterized in that, the time of carrying out in step S1 grinding is 5-7h.
15. methods as described in claim 12 or 13, is characterized in that, after adding described water soluble polymer, add the poor solvent of the described correspondence of water soluble polymer after stirring 20-40min again in step S2 in described dispersion liquid A.
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Cited By (13)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN106191952A (en) * | 2016-07-20 | 2016-12-07 | 苏州顾氏新材料有限公司 | A kind of black holes liquid and methods for making and using same thereof |
| CN106319603A (en) * | 2016-08-29 | 2017-01-11 | 苏州铱诺化学材料有限公司 | Formula of blackhole hole-leveling agent |
| CN106852026A (en) * | 2016-11-29 | 2017-06-13 | 深圳崇达多层线路板有限公司 | Suitable for the black holes production technology of HDI products |
| CN107539983A (en) * | 2017-09-30 | 2018-01-05 | 湖南国盛石墨科技有限公司 | The preparation method of graphite dispersing agent |
| CN108323036A (en) * | 2018-02-10 | 2018-07-24 | 深圳市祥盛兴科技有限公司 | A kind of blank hole liquid and black holes chemical industry skill |
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| CN114466529A (en) * | 2021-12-31 | 2022-05-10 | 广东省科学院化工研究所 | Black hole liquid for electroplating through hole of printed circuit board and preparation method and application thereof |
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Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5015339A (en) * | 1990-03-26 | 1991-05-14 | Olin Hunt Sub Iii Corp. | Process for preparing nonconductive substrates |
| TW240371B (en) * | 1993-05-17 | 1995-02-11 | Electrochemicals Inc | |
| CN1733980A (en) * | 2004-08-02 | 2006-02-15 | 吕桂生 | Electricity conductive liquid capable of directly galvanizing the printed board |
| CN101165820A (en) * | 2006-10-18 | 2008-04-23 | 比亚迪股份有限公司 | Carbon black conductive fluid |
-
2014
- 2014-07-04 CN CN201410317526.2A patent/CN104562115B/en active Active
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5015339A (en) * | 1990-03-26 | 1991-05-14 | Olin Hunt Sub Iii Corp. | Process for preparing nonconductive substrates |
| TW240371B (en) * | 1993-05-17 | 1995-02-11 | Electrochemicals Inc | |
| CN1733980A (en) * | 2004-08-02 | 2006-02-15 | 吕桂生 | Electricity conductive liquid capable of directly galvanizing the printed board |
| CN101165820A (en) * | 2006-10-18 | 2008-04-23 | 比亚迪股份有限公司 | Carbon black conductive fluid |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN106191952A (en) * | 2016-07-20 | 2016-12-07 | 苏州顾氏新材料有限公司 | A kind of black holes liquid and methods for making and using same thereof |
| CN106319603A (en) * | 2016-08-29 | 2017-01-11 | 苏州铱诺化学材料有限公司 | Formula of blackhole hole-leveling agent |
| CN106852026A (en) * | 2016-11-29 | 2017-06-13 | 深圳崇达多层线路板有限公司 | Suitable for the black holes production technology of HDI products |
| CN107539983A (en) * | 2017-09-30 | 2018-01-05 | 湖南国盛石墨科技有限公司 | The preparation method of graphite dispersing agent |
| CN108323036A (en) * | 2018-02-10 | 2018-07-24 | 深圳市祥盛兴科技有限公司 | A kind of blank hole liquid and black holes chemical industry skill |
| CN108834309A (en) * | 2018-08-30 | 2018-11-16 | 陈伟元 | A kind of graphene metallization solution and the preparation method and application thereof |
| CN111647901A (en) * | 2020-05-15 | 2020-09-11 | 湖北省哈福生物化学有限公司 | Black hole liquid and preparation method and use method thereof |
| CN111647901B (en) * | 2020-05-15 | 2023-08-25 | 湖北省哈福生物化学有限公司 | Black hole liquid and preparation method and application method thereof |
| CN112867285A (en) * | 2020-12-29 | 2021-05-28 | 深圳市贝加电子材料有限公司 | Conductive graphite hole metallization solution and preparation method and application thereof |
| CN113248979A (en) * | 2021-04-21 | 2021-08-13 | 东莞市溢美材料科技有限公司 | Preparation method of hot-melt thermosetting nano-silver conductive ink |
| CN114351197A (en) * | 2021-11-30 | 2022-04-15 | 武汉格智新材料有限公司 | Graphite shadow metallization auxiliary agent and preparation method and application thereof |
| CN114466529A (en) * | 2021-12-31 | 2022-05-10 | 广东省科学院化工研究所 | Black hole liquid for electroplating through hole of printed circuit board and preparation method and application thereof |
| CN115594171A (en) * | 2022-07-29 | 2023-01-13 | 广东利尔化学有限公司（Cn） | Carbon pore process nano graphite dispersion liquid and preparation method thereof |
| CN115433419A (en) * | 2022-09-30 | 2022-12-06 | 浙江华正新材料股份有限公司 | Resin glue solution, prepreg, circuit substrate and printed circuit board |
| CN115433419B (en) * | 2022-09-30 | 2023-12-15 | 浙江华正新材料股份有限公司 | Resin glue solution, prepreg, circuit substrate and printed circuit board |
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