CN109679402A - A kind of filling perforation filling special jack printing ink composition and printed circuit board - Google Patents
A kind of filling perforation filling special jack printing ink composition and printed circuit board Download PDFInfo
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- CN109679402A CN109679402A CN201811620072.0A CN201811620072A CN109679402A CN 109679402 A CN109679402 A CN 109679402A CN 201811620072 A CN201811620072 A CN 201811620072A CN 109679402 A CN109679402 A CN 109679402A
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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)
- Wood Science & Technology (AREA)
- Organic Chemistry (AREA)
- Inks, Pencil-Leads, Or Crayons (AREA)
- Non-Metallic Protective Coatings For Printed Circuits (AREA)
Abstract
The present invention relates to a kind of filling perforation filling special jack printing ink composition and printed circuit boards, wherein printing ink composition includes photocuring diluted alkaline aqueous developable resin and peroxide, the photocuring diluted alkaline aqueous developable resin is the photocuring diluted alkaline aqueous developable resin containing carboxyl and unsaturated double-bond in molecule, and the percentage that the weight of the peroxide accounts for printing ink composition weight is 0.1%-5.0%.Rabbet ink of the invention solves in rabbet ink that double bond reactivity is low by adding peroxide, performance deficiency problem caused by molecule cross-link degree is inadequate, realizes the excellent heat resistance, resistance to anti-thread breakage excellent and resistance to vacuolated excellent of rabbet ink.
Description
Technical field
The invention belongs to photosensitive field of electronic materials, it is related to a kind of filling perforation filling special jack printing ink composition and printing electricity
Road plate, in particular to a kind of heat resistance, special jack ink is filled in extremely excellent, resistance to anti-thread breakage, resistance to vacuolated excellent filling perforation
Composition and printed circuit board.
Background technique
With the continuous promotion of electronic product high-precision, high density and durable reliability requirement, for being filled into through-hole, leading
The requirement of permanent hole-filling composition in the hole portions such as through-hole is also higher and higher, traditional company's plug band print technique (printed circuit
Plate carries out the operation of through-hole ink plugging while the solder mask of wire mark two sides) it can no longer meet present PCB production requirement, it takes
And instead of be aluminium sheet printing technology.
The aluminium sheet printing technology, the technique generallyd use is: printing special jack ink with aluminium sheet, then uses silk
The techniques coating surface photocuring thermo-cured ink such as wire mark brush, electrostatic spraying, aerial spraying, roller coating, in 70-80 DEG C of temperature preliminary drying
It is dry, elective irradiation is carried out to composition using appropriate ultraviolet light, non-irradiation light part is cleaned up with dilute alkaline aqueous solution, left
Circuit board substrate hole in composition and surface composition be heating and curing in 60 DEG C to 160 DEG C temperature, then to printing
The surface treatments such as plate progress OSP, spray tin, heavy tin, heavy silver, change gold.
Even if, using special jack ink plugging, industry solder mask is spraying tin, heavy tin, is sinking using aluminium sheet printing technology
Silver is changed in the process of surface treatment such as gold, in hole ink (especially aperture is Φ 0.5mm) can crack, vacuole phenomena such as.
Chinese patent application CN201410821847 disclose it is a kind of suitable for can by aqueous alkali develop photocuring heat
Solidification compound and preparation method thereof, the photocuring heat-curable composition include the copolymer resin containing acrylic acid, neighbour
Cresol-novolak is denaturalized epoxy resin, Photoepolymerizationinitiater initiater, diluent, the acrylic acid in molecule at least two functional group and reacts single
Body or oligomer, inorganic filler agent, hardener for epoxy resin and stabilizer.The composition has certain change in heat resistance
Into, but degree of improvement is still to be improved.
Photocuring heat-curable composition provided by foregoing invention, after the composition is printed onto PCB circuit board through-hole,
Can mainly change in following three phases system: 1) 70-80 DEG C of prebake conditions remove solvent portion in ink；2) ultraviolet light
Irradiate photocuring, the double bond cross-linking polymerization in initiation system；3) high-temperature baking heat cure, epoxy resin is sent out under hot conditions
Raw open loop cross-linking reaction.
In Light Curing, since pigment, filler etc. are to the barrier effect of light in ink system, with ink thickness
Increase, light can successively decrease through the energy of ink, and there are great differences compared with surface ink for deep layer ink double bond crosslinking degree, especially
Rabbet ink, ink thickness can reach 200um or more (surface ink generally only has 25um), so rabbet ink is in photocuring
When hole in ink double bond cross-linking reaction degree it is very low, the performance issue showed is exactly heat resistance, resistance to anti-thread breakage, resistance to vacuolated
Etc. performances it is insufficient.
Summary of the invention
In order to solve the above technical problems, the present invention provides a kind of filling perforations to fill special jack printing ink composition, to reach
It is extremely excellent, resistance to anti-thread breakage and resistance to vacuolated excellent that consent performance reaches heat resistance.
Specifically, the present invention provides a kind of filling perforations to fill special jack printing ink composition, the printing ink composition includes
Photocuring diluted alkaline aqueous developable resin and peroxide, the photocuring diluted alkaline aqueous developable resin be in molecule containing carboxyl and
The photocuring diluted alkaline aqueous developable resin of unsaturated double-bond, the weight of the peroxide account for the percentage of printing ink composition weight
For 0.1%-5.0%.
Preferably, it is 0.5%-3.0% that the weight of peroxide, which accounts for the percentage of printing ink composition weight,.
Preferably, in above-mentioned rabbet ink composition, the peroxide accounts for the weight of photocuring diluted alkaline aqueous developable resin
Amount percentage is 2.0-12.5%.
Preferably, it is 1.12%-7.13% that peroxide, which accounts for the weight percent of photocuring diluted alkaline aqueous developable resin,.
Preferably, in above-mentioned rabbet ink composition, the peroxide be 2,2- it is bis--(tert-butyl peroxide) propane,
Hyperis, tertbutanol peroxide, hydrogen peroxide t-octyl, cumyl hydroperoxide, hydrogen peroxide di-t-butyl are different
Propylbenzene, di isopropyl benzene hydroperoxide, di isopropyl benzene hydroperoxide, hydrogen peroxide is to Meng's alkane, hydrogen peroxide tetrahydronaphthalene, the tertiary fourth of peroxidating two
Base, tert-Butylbenzene, tert-butyl peroxyisopropyl benzene, peroxide acetic acid butyl ester, peroxidating tert-butyl isobutyrate, mistake
Aoxidize the neopentanoic acid tert-butyl ester, peroxide -2-ethyl hexanoic acid tert-butyl, peroxidized t-butyl perbenzoate, phthalic peroxide
The tert-butyl ester, t-butylperoxyisopropyl carbonic ester, one of two carbonic ester of peroxidating diη-propyl or a variety of.
Preferably, in above-mentioned rabbet ink composition, the peroxide is hydrogen peroxide to Meng's alkane and peroxidating isobutyl
The mixture of tert-butyl acrylate, and hydrogen peroxide is 1 to the weight ratio of Meng's alkane and peroxidating tert-butyl isobutyrate: (0.2-5.0).
Preferably, in above-mentioned rabbet ink composition, the solid content of the photocuring diluted alkaline aqueous developable resin is 40-
80%, preferably 50-70%；The viscosity of photocuring diluted alkaline aqueous developable resin is 100-700dPa.s/25 DEG C, preferably 200-
600dPa.s/25 DEG C, the number-average molecular weight of photocuring diluted alkaline aqueous developable resin is between 500 to 5000；It is preferred that 800 to 4500
Between；The acid value of photocuring diluted alkaline aqueous developable resin is 30-180mgKOH/g, preferably 30-160mgKOH/g, more preferable 35-
130mgKOH/g。
Preferably, in above-mentioned rabbet ink composition, the photocuring diluted alkaline aqueous developable resin is made by the following method
It is standby to obtain.
Will in molecule containing there are two and the epoxy resin and molecule of more than two epoxy group in the list containing unsaturated double-bond
Carboxylic acid compound hybrid reaction obtains the resin containing hydroxyl and obtains photocuring diluted alkaline water with saturation or unsaturated acids anhydride reactant again
It can developable resin.
Preferably, it is described containing there are two and the epoxy resin of more than two epoxy group be bisphenol A epoxide resin, double F type rings
Oxygen resin, phenol aldehyde type epoxy resin, bisphenol-A epoxy resin, A Hydrogenated Bisphenol A F type epoxy resin, cycloaliphatic epoxy resin,
One of o-cresol type epoxy resin, glycolylurea epoxide resin, bisphenol-s epoxy resin and bisphenol fluorene base epoxy are more
Kind.Preferably, phenol aldehyde type epoxy resin is the multi-functional epoxy resin of line style phenolic aldehyde heat resistance, it is preferred that phenolic epoxy
Resin is o-cresol formaldehyde epoxy resin.
Preferably, the monocarboxylic acid compound containing unsaturated double-bond is methacrylic acid, acrylic acid and meat in the molecule
One of cinnamic acid is a variety of.
Preferably, the acid anhydrides is preferably itaconic anhydride, succinic anhydride, maleic anhydride, phthalic anhydride, tetrahydro benzene neighbour
Phthalate anhydride, methyl tetrahydrophthalic anhydride, hexahydrophthalic anhydride, methyl enlightening Nike acid anhydrides, trimellitic anhydride,
One of pyromellitic dianhydride and tetrahydrophthalic anhydride are a variety of.
Preferably, in above-mentioned rabbet ink composition also comprising unsaturated monomer, epoxy resin, Epoxy curing accelerators and
Photoepolymerizationinitiater initiater.
Preferably, unsaturated monomer is methyl propenoic acid glycidyl, glycidyl acrylate, allyl glycidol
Ether, 4- vinylbenzyl glycidyl ether, dipentaerythritol hexaacrylate, it is preferred that unsaturated monomer accounts for rabbet ink group
The weight percent for closing object is 1-10%, it is preferred that accounts for 3-7%.
Preferably, epoxy resin is one of phenol aldehyde type epoxy resin and glycolylurea epoxide resin or a variety of, epoxy resin
The weight percent for accounting for rabbet ink composition is 2-10%, it is preferred that epoxy resin is by phenol aldehyde type epoxy resin and glycolylurea ring
In the case that oxygen resin forms, the weight ratio of phenol aldehyde type epoxy resin and glycolylurea epoxide resin is 5: 8.
Preferably, Epoxy curing accelerators be imidazoles, 2-methylimidazole, 2- ethyl imidazol(e), 2-ethyl-4-methylimidazole,
2- phenylimidazole, 4- phenylimidazole, 1-cyanoethyl-2-phenylimidazole, 1- (2- cyanoethyl) -2-ethyl-4-methylimidazole etc.
Imdazole derivatives or Epoxy curing accelerators are dicyandiamide, benzyldimethylamine, 2,4,4- (dimethylamino)-N, N- dimethylbenzyl
The amine compounds such as base amine, 4- methoxyl group-N, N- dimethyl benzyl amine, 4- methyl-N, N- dimethyl benzyl amine or curable epoxide promote
Into agent be the hydrazine compounds such as adipic dihydrazide, sebacic dihydrazide or Epoxy curing accelerators are that the phosphatizations such as triphenylphosphine are closed
Object or Epoxy curing accelerators are guanamine, methyl guanamines, benzo guanamine, melamine, 2,4- diamino-
6- methacryloxyethyl-s-triazine, 2- vinyl -2,4- diamino-s-triazine, 2- vinyl -4,6- diamino-are equal
Triazine isocyanuric acid adduct, 2,4- diamino -6- methacryloxyethyl-s-triazine isocyanuric acid adduct etc.
Striazine derivative etc..The weight percent that Epoxy curing accelerators account for rabbet ink composition is 0.1-2.0%.
Preferably, in above-mentioned rabbet ink composition, Photoepolymerizationinitiater initiater (also referred to as photosensitizer) is styrax, styrax
The styrax and styrax alkyl ether or Photoepolymerizationinitiater initiater of methyl ether, styrax ethylether, styrax propyl ether etc. are benzene
Ethyl ketone, 2,2- dimethoxy -2- phenyl acetophenone, 2,2- diethoxy -2- phenyl acetophenone, 2,2- diethoxy -2- phenyl
The acetophenones or Photoepolymerizationinitiater initiater of acetophenone, 1,1- dichloroacetophenone etc. are 2- methyl-1-(4- (methyl thio phenyl)-2-
The aminoacetophenone class or light of morpholinyl -1- ketone, 2- benzyl -2- dimethylamino -1- (4- morphlinophenyl)-butanone -1 etc.
Polymerization initiator is 2-methylanthraquinone, 2- isopropyl thioxanthone anthraquinone, 4- isopropyl thioxanthone anthraquinone, isopropyl thioxanthone anthraquinone (isomery
Body mixture), 2- ethyl hydrazine, 2- tert-butyl anthraquinone, the Anthraquinones of 1- chloroanthraquinone etc. or Photoepolymerizationinitiater initiater be 2,4- diformazan
The thioxanthene ketone class or photopolymerization of base thioxanthones, 2,4- diethyl thioxanthone, 2-chlorothioxanthone, 2,4- diisopropylthioxanthone etc.
Initiator is the ketal class of acetophenone dimethyl ketal, benzyl dimethyl ketal etc.；Or Photoepolymerizationinitiater initiater is benzophenone etc.
Benzophenone or Photoepolymerizationinitiater initiater be xanthone class or Photoepolymerizationinitiater initiater be (2,6- Dimethoxybenzoyl)-
2,4,4- amyl phosphine oxides, bis- (2,4,6- trimethylbenzoyl)-phenyl phosphine oxides, 2,4,6- trimethyl benzoyl diphenyls
Base phosphine oxide, ethyl -2,4, the phosphinoxides or Photoepolymerizationinitiater initiater of 6- trimethylbenzoyl phenyl phosphine oxide etc. are various
Peroxide, titanocenes class initiator etc..These Photoepolymerizationinitiater initiaters can be used alone or combine two kinds or two kinds with
On be used in mixed way.It is especially preferred, Photoepolymerizationinitiater initiater be 2- methyl-1-(4- (methyl thio phenyl)-2- morpholinyl-1- ketone
Composition and isopropyl thioxanthone anthraquinone (isomer mixture), 2- methyl-1-be (4- (methyl thio phenyl)-2- morpholinyl-1- ketone
Composition and isopropyl thioxanthone anthraquinone (isomer mixture) weight ratio are 5: 1, and Photoepolymerizationinitiater initiater accounts for rabbet ink composition
Weight percent be 1-10%.
It preferably, also include filler, pigment, organic solvent, defoaming in printing ink composition in above-mentioned rabbet ink composition
Agent, dyestuff, heat polymerization inhibitors, adhesion promoter, dispersing agent, coupling agent, fire retardant, levelling agent, antioxidant, in thixotropic agent
It is one or more.
Preferably, filler is inorganic filler or organic filler.Wherein inorganic filler is preferably barium sulfate, barium titanate, oxidation
Si powder, fine-powdered silica flour, amorphous silica, talcum powder, clay, magnesium carbonate, calcium carbonate, aluminium oxide, aluminium hydroxide,
One of mica, kaolin are a variety of.Organic filler is preferably PI powder and polytetrafluorethylepowder powder.The average grain diameter of filler
D50 control is at 30 microns hereinafter, preferred filler average grain diameter D50 is less than 25 microns.Filling accounts for 20-40%.
Pigment is dark green, blue or green blue, carbon black, ultramarine, lithopone, permanent violet, permanent yellow, titanium dioxide etc., and pigment accounts for plug
The weight percent of hole printing ink composition is 0.1-1.0%.
Preferably, it is 0.5-10% that organic solvent, which accounts for the weight ratio of rabbet ink composition,.
The present invention also provides a kind of printed circuit boards, it is characterised in that circuit board passes through above-mentioned rabbet ink composition system
It is standby to obtain.
It is used to improve the heat resistance of rabbet ink composition, resistance to anti-thread breakage and resistance to vacuole the present invention also provides peroxide
Property purposes, it is characterised in that weight percent of the peroxide in rabbet ink composition be 0.1%-5%.
Preferably, in such use, the peroxide be 2,2- it is bis--(tert-butyl peroxide) propane, isopropyl peroxide
Change hydrogen, tertbutanol peroxide, hydrogen peroxide t-octyl, cumyl hydroperoxide, hydrogen peroxide di-t-butyl cumene, peroxide
Change hydrogen pinane, di isopropyl benzene hydroperoxide, hydrogen peroxide is to Meng's alkane, hydrogen peroxide tetrahydronaphthalene, di-t-butyl peroxide, peroxidating uncle
Butyl benzene, tert-butyl peroxyisopropyl benzene, peroxide acetic acid butyl ester, peroxidating tert-butyl isobutyrate, peroxidating neopentanoic acid
The tert-butyl ester, peroxide -2-ethyl hexanoic acid tert-butyl, peroxidized t-butyl perbenzoate, the phthalic peroxide tert-butyl ester, tertiary fourth
Base isopropyl peroxide carbonic ester, one of two carbonic ester of peroxidating diη-propyl or a variety of.
Preferably, in such use, the peroxide is hydrogen peroxide to Meng's alkane and peroxidating tert-butyl isobutyrate
Mixture, and hydrogen peroxide is 1 to the weight ratio of Meng's alkane and peroxidating tert-butyl isobutyrate: (0.2-5.0).
Beneficial effects of the present invention
Rabbet ink of the invention solves in rabbet ink that double bond reactivity is low by adding peroxide, molecule cross-link
Performance deficiency problem caused by degree is inadequate.
Printing ink composition of the invention realizes the excellent heat resistance, resistance to anti-thread breakage excellent, resistance to vacuolated excellent of rabbet ink
It is different.
Rabbet ink composition of the invention uses peroxide, and peroxide causes when high-temperature baking heat cure
Double bond cross-linking polymerization in composition, crosslink density greatly improve, and then show excellent heat resistance, resistance to blast hole
It is property, resistance to vacuolated, it can be used as printed circuit plate hole interior insulation welding resistance protection materials and be widely used.
Specific embodiment
Embodiment 1: the preparation of photocuring diluted alkaline aqueous developable resin
By o-cresol formaldehyde epoxy resin (Shandong holy well 704M), 203 grams, 0.5 gram of hydroquinone, diethylene glycol ether acetic acid
In 250 grams of addition three-necked flasks of ester (water-soluble solvent), stirring is heated to 100 DEG C to 110 DEG C heat preservations and dissolves 1 hour, it is ensured that is complete
After fully dissolved, 90 DEG C are cooled to, 72 grams of acrylic acid is added dropwise and N, the solution that 3 grams of N dimethyl benzylamine drip off, process in three hours
Temperature is raised to 105 DEG C to 110 DEG C after dripping and reacted 12 hours by 90-100 DEG C of temperature of middle control, and measurement acid value is less than
10mgKOH/g, material temperature cool to 90 DEG C, are added 100 grams of tetrahydrophthalic anhydride, and 90-95 DEG C keeps the temperature 4 hours, are detected with infrared spectrometer,
The peak 1780cm-1 disappears, and stops reaction, temperature is reduced to room temperature, obtains dark brown resin solution, resin viscosity is
260dPa.s/25 DEG C, solid content 60%, acid value 60mgKOH/g, number-average molecular weight 2100, obtaining photocuring diluted alkaline water can
Developable resin, abbreviation Resin A.
Embodiment 2: the preparation of rabbet ink composition
By the material mixture ratio (numerical value of each ingredient is weight value, and unit is gram) listed in following Tables 1 and 2, match respectively
Rabbet ink composition processed.Precise a variety of materials are stirred into container, with high speed disperser with 500 rpms of speed
Dispersion 15 minutes is mixed, then composition three-roll grinder is ground three times, makes the fineness of composition less than 15 microns.
The formula table of 1 rabbet ink composition embodiment 1-5 of table
| Ingredient | Embodiment 1 | Embodiment 2 | Embodiment 3 | Embodiment 4 | Embodiment 5 |
| Resin A | 450 | 401 | 446 | 441 | 431 |
| Hydrogen peroxide is to Meng's alkane | 1 | 5 | 1 | 3 | 5 |
| Peroxidating tert-butyl isobutyrate | 4 | 7 | 1 | ||
| Dipentaerythritol hexaacrylate | 45 | 45 | 45 | 45 | 45 |
| 907 | 50 | 50 | 50 | 50 | 50 |
| Isopropyl thioxanthone 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 |
| Dark green | 5 | 5 | 5 | 5 | 5 |
| BYK-354 | 8 | 8 | 8 | 8 | 8 |
| Phenol aldehyde type epoxy resin | 25 | 25 | 25 | 25 | 25 |
| Glycolylurea epoxide resin | 40 | 40 | 40 | 40 | 40 |
| Ultra-fine isocyanuric acid three-glycidyl ester | 43 | 43 | 43 | 43 | 43 |
| Diethylene glycol ether acetate | 10 | 10 | 10 | 10 | 10 |
In table 1, related substances are described as follows:
907 be Zhejiang Yang Fan photosensitizer 2- methyl-1-(4- methyl mercapto phenyl)-2- morpholinyl-1- acetone
KS-66 is the defoaming agent of Japanese SHIN-ETSU HANTOTAI chemistry
BYK-354 is the acrylic polyester class levelling agent of BYK company, Germany
The formula table of 2 rabbet ink composition embodiment 6-10 of table
| Ingredient | Embodiment 6 | Embodiment 7 | Embodiment 8 | Embodiment 9 | Embodiment 10 |
| Resin A | 421 | 411 | 450.5 | 391 | 451 |
| Hydrogen peroxide is to Meng's alkane | 5 | 20 | 0.5 | 60 | 0 |
| Peroxidating tert-butyl isobutyrate | 25 | 20 | |||
| Dipentaerythritol hexaacrylate | 45 | 45 | 45 | 45 | 45 |
| 907 | 50 | 50 | 50 | 50 | 50 |
| Isopropyl thioxanthone 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 |
| Dark green | 5 | 5 | 5 | 5 | 5 |
| BYK-354 | 8 | 8 | 8 | 8 | 8 |
| Phenol aldehyde type epoxy resin | 25 | 25 | 25 | 25 | 25 |
| Glycolylurea epoxide resin | 40 | 40 | 40 | 40 | 40 |
| Ultra-fine isocyanuric acid three-glycidyl ester | 43 | 43 | 43 | 43 | 43 |
| Diethylene glycol ether acetate | 10 | 10 | 10 | 10 | 10 |
In table 2, related substances are described as follows:
907 be Zhejiang Yang Fan photosensitizer 2- methyl-1-(4- methyl mercapto phenyl)-2- morpholinyl-1- acetone
KS-66 is the defoaming agent of Japanese SHIN-ETSU HANTOTAI chemistry
BYK-354 is the acrylic polyester class levelling agent of BYK company, Germany
The measurement of 3 rabbet ink composition properties of embodiment
Consent experiment is carried out according to the rabbet ink that Tables 1 and 2 is prepared, specific experiment process is as follows:
To thickness 2.0mm, plated through hole diameter 0.2mm, 0.3mm, 0.4mm, 0.5mm, 0.6mm, through-hole spacing 1mm's is double
Face substrate (is unpatterned, each via count 50), carries out pickling+polish-brush as pre-treatment, then utilizes semi-automatic print
The rabbet ink composition of brush machine previous embodiment and comparative example carries out aluminium flake filling perforation printing, dries in 75 DEG C of constant temperature ovens
It 50 minutes, is cooled to room temperature, take 21 rank exposure guide rules as the energy of 10 lattice, substrate is exposed, conventional using circuit board plant
Developing process develops, then, by substrate in 80 DEG C 1 hour, 120 DEG C 30 minutes, carry out in 150 DEG C of 1 hour baking ovens after
Solidification obtains evaluation substrate.
Then its heat resistance, resistance to blast hole, resistance to vacuolated, tool are measured to the circuit board Jing Guo rabbet ink compositions-treated
Bulk measurement method is as follows:
Heat resistance measurement method are as follows: it will be evaluated in gained and coat water-soluble flux on substrate cured coating film, static 1 point
Then clock is immersed in the solder bath for be redefined for 288 DEG C 10 seconds, repeat the above movement three times, pass through 50 DEG C or so of heat
Water rinses after cleaning scaling powder, to pass through expansion, the removing, hair that 50 times of magnifying glass visual detections evaluate the cured coating film in aperture
It is white.Determinating reference is as follows.
It is excellent: dipping three times after, do not observe coating and hole edge have whiten, expand, peeling；
It is good: dipping three times after, coating and hole edge have 1-2 point whiten, expand, peeling；
It is qualified: dipping three times after, coating and hole edge have 3-5 point whiten, expand, peeling；
Unqualified: after impregnating three times, coating and hole edge have 5 points or more to whiten, expand, peeling.
Resistance to spalttupfel measurement method are as follows: the evaluation substrate obtained, cut through-hole diameter 0.2mm, 0.3mm,
0.4mm, 0.5mm, 0.6mm, grinding cut face, with the solidfied material in optical microscopy observation through-hole, evaluate cured coating film in hole
The presence or absence of generation of crackle.
It is excellent: flawless in hole；
It is good: cured coating film slightly crackle in hole；
Qualified: cured coating film has crackle but is not attached to aperture in hole；
Unqualified: cured coating film has a large amount of crackles and is connected to aperture in hole.
Resistance to vacuolated measurement method are as follows: take obtained evaluation substrate, cut through-hole diameter 0.2mm, 0.3mm,
0.4mm, 0.5mm, 0.6mm, grinding cut face, with the solidfied material in optical microscopy observation through-hole, evaluate cured coating film in hole
The presence or absence of generation of vacuole.
Excellent: cured coating film is without vacuole in hole；
It is good: cured coating film vacuole quantity 1-5 in hole；
It is qualified: cured coating film vacuole quantity 6-10 in hole；
Unqualified: cured coating film vacuole quantity is greater than 10 in hole.
Specific measurement result such as the following table 3.
The performance measurement table of 3 rabbet ink composition of table
It can be seen from Table 3 that the presence of peroxide can significantly improve rabbet ink heat resistance, it is resistance to anti-thread breakage and
Resistance to vacuolated, the content of peroxide is the case where the content that 0.1-5% and peroxide account for Resin A is 2-12.5%, consent
For the performance that ink composition exhibits go out more than qualification, the content of peroxide accounts for Resin A in 0.5-3.0% and peroxide
Content the case where being 1.12-7.13%, performance that rabbet ink composition is shown is excellent.
Embodiment 4: the rabbet ink performance detection after change peroxide
The specific ingredient of peroxide in Tables 1 and 2 formula in embodiment 2 is changed, by peroxide mistake
Oxidation the tert-butyl alcohol be changed to 2,2- it is bis--(tert-butyl peroxide) propane, hydrogen peroxide t-octyl, di isopropyl benzene hydroperoxide, peroxidating
After tert-butyl benzene, peroxidating tert-butyl isobutyrate and peroxidized t-butyl perbenzoate, guaranteeing peroxide in rabbet ink group
Close object in content be 0.1-5.0% and peroxide account for Resin A weight percent be 2.0%-12.5% in the case where,
The performance of rabbet ink composition can reach the standard of qualification or more, the even up to good above standard.
Claims (10)
1. special jack printing ink composition is filled in a kind of filling perforation, the printing ink composition includes photocuring diluted alkaline aqueous developable resin
And peroxide, the photocuring diluted alkaline aqueous developable resin are the photocuring diluted alkaline containing carboxyl and unsaturated double-bond in molecule
Aqueous developable resin, the percentage that the weight of the peroxide accounts for printing ink composition weight is 0.1%-5.0%.
2. rabbet ink composition according to claim 1, it is characterised in that the weight of the peroxide accounts for ink group
The percentage of polymer weight is 0.5%-3.0%.
3. rabbet ink composition according to claim 1, it is characterised in that the peroxide accounts for photocuring diluted alkaline water
Can developable resin weight percent be 2.0-12.5%.
4. rabbet ink composition according to claim 3, it is characterised in that the peroxide accounts for photocuring diluted alkaline water
Can developable resin weight percent be 1.12%-7.13%.
5. rabbet ink composition according to claim 1-4, it is characterised in that the peroxide is 2,2-
Double-(tert-butyl peroxide) propane, hyperis, tertbutanol peroxide, hydrogen peroxide t-octyl, hydrogen peroxide isopropyl
Benzene, hydrogen peroxide di-t-butyl cumene, di isopropyl benzene hydroperoxide, di isopropyl benzene hydroperoxide, hydrogen peroxide is to Meng's alkane, hydrogen peroxide
Tetrahydronaphthalene, di-t-butyl peroxide, tert-Butylbenzene, tert-butyl peroxyisopropyl benzene, peroxide acetic acid butyl ester,
Peroxidating tert-butyl isobutyrate, tert-Butyl peroxypivalate, peroxide -2-ethyl hexanoic acid tert-butyl, perbenzoic acid uncle
Butyl ester, the phthalic peroxide tert-butyl ester, t-butylperoxyisopropyl carbonic ester, in two carbonic ester of peroxidating diη-propyl
It is one or more.
6. rabbet ink composition according to claim 5, it is characterised in that the peroxide is hydrogen peroxide to Meng
The mixture of alkane and peroxidating tert-butyl isobutyrate, and hydrogen peroxide is to the weight ratio of Meng's alkane and peroxidating tert-butyl isobutyrate
1∶(0.2-5.0)。
7. a kind of printed circuit board, it is characterised in that circuit board is combined by rabbet ink described in any one of claims 1-6
Object is prepared.
8. peroxide is used to improve heat resistance, the resistance to anti-thread breakage and resistance to vacuolated purposes of rabbet ink composition, feature
It is that weight percent of the peroxide in rabbet ink composition is 0.1%-5%.
9. purposes according to claim 8, it is characterised in that the peroxide be 2,2- it is bis--(tert-butyl peroxide) third
Alkane, hyperis, tertbutanol peroxide, hydrogen peroxide t-octyl, cumyl hydroperoxide, hydrogen peroxide di-t-butyl
Cumene, di isopropyl benzene hydroperoxide, di isopropyl benzene hydroperoxide, hydrogen peroxide is to Meng's alkane, hydrogen peroxide tetrahydronaphthalene, two uncle of peroxidating
Butyl, tert-Butylbenzene, tert-butyl peroxyisopropyl benzene, peroxide acetic acid butyl ester, peroxidating tert-butyl isobutyrate,
Tert-Butyl peroxypivalate, peroxide -2-ethyl hexanoic acid tert-butyl, peroxidized t-butyl perbenzoate, peroxidating O-phthalic
Tert-butyl acrylate, t-butylperoxyisopropyl carbonic ester, one of two carbonic ester of peroxidating diη-propyl or a variety of.
10. purposes according to claim 8, it is characterised in that the peroxide is hydrogen peroxide to Meng's alkane and peroxidating
The mixture of tert-butyl isobutyrate, and hydrogen peroxide is 1: (0.2- to the weight ratio of Meng's alkane and peroxidating tert-butyl isobutyrate
5.0)。
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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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| Application Number | Priority Date | Filing Date | Title |
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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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| CN109679402A true CN109679402A (en) | 2019-04-26 |
| CN109679402B CN109679402B (en) | 2022-02-08 |
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Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN114702925A (en) * | 2022-04-01 | 2022-07-05 | 中交第二航务工程局有限公司 | Special glue for reinforcing steel structure and preparation method thereof |
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| CN109679402B (en) | 2022-02-08 |
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