CN109957286B - Printing ink and preparation method and application thereof - Google Patents
Printing ink and preparation method and application thereof Download PDFInfo
- Publication number
- CN109957286B CN109957286B CN201910223928.9A CN201910223928A CN109957286B CN 109957286 B CN109957286 B CN 109957286B CN 201910223928 A CN201910223928 A CN 201910223928A CN 109957286 B CN109957286 B CN 109957286B
- Authority
- CN
- China
- Prior art keywords
- ink
- epoxy resin
- curing agent
- circuit board
- byk
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Active
Links
Images
Classifications
-
- 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
Landscapes
- 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 ink and a preparation method and application thereof, wherein the ink comprises the following components: the epoxy resin curing agent comprises a first epoxy resin, a second epoxy resin, an epoxy monomer, a curing agent, an inorganic filling material and an auxiliary agent. The preparation method comprises the steps of measuring the components, uniformly mixing the first epoxy resin, the second epoxy resin, the epoxy monomer and the auxiliary agent, adding the curing agent and the inorganic filling material while dispersing, grinding and defoaming to form the ink. The ink of the invention has higher heat resistance, TgMore than 200 ℃, ensures the deformation characteristic matching with a 5G high-frequency substrate when being heated, and has low thermal expansion coefficient (T is more than T)g)α2Less than 80 mu m/(m DEG C), and the thermal expansion rate of the cured hole plugging ink at unit temperature is ensured to be matched with the PCB substrate under the high-temperature condition.
Description
Technical Field
The invention belongs to the technical field of electronic materials, and particularly relates to ink as well as a preparation method and application thereof.
Background
As electronic products are becoming multifunctional and miniaturized, circuit boards such as Printed Circuit Boards (PCBs) are also being multi-layered and highly densified. This puts new demands on the material of the printed circuit board, requires the circuit board material to have higher thermal conductivity and thermal stability, and also puts higher demands on the hole plugging process and the hole plugging material of the printed circuit board.
The printed circuit board mainly comprises lines, patterns, dielectric layers, via holes, solder resist ink, silk screen printing, surface treatment layers and the like, wherein the hole plugging resin is used as an important hole burying material and is mainly used as a high density interconnect printed circuit board (HDI). The HDI board uses conventional multiply wood as the core, and successive layer stack insulating layer and circuit layer to adopt the technique of punching to punch and switch on the lamination, make monoblock printed circuit board form with bury the interlayer connection of blind hole as the main mode of switching on, can produce multilayer, stable, thinner and higher density printed circuit board that conventional multiply wood can't reach. The buried hole technology is introduced, and the used buried hole material is just plugging resin.
The hole plugging resin is used as one of raw materials for manufacturing the HDI board, and along with the continuous expansion of the market demand of the HDI boardThe amount of the additive is also increased in an explosive manner. With the advent of the 5G era, communication electronics have made higher demands on high-speed high-frequency characteristics of printed circuits, in which HDI high-frequency high-speed boards will tend to have a higher T than ordinary epoxy base materialsgA coefficient of thermal expansion (T > T) of > 200 ℃ and lowerg）α2Less than 80 μm/(m DEG C), the hole plugging material used in the processing process must be matched with the hole plugging material to meet the requirement. Ordinary hole plugging resin TgAlpha (T > Tg) of thermal expansion coefficient of 140-180 DEG C2The best Japanese mountain product can only achieve alpha at the lowest level when the temperature is more than 120 mu m/(m DEG C)2About 85 μm/(m DEG C), and cannot meet the requirements of high speed and high frequency.
Disclosure of Invention
Based on the above, the invention provides the ink with high glass transition temperature and low expansion coefficient, so that the hole plugging requirement of the high-speed high-frequency characteristic of the HDI plate is met.
An ink comprising the following components: the epoxy resin curing agent comprises a first epoxy resin, a second epoxy resin, an epoxy monomer, a curing agent, an inorganic filling material and an auxiliary agent.
Furthermore, the first epoxy resin is an epoxy resin containing a plurality of heat-resistant annular structures; the viscosity of the second epoxy resin is less than 10000mPa.s at 25 ℃.
The epoxy resin is a high-molecular matrix resin of the ink, has excellent physical property, electrical insulation property and bonding property, contains an epoxy group with strong reaction capability, can effectively improve the vitrification temperature of the ink under the condition of ensuring the printing property by matching the heat-resistant epoxy resin with the low-viscosity epoxy resin, simultaneously ensures the relatively low expansion coefficient of the ink, and reacts with the curing agent to form a highly-crosslinked network structure, thereby enhancing the thermal stability and improving the rigidity.
Furthermore, the ink comprises 10-30wt% of first epoxy resin, 10-20wt% of second epoxy resin, 0-5wt% of epoxy monomer, 2-10wt% of curing agent, 40-60wt% of inorganic filling material and 0-5wt% of auxiliary agent.
Further, the first epoxy resin is at least one of dicyclopentadiene phenol type epoxy resin, biphenyl phenol type epoxy resin, bisphenol A type novolac epoxy resin, condensed ring naphthalene type epoxy resin, 4 '-methylene bis (N, N' -diglycidyl aniline), tetraphenyl glycidyl ether ethane, triphenyl glycidyl ether methane, triglycidyl isocyanurate, tetraglycidyl diamino diphenylmethane, tetraglycidyl-1, 3-bisaminomethylcyclohexane, organosilicon modified epoxy resin, polyamide modified epoxy resin and benzoxazine modified epoxy.
Further, the second epoxy resin is at least one of bisphenol a epoxy resin, bisphenol F epoxy resin, hydrogenated bisphenol a epoxy resin, 4, 5-epoxycyclohexane-1, 2-dimethyldiglycidyl ester, 2- (3, 4-epoxycyclohexyl) -5, 5-spiro (3, 4-epoxycyclohexyl) -1, 3-dioxane homopolymer, 1, 4-cyclohexanedimethanol bis (3, 4-epoxycyclohexane carboxylate), bis ((3, 4-epoxycyclohexyl) methyl) adipate, and triglycidyl p-aminophenol.
Further, the epoxy monomer is p-tert-butylphenyl glycidyl ether, o-tolyl glycidyl ether, phenyl glycidyl ether, ethylene glycol diglycidyl ether, diethylene glycol diglycidyl ether, triethylene glycol diglycidyl ether, dipropylene glycol glycidyl ether, 1, 4-butanediol diglycidyl ether, 1, 4-cyclohexanedimethanol diglycidyl ether, 1, 2-dihexanediol diglycidyl ether, 1, 6-hexanediol diglycidyl ether, neopentyl glycol diglycidyl ether, resorcinol diglycidyl ether, glycerol polyglycidyl ether, trimethylolpropane triglycidyl ether, castor oil triglycidyl ether, pentaerythritol tetraglycidyl ether, sorbitol glycidyl ether, azacyclic polyglycidyl ether, tertiary carbonic acid glycidyl ester, dimer acid diglycidyl ester, hexahydrophthalic acid diglycidyl ester, and the like, At least one of diglycidyl methyltetrahydrophthalate and diglycidyl adipate.
Further, the curing agent comprises at least one of imidazoles, acid anhydrides and amines; the curing agent has good physical and mechanical properties after being cured at a proper baking temperature.
Further, the amine curing agent is at least one of DDS and DDM.
Further, the anhydride 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-undecylimidazole, 2-heptadecylimidazole, 1-cyanoethyl-2-ethyl-4-methylimidazole, 1-cyanoethyl-2-undecylimidazole trimellitate, 1-cyanoethyl-2-phenylimidazole trimellitate, 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-undecylimidazole-1-ethyl) -S-triazine, 2-phenyl-4, 5-dimethyloimidazole, 2-phenyl-4-methyl-5-hydroxymethylimidazole, 1-cyanoethyl-2-phenyl-4, 5-bis (cyanoethoxymethylene) imidazole, 1-dodecyl-2-methyl-3-benzylimidazole chloride, 1, 3-dibenzyl-2-methylimidazolium chloride, boron trifluoride-amine complex (BF)3-MEA、BF3-BZA、BF3DMA), aromatic diazonium salts, diaryliodonium salts, triarylsulfonium salts, and metallocene compounds.
Further, the inorganic filling material is at least one of barium sulfate, talcum powder, crystalline silica, fused silica, amorphous silica, nano silica, magnesium carbonate, calcium carbonate, nano calcium carbonate, alumina, aluminum hydroxide and silicon micropowder.
Further, the auxiliary agent comprises a wetting dispersant and/or a defoaming agent. Further, the wetting dispersant is selected from BYK-110 and BYK-111 produced by Bik chemical of Germany, Disponer 904 and Disponer 904S produced by Haimines special chemical, 2400SC and 20000 produced by Luborun.
Further, the defoaming agent is selected from BYK-A550, BYK-A515 and BYK-A506 produced by German Bike chemical, H10 and FS80 produced by Dow Corning, Foamex 1495 and Foamex 842 produced by Digao. The wetting dispersant can uniformly disperse all components, and the defoaming agent is favorable for discharging bubbles in the slurry. The auxiliary agent can improve the excellent stability of the ink dispersion system according to the type of the auxiliary agent, improve the curing quality of the ink and improve the stability.
Furthermore, the ink is used for the hole plugging process of the circuit board.
A method of making an ink comprising: weighing the components according to the components contained in the ink and the content of the components, uniformly mixing the first epoxy resin, the second epoxy resin, the epoxy monomer and the auxiliary agent, adding the curing agent and the inorganic filling material while dispersing, grinding the slurry to a certain fineness, and defoaming to form the ink.
Further, after adding a curing agent and an inorganic filling material while dispersing, controlling the temperature below 50 ℃, dispersing at a high speed for 15-20min, grinding for at least 3 times by three rollers to a certain fineness, wherein the fineness is less than or equal to 15 microns, transferring to a vacuum stirring defoaming machine for defoaming until no bubbles emerge from the materials, and finally subpackaging the materials and carrying out centrifugal defoaming to obtain the ink.
The ink is applied to a circuit board.
A hole plugging method for a circuit board is characterized in that after a conductive material is formed in a micropore of the circuit board, hole plugging treatment is carried out by adopting the ink.
Further, the ink is stored at the temperature below 10 ℃ before use, is unfrozen at room temperature for more than 12 hours when used, is filled in holes by a vertical vacuum or horizontal printer printing mode, is cured by hot baking after hole plugging, and is ground and flattened, namely the hole plugging process is completed.
Compared with the prior art, the invention has the beneficial effects that:
1) the heat resistance of the hole plugging ink after curing is improved, and the T isgThe temperature is higher than 200 ℃, and the deformation characteristic of the material is matched with that of a 5G high-frequency base material when the material is heated.
2) The thermal expansion coefficient of the hole plugging ink is reduced, and the (T > T)g）α2Less than 80 mu m/(m DEG C) to ensure the cured product under the high temperature conditionThe thermal expansion rate of the hole plugging ink at unit temperature is matched with that of a PCB substrate and is as close to or consistent as possible.
3) The hole-plugging ink has 100 percent of solid content, does not discharge VOC when in use, and is relatively environment-friendly.
Drawings
FIG. 1 is a process flow diagram of a method of making an ink according to an embodiment of the invention.
Detailed Description
In order to make the technical problems, technical solutions and advantageous effects to be solved by the present invention more clearly apparent, the present invention is further described in detail below with reference to the following embodiments. It should be understood that the specific embodiments described herein are merely illustrative of the invention and are not intended to limit the invention.
An ink comprising the following components: the epoxy resin curing agent comprises a first epoxy resin, a second epoxy resin, an epoxy monomer, a curing agent, an inorganic filling material and an auxiliary agent. The first epoxy resin is an epoxy resin containing a plurality of heat-resistant annular structures; the viscosity of the second epoxy resin is less than 10000mPa.s at 25 ℃.
In a specific embodiment, the ink comprises 10-30wt% of first epoxy resin, 10-20wt% of second epoxy resin, 0-5wt% of monomer, 2-10wt% of curing agent, 40-60wt% of inorganic filling material and 0-5wt% of auxiliary agent. Wherein the mass percentage of the first epoxy resin can be specifically 10%, 20%, 30%, and the like; the mass percentage of the second epoxy resin can be specifically 10%, 15%, 20% and the like; the mass percentage of the epoxy monomer can be specifically 1%, 2%, 3%, 4%, 5% and the like; the mass percentage of the curing agent can be specifically 2%, 5%, 8%, 10% and the like; the inorganic filling material can be specifically 40%, 45%, 50%, 60% and the like in percentage by mass; the mass percentage of the auxiliary agent can be 1%, 2%, 3%, 4% and 5%.
In a specific embodiment, the first epoxy resin is at least one of dicyclopentadiene phenol type epoxy resin, biphenyl phenol type epoxy resin, bisphenol a type novolac epoxy resin, fused ring naphthalene type epoxy resin, 4 '-methylene bis (N, N' -diglycidyl aniline), tetraphenyl glycidyl ether ethane, triphenyl glycidyl ether methane, triglycidyl isocyanurate, tetraglycidyl diaminodiphenylmethane, tetraglycidyl-1, 3-bisaminomethylcyclohexane, silicone modified epoxy resin, polyamide modified epoxy resin, and benzoxazine modified epoxy.
In a specific embodiment, the second epoxy resin is at least one of bisphenol a epoxy resin, bisphenol F epoxy resin, hydrogenated bisphenol a epoxy resin, 4, 5-epoxycyclohexane-1, 2-dimethyldiglycidyl ester, 2- (3, 4-epoxycyclohexyl) -5, 5-spiro (3, 4-epoxycyclohexyl) -1, 3-dioxane homopolymer, 1, 4-cyclohexanedimethanol bis (3, 4-epoxycyclohexane carboxylate), bis ((3, 4-epoxycyclohexyl) methyl) adipate, and triglycidyl p-aminophenol.
In specific examples, the epoxy monomer is p-tert-butylphenyl glycidyl ether, o-tolyl glycidyl ether, phenyl glycidyl ether, ethylene glycol diglycidyl ether, diethylene glycol diglycidyl ether, triethylene glycol diglycidyl ether, dipropylene glycol glycidyl ether, 1, 4-butanediol diglycidyl ether, 1, 4-cyclohexanedimethanol diglycidyl ether, 1, 2-dihexanediol diglycidyl ether, 1, 6-hexanediol diglycidyl ether, neopentyl glycol diglycidyl ether, resorcinol diglycidyl ether, glycerol polyglycidyl ether, trimethylolpropane triglycidyl ether, castor oil triglycidyl ether, pentaerythritol tetraglycidyl ether, sorbitol glycidyl ether, azacyclo polyglycidyl ether, tertiary carbonic acid glycidyl ester, dimer acid glycidyl ester, di-poly-glycidyl ester, di-n-butyl-phenyl glycidyl ether, ethylene glycol diglycidyl ether, diethylene glycol diglycidyl ether, 1, 2-hexanediol diglycidyl ether, 1, 6-hexanediol diglycidyl ether, neopentyl glycol diglycidyl ether, resorcinol diglycidyl ether, glycerol polyglycidyl ether, trimethylolpropane triglycidyl ether, castor oil triglycidyl ether, pentaerythritol tetraglycidyl ether, sorbitol, glycidyl ether, and mixtures thereof, At least one of diglycidyl hexahydrophthalate, diglycidyl methyltetrahydrophthalate and diglycidyl adipate.
In a specific embodiment, the curing agent comprises at least one of imidazoles, acid anhydrides and amines; the curing agent has good physical and mechanical properties after being cured at a proper baking temperature.
In a specific embodiment, the amine curing agent is at least one of DDS and DDM.
In specific examples, the acid anhydride curing agent is phthalic anhydride, BTDA, DSDA, THPA, NA, MCTC.
In specific examples, the imidazole-based curing agent is selected from the group consisting of PN-23, PN-31, PN-40, PN-50, PN-H, 2-undecylimidazole, 2-heptadecylimidazole, 1-cyanoethyl-2-ethyl-4-methylimidazole, 1-cyanoethyl-2-undecylimidazolium trimellitate, 1-cyanoethyl-2-phenylimidazolium trimellitate, 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, and mixtures thereof, 2, 4-diamino-6- (2-undecylimidazole-1-ethyl) -S-triazine, 2-phenyl-4, 5-dimethyloimidazole, 2-phenyl-4-methyl-5-hydroxymethylimidazole, 1-cyanoethyl-2-phenyl-4, 5-bis (cyanoethoxymethylene) imidazole, 1-dodecyl-2-methyl-3-benzylimidazole chloride, 1, 3-dibenzyl-2-methylimidazolium chloride, boron trifluoride-amine complex (BF)3-MEA、BF3-BZA、BF3DMA), aromatic diazonium salts, diaryliodonium salts, triarylsulfonium salts, and metallocene compounds.
In a specific embodiment, the inorganic filler is at least one of barium sulfate, talc powder, crystalline silica, fused silica, amorphous silica, nano silica, magnesium carbonate, calcium carbonate, nano calcium carbonate, alumina, aluminum hydroxide, and silica micropowder.
In a specific embodiment, the auxiliary agent comprises a wetting dispersant and a defoaming agent. The wetting dispersant is selected from BYK-110 and BYK-111 produced by German Pico chemistry, Disponer 904 and Disponer 904S produced by Haimines special chemistry, 2400SC and 20000 produced by Luborun.
In a specific embodiment, the foam-breaker is selected from BYK-A550, BYK-A515, BYK-A506, Dow Corning H10, FS80, Digao Foamex 1495, Foamex 842. The wetting dispersant can uniformly disperse all components, and the defoaming agent is favorable for discharging bubbles in the slurry. The auxiliary agent can improve the excellent stability of the ink dispersion system according to the type of the auxiliary agent, improve the curing quality of the ink and improve the stability.
A method for preparing printing ink, which comprises the following steps,
step S01: weighing the components according to the components contained in the ink and the content of the components;
step S02: uniformly mixing the first epoxy resin, the second epoxy resin, the epoxy monomer and the auxiliary agent;
step S03: and adding a curing agent and an inorganic filling material while dispersing, grinding the slurry to a certain fineness, and defoaming to form the ink.
And S03, specifically, adding a curing agent and an inorganic filling material while dispersing, controlling the temperature below 50 ℃, dispersing at a high speed for 15-20min, carrying out three-roll grinding for at least 3 times until the inorganic filling material reaches a certain fineness and the fineness is less than or equal to 15 microns, transferring to a vacuum stirring defoaming machine for defoaming until no bubbles emerge from the material, and finally subpackaging the material and carrying out centrifugal defoaming to obtain the ink.
A hole plugging method for circuit board is to form conductive material in the micro-hole of the circuit board and then to use the ink to perform hole plugging treatment. The conductive material can be formed by electroplating, evaporation, deposition, etc., and the conductive material can be silver, copper, gold, etc. The ink is stored at the temperature below 10 ℃ before use, is thawed at room temperature for more than 12h when used, is filled in holes by a vertical vacuum or horizontal printer printing mode, is baked and cured by heating after hole plugging, and is ground and flattened, namely the hole plugging process is completed.
The present invention will now be described in further detail by taking the ink and the preparation method as examples.
Example 1
The embodiment provides an ink, which comprises the following components in percentage by mass: 20% of 4, 4' -methylenebis (N, N-diglycidylaniline), 20% of triglycidyl p-aminophenol, 2% of 1, 4-cyclohexanedimethanol diglycidyl ether, 0.2% of DDS, 2.8% of 2-methylimidazole isocyanurate, 53.8% of calcium carbonate, BYK-1101% and BYK-A5500.2%.
The preparation method comprises the following steps:
s11: 4, 4' -methylene bis (N, N-diglycidyl aniline), triglycidyl-p-aminophenol, 1, 4-cyclohexanedimethanol diglycidyl ether, BYK-110 and BYK-A550 are mixed according to the ratio and then are uniformly dispersed at high speed by a dispersion machine;
s12: adding DDS, 2-methylimidazole trimeric isocyanate and calcium carbonate while dispersing, controlling the temperature below 50 ℃, dispersing for 15-20min at high speed, and grinding for at least 3 times by three rollers until the fineness is 15 mu m;
s13: and (4) defoaming by using a vacuum stirring defoaming machine until no bubbles emerge from the materials, and finally subpackaging the materials and carrying out centrifugal defoaming to obtain the ink.
Example 2
The embodiment provides an ink, which comprises the following components in percentage by mass: 10% of 4, 4' -methylenebis (N, N-diglycidylaniline), 10% of tetraglycidyl-1, 3-bisaminomethylcyclohexane, 20.3% of triglycidyl p-aminophenol, 1% of p-tert-butylphenyl glycidyl ether, 1.5% of trimethylolpropane triglycidyl ether, 0.2% of DDS, 2.8% of 2-methylimidazole triisocyanate, 53% of calcium carbonate, BYK-1101% and BYK-A5500.2%.
The preparation method refers to the preparation method of example 1.
Example 3
The embodiment provides an ink, which comprises the following components in percentage by mass: 18% of 4, 4' -methylenebis (N, N-diglycidylaniline), 20% of triglycidyl p-aminophenol, 2% of 1, 4-cyclohexanedimethanol diglycidyl ether, 2.6% of 2-methylimidazole triisocyanate, 46.2% of barium sulfate, 10% of talcum powder, BYK-1101% and BYK-A5500.2%.
The preparation method refers to the preparation method of example 1.
Example 4
The embodiment provides an ink, which comprises the following components in percentage by mass: 10% of triphenyl glycidyl ether methane, 20% of triglycidyl p-aminophenol, 5% of bisphenol A epoxy resin, 2% of trimethylolpropane triglycidyl ether, 2.6% of 2-methylimidazole isocyanurate, 24.2% of fused silica, 35% of calcium carbonate, BYK-1101% and BYK-A5500.2%.
The preparation method refers to the preparation method of example 1.
Example 5
The embodiment provides an ink, which comprises the following components in percentage by mass: 20% of 4,4 '-methylenebis (N, N' -diglycidylaniline), 20% of triglycidyl-p-aminophenol, 2% of 1, 4-cyclohexanedimethanol diglycidyl ether, 0.2% of DDS, 2.6% of 2, 4-diamino-6- (2-undecylimidazole-1-ethyl) -S-triazine, 54.2% of calcium carbonate, BYK-1100.8% and BYK-A5500.2%.
The preparation method refers to the preparation method of example 1.
Example 6
The embodiment provides an ink, which comprises the following components in percentage by mass: 4,4 '-methylenebis (N, N' -diglycidylaniline) 10%, tetraglycidyl-1, 3-bisaminomethylcyclohexane 10%, triglycidyl-p-aminophenol 20%, p-tert-butylphenyl glycidyl ether 1%, trimethylolpropane triglycidyl ether 1.5%, DDS0.2%, 2, 4-diamino-6- (2-undecylimidazole-1-ethyl) -S-triazine 2.5%, calcium carbonate 53.6%, BYK-1101%, BYK-A5500.2%.
The preparation method refers to the preparation method of example 1.
Example 7
The embodiment provides an ink, which comprises the following components in percentage by mass: 18% of 4,4 '-methylenebis (N, N' -diglycidylaniline), 20% of triglycidyl-p-aminophenol, 2% of 1, 4-cyclohexanedimethanol diglycidyl ether, 2.5% of 2, 4-diamino-6- (2-undecylimidazole-1-ethyl) -S-triazine, 0.5% of fused silica, 45.8% of barium sulfate, 10% of talcum powder, BYK-1101% and BYK-A5500.2%.
The preparation method refers to the preparation method of example 1.
Example 8
The embodiment provides an ink, which comprises the following components in percentage by mass: 10% of triphenyl glycidyl ether methane, 20% of triglycidyl p-aminophenol, 5% of bisphenol A epoxy resin, 2% of trimethylolpropane triglycidyl ether, 2.5% of 2, 4-diamino-6- (2-undecylimidazole-1-ethyl) -S-triazine, 24.3% of fused silica, 35% of calcium carbonate, BYK-1101% and BYK-A5500.2%.
The preparation method refers to the preparation method of example 1.
The inks were tested as follows:
the inks and the common resins of examples 1 to 8 were inserted into the holes of the high-frequency plate by a printer, and the printing efficiency was an index reflecting the printing performance of the ink, i.e., the printing rate, under the condition that the filling of the holes was ensured.
The inks of examples 1 to 8 and the common resin were thermally set after plugging the holes by a printer using a high frequency plate under the following curing conditions: when the thickness of the plate is less than or equal to 1.0mm, the temperature is 150 ℃ for 60 min; when the thickness is more than 1.0mm and less than or equal to 2.0mm, the temperature is 110 ℃ for 30min and 150 ℃ for 60 min; when the thickness is larger than 2.0mm, 90 ℃ 30min +110 ℃ 30min +150 ℃ 60 min. After curing, the cured product is ground flat (redundant hole plugging ink on the surface is removed) by the same grinding equipment under the same condition for required times to judge the difficulty degree of grinding.
After the inks of examples 1 to 8 and common resin are adopted to fill the pores, cured and ground flat, a magnifier is used to observe whether the surface has hollow depressions; and taking the slices to observe whether bubbles and cracks exist in the holes.
The ink and the common resin of the embodiment 1 to the embodiment 8 are adopted to plug holes, then the copper deposition and electroplating are carried out, the sample piece is taken and passes through 6 times of reflow soldering and 6 times of thermal shock (the sample piece is immersed into a lead-tin furnace with 288 ℃ for 10s and is repeated after cooling), then the sample piece is taken, the structural change in the hole is observed by a microscope, and the judgment is carried out according to the existence of tension crack, jack-up or jack-up.
After curing the inks of examples 1-8 and the conventional plugging resin, square blocks of 5X 5mm were formed and sent to a third party testing facility for TgAnd CTE (T < T)g）、CTE（T＞Tg）。
The test results are shown in Table 1.
TABLE 1
As can be seen from Table 1, the inks of examples 1 to 8 of the present invention are superior to the conventional resins in reflow soldering and thermal shock, and the hole plugging ink has good heat resistance after curing, and TgThe temperature is higher than 200 ℃, so that the deformation characteristic of the hole plugging ink is matched with that of a 5G high-frequency substrate when the hole plugging ink is heated. The coefficient of thermal expansion of the taphole ink is low, with CTE (T < T)g）α1＜60μm/（m.℃）、CTE（T＞Tg）α2Less than 80 mu m/(m DEG C), the thermal expansion rate of the cured hole plugging ink at unit temperature is ensured to be matched with the PCB substrate under the high-temperature condition, and the thermal expansion rate is close to or consistent with the PCB substrate as much as possible.
The technical features of the embodiments described above may be arbitrarily combined, and for the sake of brevity, all possible combinations of the technical features in the embodiments described above are not described, but should be considered as being within the scope of the present specification as long as there is no contradiction between the combinations of the technical features.
The above-mentioned embodiments only express several embodiments of the present invention, and the description thereof is more specific and detailed, but not construed as limiting the scope of the invention. It should be noted that, for a person skilled in the art, several variations and modifications can be made without departing from the inventive concept, which falls within the scope of the present invention. Therefore, the protection scope of the present patent shall be subject to the appended claims.
Claims (8)
1. An ink, characterized by: the ink consists of the following components: the epoxy resin curing agent comprises a first epoxy resin, a second epoxy resin, an epoxy monomer, a curing agent, an inorganic filling material and an auxiliary agent;
the first epoxy resin is an epoxy resin containing a plurality of heat-resistant annular structures; and said second epoxy resin has a viscosity of less than 10000mPa.s at 25 ℃;
the ink consists of the following components: 10-30wt% of first epoxy resin, 10-20wt% of second epoxy resin, 0-5wt% of epoxy monomer, 2-10wt% of curing agent, 40-60wt% of inorganic filling material and 0-5wt% of auxiliary agent;
the first epoxy resin is at least one of 4,4 '-methylene bis (N, N' -diglycidyl aniline), triphenyl glycidyl ether methane and tetraglycidyl-1, 3-bisaminomethylcyclohexane;
the second epoxy resin is at least one of bisphenol A epoxy resin and triglycidyl p-aminophenol;
the epoxy monomer is at least one of p-tert-butyl phenyl glycidyl ether, 1, 4-cyclohexanedimethanol diglycidyl ether and trimethylolpropane triglycidyl ether.
2. The ink of claim 1, wherein: the curing agent is at least one of imidazoles, acid anhydrides and amines;
the inorganic filling material is at least one of barium sulfate, talcum powder, crystalline silica, fused silica, amorphous silica, nano-silica, magnesium carbonate, calcium carbonate, aluminum oxide, aluminum hydroxide and silicon micropowder;
the auxiliary agent is a wetting dispersant and/or a defoaming agent.
3. The ink of claim 2, wherein: the amine curing agent is at least one of DDS and DDM;
the anhydride curing agent is phthalic anhydride, BTDA, DSDA, THPA, NA and MCTC;
the imidazole curing agent is PN-23, PN-40, PN-H, 2-undecylimidazole, 2-heptadecylimidazole, 1-cyanoethyl-2-ethyl-4-methylimidazole, 1-cyanoethyl-2-undecylimidazole trimellitate, 1-cyanoethyl-2-phenylimidazole trimellitate, 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-methyl-4-methylimidazole-1-ethyl) -S-triazine, or a mixture thereof, 2, 4-diamino-6- (2-undecylimidazole-1-ethyl) -S-triazine, 2-phenyl-4, 5-dimethyloimidazole, 2-phenyl-4-methyl-5-hydroxymethylimidazole, 1-cyanoethyl-2-phenyl-4, 5-bis (cyanoethoxymethylene) imidazole, 1-dodecyl-2-methyl-3-benzylimidazole chloride, 1, 3-dibenzyl-2-methylimidazolium chloride;
the wetting dispersant is selected from BYK-110 and BYK-111 produced by German Pico chemistry, Disponer 904 and Disponer 904S produced by Haimines special chemistry, 2400SC and 20000 produced by Luborun;
the defoaming agent is selected from BYK-A550, BYK-A515 and BYK-A506 produced by German Pico chemistry, H10 and FS80 produced by Dow Corning, Foamex 1495 and Foamex 842 produced by Digao.
4. An ink according to any one of claims 1 to 3, characterized in that: the ink is used for a circuit board hole plugging process.
5. A method of making an ink, comprising:
the ink according to any one of claims 1 to 3 containing the components and the amounts of the components are measured;
and uniformly mixing the first epoxy resin, the second epoxy resin, the epoxy monomer and the auxiliary agent, adding the curing agent and the inorganic filling material while dispersing, grinding and defoaming to form the ink.
6. Use of an ink according to any one of claims 1 to 3 in a circuit board.
7. A method for plugging a hole in a circuit board, comprising: forming a conductive material in the micro via of the circuit board, followed by a via-filling process using the ink of any one of claims 1 to 3.
8. A method for plugging a circuit board according to claim 7, wherein: the hole plugging treatment by using the ink is specifically to fill holes in the circuit board by a vertical vacuum or horizontal printer printing mode, bake and solidify the circuit board after hole plugging, and then grind and grind the circuit board.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201910223928.9A CN109957286B (en) | 2019-03-22 | 2019-03-22 | Printing ink and preparation method and application thereof |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201910223928.9A CN109957286B (en) | 2019-03-22 | 2019-03-22 | Printing ink and preparation method and application thereof |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN109957286A CN109957286A (en) | 2019-07-02 |
| CN109957286B true CN109957286B (en) | 2021-11-23 |
Family
ID=67024814
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201910223928.9A Active CN109957286B (en) | 2019-03-22 | 2019-03-22 | Printing ink and preparation method and application thereof |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN109957286B (en) |
Families Citing this family (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| 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 |
| 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 |
| CN114133784B (en) * | 2022-01-05 | 2023-03-24 | 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 |
| CN116313226B (en) * | 2023-05-12 | 2023-08-04 | 浙江飞宜光电能源科技有限公司 | Low-temperature curing silver paste and preparation method thereof |
Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| 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 |
-
2019
- 2019-03-22 CN CN201910223928.9A patent/CN109957286B/en active Active
Patent Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| 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 |
Also Published As
| Publication number | Publication date |
|---|---|
| CN109957286A (en) | 2019-07-02 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN109957286B (en) | Printing ink and preparation method and application thereof | |
| CN100539803C (en) | Lead-free compatible high frequency copper clad laminate and preparation method thereof | |
| CN105415778B (en) | A kind of halogen-less high frequency high speed copper-clad plate and preparation method thereof | |
| JP5238342B2 (en) | Thermosetting resin composition for hole filling of printed wiring board and printed wiring board using the same | |
| JP2016166347A (en) | Resin composition, low dielectric constant resin sheet, prepreg, metal foil-clad laminate, high frequency circuit board and multilayer wire board | |
| CN114710886B (en) | Ink hole plugging method for high-heat-conductivity PCB | |
| KR101573170B1 (en) | Composite resin composition for plugging hole | |
| CN113165063B (en) | Magnetic paste | |
| CN111040378B (en) | Solvent-free resin composition and application thereof | |
| JP7198156B2 (en) | Halogen-free flame-retardant thermosetting resin composition, resin rubber liquid, prepreg for printed circuit, insulating board, metal clad laminate and printed wiring board | |
| CN110204862B (en) | Resin composition, prepreg, laminate, metal-clad laminate, and printed wiring board | |
| KR102653973B1 (en) | magnetic paste | |
| CN104908389A (en) | Prepreg, metal-clad laminate and printed circuit board | |
| CN112048155A (en) | Glue solution for halogen-free medium-Tg loss copper-clad plate and preparation method and application thereof | |
| CN109929220B (en) | Insulating heat-conducting slurry and preparation method and application thereof | |
| CN110291152B (en) | Thermosetting resin composition, cured product thereof, and printed wiring board | |
| TW201406851A (en) | Resin compositions and uses of the same | |
| CN103649185A (en) | Prepreg, laminated plate, semiconductor package, and method for producing laminated plate | |
| KR101564197B1 (en) | Composite resin composition for plugging hole | |
| CN111748078B (en) | Curable resin composition for pore-filling | |
| WO2014153911A1 (en) | Thermosetting resin composition and printed circuit board filled with same | |
| Lim et al. | Low temperature-cured electrically conductive pastes for interconnection on electronic devices | |
| CN110370750A (en) | Highly heat-conductive copper-clad plate and preparation method | |
| JP2011124077A (en) | Insulating sheet, laminated structure, and manufacturing method of laminated structure | |
| JP5670136B2 (en) | Insulating sheet and laminated structure |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| GR01 | Patent grant | ||
| GR01 | Patent grant |