CN109810559A - The dumb light solder mask of polymolecularity - Google Patents
The dumb light solder mask of polymolecularity Download PDFInfo
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- CN109810559A CN109810559A CN201910151381.6A CN201910151381A CN109810559A CN 109810559 A CN109810559 A CN 109810559A CN 201910151381 A CN201910151381 A CN 201910151381A CN 109810559 A CN109810559 A CN 109810559A
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Abstract
The invention belongs to technical field of ink, it is related to a kind of dumb light solder mask of polymolecularity, its formula includes: the acrylate compounds with carboxyl of 30 mass parts, the inorganic delustring filler of 0.5~20 mass parts, the organic quenching filler of 0.5~20 mass parts, the surfactant of 0.1~20 mass parts, the epoxy resin of 5~30 mass parts, the photoinitiator of 1~5 mass parts, the pigment of 1~5 mass parts, the organic solvent of the additive of 0.1~5 mass parts and 5~20 mass parts, the surfactant is at least block macromolecular of type containing AB surfactant, Gemini type surfactant, Bola type surfactant, any one of Dendrimer type surfactant.Solder mask of the invention is able to maintain that the photobehavior and various patience of solder mask, and has good flatting efficiency and preferable dispersibility.
Description
Technical field
The present invention relates to technical field of ink, in particular to the dumb light solder mask of a kind of polymolecularity.
Background technique
Solder mask is mainly used in the production process of printed wiring board, by forming welding resistance for route and copper face covering
Coating is patterned, the problems such as bridge joint short circuit occurs when subsequent welding is prevented, prevents moisture, acid or alkali environment and electrolyte encroachment line
Road can provide prolonged insulation environment for wiring board.The glossiness to be formed a film according to solder mask in print circuit board surface
Situation can be divided into the types such as light, semi-matte, dumb light.In recent years, it is required with to product appearance and to route secrecy etc.
Continuous promotion, dumb light solder mask (refer in particular to coating gloss that 60 degree of angles of incidence of light measure below 20) obtained people
More and more concerns, the coating surface formed is fog-like, visual effect it is soft it is containing do not hurt eye, design fashionable has matter
Sense, especially dark dumb light ink coating are strong to internal element and route function of keeping secret.
In order to reach matte effect, common method is the inorganic filler or organic filler that addition has extinction effect, but
There are many shortcomings that being this method, are simply listed below:
1) in order to reach good extinction effect, delustring filler additive amount is larger, is equivalent to and dilutes other resin components
Ratio, reduce the photo-thermal curing reactivity of solder mask to a certain extent；Delustring filler and other in solder mask simultaneously
The intersolubility and poor dispersion of the ingredients such as resin cause solder mask the quality problems such as to occur settling in transport and use；
2) dumb light soldermask coatings surface is easy to appear uneven problem, strong to light diffuse reflection effect, influences welding resistance oil
The photo-hardening degree of ink will lead to and the problems such as photobehavior is insufficient, the various patience of coating are insufficient occurs.
Summary of the invention
The main purpose of the present invention is to provide a kind of dumb light solder masks of polymolecularity, can guarantee good delustring
Efficiency and preferable dispersibility.
The present invention is achieved through the following technical solutions above-mentioned purpose: a kind of dumb light solder mask of polymolecularity, formula
It include: the acrylate compounds with carboxyl, the inorganic delustring filler of 0.5~20 mass parts, 0.5~20 matter of 30 mass parts
Measure the organic quenching filler of part, the surfactant of 0.1~20 mass parts, the epoxy resin of 5~30 mass parts, 1~5 mass parts
Photoinitiator, the pigment of 1~5 mass parts, the additive of 0.1~5 mass parts and 5~20 mass parts organic solvent, it is described
Surfactant is at least block macromolecular of type containing AB surfactant, Gemini type surfactant, Bola type surface-active
Any one of agent, Dendrimer type surfactant.
Specifically, the surfactant is AB type block macromolecular surfactant and Dendrimer type surface-active
For the 1:1 mass of agent than mixture, the AB type block macromolecular surfactant is PBA-b-PDMAEA, the Dendrimer
Type surfactant is PAMAM.
Specifically, organic solvent is the mixture of the different a variety of organic solvents of boiling range.
Further, the organic solvent is the mixture of 6# solvent for extraction, 120# solvent naphtha and 200# solvent naphtha.
Specifically, the photoinitiator includes benzoin and its derivative, acetophenone and its derivative, anthraquinone and its derivative
In object, thioxanthones and its derivative, ketal and its derivative, benzophenone and its derivative and tertiary amine and its derivative at least
It is a kind of.
Specifically, the additive includes at least one of levelling agent, defoaming agent and coalescing agent.
By adopting the above technical scheme, the beneficial effect of technical solution of the present invention is:
Solder mask of the invention is able to maintain that the photobehavior and various patience of solder mask, and has good delustring
Efficiency and preferable dispersibility.
Specific embodiment
Invention is further described in detail combined with specific embodiments below.
In dustless laboratory, raw material is stirred and evenly mixed by the proportion in table 1, Examples 1 to 4 and comparative example 1~6 is made
Light heat dual curing solder mask.
Table 1:
Wherein the acrylate compounds with carboxyl used in embodiment refer to carboxy polyethylene glycol acrylate,
Epoxy resin is bisphenol-A, and inorganic delustring filler selects Degussa silica flatting silica OK500；Organic quenching filler is selected poly-
Amide waxe micro mist NEW-0401C；Surfactant be AB type block macromolecular surfactant PBA-b-PDMAEA with
The 1:1 mass of Dendrimer type surfactant PAMAM compares mixture；Organic solvent is 6#, 120#, 200# solvent naphtha each 1/3
The mixture of mass ratio；Photoinitiator is IRG 907；Pigment is carbon black；Additive is TEGO-A116 levelling agent；Organic solvent
For butyl carbitol.
SOFT ETCHING pre-treatment is carried out to flexible circuit copper-clad plate FCCL (12~25 μm of PI thickness 18 μm thick with copper), so
Silk-screen printing solder mask is carried out with the halftone of 100 mesh on its surface afterwards, is heated using heated air circulation type drying oven at 80 DEG C
30min forms the solder mask coating of 20 μm of film thickness (error ± 2 μm).If corresponding roll-to-roll processing procedure needs pre- at 110 DEG C
Roasting 5~20min, can relatively rapid form solder mask coating.
(1) dry to touch is tested
Using the EXM-1201 exposure machine of ORC CORPORATION, with 200~500mJ/cm2Light exposure and minus figure
Case mask is irradiated solder mask coating.What the impression and negative pattern mask (such as film) of inspection ink coating were removed
Complexity carries out dry to touch evaluation.
Dry to touch evaluation criterion is as follows:
Zero: ink coating absolutely not impression, mask can be removed easily；
×: ink coating has obvious impression, and mask is difficult to remove or be stained with mask.
(2) developability is tested
Carry out 60s's in the aqueous sodium carbonate for 1% mass fraction for substrate being impregnated under the conditions of 30 DEG C of temperature
Development, spray pressure 1kg/cm2, to flexible print circuit board plate face visual detection, carry out developability evaluation.
Developability evaluation criterion is as follows:
Zero: can develop, solder mask coating state is good；
×: exposure portion is dissolved in developer solution or unexposed portion is undissolved in developer solution, leads to not to form good resistance
Weld pattern.
(3) photobehavior
After 20 μm of silk-screen printing film thickness of solder mask coating, with 500mJ/cm2Light exposure and STOUFFER exposure guide rule
(21Steps) is irradiated solder mask coating, observes specimen surface after 60s development, passes through the soldermask coatings completely retained
Number of segment, obtain sensitivity number of segment.Herein, the demand according to existing market and client to solder mask product, photosensitive number of segment is at 8 sections
The above are qualifications.
(4) adhesive force is tested
The flexible circuit board for completing technique is placed in 150 DEG C of baking oven and is toasted 1 hour, test sample plate is made into, using painting
Layer frame method carries out adhesive force test to template, cuts solder mask coating to substrate surface using cutting tool, forms grid
Shape scratch, then with being torn after the adherency of 3M adhesive tape, check the peeling conditions of coating, then grade to the adhesion condition of coating.
Adhesive force evaluation criterion is as follows:
Zero: adhesive force is high, and no any peeling occurs；
×: poor adhesive force occurs coating stripping or falls off.
(5) flexibility is tested
A.180 50 bendings are spent, around 1 millimeter of diameter of folding；
B.360 the dead folding of degree is primary.
Flexible appraisal standard is as follows:
Zero: flexibility is high, and appearance is without obvious folding line, no cracking or peeling after items bending experiment；
×: flexibility is poor, and appearance has folding line after items bending experiment, and has cracking or peeling.
(6) glossiness is tested
Using the micro-TRI-gloss instrument of BYK Gardner society, to the interval of template solder mask coating surface
Then 3 × 3 o'clock of 1cm are recorded gloss range, are accurate to 1 with its surface gloss of 60 degree of incident angular measurement.Herein,
Demand according to existing market and client to dumb light solder mask product, represent the gloss value of dumb light degree 15 the following are
Qualification, numerical value is smaller, and dumb light degree is higher.
(7) insulation reliability test
Apply the bias voltage of DC 100V, the condition of 25~65 DEG C of temperature cycles to the IPC-B comb-type electrode on template
Under, it is placed one week in the constant temperature and humidity cabinet of 90%R.H..Then it is handled one minute under conditions of room temperature and DC500V, with ten thousand
Resistance value measurement and optical microphotograph sem observation are carried out with table.
Zero: insulating properties does not observe surface variation almost without decline completely；
×: insulating properties decline is obvious, and transport phenomena occurs for copper ion.
(8) thermal impact of resistance to scolding tin is tested
Test sample plate is sprayed into rosin flux, 270 DEG C is subsequently placed in and melts in molten scolding tin and impregnate 30 seconds, trichlorine is used after taking-up
Ethane is clean, air-dries, visual detection.
The thermal impact of resistance to scolding tin evaluation criterion is as follows:
Zero: it is non-discolouring without any variation during resistance to scolding tin thermal shock, it does not fall off, does not swell；
×: it changes during resistance to scolding tin thermal shock, such as changes colour, falls off, swells.
(9) resistance toization nickel gold performance test
After 5 μm of Ni, 0.03 μm of Au plating, then with tearing after the adherency of 3M adhesive tape, check the peeling conditions of coating, it is then right
The adhesion condition of coating is graded.
Resistance toization nickel gold Performance evaluation criterion is as follows:
Zero: no any peeling occurs；
×: coating stripping occurs or falls off.
(10) acid resistance is tested
Test sample plate is soaked in half an hour in the H2SO4 aqueous solution of 10% volume fraction by room temperature, uses deionization after taking-up
Water is cleaned, and is air-dried, visual detection.
Acid resistance evaluation criterion is as follows:
Zero: it is non-discolouring without any variation, it does not fall off, does not swell；
×: it changes, such as changes colour, falls off, swells.
(11) alkali resistance is tested
Test sample plate is soaked in half an hour in the NaOH aqueous solution of 10% mass fraction by room temperature, uses deionized water after taking-up
It cleans, air-dries, visual detection.
Alkali resistance evaluation criterion is as follows:
Zero: it is non-discolouring without any variation, it does not fall off, does not swell；
×: it changes, such as changes colour, falls off, swells.
(12) solvent resistance is tested
Test sample plate is soaked in half an hour in PMA (propylene glycol methyl ether acetate) solution by room temperature, uses deionization after taking-up
Water is cleaned, and is air-dried, visual detection.
Solvent resistance evaluation criterion is as follows:
Zero: it is non-discolouring without any variation, it does not fall off, does not swell；
×: it changes, such as changes colour, falls off, swells.
As a result as follows:
Table 2: the performance evaluation results of solder mask and coating
The test result shown in the table 2 can be seen that
1. inorganic delustring filler and organic quenching filler can effectively reduce solder mask coating surface glossiness, but add
It measures larger, is equivalent to the ratio of other resin components that dilutes, and intersolubility and poor dispersion with other resin components,
The photo-thermal curing reactivity of solder mask is reduced to a certain extent.At the same time, dumb light soldermask coatings surface is easy to appear recessed
Convex injustice problem, it is strong to light diffuse reflection effect, the photo-hardening degree of solder mask is influenced, will lead to and occur in comparative example 1~4
The sensitivity number of segment of appearance declines, and the problem of the thermal impact of resistance to scolding tin and resistance toization nickel gold performance deficiency.
But if adding surfactant in right amount, by experiment, referred in the discovery especially addition present invention novel
Surfactant-AB type block macromolecular surfactant PBA-b-PDMAEA and Dendrimer type surfactant PAMAM is each
50%, it can effectively enhance inorganic and surface-active and surface wettability of organic quenching filler, enhance chemical stability and viscosity
It is evenly dispersed in solder mask to reach it, and enhances solder mask coating surface planarization for stability, and it is recessed to reduce its surface
The excessive light diffusing reflection of convex injustice bring, under the premise of guaranteeing that dumb light degree is qualified, effectively increase sensitivity with it is various
Patience.
2. if being easier to occur dispersing uneven, heavy only add inorganic delustring filler or a kind of ingredient of organic quenching filler
Drop, the problems such as chemically unstable or viscosity are unstable, are unable to reach effective dumb light degree, need inorganic delustring filler with it is organic
Delustring filler is used in combination, and can be only achieved good extinction effect, referring to comparative example 5~6.
3. boiling point different solvents group is combined into the concocting method of the most effective dumb light solder mask solvent after experiment is attempted,
High boiling organic solvent in low is used by collocation, solvent volatilization occurs in different temperature zones, solder mask coating can be enhanced
The irregularities on surface advantageously promote the matte effect on its surface.
To sum up, solder mask of the invention is able to maintain that the photobehavior and various patience of solder mask, and has good
Flatting efficiency and preferable dispersibility.
In addition to ingredient used in embodiment, under the acrylate compounds with carboxyl can also be chosen including but not limited to
Any one of column compound or at least both any combination: ω-carboxyl-polycaprolactone-acrylate, acrylic acid
One ester of phthalic acid of hydroxy methyl, one ester of phthalic acid of Hydroxyethyl Acrylate, the adjacent benzene of hydroxypropyl acrylate
One ester of dioctyl phthalate, one ester of phthalic acid of hydroxy butyl acrylate, one ester of phthalic acid of dihydroxypropyl pentyl ester, propylene
One ester of phthalic acid of the sour own ester of hydroxyl, one ester of phthalic acid of dihydroxypropyl heptyl ester, the neighbour of dihydroxypropyl monooctyl ester
One ester of phthalic acid, one ester of phthalic acid of dihydroxypropyl nonyl ester, the phthalic acid of dihydroxypropyl -2- ethylhexyl
One ester, one ester of phthalic acid of dihydroxypropyl last of the ten Heavenly stems ester, one ester of phthalic acid of dihydroxypropyl hendecane ester, acrylic acid
One ester of succinic acid of hydroxy methyl, one ester of succinic acid of Hydroxyethyl Acrylate, one ester of succinic acid of hydroxypropyl acrylate, third
One ester of succinic acid of olefin(e) acid hydroxybutyl, one ester of succinic acid of dihydroxypropyl pentyl ester, the succinic acid one of the own ester of dihydroxypropyl
Ester, itaconic acid, crotonic acid, maleic acid, fumaric acid, iso-crotonic acid and its acid anhydrides, the hexahydro O-phthalic of dihydroxypropyl methyl esters
A sour ester, one ester of hexahydrophthalic acid of Hydroxyethyl Acrylate, the hexahydro O-phthalic of (methyl) hydroxypropyl acrylate
A sour ester, one ester of hexahydrophthalic acid of hydroxy butyl acrylate, one ester of hexahydrophthalic acid of dihydroxypropyl pentyl ester,
One ester of hexahydrophthalic acid of the own ester of dihydroxypropyl, one ester of hexahydrophthalic acid of dihydroxypropyl heptyl ester, acrylic acid
One ester of hexahydrophthalic acid of hydroxyl monooctyl ester, one ester of hexahydrophthalic acid of dihydroxypropyl nonyl ester, dihydroxypropyl -2-
One ester of hexahydrophthalic acid of ethylhexyl, one ester of hexahydrophthalic acid of dihydroxypropyl last of the ten Heavenly stems ester, dihydroxypropyl ten
One ester of hexahydrophthalic acid of one alkyl ester, one ester of hexahydrophthalic acid of ten diester of dihydroxypropyl etc..
Silica, talcum powder, barium sulfate, aluminum stearate, calcium stearate etc. can be selected in inorganic delustring filler.
Organic quenching filler can be selected the alkene such as cellulose acetate, low molecular weight polyethylene and polypropylene, rilanit special,
Polyamide wax micropowder etc..
Surfactant is used to enhance the dispersibility and intersolubility of delustring filler, can be selected from AB type block macromolecular surface
Activating agent, Gemini type surfactant, Bola type surfactant, in Dendrimer type surfactant.
Wherein, the A block of AB type block macromolecular and B block are analogous respectively to hydrophilic head base and hydrophobic tail chain, it is specific and
Speech, A block is the anchoring group of close pigment, and B block is the solvation tail chain of solvophilic.A block is usually acid, amine, alcohol, phenol etc.
Functional group is adsorbed on particle surface by interactions such as ionic bond, covalent bond, coordinate bond, hydrogen bond and Van der Waals forces, due to containing
There are multiple absorption points, can make to adsorb even closer and lasting.B block is usually polyethers, polyester, polyolefin, polyacrylate
Equal groups, are respectively suitable for polarity and nonpolar solvent.BYK, CIBA, RHODIA, Shenzhen Haichuan Company are all developing this at present
Class product；
Gemini type surfactant, also known as dimeric type surfactant are dimer oligo surfactants, are led to
It crosses chemical bond connecting method and greatlys improve surface-active and wetability.
Bola type surfactant, by one or more chemical combination of hydrophobic chain connecting key altogether of two polar head-groups
Object, it gains the name because being similar to a kind of weapon Bola of South America original inhabitant.The hydrophobic grouping at molecule both ends plays association, is equivalent to
2 end bases of Bola type surfactant.Hydrophilic chain is equivalent to the connection chain of Bola type surfactant, can provide chemical steady
Qualitative and viscosity stability.
Dendrimer type surfactant, shape is similar to dendritic macromole, from a central core molecule, by propping up
Change monomer and spread the structure extended step by step, its advantage is that having pigment dispersion stability at a low viscosity.Because by pair
Its end group modification can produce multiple pigment affinity groups, reinforce the interaction with pigment.Further, since its molecular structure
Unanimously, and shape approximation elliposoidal, it is easier to obtain lower viscosity in dispersion.
Epoxy resin can also be selected from brominated epoxy resin, phenolic resin varnish type epoxy resin, bisphenol f type epoxy resin,
Bisphenol-A epoxy resin, glycidyl amine type epoxy resin, hydantoins type epoxy resin, alicyclic epoxy resin, three
Hydroxy phenyl methane type epoxy resin, union II toluene phenol-type epoxy resin or united phenol-type epoxy resin or their mixture；
Bisphenol-s epoxy resin, phenol novolak type epoxy resin, bisphenol A novolac type epoxy resin, four hydroxy phenyl ethane type epoxy resin, hetero ring type asphalt mixtures modified by epoxy resin
Rouge, o-phthalic acid diglycidyl ester resin, four glycidyl group xylenol ethane resin, containing Naphthol-based Epoxy Resin, have
The epoxy resin of dicyclopentadiene skeleton, glycidyl methacrylate copolymerization are epoxy resin, N-cyclohexylmaleimide
With the copolymerization epoxy resin of glycidyl methacrylate, CTBN modified epoxy, vinylcyclohexene dicyclic oxide,
(3 ', 4 '-epoxycyclohexyl-methyl) -3,4- epoxycyclohexane carboxylate, (3 ', 4 '-epoxies -6 '-methylcyclohexylmethyl) -3,
Cycloaliphatic epoxy resins such as 4- epoxy -6- methylcyclohexanecarboxylic acid ester etc..
Photoinitiator include benzoin and its derivative, acetophenone and its derivative, anthraquinone and its derivative, thioxanthones and
Its derivative, ketal and its derivative, benzophenone and its derivative and at least one of tertiary amine and its derivative.As benzene
Acyloin Derivatives, such as benzoin methylether, benzoin ethyl ether, benzoin iso-propylether etc.；As acetophenone derivs, such as 2,2-
Dimethoxy -2- phenyl acetophenone, 2,2- diethoxy -2- phenyl acetophenone, 1,1- dichloroacetophenone etc.；As anthraquinone-derivative
Object, such as 2-methylanthraquinone, 2- ethyl hydrazine, 2- tert-butyl anthraquinone, 1- chloroanthraquinone etc.；As thioxanthone derivates, such as 2,
4- dimethyl thioxanthone, 2,4- diethyl thioxanthone, 2-chlorothioxanthone, 2,4- diisopropylthioxanthone etc.；It is derivative as ketal
Object, such as acetophenone dimethyl ketal, benzil dimethyl ketal etc.；As benzophenone derivates, such as 4- benzoyl
Diphenylsulfide, 4- benzoyl -4 '-dimethyl diphenyl sulfide, 4- benzoyl -4 '-ethyl diphenyl thioether, 4- benzoyl
Base -4 '-propyl diphenylsulfide etc.；As tertiary amine compound, for example, ethanolamine compound, with dialkyl amido benzene structure
Compound, for example, 4,4 '-dimethylamino benzophenones, 4,4 '-diethylamino benzophenone, 7- (diethylamino) -4-
The cumarins containing dialkyl amido such as methyl -2H-1- chromen-2-one-(7- (diethylamino) -4- methylcoumarin)
Close object, ethyl 4-dimethylaminobenzoate, 2- dimethyl amino benzoate, 4- dimethylaminobenzoic acid (positive fourth oxygen
Base) ethyl ester, ESCAROL 507 isopentyl ethyl ester, 4- dimethylaminobenzoic acid 2- ethylhexyl etc..
It is black etc. that pigment is also selected from green phthalocyanine blue, phthalocyanine green, iodine, two diazonium Huangs, crystal violet, titanium dioxide, naphthalene.
It is also an option that in olefin(e) acid class levelling agent, fluorine class levelling agent and high score subclass levelling agent in additive as levelling agent
At least one.Additive can also be defoaming agent, coalescing agent.It can choose selected from organosiloxane and gather as defoaming agent
At least one of ethers.Coalescing agent in propandiol butyl ether, propylene glycol methyl ether acetate and alcohol ester 12 at least one
Kind.
The different organic solvent of boiling point includes but is not limited to any one of following compounds or at least any the two
Combination: low boiling point solvent oil, such as 6# solvent for extraction, boiling range is 60~90 DEG C；Medium-boiling solvent oil, such as rubber solvent naphtha,
Such as 120# solvent naphtha, boiling range is 80~120 DEG C；High boiling point solvent oil, such as 200# solvent naphtha, boiling range is 140~200 DEG C.
Above-described is only some embodiments of the present invention.For those of ordinary skill in the art, not
Under the premise of being detached from the invention design, various modifications and improvements can be made, these belong to protection model of the invention
It encloses.
Claims (6)
1. a kind of dumb light solder mask of polymolecularity, it is characterised in that formula includes: the propylene with carboxyl of 30 mass parts
Ester compound, the inorganic delustring filler of 0.5~20 mass parts, the organic quenching filler of 0.5~20 mass parts, 0.1~20 matter
Measure the surfactant of part, the epoxy resin of 5~30 mass parts, the photoinitiator of 1~5 mass parts, 1~5 mass parts pigment,
The organic solvent of the additive of 0.1~5 mass parts and 5~20 mass parts, the surfactant are that at least the block of type containing AB is high
Molecular surface active agent, Gemini type surfactant, Bola type surfactant, in Dendrimer type surfactant
It is any.
2. the dumb light solder mask of polymolecularity according to claim 1, it is characterised in that: the surfactant is AB
For the 1:1 mass of type block macromolecular surfactant and Dendrimer type surfactant than mixture, the AB type block is high
Molecular surface active agent is PBA-b-PDMAEA, and the Dendrimer type surfactant is PAMAM.
3. the dumb light solder mask of polymolecularity according to claim 1, it is characterised in that: organic solvent is that boiling range is different
A variety of organic solvents mixture.
4. the dumb light solder mask of polymolecularity according to claim 3, it is characterised in that: the organic solvent is that 6# takes out
The mixture of extraction solvent oil, 120# solvent naphtha and 200# solvent naphtha.
5. the dumb light solder mask of polymolecularity according to claim 1, it is characterised in that: the photoinitiator includes benzene
Acyloin and its derivative, acetophenone and its derivative, anthraquinone and its derivative, thioxanthones and its derivative, ketal and its derivative
Object, benzophenone and its derivative and at least one of tertiary amine and its derivative.
6. the dumb light solder mask of polymolecularity according to claim 1, it is characterised in that: the additive includes levelling
At least one of agent, defoaming agent and coalescing agent.
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| CN113652133A (en) * | 2021-07-14 | 2021-11-16 | 湖北敏捷志成标识科技有限公司 | Amphiphilic printing coating and preparation method and application thereof |
| CN114058212A (en) * | 2021-11-18 | 2022-02-18 | 惠州市艾比森光电有限公司 | Black matte ink, PCB and preparation method thereof |
| CN114395287A (en) * | 2021-12-30 | 2022-04-26 | 广州斯达利电子原料有限公司 | Solder resist ink, solder resist layer and Mini-LED printed circuit board |
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