CN104562115B - Blank hole liquid for printed circuit board and preparation method thereof - Google Patents
Blank hole liquid for printed circuit board and preparation method thereof Download PDFInfo
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- CN104562115B CN104562115B CN201410317526.2A CN201410317526A CN104562115B CN 104562115 B CN104562115 B CN 104562115B CN 201410317526 A CN201410317526 A CN 201410317526A CN 104562115 B CN104562115 B CN 104562115B
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- blank hole
- hole liquid
- liquid
- parts
- water soluble
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- 239000007788 liquid Substances 0.000 title claims abstract description 89
- 238000002360 preparation method Methods 0.000 title abstract description 10
- 239000002245 particle Substances 0.000 claims abstract description 50
- 239000006185 dispersion Substances 0.000 claims abstract description 38
- 229920003169 water-soluble polymer Polymers 0.000 claims abstract description 32
- 239000002904 solvent Substances 0.000 claims abstract description 21
- 239000004094 surface-active agent Substances 0.000 claims abstract description 15
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 68
- 239000010439 graphite Substances 0.000 claims description 63
- 229910002804 graphite Inorganic materials 0.000 claims description 63
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 31
- 238000000034 method Methods 0.000 claims description 29
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 claims description 21
- 239000002736 nonionic surfactant Substances 0.000 claims description 21
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 19
- 239000003960 organic solvent Substances 0.000 claims description 14
- 239000013530 defoamer Substances 0.000 claims description 13
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 claims description 12
- 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
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 9
- 238000003756 stirring Methods 0.000 claims description 7
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound 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
- 229920003171 Poly (ethylene oxide) Polymers 0.000 claims description 5
- 239000004372 Polyvinyl alcohol Substances 0.000 claims description 5
- 239000003795 chemical substances by application Substances 0.000 claims description 5
- 229920002451 polyvinyl alcohol Polymers 0.000 claims description 5
- KWYUFKZDYYNOTN-UHFFFAOYSA-M potassium hydroxide Substances [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 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
- 229920000036 polyvinylpyrrolidone Polymers 0.000 claims description 4
- 235000013855 polyvinylpyrrolidone Nutrition 0.000 claims description 4
- 239000001267 polyvinylpyrrolidone Substances 0.000 claims description 4
- 241001272567 Hominoidea Species 0.000 claims description 3
- 229910020451 K2SiO3 Inorganic materials 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
- RBNPOMFGQQGHHO-UHFFFAOYSA-N glyceric acid Chemical compound OCC(O)C(O)=O RBNPOMFGQQGHHO-UHFFFAOYSA-N 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
- 229910052911 sodium silicate Inorganic materials 0.000 claims description 3
- 229920001495 poly(sodium acrylate) polymer Polymers 0.000 claims description 2
- NNMHYFLPFNGQFZ-UHFFFAOYSA-M sodium polyacrylate Chemical compound [Na+].[O-]C(=O)C=C NNMHYFLPFNGQFZ-UHFFFAOYSA-M 0.000 claims description 2
- JZZIHCLFHIXETF-UHFFFAOYSA-N dimethylsilicon Chemical compound C[Si]C JZZIHCLFHIXETF-UHFFFAOYSA-N 0.000 claims 1
- 239000003921 oil Substances 0.000 claims 1
- 150000004040 pyrrolidinones Chemical class 0.000 claims 1
- 230000006641 stabilisation Effects 0.000 abstract description 13
- 238000011105 stabilization Methods 0.000 abstract description 13
- 238000005253 cladding Methods 0.000 abstract description 11
- 229920001477 hydrophilic polymer Polymers 0.000 abstract description 9
- 229920000642 polymer Polymers 0.000 abstract description 4
- 239000006229 carbon black Substances 0.000 description 15
- 235000019241 carbon black Nutrition 0.000 description 15
- 239000011248 coating agent Substances 0.000 description 10
- 238000000576 coating method Methods 0.000 description 10
- 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
- 239000000725 suspension Substances 0.000 description 9
- 230000008569 process Effects 0.000 description 8
- 239000002270 dispersing agent Substances 0.000 description 7
- 230000004048 modification Effects 0.000 description 7
- 238000012986 modification Methods 0.000 description 7
- 238000007747 plating Methods 0.000 description 7
- SECXISVLQFMRJM-UHFFFAOYSA-N N-Methylpyrrolidone Chemical compound CN1CCCC1=O SECXISVLQFMRJM-UHFFFAOYSA-N 0.000 description 6
- 235000013339 cereals Nutrition 0.000 description 6
- 238000005516 engineering process Methods 0.000 description 6
- 239000000243 solution 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
- 238000001465 metallisation Methods 0.000 description 5
- 239000000758 substrate Substances 0.000 description 5
- 230000010148 water-pollination Effects 0.000 description 5
- 230000006698 induction Effects 0.000 description 4
- 239000011734 sodium Substances 0.000 description 4
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 description 3
- WSFSSNUMVMOOMR-UHFFFAOYSA-N Formaldehyde Chemical compound O=C WSFSSNUMVMOOMR-UHFFFAOYSA-N 0.000 description 3
- 239000002202 Polyethylene glycol Substances 0.000 description 3
- 239000007864 aqueous solution Substances 0.000 description 3
- 229920002521 macromolecule Polymers 0.000 description 3
- 238000004519 manufacturing process Methods 0.000 description 3
- 229920001223 polyethylene glycol Polymers 0.000 description 3
- 230000000284 resting effect Effects 0.000 description 3
- 238000012360 testing method Methods 0.000 description 3
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 2
- 229910020489 SiO3 Inorganic materials 0.000 description 2
- BQODPTQLXVVEJG-UHFFFAOYSA-N [O].C=C Chemical group [O].C=C BQODPTQLXVVEJG-UHFFFAOYSA-N 0.000 description 2
- 238000010521 absorption reaction Methods 0.000 description 2
- 230000003213 activating effect Effects 0.000 description 2
- 238000004220 aggregation Methods 0.000 description 2
- 230000002776 aggregation Effects 0.000 description 2
- 238000013329 compounding Methods 0.000 description 2
- 238000000151 deposition Methods 0.000 description 2
- 238000003795 desorption Methods 0.000 description 2
- 229940008099 dimethicone Drugs 0.000 description 2
- 239000004205 dimethyl polysiloxane Substances 0.000 description 2
- 235000013870 dimethyl polysiloxane Nutrition 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 239000008187 granular material Substances 0.000 description 2
- 239000010410 layer Substances 0.000 description 2
- 239000003094 microcapsule Substances 0.000 description 2
- 229920000435 poly(dimethylsiloxane) Polymers 0.000 description 2
- 238000011160 research Methods 0.000 description 2
- 239000004575 stone Substances 0.000 description 2
- 238000005728 strengthening Methods 0.000 description 2
- DNIAPMSPPWPWGF-GSVOUGTGSA-N (R)-(-)-Propylene glycol Chemical compound C[C@@H](O)CO DNIAPMSPPWPWGF-GSVOUGTGSA-N 0.000 description 1
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 1
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 description 1
- 239000004743 Polypropylene Substances 0.000 description 1
- 230000001070 adhesive effect Effects 0.000 description 1
- 238000000149 argon plasma sintering Methods 0.000 description 1
- ZFSFDELZPURLKD-UHFFFAOYSA-N azanium;hydroxide;hydrate Chemical compound N.O.O ZFSFDELZPURLKD-UHFFFAOYSA-N 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000033228 biological regulation Effects 0.000 description 1
- 235000008429 bread Nutrition 0.000 description 1
- 230000000711 cancerogenic effect Effects 0.000 description 1
- 231100000315 carcinogenic Toxicity 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 239000003638 chemical reducing agent Substances 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
- 239000012535 impurity Substances 0.000 description 1
- 238000001802 infusion Methods 0.000 description 1
- 238000009413 insulation Methods 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
- 239000000463 material Substances 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
- 238000005191 phase separation Methods 0.000 description 1
- 230000000704 physical effect Effects 0.000 description 1
- 229920001155 polypropylene Polymers 0.000 description 1
- 229920000136 polysorbate Polymers 0.000 description 1
- 239000000843 powder Substances 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
- 229910052708 sodium Inorganic materials 0.000 description 1
- 241000894007 species Species 0.000 description 1
- 238000003860 storage Methods 0.000 description 1
- 239000006228 supernatant Substances 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 kind of blank hole liquid for printed circuit board and preparation method thereof, blank hole liquid includes conductive matrices, surfactant, water soluble polymer and its corresponding poor solvent, alkaline matter and decentralized medium, the preparation method of blank hole liquid includes being added to conductive matrices, surfactant in decentralized medium, water soluble polymer is added after being ground, the corresponding poor solvent of water soluble polymer is added after being stirred vigorously, alkaline matter is finally added and is formed blank hole liquid.Blank hole liquid for printed circuit board of the invention in blank hole liquid by adding water soluble polymer and its corresponding poor solvent, form the blank hole liquid of the conductive matrices of hydrophilic polymer cladding, using the steric hindrance and electrostatic repulsion of particle surface long-chain polymer, the dispersion stabilization of blank hole liquid is greatly enhanced.
Description
Technical field
The present invention relates to the manufacture field of printed circuit board, more particularly to a kind of make the black of printed circuit board Direct Electroplating
Hole liquid and preparation method thereof.
Background technology
With continuous portability, the miniaturization of communication electronic device, the integrated level more and more higher of the printed circuit board of use.
The wiring of printed circuit board plate face is more and more closeer, and the associated through-hole aperture for playing interlayer conduction and footpath depth ratio are increasingly
Small, this just proposes requirements at the higher level to the hole metallization treatment of printed circuit board.Existing hole metallization printed circuit board manufacture
Technique, first using chemical-copper-plating process so that the non-conductor hole wall surface metallization of through hole, then electro-coppering thickeies.It is this
Although manufacturing process can be successfully fabricated hole metallization printed board, but the problem that chemical-copper-plating process therein is present has:
(1) complex process, it is difficult to operation and maintenance;(2) technological process is long, water consumption is big, wastewater treatment is difficult;(3) done using formaldehyde
Reducing agent, not only endangers ecological environment, and have carcinogenic danger.Based on the problem that chemical-copper-plating process is present, people are always
The research of the directly electroplating technology of cancellation chemical-copper-plating process is devoted to, wherein one of more ripe technique is outstanding using carbon black
The directly electroplating technology of supernatant liquid --- black holes technology.
Black holes technology is, separately or cooperatively as conductive matrices, to make dispersion suspension using carbon black or graphite, and device to hole is entered
The method of row conductive treatment.Compared with chemical-copper-plating process, black holes technology has technique simplification, non-environmental-pollution, cost
The advantages of reduction, the core of its technique is the formula and performance of blank hole liquid.Current PCB Hole Metallization Direct Electroplating work
The blank hole liquid that skill is used is (such as:Chinese patent CN1733980 A, United States Patent (USP) US5015339, US5389270 and US
P4724005 A etc.), be with water as decentralized medium, suspension of the carbon black/graphite particle as conductive matrices, due to carbon black/graphite
Hydrophily it is poor, cause suspension unstable, easily there is coagulation, had a strong impact on the performance of blank hole liquid.In order to improve
The stability of dispersion liquid, is typically with adding the side of dispersant (low molecular weight surfactant activity and/or high molecular surfactant)
Method, because the dispersant for adding is, in carbon black/graphite surface, there is the balance of absorption and desorption by physical action absorption, and divides
The desorption of powder can cause carbon black/graphite particle to reassemble during storage, settle, it is impossible to fundamentally solve carbon black/stone
The problem of black stability of suspension.
The content of the invention
To solve the above problems, the present invention provides a kind of blank hole liquid for printed circuit board and preparation method thereof, passes through
In the method for conductive matrices Surface coating hydrophilic polymer, using the steric hindrance of conductive matrices surface long-chain polymer and quiet
Electric repulsion, greatly enhances the dispersion stabilization of blank hole liquid.
To reach above-mentioned purpose, the present invention uses following technical scheme:
The invention discloses a kind of blank hole liquid for printed circuit board, including conductive matrices, surfactant, water solubility
Macromolecule and its corresponding poor solvent, alkaline matter and decentralized medium.
Preferably, the water soluble polymer and its corresponding poor solvent include:Sodium carboxymethylcellulose (CMC) // second
Alcohol, Sodium Polyacrylate (PA-Na) // ethanol or acetone, polyvinyl alcohol (PVA) // isopropanol or acetone or ethylene glycol, polyethylene pyrrole
Pyrrolidone (PVP) // acetone, sodium alginate (SA-Na) // ethanol.
Preferably, the surfactant includes nonionic surfactant, and the nonionic surfactant includes poly-
Oxygen ethylene type nonionic surfactant and polyvalent alcohol type nonionic surfactant.
Preferably, the Determination of Polyoxyethylene Non-ionic Surfactants includes polyethylene glycol (PEG), aliphatic alcohol polyethenoxy
One or more in ether (paregal O), APES (OP-10), NPE (TX-10)
Mixture;The polyvalent alcohol type nonionic surfactant includes in Tween 80, polysorbate60, polysorbate40, polysorbas20
Plant or two or more mixtures.
Preferably, the conductive matrices include graphite particle;The alkaline matter includes NaOH, KOH, NH4In OH one
Plant or two or more mixtures;The decentralized medium includes deionized water.
Preferably, the blank hole liquid also includes organic solvent, and the organic solvent includes 1-METHYLPYRROLIDONE (NMP).
Preferably, the blank hole liquid also includes defoamer, and the defoamer includes dimethicone, tributyl phosphate
(TBP), one or more the mixture in polyoxyethylene glycerol ether.
Preferably, the blank hole liquid also includes inorganic bond, and the inorganic bond includes Na2SiO3、K2SiO3In
One or two mixture.
Preferably, the parts by weight ratio of each component of the blank hole liquid is:The conductive matrices are 2-5 parts;The table
Face activating agent is 0.8-1.2 parts;The water soluble polymer and its corresponding poor solvent are respectively 1-2 parts and 15-25 parts;Institute
Alkaline matter is stated for 2-4 parts;The decentralized medium is 50-70 parts.
Preferably, the blank hole liquid is also including parts by weight ratio:8-12 parts of organic solvent, 0.4-1.0 part disappears
Infusion, 0.5-1.5 parts of inorganic bond.
Preferably, the pH value of the blank hole liquid is 9-13.
The invention also discloses a kind of method for preparing blank hole liquid as described above, comprise the following steps successively:S1:By institute
State conducting medium and the surfactant is added in the decentralized medium, be ground, form uniform dispersion liquid A;S2:
To the water soluble polymer is added in the dispersion liquid A, the described corresponding bad molten of water soluble polymer is added after stirring
Agent, forms dispersion liquid B;S3:To alkaline matter is added in the dispersion liquid B, stir to form the blank hole liquid.
Preferably, also include being added to organic solvent, defoamer in the decentralized medium before being ground in step S1;
Step S3 also includes to adding inorganic bond in the dispersion liquid B before being stirred.
Preferably, the time being ground in step S1 is 5-7h.
Preferably, after in step S2 to the water soluble polymer is added in the dispersion liquid A, after stirring 20-40min again
Add the described corresponding poor solvent of water soluble polymer.
Present invention beneficial effect compared with prior art includes:Blank hole liquid for printed circuit board of the invention and its
Preparation method, by adding water soluble polymer and its corresponding poor solvent in blank hole liquid, water soluble polymer is right at its
Under the induction of the poor solvent answered, with conductive matrices as core is separated out, mutually condensed in water, aqueous high molecular chain passes through secondary or physical bond
Power is adhere tightly to conductive matrices surface, is coated on around conductive matrices, forms the conductive matrices of hydrophilic polymer cladding
Blank hole liquid, using the steric hindrance and electrostatic repulsion of particle surface long-chain polymer, greatly enhances the dispersion stabilization of blank hole liquid.
In preferred scheme:Conductive matrices in black holes formula of liquid include graphite particle;Surfactant includes polyoxyethylene
Type nonionic surfactant and polyvalent alcohol type nonionic surfactant, both compounding uses, in granular graphite sublist
Bread covers the treatment of the hydrophily before water soluble polymer, improves the tack of graphite particle and the dispersion stabilization of blank hole liquid.More
Plus preferably, organic solvent, defoamer and inorganic bond also being included in black holes formula of liquid, wherein organic solvent is used for granular graphite
Hydrophily treatment before sub- Surface coating water soluble polymer, and be conducive to strengthening graphite particle and non-ionic surface active
Compatibility between agent;The addition of defoamer ensures that printed circuit board obtains uniform conductive substrates graphite linings, so as to prevent
There is the local phenomenon without coating in printed circuit board;Inorganic bond is used to improve the bonding between graphite particle and insulating substrate
Performance.
Specific embodiment
With reference to preferred embodiment the invention will be further described.
Embodiments of the invention provide a kind of blank hole liquid for printed circuit board, including conductive matrices, surfactant,
Water soluble polymer and its corresponding poor solvent, alkaline matter and decentralized medium, preferably also include organic solvent, defoamer and
Inorganic bond.
Wherein conductive matrices include graphite particle, compared to carbon black particle, because graphite has thin type sheet crystal structure,
Electronic energy is shifted in two dimensional surface, so can assign aperture and the more preferable electric conductivity of deep hole after film forming on hole wall, also makes to lead
Electric layer becomes thinner.The average grain diameter of the graphite particle in the present embodiment should be less than 2 μm, is advisable with less than 1 μm, more preferably
Less than 0.7 μm;If graphite particle average grain diameter is more than 2 μm, its electric conductivity can be reduced, can also reduce coated metal with insulation
Tack between base material;Content of the graphite particle in suspension should be less than 6wt%, preferably 2-5wt%;If carbon particle
Content is higher than 6wt%, then the tack between coating and insulating substrate and Copper Foil can be caused bad, and if carbon particle content is low
In 1wt%, then can be too low due to carbon particle density, it is difficult to obtain the basalis of sufficient conductivity, and then can produce local without plating
Layer phenomenon.
Surfactant includes nonionic surfactant, and nonionic surfactant includes polyoxyethylene-type nonionic table
Face activating agent and polyvalent alcohol type nonionic surfactant, wherein Determination of Polyoxyethylene Non-ionic Surfactants include poly- second two
Alcohol (PEG), AEO (paregal O), APES (OP-10) and NPE
(TX-10) etc.;Polyvalent alcohol type nonionic surfactant is TWEEN Series, such as:Tween 80, polysorbate60, polysorbate40 and tell
Temperature 20 etc..Both oxygen ethylene type and polyvalent alcohol type nonionic surfactant compounding use, coat water-soluble for graphite particle
Property macromolecule before hydrophily treatment, improve carbon particle tack and blank hole liquid stability.
Water soluble polymer and its corresponding poor solvent are respectively:Sodium carboxymethylcellulose (CMC) // ethanol, polypropylene
Sour sodium (PA-Na) // ethanol or acetone, polyvinyl alcohol (PVA) // isopropanol or acetone or ethylene glycol, polyvinylpyrrolidone
(PVP) // acetone, sodium alginate (SA-Na) // ethanol.Its effect is:Water soluble polymer under the induction of poor solvent, with
Graphite particle mutually condenses to separate out core in water, and aqueous high molecular chain is adhere tightly to granular graphite sublist by physics bonding force
Face, is coated on around graphite particle, the graphite particle dispersion liquid of hydrophilic polymer cladding is formed, so as to significantly improve blank hole liquid
Dispersion stabilization.
Alkaline matter includes NaOH, KOH, NH4OH etc., wherein be preferred with KOH, is used to adjust the pH value of blank hole liquid to 9-
13, referred to as 10-12 is preferred with pH, it is ensured that the dispersion stabilization and Graphite particle surfaces of blank hole liquid are negatively charged, promote granular graphite
Son is adsorbed in adjusted rear positively charged hole wall surface, forms complete graphite coating.
Decentralized medium includes deionized water (DI water), mainly grasps ashamed with plating is easy in view of cost, and it does not contain logical
The impurity such as Ca, I, the F contained in ordinary water, to reduce the contamination and interference of foreign ion in electroplating work procedure.
Organic solvent includes 1-METHYLPYRROLIDONE (NMP), for the parent before graphite particle cladding water soluble polymer
Aqueous treatment, is conducive to strengthening the compatibility between graphite particle and nonionic surfactant.
Defoamer is including dimethicone, tributyl phosphate (TBP), polyoxyethylene glycerol ether etc., it is ensured that obtain uniform
Conductive substrates graphite linings, prevent local without coating phenomenon.
Inorganic bond includes Na2SiO3、K2SiO3Deng, it is intended to improve the adhesive property between carbon particle and insulating substrate.
Above each component usage ratio parts by weight are preferably:Graphite particle:2-5 parts;Polyoxyethylene-type // polyvalent alcohol
Type nonionic surfactant:0.6-0.8 parts // 0.2-0.4 parts;Water soluble polymer // corresponding poor solvent:1-2 parts //
15-25 parts;Alkaline matter:2-4 parts;Organic solvent:8-12 parts;Defoamer:0.4-1.0 parts;Inorganic bond:0.5-1.5 parts.
Another embodiment of the present invention additionally provides a kind of preparation method of the blank hole liquid for printed circuit board, wraps successively
Include following steps:
S1:Conductive matrices, surfactant are added in decentralized medium, the ball milling 5-7h in ball mill, form uniform
Dispersion liquid A;
S2:To water soluble polymer is added in dispersion liquid A, 20-40min is stirred vigorously, is subsequently adding water soluble polymer
Poor solvent, induction water soluble polymer mutually condenses in water, with graphite particle to separate out core, is tightly coated on graphite particle all
Enclose, form the dispersion liquid B of the graphite particle of hydrophilic polymer cladding;
S3:To alkaline matter is added in dispersion liquid B, it is 9-13 to stir and allocate blank hole liquid to pH value.
In a preferred embodiment, also include for organic solvent, defoamer being added to decentralized medium before ball milling in step S1
In;Also including to adding inorganic bond in dispersion liquid B before being stirred in step S3.
In more preferred embodiment, in step S2 in dispersion liquid A add water soluble polymer be with 5wt%
The aqueous solution form of water soluble polymer is added, and the mass fraction of the wherein water in the solution is counted in decentralized medium.
Technical scheme is described further with reference to specific embodiment.
Embodiment one is as shown in table 1 to each component and its content of the blank hole liquid of embodiment five:
The embodiment one of table 1 is formulated and matches to the blank hole liquid preparing raw material of embodiment five
It is following (by taking embodiment one as an example) that various embodiments above prepares blank hole liquid step:
S1:By 4g graphite, 0.7gPEG, 0.3g polysorbate60,10gNMP, 0.6gTBP and 25g DI water, in ball mill
Ball milling 6h, obtains uniform graphite dispersing solution;
S2:In to the graphite dispersing solution obtained in S1, the CMC aqueous solution of the 5wt% of the 30ml for preparing in advance is added dropwise to
(CMC about 1.5g, DI water about 30g are included wherein in the CMC aqueous solution), while being stirred vigorously 30min, is then added dropwise CMC not
Good solvent ethanol 20g, induction CMC mutually condenses in water, is adhered to by physics bonding force with graphite particle as core, CMC strands is separated out
In Graphite particle surfaces, it is coated on around graphite particle, forms the dispersion liquid of the graphite particle of hydrophilic polymer cladding;
S3:In the dispersion liquid of the graphite particle of the hydrophilic polymer cladding obtained in S2,1g Na are added2SiO3And 3g
NH4OH, is uniformly mixed and allocates dispersion pH value to 10-12, forms blank hole liquid.
Comparative example:
Blank hole liquid is prepared using the method for directly addition dispersant, is formulated with embodiment 1, be simply not added with water soluble polymer
The poor solvent ethanol of CMC, preparation process is as follows:
S1:By 0.7gPEG, 0.3g polysorbate60,1.5gCMC, 10gNMP, 0.6gTBP and 1gNa2SiO3It is dissolved in NH4OH water
Solution (NH4OH:3g;DI water:20g), continuous phase is formed, 4g graphite is subsequently adding, in this dense suspension input ball mill
Ball milling 6h, obtains uniform graphite dispersing solution;
S2:To 35gDI water is added in the graphite dense suspension that the ball milling obtained in S1 is crossed, it is uniformly mixed, dilutes
To the black holes initial concentration of regulation.
The dispersion stabilization test result of various embodiments above and comparative example gained graphite suspension:
The average grain diameter of graphite particle can reflect the aggregation of graphite particle with the situation of change of resting period in blank hole liquid
Degree (i.e. dispersion stabilization), average grain diameter increases over time more, illustrates that graphite particle clustering phenomena is more serious, in water
Dispersion stabilization is poorer.Graphite average particle size is tested using light scattering particle size analyzer, graphite particle is contrasted with this
Hydrophilic macromolecule coating modification (embodiment one to embodiment five) and the dispersion effect for directly adding dispersant method (comparative example),
Test result is as shown in table 2 below:
The embodiment one of table 2 to embodiment five and comparative example test result
From table 2, the blank hole liquid (stone obtained using water soluble polymer coating modification in embodiment one to embodiment five
Black dispersion liquid system) stability far above the directly blank hole liquid (graphite dispersing solution) of addition dispersant, embodiment in comparative example
Graphite particle particle diameter in one to embodiment five changes little with the extension of resting period, even if after depositing 4 months, average grain diameter
Also only increased to no more than 250nm (the@4months of growth rate < 25%) from initial 200nm or so, remain to meet use and want
Ask, absolutely prove that being coated on Graphite particle surfaces, the water soluble polymer under condensed state can effectively prevent graphite particle
Aggregation, so as to substantially increase the dispersion stabilization of blank hole liquid;And use the blank hole liquid that directly addition dispersant method is obtained
Dispersion stabilization is poor, and its graphite particle particle diameter is larger with the extension increase degree of resting period, after depositing 4 months, average grain
Footpath increases above 1700nm (the@4months of growth rate > 790%) from initial 200nm or so, can not again meet and use
It is required that.
Embodiments of the invention overcome the deficiencies in the prior art, there is provided one kind is than directly addition dispersant method more
Plus the blank hole liquid (carbon black/graphite suspension system) of stabilization.Hydrophilic polymer is coated by carbon black/Graphite particle surfaces
Method (phase separation method cladding), forms the carbon black/graphite microcapsule granule of hydrophilic polymer cladding, using particle surface long-chain
The steric hindrance and electrostatic repulsion of polymer, can greatly enhance the dispersion stabilization of blank hole liquid.With other carbon blacks/graphite hydrophily
Method of modifying, such as:Oxidation modification, graft modification etc. are compared, and coating modification is unrelated with the species of carbon black/graphite, especially phase point
The polymerisation of complexity can be avoided from method coating modification, there is stronger operability than micro-emulsion polymerization cladding process.Therefore, parent
The preparation of the carbon black/graphite microcapsule granule of waterborne polymeric cladding is probably the trend of the hydrophilically modified research of carbon black/graphite.
Above content is to combine specific preferred embodiment further description made for the present invention, it is impossible to assert
Specific implementation of the invention is confined to these explanations.For those skilled in the art, do not taking off
On the premise of present inventive concept, some equivalent substitutes or obvious modification can also be made, and performance or purposes are identical, all should
When being considered as belonging to protection scope of the present invention.
Claims (13)
1. a kind of blank hole liquid for printed circuit board, it is characterised in that including conductive matrices, surfactant, water-soluble high
Molecule and its corresponding poor solvent, alkaline matter and decentralized medium;Wherein described conducting medium includes graphite particle, the water
Soluble macromolecular and its corresponding poor solvent include:Sodium carboxymethylcellulose // ethanol, Sodium Polyacrylate // ethanol or acetone,
Polyvinyl alcohol // isopropanol or acetone or ethylene glycol, polyvinylpyrrolidone // acetone, sodium alginate // ethanol, wherein described black
The parts by weight ratio of each component of hole liquid is:The conductive matrices are 2-5 parts;The surfactant is 0.8-1.2 parts;Institute
State respectively 1-2 parts and 15-25 parts of water soluble polymer and its corresponding poor solvent;The alkaline matter is 2-4 parts;It is described
Decentralized medium is 50-70 parts.
2. blank hole liquid as claimed in claim 1, it is characterised in that the surfactant includes nonionic surfactant,
The nonionic surfactant includes Determination of Polyoxyethylene Non-ionic Surfactants and polyvalent alcohol type non-ionic surface active
Agent.
3. blank hole liquid as claimed in claim 2, it is characterised in that the Determination of Polyoxyethylene Non-ionic Surfactants includes poly-
In ethylene glycol, AEO, APES, NPE one or more
Mixture;The polyvalent alcohol type nonionic surfactant includes the one kind in Tween 80, polysorbate60, polysorbate40, polysorbas20
Or two or more mixtures.
4. blank hole liquid as claimed in claim 1, it is characterised in that the alkaline matter includes NaOH, KOH, NH4In OH one
Plant or two or more mixtures;The decentralized medium includes deionized water.
5. blank hole liquid as claimed in claim 1, it is characterised in that also including organic solvent, the organic solvent includes N- first
Base pyrrolidones.
6. blank hole liquid as claimed in claim 1, it is characterised in that also including defoamer, the defoamer includes dimethyl-silicon
One or more mixture in oil, tributyl phosphate, polyoxyethylene glycerol ether.
7. blank hole liquid as claimed in claim 1, it is characterised in that also including inorganic bond, the inorganic bond includes
Na2SiO3、K2SiO3In one or two mixture.
8. blank hole liquid as claimed in claim 1, it is characterised in that the blank hole liquid is also including parts by weight ratio:8-12
The organic solvent of part, 0.4-1.0 parts of defoamer, 0.5-1.5 parts of inorganic bond.
9. the blank hole liquid as described in any one of claim 1 to 8, it is characterised in that the pH value of the blank hole liquid is 9-13.
10. a kind of method for preparing the blank hole liquid described in any one of Claims 1-4, it is characterised in that successively including following step
Suddenly:
S1:The conducting medium and the surfactant are added in the decentralized medium, are ground, form uniform
Dispersion liquid A;
S2:To the water soluble polymer is added in the dispersion liquid A, the described corresponding of water soluble polymer is added after stirring
Poor solvent, forms dispersion liquid B;
S3:To alkaline matter is added in the dispersion liquid B, stir to form the blank hole liquid.
11. methods as claimed in claim 10, it is characterised in that be ground in step S1 before also include by organic solvent,
Defoamer is added in the decentralized medium;Step S3 also includes to adding inorganic bond in the dispersion liquid B before being stirred
Agent.
12. method as described in claim 10 or 11, it is characterised in that the time being ground in step S1 is 5-7h.
13. method as described in claim 10 or 11, it is characterised in that described to being added in the dispersion liquid A in step S2
After water soluble polymer, the described corresponding poor solvent of water soluble polymer is added after stirring 20-40min.
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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 |
CN108834309B (en) * | 2018-08-30 | 2020-07-31 | 陈伟元 | Graphene metallization solution and preparation method and application 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 |
CN112867285B (en) * | 2020-12-29 | 2022-10-04 | 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 |
CN114351197B (en) * | 2021-11-30 | 2023-04-28 | 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 |
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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