CN109957286A - Ink and its preparation method and application - Google Patents

Ink and its preparation method and application Download PDF

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Publication number
CN109957286A
CN109957286A CN201910223928.9A CN201910223928A CN109957286A CN 109957286 A CN109957286 A CN 109957286A CN 201910223928 A CN201910223928 A CN 201910223928A CN 109957286 A CN109957286 A CN 109957286A
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Prior art keywords
epoxy resin
ink
ether
agent
glycidyl
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Granted
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CN201910223928.9A
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Chinese (zh)
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CN109957286B (en
Inventor
王亮亮
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Shenzhen Flexible New Material Technology Co Ltd
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Shenzhen Flexible New Material Technology Co Ltd
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    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
    • C09D11/00—Inks
    • C09D11/02—Printing inks
    • C09D11/03—Printing inks characterised by features other than the chemical nature of the binder
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
    • C09D11/00—Inks
    • C09D11/02—Printing inks
    • C09D11/10—Printing inks based on artificial resins
    • C09D11/102—Printing inks based on artificial resins containing macromolecular compounds obtained by reactions other than those only involving unsaturated carbon-to-carbon bonds
    • 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
    • H05K3/0094—Filling or covering plated through-holes or blind plated vias, e.g. for masking or for mechanical reinforcement
    • 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
    • H05K2201/09—Shape and layout
    • H05K2201/09209—Shape and layout details of conductors
    • H05K2201/095—Conductive through-holes or vias
    • H05K2201/0959—Plated through-holes or plated blind vias filled with insulating material

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  • Chemical & Material Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Materials Engineering (AREA)
  • Wood Science & Technology (AREA)
  • Organic Chemistry (AREA)
  • Manufacturing & Machinery (AREA)
  • Microelectronics & Electronic Packaging (AREA)
  • General Chemical & Material Sciences (AREA)
  • Epoxy Resins (AREA)

Abstract

The invention discloses a kind of ink and its preparation method and application, the ink includes following component: the first epoxy resin, the second epoxy resin, epoxy monomer, curing agent, inorganic filling material and auxiliary agent.Preparation method includes measuring each component, and the first epoxy resin, the second epoxy resin, epoxy monomer and auxiliary agent are carried out after mixing, curing agent and inorganic filling material to be added in dispersion, grinds and deaeration processing forms the ink.Ink of the invention heat resistance with higher, Tg200 DEG C of >, guarantee to match when heated with 5G high frequency substrate deformation behavior, while its thermal expansion coefficient is low, (T > Tg)α280 μm of </(m. DEG C) guarantees that the expanded by heating rate under rabbet ink unit temperature after solidification matches with PCB substrate under the high temperature conditions.

Description

Ink and its preparation method and application
Technical field
The invention belongs to technical field of electronic materials, and in particular to a kind of ink and its preparation method and application.
Background technique
As electronic product is increasingly intended to multifunction, miniaturization, circuit board such as printed circuit board (PCB) is also to more Stratification, densification development.This proposes new requirement to the material of printed circuit board, it is desirable that wiring board material is with higher to lead Hot and thermal stability, at the same this to the jack process and consent material of printed circuit board it is also proposed that requirements at the higher level.
Printed circuit board is mainly by the structures such as route and figure, dielectric layer, via hole, anti-solder ink, silk-screen, surface-treated layer At wherein plug socket resin is mainly used for making holes on high density interconnected printed circuit board (HDI) as important buried via hole material.HDI plate is with normal The multi-layer board of rule is core plate, then successively superposition insulating layer and line layer, and carries out punching conducting to lamination using cheesing techniques, is made Monolith printed circuit board is formd to be connected with the interlayer that buried blind via is main conduction mode, and can produce conventional multilayer plate can not Multilayer, the stabilization, thinner and more highdensity printed circuit board reached.And this technique for introducing buried via hole, it is used to bury Porous materials are exactly plug socket resin.
One of the raw material that plug socket resin makes as HDI plate, with the continuous expansion of the HDI plate market demand, dosage Also at explosive growth.With the arrival in 5G epoch, communications electronics propose the high-speed high frequency characteristic of printed circuit higher Requirement, wherein HDI high-frequency high-speed plate will be trend of the times, and such high-speed high frequency substrate compared to common epoxy base material all With higher Tg200 DEG C of > and more low thermal coefficient of expansion (T > Tg)α280 μm of </(m. DEG C) uses plug in process Porous materials also matching must can just be met the requirements.Common plug socket resin TgIt is 140~180 DEG C, (the T > of thermal expansion coefficient Tg)α2120 μm of >/(m. DEG C), best Japanese mountain Rong product is minimum can only also to accomplish α2It is 85 μm/(m. DEG C) Zuo You, Wu Faman Sufficient high-speed high frequency requirement.
Summary of the invention
Based on this, the present invention proposes a kind of high glass transition temperature, low-expansion ink, to meet the height of HDI plate The consent requirement of fast high frequency characteristics.
A kind of ink, including following component: the first epoxy resin, the second epoxy resin, epoxy monomer, curing agent, inorganic Packing material and auxiliary agent.
Further, first epoxy resin is the epoxy resin containing multiple heat-resisting cyclic structures；Described The viscosity of diepoxy resin is 25 DEG C and is lower than 10000mPa.s.
Epoxy resin is the macromolecule matrix resin of ink, has excellent physical property, electrical insulation capability and caking property Energy epoxy resin contains the very strong epoxy group of respond, epoxy resin and low viscosity epoxy tree of the present invention using heat resistance Rouge matching, can effectively improve the glass transition temperature of ink under conditions of guaranteeing printing performance, while ensure that ink is opposite The lower coefficient of expansion, epoxy resin react to form highly cross-linked network structure with curing agent, enhance thermal stability, improve rigid Property.
Further, the ink includes the first epoxy resin of 10-30wt%, the second epoxy resin of 10-20wt%, 0- 5wt% epoxy monomer, 2-10wt% curing agent, 40-60wt% inorganic filling material, 0-5wt% auxiliary agent.
Further, first epoxy resin is dicyclopentadiene phenol type epoxy resin, biphenyl phenol type epoxy Resin, bisphenol A-type novolac epoxy resin, novolac epoxy resin, condensed ring naphthalene type epoxy resin, 4,4 '-methylene, two (N, N '-two Glycidyl aniline), tetraphenyl glycidyl ether ethane, trisphenyl glycidyl ether methane, triglycidyl group trimerization It is the double aminomethyl cyclohexanes of isocyanates, four glycidyl group diaminodiphenyl-methane, four glycidyl group -1,3-, organic At least one of silicon modified epoxy resin, polyamide modified epoxy resin, benzoxazine modified epoxy.
Further, second epoxy resin is bisphenol A epoxide resin, bisphenol F epoxy resin, hydrogenated bisphenol A ring Oxygen resin, 4,5- 7-oxa-bicyclo[4.1.0-1,2- dimethyl 2-glycidyl ester, 2- (3,4- epoxycyclohexyl)-5,5- spiral shell (3,4- ring Oxygen cyclohexyl) -1,3- dioxane homopolymer, bis- (the 3,4- 7-oxa-bicyclo[4.1.0 formic acid) esters of 1,4 cyclohexane dimethanol, it is bis- ((3, 4- epoxycyclohexyl) methyl) adipate ester, at least one of triglycidyl group para-aminophenol.
Further, the epoxy monomer is to tert-butyl-phenyl glycidol ether, o-tolyl glycidol ether, benzene Base glycidol ether, ethylene glycol diglycidylether, diethylene glycol and glycidol ether, Triethylene Glycol Diglycidyl Ether, two Propylene glycol glycidyl ether, 1,4- butanediol diglycidyl ether, 1,4 cyclohexane dimethanol diglycidyl ether, 1,2- bis- oneself Hexanediol diglycidyl ether, 1,6 hexanediol diglycidylether, neopentylglycol diglycidyl ether, resorcinol two shrink sweet Oily ether, glycerol polyglycidyl ether, trihydroxymethylpropanyltri diglycidyl ether, castor oil triglycidyl ether, pentaerythrite four Glycidol ether, sorbierite glycidol ether, azacyclo- polyglycidyl ether, tertiary carbonic acid glycidyl ester, dimeric dibasic acid and shrink Glyceride, hexahydrophthalic acid 2-glycidyl ester, methyl tetrahydrophthalic acid 2-glycidyl ester, adipic acid two shrink At least one of glyceride.
Further, the curing agent includes at least one of imidazoles, anhydride, amine；Curing agent is suitable Baking temperature under, after solidification have good physical and mechanical property.
Further, the amine curing agent is at least one of DDS, DDM.
Further, the acid anhydride type curing agent is phthalic anhydride, BTDA, DSDA, THPA, NA, MCTC.
Further, the imidazole curing agent is PN-23, PN-31, PN-40, PN-50, PN-H, 2- undecyl Imidazoles, 2- heptadecyl imidazole, 1- cyanoethyl -2-ethyl-4-methylimidazole, the inclined benzene three of 1- cyanoethyl -2- undecyl imidazole Formates, 1-cyanoethyl-2-phenylimidazole trimellitic acid salt, 2-methylimidazole isocyanurate, 2- phenylimidazole trimerization Isocyanates, 2,4- diamino -6- (2-methylimidazole -1- ethyl)-S- triazine, 2,4- diamino -6- (2- ethyl -4- methyl Imidazoles -1- ethyl)-S- triazine, 2,4- diamino -6- (2- undecyl imidazole -1- ethyl)-S- triazine, 2- phenyl -4,5- two Hydroxy methylimidazole, 2 phenyl 4 methyl 5 hydroxy methylimidazole, 1- cyanoethyl -2- phenyl -4,5- bis- (cyanogen ethoxy methylene) miaow Azoles, -3 benzylimidazolium chloride of 1- dodecyl -2- methyl, 1,3- dibenzyl -2-methylimidazole chloride, boron trifluoride-amine Complex compound (BF3-MEA、BF3-BZA、BF3- DMA), aromatic diazonium salt, diaryl iodonium salt, triarylsulfonium salt, metallocene Based compound.
Further, the inorganic filling material be barium sulfate, talcum powder, crystalline silica, fused silica, Amorphous silica, nano silica, magnesium carbonate, calcium carbonate, nanometer calcium carbonate, aluminium oxide, aluminium hydroxide, in silicon powder At least one.
Further, the auxiliary agent includes wetting dispersing agent and/or deaeration agent.Further, the wetting and dispersing Agent BYK-110, BYK-111 selected from Germany's Bi Ke chemical production, the Disponer 904 of this special chemical of hamming production, The 2400SC of Disponer 904S, Lu Borun production, 20000.
Further, the defoaming agent is selected from BYK-A550, BYK-A515, BYK- of Germany's Bi Ke chemical production A506, H10, FS80 of DOW CORNING production, Foamex 1495, the Foamex 842 of Digao production.The wetting dispersing agent can be each Component is uniformly dispersed, and the deaeration agent is conducive to that bubble is discharged in slurry.The auxiliary agent can be mentioned according to the type of auxiliary agent Ink dispersion described in height is excellent stability, and improves the solidification quality of the ink, improves stability.
Further, the ink is for circuit board jack process.
A kind of preparation method of ink, comprising: measure each group according to component contained by the ink and each component content Point, the first epoxy resin, the second epoxy resin, epoxy monomer and auxiliary agent are carried out after mixing, solidification to be added in dispersion Slurry is ground to certain fineness by agent and inorganic filling material, and deaeration processing forms the ink.
Further, after curing agent and inorganic filling material being added in dispersion, temperature is controlled at 50 DEG C hereinafter, high speed point After dissipating 15-20min, at least 3 times are ground to certain fineness through three rollers, fineness is less than or equal to 15 μm, and it is de- to transfer to vacuum stirring The deaeration of bubble machine has finally dispensed material and has carried out evacuation and centrifugal degassing to get ink is arrived until material bubble-free is emerged.
The application of the ink in the circuit board.
A kind of circuit board method for plugging, in the micropore of circuit board formed conductive material after, using the ink into The processing of row consent.
Further, using preceding as 10 DEG C or less preservations, thaw at RT 12h or more when use passes through for the ink The mode filling perforation of vertical vacuum or horizontal press printing, through hot baking-curing after consent, then by polishing, i.e. consent work Skill is completed.
Compared with prior art, the beneficial effects of the present invention are:
1) heat resistance after rabbet ink solidifies, T are improvedg200 DEG C of >, guarantee when heated with 5G high frequency substrate shape Become characteristic to match.
2) thermal expansion coefficient of rabbet ink is reduced, (T > Tg)α280 μm of </(m. DEG C), guarantees in hot conditions Under, the expanded by heating rate under rabbet ink unit temperature after solidification matches with PCB substrate, close as far as possible or consistent.
3) rabbet ink is 100% solid content, and VOC free discharges when use, relatively environmentally friendly.
Detailed description of the invention
Fig. 1 is the process flow chart of the preparation method of ink of the embodiment of the present invention.
Specific embodiment
In order to make the technical problem to be solved in the present invention, technical solution and beneficial effect are more clearly understood, below in conjunction with Embodiment, the present invention will be described in further detail.It should be appreciated that specific embodiment described herein is used only for explaining The present invention is not intended to limit the present invention.
A kind of ink, including following component: the first epoxy resin, the second epoxy resin, epoxy monomer, curing agent, inorganic Packing material and auxiliary agent.First epoxy resin is the epoxy resin containing multiple heat-resisting cyclic structures；Described second The viscosity of epoxy resin is 25 DEG C and is lower than 10000mPa.s.
In the particular embodiment, the ink includes the first epoxy resin of 10-30wt%, the second ring of 10-20wt% Oxygen resin, 0-5wt% monomer, 2-10wt% curing agent, 40-60wt% inorganic filling material, 0-5wt% auxiliary agent.It is wherein described The mass percent of first epoxy resin can be specially 10%, 20%, 30%, etc.；The quality of second epoxy resin Percentage can be specially 10%, 15%, 20% etc.；The mass percent of the epoxy monomer can be specially 1%, 2%, 3%, 4%, 5% etc.；The mass percent of the curing agent can be specially 2%, 5%, 8%, 10% etc.；Described is inorganic The mass percent of packing material can be specially 40%, 45%, 50%, 60% etc.；The mass percent of the auxiliary agent can Think 1%, 2%, 3%, 4%, 5%.
In the particular embodiment, first epoxy resin is dicyclopentadiene phenol type epoxy resin, biphenyl benzene Phenol-type epoxy resin, bisphenol A-type novolac epoxy resin, novolac epoxy resin, condensed ring naphthalene type epoxy resin, 4,4 '-methylene two (N, N '-diglycidylaniline), tetraphenyl glycidyl ether ethane, trisphenyl glycidyl ether methane, three shrinks are sweet The double amino methyl hexamethylenes of oil base isocyanuric acid ester, four glycidyl group diaminodiphenyl-methane, four glycidyl group -1,3- At least one of alkane, modifying epoxy resin by organosilicon, polyamide modified epoxy resin, benzoxazine modified epoxy.
In the particular embodiment, second epoxy resin is bisphenol A epoxide resin, bisphenol F epoxy resin, hydrogenation Bisphenol A epoxide resin, 4,5- 7-oxa-bicyclo[4.1.0-1,2- dimethyl 2-glycidyl ester, 2- (3,4- epoxycyclohexyl)-5,5- spiral shell Bis- (the 3,4- 7-oxa-bicyclo[4.1.0 formic acid) esters of (3,4- epoxycyclohexyl) -1,3- dioxane homopolymer, 1,4 cyclohexane dimethanol, At least one of bis- ((3,4- epoxycyclohexyl) methyl) adipate esters, triglycidyl group para-aminophenol.
In the particular embodiment, the epoxy monomer is to shrink to tert-butyl-phenyl glycidol ether, o-tolyl Glycerin ether, phenyl glycidyl ether, ethylene glycol diglycidylether, diethylene glycol and glycidol ether, triethylene glycol two shrink Glycerin ether, dipropylene glycol glycidol ether, 1,4- butanediol diglycidyl ether, 1,4 cyclohexane dimethanol 2-glycidyl Ether, bis- hexanediol diglycidyl ether of 1,2-, 1,6 hexanediol diglycidylether, neopentylglycol diglycidyl ether, isophthalic Diphenol diglycidyl ether, glycerol polyglycidyl ether, trihydroxymethylpropanyltri diglycidyl ether, castor oil three-glycidyl Ether, four glycidol ether of pentaerythrite, sorbierite glycidol ether, azacyclo- polyglycidyl ether, tertiary carbonic acid glycidyl ester, Dimeric dibasic acid and ethylene oxidic ester, hexahydrophthalic acid 2-glycidyl ester, methyl tetrahydrophthalic acid 2-glycidyl ester, At least one of adipic acid 2-glycidyl ester.
In the particular embodiment, the curing agent includes at least one of imidazoles, anhydride, amine；Solidification Agent has good physical and mechanical property under suitable baking temperature after solidification.
In the particular embodiment, the amine curing agent is at least one of DDS, DDM.
In the particular embodiment, the acid anhydride type curing agent be phthalic anhydride, BTDA, DSDA, THPA, NA, MCTC。
In the particular embodiment, the imidazole curing agent is PN-23, PN-31, PN-40, PN-50, PN-H, 2- Undecyl imidazole, 2- heptadecyl imidazole, 1- cyanoethyl -2-ethyl-4-methylimidazole, 1- cyanoethyl -2- undecyl miaow Azoles trimellitic acid salt, 1-cyanoethyl-2-phenylimidazole trimellitic acid salt, 2-methylimidazole isocyanurate, 2- phenyl Imidazoles isocyanurate, 2,4- diamino -6- (2-methylimidazole -1- ethyl)-S- triazine, 2,4- diamino -6- (2- second Base -4-methylimidazole -1- ethyl)-S- triazine, 2,4- diamino -6- (2- undecyl imidazole -1- ethyl)-S- triazine, 2- benzene Base -4,5- hydroxymethyl-imidazole, 2 phenyl 4 methyl 5 hydroxy methylimidazole, bis- (cyanogen ethoxy of 1- cyanoethyl -2- phenyl -4,5- Methylene) imidazoles, -3 benzylimidazolium chloride of 1- dodecyl -2- methyl, 1,3- dibenzyl -2-methylimidazole chloride, three Boron fluoride-amine complex (BF3-MEA、BF3-BZA、BF3- DMA), aromatic diazonium salt, diaryl iodonium salt, triaryl matte Salt, metallocene based compound.
In the particular embodiment, the inorganic filling material is barium sulfate, talcum powder, crystalline silica, melting Silica, amorphous silica, nano silica, magnesium carbonate, calcium carbonate, nanometer calcium carbonate, aluminium oxide, hydroxide At least one of aluminium, silicon powder.
In the particular embodiment, the auxiliary agent includes wetting dispersing agent and deaeration agent.The wetting dispersing agent choosing From BYK-110, BYK-111 of German Bi Ke chemical production, Disponer 904, the Disponer of the production of this special chemical of hamming The 2400SC of 904S, Lu Borun production, 20000.
In the particular embodiment, the defoaming agent be selected from Germany's Bi Ke chemical production BYK-A550, BYK-A515, BYK-A506, H10, FS80 of DOW CORNING production, Foamex 1495, the Foamex 842 of Digao production.The wetting dispersing agent Energy each component is uniformly dispersed, and the deaeration agent is conducive to that bubble is discharged in slurry.The auxiliary agent according to the type of auxiliary agent, It is excellent stability that the ink dispersion, which can be improved, and improves the solidification quality of the ink, improves stabilization Property.
A kind of preparation method of ink,
Step S01: each component is measured according to component contained by ink and each component content；
Step S02: the first epoxy resin, the second epoxy resin, epoxy monomer and auxiliary agent are carried out uniformly mixed；
Step S03: curing agent and inorganic filling material is added in dispersion, slurry is ground to certain fineness, and deaeration Processing forms the ink.
Wherein, step S03 step is specially after curing agent and inorganic filling material is added in dispersion, to control temperature at 50 DEG C Hereinafter, after high speed dispersion 15-20min, grind at least 3 times through three rollers and arrive certain fineness to inorganic filling material, fineness less than etc. In 15 μm, transfer to be stirred under vacuum the deaeration of deaeration machine until material bubble-free is emerged, finally dispensed material and carry out from Heart deaeration to get arrive ink.
A kind of circuit board method for plugging, forms conductive material in the micropore of circuit board, later using the ink into The processing of row consent.The conductive material formed method can for plating, vapor deposition, deposition the methods of, conductive material can for silver, Copper, gold etc..The ink using preceding as 10 DEG C or less preservations, thaw at RT 12h or more when use, by vertical vacuum or The mode filling perforation of horizontal press printing, through hot baking-curing after consent, then by polishing, i.e. jack process completion.
Now by taking ink and preparation method as an example, the present invention is further described in detail.
Embodiment 1
A kind of ink is present embodiments provided, the ink includes following mass percent: 4,4 '-methylene two (N, N- diglycidylaniline) 20%, triglycidyl group para-aminophenol 20%, 1,4 cyclohexane dimethanol two shrink Glycerin ether 2%, DDS0.2%, 2-methylimidazole isocyanurate 2.8%, calcium carbonate 53.8%, BYK-110 1%, BYK- A550 0.2%.
Preparation method includes the following steps:
S11: by 4,4 '-methylene two (N, N- diglycidylaniline), triglycidyl group para-aminophenol, 1,4- Cyclohexanedimethanodiglycidyl diglycidyl ether, BYK-110, BYK-A550 are by uniform through dispersion machine high speed dispersion after ratio cooperation；
S12: is added DDS, 2-methylimidazole isocyanurate, calcium carbonate in dispersion, control temperature at 50 DEG C hereinafter, After high speed dispersion 15-20min, ground at least 3 times to 15 μm of certain fineness through three rollers；
S13: being stirred under vacuum the deaeration of deaeration machine until material bubble-free is emerged, and has finally dispensed material and be centrifuged de- Bubble, as ink.
Embodiment 2
A kind of ink is present embodiments provided, the ink includes following mass percent: 4,4 '-methylene two (N, N- diglycidylaniline) 10%, four glycidyl group -1,3- double aminomethyl cyclohexanes 10%, triglycidyl group Para-aminophenol 20.3%, to tert-butyl-phenyl glycidol ether 1%, trihydroxymethylpropanyltri diglycidyl ether 1.5%, DDS 0.2%, 2-methylimidazole isocyanurate 2.8%, calcium carbonate 53%, BYK-110 1%, BYK-A550 0.2%.
Preparation method of the preparation method referring to embodiment 1.
Embodiment 3
A kind of ink is present embodiments provided, the ink includes following mass percent: 4,4 '-methylene two (N, N- diglycidylaniline) 18%, triglycidyl group para-aminophenol 20%, 1,4 cyclohexane dimethanol two shrink Glycerin ether 2%, 2-methylimidazole isocyanurate 2.6%, barium sulfate 46.2%, talcum powder 10%, BYK-110 1%, BYK-A550 0.2%.
Preparation method of the preparation method referring to embodiment 1.
Embodiment 4
A kind of ink is present embodiments provided, the ink includes following mass percent: triphenyl glycidol Ether methane 10%, triglycidyl group para-aminophenol 20%, bisphenol A epoxide resin 5%, trimethylolpropane tris glycidol Ether 2%, 2-methylimidazole isocyanurate 2.6%, fused silica 24.2%, calcium carbonate 35%, BYK-110 1%, BYK-A550 0.2%.
Preparation method of the preparation method referring to embodiment 1.
Embodiment 5
A kind of ink is present embodiments provided, the ink includes following mass percent: 4,4 '-methylene two (N, N '-diglycidylaniline) 20%, triglycidyl group para-aminophenol 20%, 1,4 cyclohexane dimethanol two shrink Glycerin ether 2%, DDS 0.2%, 2,4- diamino -6- (2- undecyl imidazole -1- ethyl)-S- triazine 2.6%, calcium carbonate 54.2%, BYK-110 0.8%, BYK-A5500.2%.
Preparation method of the preparation method referring to embodiment 1.
Embodiment 6
A kind of ink is present embodiments provided, the ink includes following mass percent: 4,4 '-methylene two (N, N '-diglycidylaniline) 10%, four glycidyl group -1,3- double aminomethyl cyclohexanes 10%, three-glycidyl Base para-aminophenol 20%, to tert-butyl-phenyl glycidol ether 1%, trihydroxymethylpropanyltri diglycidyl ether 1.5%, DDS 0.2%, 2,4- diamino -6- (2- undecyl imidazole -1- ethyl)-S- triazine 2.5%, calcium carbonate 53.6%, BYK-110 1%, BYK-A550 0.2%.
Preparation method of the preparation method referring to embodiment 1.
Embodiment 7
A kind of ink is present embodiments provided, the ink includes following mass percent: 4,4 '-methylene two (N, N '-diglycidylaniline) 18%, triglycidyl group para-aminophenol 20%, 1,4 cyclohexane dimethanol two shrink Glycerin ether 2%, 2,4- diamino -6- (2- undecyl imidazole -1- ethyl)-S- triazine 2.5%, fused silica 0.5%, Barium sulfate 45.8%, talcum powder 10%, BYK-110 1%, BYK-A5500.2%.
Preparation method of the preparation method referring to embodiment 1.
Embodiment 8
A kind of ink is present embodiments provided, the ink includes following mass percent: triphenyl glycidol Ether methane 10%, triglycidyl group para-aminophenol 20%, bisphenol A epoxide resin 5%, trimethylolpropane tris glycidol Ether 2%, 2,4- diamino -6- (2- undecyl imidazole -1- ethyl)-S- triazine 2.5%, fused silica 24.3%, carbon Sour calcium 35%, BYK-110 1%, BYK-A550 0.2%.
Preparation method of the preparation method referring to embodiment 1.
The ink test as follows:
The ink of embodiment 1- embodiment 8 and common plug socket resin are filled in high frequency plate hole by printing machine, guaranteed Under conditions of consent is full, printing efficiency is the index for reflecting ink printing performance, i.e. printing rate.
The ink of embodiment 1- embodiment 8 and ordinary resin are passed through into thermosetting after printing machine consent, solidified bars with high frequency plate Part are as follows: when plate thickness≤1.0mm, 150 DEG C of * 60min；When 1.0mm < plate thickness≤2.0mm, 110 DEG C of * 30min+150 DEG C * 60min； When plate thickness > 2.0mm, 90 DEG C of * 30min+110 DEG C * 30min+150 DEG C * 60min.After solidification through same milling apparatus under the conditions of Number needed for polishing and (eliminating the rabbet ink of excess surface) differentiates the complexity of grinding.
Using apply the ink of 1- embodiment 8 and common plug socket resin consent solidification polish after, with amplification sem observation surface It is recessed with the presence or absence of cavity；Whether take has bubble, crackle in sections observation hole.
Using, through heavy copper plating, coupongs cross 6 Reflow Solderings after the ink and ordinary resin consent of embodiment 1- embodiment 8 With 6 thermal shocks (being immersed into 10s in 288 DEG C of slicker solder furnace, be repeated in after cooling), then slice, microscope are taken from print Structure change in peep hole, whether there is or not the height of drawing crack, jack-up or jack-up to judge.
After the ink of embodiment 1- embodiment 8 and the solidification of common plug socket resin, the square sample block of 5*5*5mm is made, And third party testing agency is sent to survey TgWith CTE (T < Tg), CTE (T > Tg)。
Test result is shown in Table 1.
Table 1
Seen from table 1, the ink of 1-8 of the embodiment of the present invention is compared with ordinary resin, and Reflow Soldering and thermal shock are more excellent, consent It is heat-resist after ink solidification, Tg200 DEG C of >, ensure that rabbet ink when heated with 5G high frequency substrate deformation behavior phase Matching.The thermal expansion coefficient of rabbet ink is low, CTE (T < Tg)α160 μm of </(m. DEG C), CTE (T > Tg)α280 μm/(m. of < DEG C), guarantee that the expanded by heating rate under rabbet ink unit temperature after solidification matches with PCB substrate under the high temperature conditions, to the greatest extent Amount is close or consistent.
Each technical characteristic of embodiment described above can be combined arbitrarily, for simplicity of description, not to above-mentioned reality It applies all possible combination of each technical characteristic in example to be all described, as long as however, the combination of these technical characteristics is not deposited In contradiction, all should be considered as described in this specification.
The embodiments described above only express several embodiments of the present invention, and the description thereof is more specific and detailed, but simultaneously It cannot therefore be construed as limiting the scope of the patent.It should be pointed out that coming for those of ordinary skill in the art It says, without departing from the inventive concept of the premise, various modifications and improvements can be made, these belong to protection of the invention Range.Therefore, the scope of protection of the patent of the invention shall be subject to the appended claims.

Claims (10)

1. a kind of ink, it is characterised in that: the ink includes following component: the first epoxy resin, the second epoxy resin, ring Oxygen monomer, curing agent, inorganic filling material and auxiliary agent.
2. ink according to claim 1, it is characterised in that: first epoxy resin is to contain multiple heat-resisting ring-types The epoxy resin of structure；Viscosity with second epoxy resin is 25 DEG C and is lower than 10000mPa.s.
3. ink according to claim 1, it is characterised in that: the ink includes:
The first epoxy resin of 10-30wt%, the second epoxy resin of 10-20wt%, 0-5wt% epoxy monomer, 2-10wt% solidification Agent, 40-60wt% inorganic filling material, 0-5wt% auxiliary agent.
4. ink according to claim 1, it is characterised in that: first epoxy resin is dicyclopentadiene phenol type Epoxy resin, biphenyl phenol type epoxy resin, bisphenol A-type novolac epoxy resin, novolac epoxy resin, condensed ring naphthalene type asphalt mixtures modified by epoxy resin Rouge, 4,4 '-methylene two (N, N '-diglycidylaniline), tetraphenyl glycidyl ether ethane, triphenyl glycidol Ether methane, triglycidyl group isocyanuric acid ester, four glycidyl group diaminodiphenyl-methane, four glycidyl group -1, The bis- aminomethyl cyclohexanes of 3-, modifying epoxy resin by organosilicon, polyamide modified epoxy resin, in benzoxazine modified epoxy It is at least one；And/or
Second epoxy resin is bisphenol A epoxide resin, bisphenol F epoxy resin, hydrogenated bisphenol A epoxy resin, 4,5- ring Oxygen hexamethylene -1,2- dimethyl 2-glycidyl ester, 2- (3,4- epoxycyclohexyl) -5,5- spiral shell (3,4- epoxycyclohexyl) -1, Bis- (the 3,4- 7-oxa-bicyclo[4.1.0 formic acid) esters of 3- dioxane homopolymer, 1,4 cyclohexane dimethanol, bis- ((3,4- epoxycyclohexyls) Methyl) adipate ester, at least one of triglycidyl group para-aminophenol；And/or
The epoxy monomer be to tert-butyl-phenyl glycidol ether, o-tolyl glycidol ether, phenyl glycidyl ether, Ethylene glycol diglycidylether, diethylene glycol and glycidol ether, Triethylene Glycol Diglycidyl Ether, dipropylene glycol glycidol Ether, 1,4- butanediol diglycidyl ether, 1,4 cyclohexane dimethanol diglycidyl ether, bis- hexylene glycol 2-glycidyl of 1,2- Ether, 1,6 hexanediol diglycidylether, neopentylglycol diglycidyl ether, resorcinolformaldehyde resin, glycerol contract more Water glycerin ether, trihydroxymethylpropanyltri diglycidyl ether, castor oil triglycidyl ether, four glycidol ether of pentaerythrite, mountain Pears alcohol glycidol ether, azacyclo- polyglycidyl ether, tertiary carbonic acid glycidyl ester, dimeric dibasic acid and ethylene oxidic ester, hexahydro are adjacent Phthalic acid 2-glycidyl ester, methyl tetrahydrophthalic acid 2-glycidyl ester, in adipic acid 2-glycidyl ester extremely Few one kind；And/or
The curing agent includes at least one of imidazoles, anhydride, amine；And/or
The inorganic filling material is barium sulfate, talcum powder, crystalline silica, fused silica, unformed titanium dioxide At least one of silicon, nano silica, magnesium carbonate, calcium carbonate, nanometer calcium carbonate, aluminium oxide, aluminium hydroxide, silicon powder； And/or
The auxiliary agent includes wetting dispersing agent and/or deaeration agent.
5. ink according to claim 4, it is characterised in that: the amine curing agent is at least one in DDS, DDM Kind；And/or
The acid anhydride type curing agent is phthalic anhydride, BTDA, DSDA, THPA, NA, MCTC；And/or
The imidazole curing agent is PN-23, PN-31, PN-40, PN-50, PN-H, 2- undecyl imidazole, 2- heptadecane Base imidazoles, 1- cyanoethyl -2-ethyl-4-methylimidazole, 1- cyanoethyl -2- undecyl imidazole trimellitic acid salt, 1- cyanogen second Base -2- phenylimidazole trimellitic acid salt, 2-methylimidazole isocyanurate, 2- phenylimidazole isocyanurate, 2,4- Diamino -6- (2-methylimidazole -1- ethyl)-S- triazine, 2,4- diamino -6- (2-ethyl-4-methylimidazole -1- ethyl) - S- triazine, 2,4- diamino -6- (2- undecyl imidazole -1- ethyl)-S- triazine, 2 pheny1 4,5 dihydroxymethyl imidazole, 2- Phenyl -4- methyl -5- hydroxy methylimidazole, 1- cyanoethyl -2- phenyl -4,5- bis- (cyanogen ethoxy methylene) imidazoles, 1- dodecyl - - 3 benzylimidazolium chloride of 2- methyl, 1,3- dibenzyl -2-methylimidazole chloride, boron trifluoride-amine complex, aromatic series weight Nitrogen salt, diaryl iodonium salt, triarylsulfonium salt, metallocene based compound；And/or
The wetting dispersing agent is selected from BYK-110, BYK-111 of Germany's Bi Ke chemical production, the production of this special chemical of hamming Disponer904, Disponer904S, Lu Borun production 2400SC, 20000；And/or
The defoaming agent is selected from BYK-A550, BYK-A515, BYK-A506 of Germany's Bi Ke chemical production, DOW CORNING production H10, FS80, Foamex1495, Foamex842 of Digao production.
6. ink according to any one of claims 1-5, it is characterised in that: the ink is for circuit board consent work Skill.
7. a kind of preparation method of ink characterized by comprising
Each component is measured according to component contained by ink described in any one of claims 1-6 and each component content；
First epoxy resin, the second epoxy resin, epoxy monomer and auxiliary agent are carried out after mixing, solidification to be added in dispersion Agent and inorganic filling material, grind and deaeration processing forms the ink.
8. the application of ink described in any one of claims 1-6 in the circuit board.
9. a kind of circuit board method for plugging, characterized by comprising: form conductive material in the micropore of circuit board, use later Ink described in any one of claims 1-6 carries out consent processing.
10. a kind of circuit board method for plugging according to claim 9, it is characterised in that: carried out using the ink Consent processing specifically by vertical vacuum or the mode of horizontal press printing to circuit board filling perforation, it is solid through heat baking after consent Change, then by polishing.
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Cited By (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN110831336A (en) * 2019-11-11 2020-02-21 珠海崇达电路技术有限公司 Resin hole plugging method for large-aperture back drilling hole
CN112778822A (en) * 2021-01-06 2021-05-11 厦门三德信科技股份有限公司 Cover plate ink based on cationic photoinitiator and preparation method thereof
CN113194614A (en) * 2021-05-06 2021-07-30 惠州市聚诚盛电子科技有限公司 Circuit board processing method
CN114133784A (en) * 2022-01-05 2022-03-04 浩力森化学科技（江苏）有限公司 Cationic electrodeposition coating composition
CN114133786A (en) * 2022-01-19 2022-03-04 江苏可信电子材料有限公司 Crack-resistant solder-resist hole plugging ink and preparation method thereof
CN116313226A (en) * 2023-05-12 2023-06-23 浙江飞宜光电能源科技有限公司 Low-temperature curing silver paste and preparation method thereof

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CN102732096A (en) * 2012-07-10 2012-10-17 依利安达电子（昆山）有限公司 Halogen-free flame-retardant solvent-free double-curing ink composition and preparation method thereof

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CN102732096A (en) * 2012-07-10 2012-10-17 依利安达电子（昆山）有限公司 Halogen-free flame-retardant solvent-free double-curing ink composition and preparation method thereof

Cited By (8)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN110831336A (en) * 2019-11-11 2020-02-21 珠海崇达电路技术有限公司 Resin hole plugging method for large-aperture back drilling hole
CN110831336B (en) * 2019-11-11 2020-10-27 珠海崇达电路技术有限公司 Resin hole plugging method for large-aperture back drilling hole
CN112778822A (en) * 2021-01-06 2021-05-11 厦门三德信科技股份有限公司 Cover plate ink based on cationic photoinitiator and preparation method thereof
CN112778822B (en) * 2021-01-06 2023-03-10 厦门三德信科技股份有限公司 Cover plate ink based on cationic photoinitiator and preparation method thereof
CN113194614A (en) * 2021-05-06 2021-07-30 惠州市聚诚盛电子科技有限公司 Circuit board processing method
CN114133784A (en) * 2022-01-05 2022-03-04 浩力森化学科技（江苏）有限公司 Cationic electrodeposition coating composition
CN114133786A (en) * 2022-01-19 2022-03-04 江苏可信电子材料有限公司 Crack-resistant solder-resist hole plugging ink and preparation method thereof
CN116313226A (en) * 2023-05-12 2023-06-23 浙江飞宜光电能源科技有限公司 Low-temperature curing silver paste and preparation method thereof

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