CN109679402B - Hole plugging ink composition special for hole plugging and filling and printed circuit board - Google Patents
Hole plugging ink composition special for hole plugging and filling and printed circuit board Download PDFInfo
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- CN109679402B CN109679402B CN201811620072.0A CN201811620072A CN109679402B CN 109679402 B CN109679402 B CN 109679402B CN 201811620072 A CN201811620072 A CN 201811620072A CN 109679402 B CN109679402 B CN 109679402B
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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
- C09D11/10—Printing inks based on artificial resins
- C09D11/101—Inks specially adapted for printing processes involving curing by wave energy or particle radiation, e.g. with UV-curing following the printing
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- H—ELECTRICITY
- H05—ELECTRIC TECHNIQUES NOT OTHERWISE PROVIDED FOR
- H05K—PRINTED CIRCUITS; CASINGS OR CONSTRUCTIONAL DETAILS OF ELECTRIC APPARATUS; MANUFACTURE OF ASSEMBLAGES OF ELECTRICAL COMPONENTS
- 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
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- Microelectronics & Electronic Packaging (AREA)
- Life Sciences & Earth Sciences (AREA)
- Materials Engineering (AREA)
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- Organic Chemistry (AREA)
- Inks, Pencil-Leads, Or Crayons (AREA)
- Non-Metallic Protective Coatings For Printed Circuits (AREA)
Abstract
The invention relates to a hole-plugging ink composition special for filling holes and a printed circuit board, wherein the ink composition comprises a photocuring diluted alkali water developable resin and peroxide, the photocuring diluted alkali water developable resin contains carboxyl and unsaturated double bonds in molecules, and the weight of the peroxide accounts for 0.1-5.0% of the weight of the ink composition. The hole plugging ink solves the problem of performance defects caused by low double bond reaction rate and insufficient molecular crosslinking degree in the hole plugging ink by adding peroxide, and realizes excellent heat resistance, crack resistance and cavitation resistance of the hole plugging ink.
Description
Technical Field
The invention belongs to the field of photosensitive electronic materials, relates to a hole-filling ink composition special for filling holes and a printed circuit board, and particularly relates to a hole-filling ink composition special for filling holes and a printed circuit board, which have excellent heat resistance, crack resistance and cavitation resistance.
Background
With the increasing requirements of high precision, high density, durability and reliability of electronic products, the requirements of permanent hole-filling compositions filled in holes such as through holes and via holes are also increasing, and the traditional continuous-plugging tape printing process (the printed circuit board performs hole-filling operation of through hole ink while screen printing solder resist ink on two sides) cannot meet the current PCB manufacturing requirements, and replaces the traditional continuous-plugging tape printing process with an aluminum plate printing process.
The aluminum plate printing process generally adopts the following processes: printing special hole plugging ink on an aluminum plate, coating surface photocuring thermocuring ink by adopting the processes of screen printing, electrostatic spraying, air spraying, roll coating and the like, pre-drying at the temperature of 70-80 ℃, selectively irradiating the composition by adopting proper ultraviolet rays, cleaning the part without the irradiated light by using dilute alkali aqueous solution, heating and curing the remaining composition in the holes of the circuit board substrate and the surface composition at the temperature of 60-160 ℃, and then carrying out surface treatment on the printed board, such as OSP (organic solderability preservative), tin spraying, tin precipitation, silver precipitation, gold dissolution and the like.
Even if an aluminum plate printing process is adopted, and the hole is plugged by adopting special hole plugging ink, the phenomenon that the ink in the hole (particularly the diameter of phi 0.5mm) cracks, vacuoles and the like can be generated in the surface treatment processes of tin spraying, tin depositing, silver depositing, gold dissolving and the like of the solder resist ink in the industry.
Chinese patent application CN201410821847 discloses a photo-curing and thermosetting composition suitable for being developed by an alkaline aqueous solution and a preparation method thereof, wherein the photo-curing and thermosetting composition comprises a copolymer resin containing acrylic acid, an o-cresol formaldehyde modified epoxy resin, a photo-polymerization initiator, a diluent, an acrylic acid reaction monomer or oligomer with at least 2 functional groups in the molecule, an inorganic filler, a curing agent for the epoxy resin and a stabilizer. The compositions have improved heat resistance, but the degree of improvement is still to be improved.
After the photo-curing and thermosetting composition provided by the invention is printed in a through hole of a PCB, the system changes mainly in the following three stages: 1) pre-baking at 70-80 deg.C to remove solvent in the ink; 2) irradiating ultraviolet light for curing to initiate double bond crosslinking polymerization reaction in the system; 3) and (3) baking at high temperature for thermosetting, wherein the epoxy resin generates ring-opening crosslinking reaction under the high-temperature condition.
In the photocuring process, due to the blocking effect of pigments, fillers and the like on light in an ink system, the energy of light penetrating through the ink is reduced along with the increase of the thickness of the ink, the crosslinking degree of double bonds of deep ink is greatly different from that of surface ink, particularly, the thickness of the ink of the hole plugging ink can reach more than 200um (the surface ink is generally only 25um), so that the crosslinking reaction degree of the double bonds of the ink in the hole is very low during photocuring of the hole plugging ink, and the expressed performance problems are insufficient performances such as heat resistance, crack resistance, vacuity resistance and the like.
Disclosure of Invention
In order to solve the technical problems, the invention provides a hole plugging ink composition special for filling holes, so as to achieve the purpose of achieving excellent hole plugging performance, such as excellent heat resistance, crack resistance and cavitation resistance.
Specifically, the invention provides a special hole plugging ink composition for filling holes, which comprises a photocuring dilute alkali water developable resin and peroxide, wherein the photocuring dilute alkali water developable resin contains carboxyl and unsaturated double bonds in molecules, and the weight of the peroxide accounts for 0.1-5.0% of the weight of the ink composition.
Preferably, the peroxide is present in an amount of 0.5% to 3.0% by weight of the ink composition.
Preferably, in the above hole-plugging ink composition, the peroxide is present in an amount of 2.0 to 12.5% by weight based on the photocurable dilute alkali-water developable resin.
Preferably, the peroxide is present in an amount of 1.12% to 7.13% by weight of the photocurable dilute aqueous alkali developable resin.
Preferably, in the above hole plugging ink composition, the peroxide is one or more of 2, 2-bis- (t-butyl peroxide) propane, isopropyl hydroperoxide, t-butyl peroxide, t-octyl hydroperoxide, cumene hydroperoxide, di-t-butyl cumene hydroperoxide, pinane hydroperoxide, p-menthane hydroperoxide, tetralin hydroperoxide, di-t-butyl peroxide, t-butyl cumene hydroperoxide, t-butyl peroxyacetate, t-butyl peroxyisobutyrate, t-butyl peroxypivalate, t-butyl peroxy-2-ethylhexanoate, t-butyl peroxybenzoate, t-butyl peroxyphthalate, t-butyl peroxyisopropyl carbonate, and di-n-propyl peroxydicarbonate.
Preferably, in the above-mentioned hole-filling ink composition, the peroxide is a mixture of p-menthane peroxide and tert-butyl peroxyisobutyrate, and the weight ratio of p-menthane peroxide to tert-butyl peroxyisobutyrate is 1: (0.2-5.0).
Preferably, in the above-mentioned hole-plugging ink composition, the solid content of the photocurable dilute alkali water developable resin is 40 to 80%, preferably 50 to 70%; the viscosity of the light-cured dilute alkali water developable resin is 100-700dPa.s/25 ℃, preferably 200-600dPa.s/25 ℃, and the number-average molecular weight of the light-cured dilute alkali water developable resin is 500-5000; preferably between 800 and 4500; the acid value of the photocurable dilute alkali water developable resin is 30 to 180mgKOH/g, preferably 30 to 160mgKOH/g, and more preferably 35 to 130 mgKOH/g.
Preferably, in the above hole-plugging ink composition, the photocurable dilute alkali water developable resin is prepared by the following method.
Mixing epoxy resin containing two or more epoxy groups in the molecule and monocarboxylic acid compound containing unsaturated double bond in the molecule to react to obtain resin containing hydroxyl, and reacting with saturated or unsaturated acid anhydride to obtain the light-cured dilute alkali water developable resin.
Preferably, the epoxy resin containing two or more epoxy groups is one or more of bisphenol a epoxy resin, bis F-type epoxy resin, novolac-type epoxy resin, hydrogenated bisphenol a-type epoxy resin, hydrogenated bisphenol F-type epoxy resin, alicyclic epoxy resin, o-cresol-type epoxy resin, hydantoin epoxy resin, bisphenol S-type epoxy resin, and bisphenol fluorenyl epoxy resin. Preferably, the novolac epoxy resin is novolac heat-resistant multifunctional epoxy resin, and preferably, the novolac epoxy resin is o-cresol novolac epoxy resin.
Preferably, the monocarboxylic acid compound having an unsaturated double bond in the molecule is one or more of methacrylic acid, acrylic acid and cinnamic acid.
Preferably, the acid anhydride is one or more of itaconic anhydride, succinic anhydride, maleic anhydride, phthalic anhydride, tetrahydrophthalic anhydride, methyltetrahydrophthalic anhydride, hexahydrophthalic anhydride, methyldinac anhydride, trimellitic anhydride, pyromellitic dianhydride, and tetrahydrophthalic anhydride.
Preferably, the hole-plugging ink composition further comprises an unsaturated monomer, an epoxy resin, an epoxy curing accelerator, and a photopolymerization initiator.
Preferably, the unsaturated monomer is glycidyl methacrylate, glycidyl acrylate, allyl glycidyl ether, 4-vinylbenzyl glycidyl ether, dipentaerythritol hexaacrylate, and preferably, the unsaturated monomer is present in an amount of 1 to 10 weight percent, preferably 3 to 7 weight percent, of the via hole ink composition.
Preferably, the epoxy resin is one or more of novolac epoxy resin and hydantoin epoxy resin, the weight percentage of the epoxy resin in the pore-filling ink composition is 2-10%, and in the case that the epoxy resin is composed of novolac epoxy resin and hydantoin epoxy resin, the weight ratio of novolac epoxy resin to hydantoin epoxy resin is 5: 8.
Preferably, the epoxy curing accelerator is an imidazole derivative such as imidazole, 2-methylimidazole, 2-ethylimidazole, 2-ethyl-4-methylimidazole, 2-phenylimidazole, 4-phenylimidazole, 1-cyanoethyl-2-phenylimidazole, 1- (2-cyanoethyl) -2-ethyl-4-methylimidazole, or the epoxy curing accelerator is an amine compound such as dicyandiamide, benzyldimethylamine, 4- (dimethylamino) -N, N-dimethylbenzylamine, 4-methoxy-N, N-dimethylbenzylamine, 4-methyl-N, N-dimethylbenzylamine, or the epoxy curing accelerator is a hydrazine compound such as adipic acid dihydrazide, sebacic acid dihydrazide, or the epoxy curing accelerator is a phosphorus compound such as triphenylphosphine, or the epoxy curing accelerator may be a triazine derivative such as guanamine, methylguanamine, benzoguanamine, melamine, 2, 4-diamino-6-methacryloyloxyethyl-s-triazine, 2-vinyl-2, 4-diamino-s-triazine, 2-vinyl-4, 6-diamino-s-triazine-isocyanuric acid adduct, or 2, 4-diamino-6-methacryloyloxyethyl-s-triazine-isocyanuric acid adduct. The epoxy curing accelerator accounts for 0.1 to 2.0 percent of the weight of the hole plugging ink composition.
Preferably, in the hole plugging ink composition, the photopolymerization initiator (also referred to as a photosensitizer) is benzoin such as benzoin, benzoin methyl ether, benzoin ethyl ether, benzoin propyl ether, or benzoin alkyl ether, or the photopolymerization initiator is acetophenone such as acetophenone, 2-dimethoxy-2-phenylacetophenone, 2-diethoxy-2-phenylacetophenone, or 1, 1-dichloroacetophenone, or the photopolymerization initiator is aminoacetone such as 2-methyl-1- (4- (methylthiophenyl) -2-morpholinyl-1-one, or 2-benzyl-2-dimethylamino-1- (4-morpholinophenyl) -butanone-1, or anthraquinones such as 2-methylanthraquinone, 2-isopropylthioxanthone, 4-isopropylthioxanthone, isopropylthioxanthone (isomer mixture), 2-ethylanthraquinone, 2-tert-butylanthraquinone and 1-chloroanthraquinone as photopolymerization initiators, thioxanthones such as 2, 4-dimethylthioxanthone, 2, 4-diethylthioxanthone, 2-chlorothioxanthone and 2, 4-diisopropylthioxanthone as photopolymerization initiators, and ketals such as acetophenone dimethyl ketal and benzyl dimethyl ketal as photopolymerization initiators; or the photopolymerization initiator is benzophenone such as benzophenone, or the photopolymerization initiator is xanthone, or the photopolymerization initiator is phosphine oxide such as (2, 6-dimethoxybenzoyl) -2, 4, 4-pentylphosphine oxide, bis (2, 4, 6-trimethylbenzoyl) -phenylphosphine oxide, 2, 4, 6-trimethylbenzoyl diphenylphosphine oxide, ethyl-2, 4, 6-trimethylbenzoyl phenylphosphine oxide, or the photopolymerization initiator is various peroxides, titanocene initiators, or the like. These photopolymerization initiators may be used alone or in combination of two or more. Particularly preferably, the photopolymerization initiator is a composition of 2-methyl-1- (4- (methylthiophenyl) -2-morpholinyl-1-one and isopropylthioxanthone (isomer mixture), the weight ratio of the composition of 2-methyl-1- (4- (methylthiophenyl) -2-morpholinyl-1-one and isopropylthioxanthone (isomer mixture) is 5: 1, and the photopolymerization initiator accounts for 1-10% of the weight of the taphole ink composition.
Preferably, in the hole-plugging ink composition, the ink composition further comprises one or more of a filler, a pigment, an organic solvent, an antifoaming agent, a dye, a thermal polymerization inhibitor, an adhesion promoter, a dispersant, a coupling agent, a flame retardant, a leveling agent, an antioxidant and a thixotropic agent.
Preferably, the filler is an inorganic filler or an organic filler. Wherein the inorganic filler is preferably one or more of barium sulfate, barium titanate, silicon oxide powder, fine powdery quartz powder, amorphous silica, talcum powder, clay, magnesium carbonate, calcium carbonate, aluminum oxide, aluminum hydroxide, mica and kaolin. The organic filler is preferably PI powder and polytetrafluoroethylene powder. The average particle diameter D50 of the filler is controlled below 30 microns, and the average particle diameter D50 of the filler is preferably less than 25 microns. The additive accounts for 20-40%.
The pigment is phthalocyanine green, phthalocyanine blue, carbon black, ultramarine, lithopone, permanent violet, permanent yellow, titanium pigment, etc., and accounts for 0.1-1.0 wt% of the hole-plugging ink composition.
Preferably, the organic solvent is present in an amount of 0.5 to 10% by weight of the pore-filling ink composition.
The invention also provides a printed circuit board which is characterized in that the circuit board is prepared by the hole plugging ink composition.
The invention also provides the use of a peroxide for improving the heat resistance, crack resistance and cavitation resistance of a hole-plugging ink composition, characterized in that the weight percentage of the peroxide in the hole-plugging ink composition is 0.1-5%.
Preferably, in the above-mentioned uses, the peroxide is one or more of 2, 2-bis- (t-butyl peroxide) propane, isopropyl hydroperoxide, t-butyl peroxide, t-octyl hydroperoxide, cumene hydroperoxide, di-t-butylcumene hydroperoxide, pinane hydroperoxide, p-menthane hydroperoxide, tetralin hydroperoxide, di-t-butyl peroxide, t-butylcumene hydroperoxide, t-butyl peroxyacetate, t-butyl peroxyisobutyrate, t-butyl peroxypivalate, t-butyl peroxy-2-ethylhexanoate, t-butyl peroxybenzoate, t-butyl peroxyphthalate, t-butyl peroxyisopropyl carbonate, di-n-propyl peroxydicarbonate.
Preferably, in the above application, the peroxide is a mixture of p-menthane peroxide and tert-butyl peroxyisobutyrate, and the weight ratio of the p-menthane peroxide to the tert-butyl peroxyisobutyrate is 1 to (0.2-5.0).
The invention has the advantages of
The hole plugging ink solves the problem of performance defects caused by low double bond reaction rate and insufficient molecular crosslinking degree in the hole plugging ink by adding peroxide.
The ink composition of the present invention realizes excellent heat resistance, excellent crack resistance and excellent cavitation resistance of the via hole ink.
The hole-plugging ink composition disclosed by the invention uses peroxide, the peroxide initiates a double bond crosslinking polymerization reaction in the composition when being baked and thermally cured at a high temperature, the crosslinking density is greatly improved, and further, the hole-plugging ink composition shows excellent heat resistance, explosion-proof hole resistance and cavitation-proof property, and can be widely used as a hole-insulating solder-resisting protective material of a printed circuit board.
Detailed Description
Example 1: preparation of photocuring dilute alkali water developable resin
Adding 203 g of o-cresol formaldehyde epoxy resin (Shandong Shengquan 704M), 0.5 g of hydroquinone and 250 g of diethylene glycol ethyl ether acetate (water-soluble solvent) into a three-neck flask, stirring, heating to 100-110 ℃, preserving heat for dissolving for 1 hour, cooling to 90 ℃ after complete dissolution is ensured, dripping 72 g of acrylic acid and 3 g of N, N dimethylbenzylamine into the three-neck flask, controlling the temperature to be 90-100 ℃ in the process, raising the temperature to 105-110 ℃ after dripping is finished, reacting for 12 hours, measuring the acid value to be less than 10mgKOH/g, cooling to 90 ℃, adding 100 g of tetrahydrophthalic anhydride, preserving heat for 4 hours at 90-95 ℃, detecting by an infrared spectrometer, eliminating the peak of 1780cm-1, stopping the reaction, reducing the temperature to room temperature to obtain a tea brown resin solution, wherein the resin viscosity is 260dPa.s/25 ℃, the solid content is 60mgKOH/g, and the acid value is 60mgKOH/g, the number average molecular weight is 2100, and the photocuring dilute alkali water developable resin, resin A for short, is obtained.
Example 2: preparation of Via ink compositions
The hole plugging ink compositions were prepared according to the material ratios (numerical values of the respective components are weight values in grams) as listed in tables 1 and 2 below, respectively. The materials were accurately weighed into a container, dispersed by stirring with a high-speed disperser at 500 revolutions per minute for 15 minutes, and then the composition was ground three times with a three-roll mill to a fineness of less than 15 μm.
Table 1 formulation table for example 1-5 of the ink compositions for plugging the hole
| Composition (I) | Example 1 | Example 2 | Example 3 | Example 4 | Example 5 |
| Resin A | 450 | 401 | 446 | 441 | 431 |
| P-menthane hydroperoxide | 1 | 5 | 1 | 3 | 5 |
| Tert-butyl peroxyisobutyrate | 4 | 7 | 1 | ||
| Dipentaerythritol hexaacrylate | 45 | 45 | 45 | 45 | 45 |
| 907 | 50 | 50 | 50 | 50 | 50 |
| Isopropyl thia anthraquinone | 10 | 10 | 10 | 10 | 10 |
| Barium sulfate | 280 | 280 | 280 | 280 | 280 |
| Fumed silica | 12 | 12 | 12 | 12 | 12 |
| KS-66 | 13 | 13 | 13 | 13 | 13 |
| Melamine | 8 | 8 | 8 | 8 | 8 |
| Phthalocyanine green | 5 | 5 | 5 | 5 | 5 |
| BYK-354 | 8 | 8 | 8 | 8 | 8 |
| Phenolic epoxy resin | 25 | 25 | 25 | 25 | 25 |
| Hydantoin epoxy resin | 40 | 40 | 40 | 40 | 40 |
| Ultra-fine triglycidyl isocyanurate | 43 | 43 | 43 | 43 | 43 |
| Diethylene glycol Ether acetate | 10 | 10 | 10 | 10 | 10 |
In table 1, the relevant substances are illustrated below:
907 is Zhejiang poplar sail photosensitizer 2-methyl-1- (4-methylthiophenyl) -2-morpholinyl-1-acetone
KS-66 is an antifoaming agent of Japan Beacon chemistry
BYK-354 is an acrylic polyester leveling agent of BYK company of Germany
TABLE 2 formulation tables for Example 6-10 taphole ink compositions
| Composition (I) | Example 6 | Example 7 | Example 8 | Example 9 | Example 10 |
| Resin A | 421 | 411 | 450.5 | 391 | 451 |
| P-menthane hydroperoxide | 5 | 20 | 0.5 | 60 | 0 |
| Tert-butyl peroxyisobutyrate | 25 | 20 | |||
| Dipentaerythritol hexaacrylate | 45 | 45 | 45 | 45 | 45 |
| 907 | 50 | 50 | 50 | 50 | 50 |
| Isopropyl thia anthraquinone | 10 | 10 | 10 | 10 | 10 |
| Barium sulfate | 280 | 280 | 280 | 280 | 280 |
| Fumed silica | 12 | 12 | 12 | 12 | 12 |
| KS-66 | 13 | 13 | 13 | 13 | 13 |
| Melamine | 8 | 8 | 8 | 8 | 8 |
| Phthalocyanine green | 5 | 5 | 5 | 5 | 5 |
| BYK-354 | 8 | 8 | 8 | 8 | 8 |
| Phenolic epoxy resin | 25 | 25 | 25 | 25 | 25 |
| Hydantoin epoxy resin | 40 | 40 | 40 | 40 | 40 |
| Ultra-fine triglycidyl isocyanurate | 43 | 43 | 43 | 43 | 43 |
| Diethylene glycol Ether acetate | 10 | 10 | 10 | 10 | 10 |
In table 2, the relevant substances are illustrated below:
907 is Zhejiang poplar sail photosensitizer 2-methyl-1- (4-methylthiophenyl) -2-morpholinyl-1-acetone
KS-66 is an antifoaming agent of Japan Beacon chemistry
BYK-354 is an acrylic polyester leveling agent of BYK company of Germany
Example 3 measurement of Performance of ink composition for plugging pores
The plugging inks prepared in tables 1 and 2 were used for plugging holes, and the specific procedure was as follows:
a double-sided substrate (not patterned, 50 through holes per through hole) having a thickness of 2.0mm, a plated through hole diameter of 0.2mm, 0.3mm, 0.4mm, 0.5mm, 0.6mm and a through hole pitch of 1mm was subjected to acid washing and brushing as a pretreatment, then hole-filling printing of an aluminum sheet was performed using the hole-filling ink composition of the foregoing examples and comparative examples using a semiautomatic printer, dried in a 75 ℃ constant temperature oven for 50 minutes, cooled to room temperature, exposed to light with an energy of a 21-step exposure scale of 10 lattices, developed by a conventional development process of a circuit board factory, and then post-cured in an oven at 80 ℃ for 1 hour, 120 ℃ for 30 minutes, and 150 ℃ for 1 hour to obtain an evaluation substrate.
Then measuring the heat resistance, the blast hole resistance and the cavitation resistance of the circuit board treated by the hole plugging ink composition, wherein the specific measuring method comprises the following steps:
the heat resistance measurement method comprises the following steps: the obtained cured coating film of the evaluation substrate was coated with a water-soluble flux, left to stand for 1 minute, and then immersed in a solder bath set to 288 ℃ in advance for 10 seconds, the above operations were repeated three times, the flux was washed away by hot water rinsing at about 50 ℃, and then the swelling, peeling, and whitening of the cured coating film at the evaluation orifice were visually detected with a 50-fold magnifying glass. The criteria for determination are as follows.
And (3) excellent: after dipping for three times, no whitening, expansion and peeling phenomena of the coating and the hole edge are observed;
good: after dipping for three times, the coating and the hole edge have the phenomena of whitening, expansion and peeling at 1-2 points;
and (4) qualification: after dipping for three times, the coating and the hole edge have the phenomena of whitening, expansion and peeling at 3-5 points;
unqualified: after dipping for three times, the coating and the hole edge have more than 5 points of whitening, swelling and stripping phenomena.
The method for measuring the crack resistance comprises the following steps: the obtained evaluation substrate was cut into through holes of 0.2mm, 0.3mm, 0.4mm, 0.5mm and 0.6mm in diameter, the cut surfaces were polished, and the presence or absence of cracks in the cured coating film in the holes was evaluated by observing the cured product in the through holes with an optical microscope.
And (3) excellent: no crack is generated in the hole;
good: the cured coating in the hole has slight cracks;
and (4) qualification: the cured coating film in the hole had cracks but was not connected to the orifice;
unqualified: the cured coating film in the hole had a large number of cracks and was connected to the orifice.
The measuring method of the cavitation resistance comprises the following steps: the obtained evaluation substrate was cut into through holes of 0.2mm, 0.3mm, 0.4mm, 0.5mm and 0.6mm in diameter, the cut surfaces were polished, and the cured product in the through holes was observed with an optical microscope to evaluate the presence or absence of the occurrence of voids in the cured coating film in the holes.
And (3) excellent: the cured coating in the hole has no vacuole;
good: the number of the curing coating vacuoles in the holes is 1-5;
and (4) qualification: the number of the curing coating vacuoles in the holes is 6-10;
unqualified: the number of the pores of the cured coating film is more than 10.
The specific measurement results are shown in table 3 below.
Table 3 performance measurement table for via-hole ink composition
As can be seen from Table 3, the presence of peroxide significantly improves the heat resistance, crack resistance and cavitation resistance of the via-hole ink, with the performance exhibited by the via-hole ink composition being above acceptable when the peroxide content is 0.1-5% and the peroxide content is 2-12.5% of resin A, and the performance exhibited by the via-hole ink composition being superior when the peroxide content is 0.5-3.0% and the peroxide content is 1.12-7.13% of resin A.
Example 4: hole plugging ink performance detection after peroxide modification
After the specific components of the peroxide in the formulations of tables 1 and 2 in example 2 are changed, and the tert-butyl peroxide is changed into 2, 2-bis- (tert-butyl peroxide) propane, tert-octyl hydroperoxide, pinane hydroperoxide, tert-butyl peroxide, tert-butyl peroxyisobutyrate and tert-butyl peroxybenzoate, the performance of the hole-plugging ink composition can reach the standard above the standard, even reach the standard above the standard below the standard, under the condition that the content of the peroxide in the hole-plugging ink composition is ensured to be 0.1-5.0% and the weight percentage of the peroxide in the resin A is 2.0-12.5%.
Claims (2)
1. The special hole-plugging ink composition for filling holes comprises a photocuring diluted alkali water developable resin and peroxide, wherein the photocuring diluted alkali water developable resin contains carboxyl and unsaturated double bonds in molecules, the weight of the peroxide accounts for 0.5-3.0% of the weight of the ink composition, the weight of the peroxide accounts for 1.12-7.13% of the photocuring diluted alkali water developable resin, the peroxide is a mixture of hydrogen peroxide and tert-butyl peroxyisobutyrate, the weight ratio of the hydrogen peroxide to the menthane and the tert-butyl peroxyisobutyrate is 1 (0.2-5.0), the hole-plugging ink composition further comprises unsaturated monomers, epoxy resin, an epoxy curing accelerator and a photopolymerization initiator, and the hole-plugging ink composition further comprises a filler, Pigment, organic solvent, defoaming agent, dye, thermal polymerization inhibitor, adhesion promoter, dispersant, coupling agent, fire retardant, leveling agent, antioxidant and thixotropic agent.
2. A printed circuit board prepared from the via hole ink composition of claim 1.
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| CN201811620072.0A CN109679402B (en) | 2018-12-27 | 2018-12-27 | Hole plugging ink composition special for hole plugging and filling and printed circuit board |
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| CN109679402B true CN109679402B (en) | 2022-02-08 |
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| CN104974594A (en) * | 2015-07-13 | 2015-10-14 | 深圳市容大感光科技股份有限公司 | Printing ink composition with water-soluble solvent, application of printing ink composition, and printed circuit board |
| CN105086604A (en) * | 2015-07-13 | 2015-11-25 | 深圳市容大感光科技股份有限公司 | Printing ink composition, application thereof and printed circuit board |
| CN107203095A (en) * | 2017-07-19 | 2017-09-26 | 江苏广信感光新材料股份有限公司 | A kind of solvable photosensitive composite of white alkali and preparation method and application |
| CN107329368A (en) * | 2017-07-05 | 2017-11-07 | 江苏广信感光新材料股份有限公司 | A kind of solvable photosensitive composite of alkali and preparation method and application |
| CN108003698A (en) * | 2017-12-31 | 2018-05-08 | 深圳市容大感光科技股份有限公司 | A kind of high temperature resistant welding resistance ink and its wiring board |
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2018
- 2018-12-27 CN CN201811620072.0A patent/CN109679402B/en active Active
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| CN104570606A (en) * | 2014-12-24 | 2015-04-29 | 欧利生东邦涂料（东莞）有限公司 | Photocuring and thermosetting composition and preparation method thereof as well as printing ink for printed circuit board |
| CN104974594A (en) * | 2015-07-13 | 2015-10-14 | 深圳市容大感光科技股份有限公司 | Printing ink composition with water-soluble solvent, application of printing ink composition, and printed circuit board |
| CN105086604A (en) * | 2015-07-13 | 2015-11-25 | 深圳市容大感光科技股份有限公司 | Printing ink composition, application thereof and printed circuit board |
| CN107329368A (en) * | 2017-07-05 | 2017-11-07 | 江苏广信感光新材料股份有限公司 | A kind of solvable photosensitive composite of alkali and preparation method and application |
| CN107203095A (en) * | 2017-07-19 | 2017-09-26 | 江苏广信感光新材料股份有限公司 | A kind of solvable photosensitive composite of white alkali and preparation method and application |
| CN108003698A (en) * | 2017-12-31 | 2018-05-08 | 深圳市容大感光科技股份有限公司 | A kind of high temperature resistant welding resistance ink and its wiring board |
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| CN109679402A (en) | 2019-04-26 |
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