CN110054929A - One kind having imide structure photosensitive-ink and its application - Google Patents
One kind having imide structure photosensitive-ink and its application Download PDFInfo
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- CN110054929A CN110054929A CN201910113424.1A CN201910113424A CN110054929A CN 110054929 A CN110054929 A CN 110054929A CN 201910113424 A CN201910113424 A CN 201910113424A CN 110054929 A CN110054929 A CN 110054929A
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- anhydride
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
- C09D11/00—Inks
- C09D11/02—Printing inks
- C09D11/03—Printing inks characterised by features other than the chemical nature of the binder
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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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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
- C09D11/00—Inks
- C09D11/02—Printing inks
- C09D11/10—Printing inks based on artificial resins
- C09D11/102—Printing inks based on artificial resins containing macromolecular compounds obtained by reactions other than those only involving unsaturated carbon-to-carbon bonds
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- Chemical Kinetics & Catalysis (AREA)
- General Chemical & Material Sciences (AREA)
- Inks, Pencil-Leads, Or Crayons (AREA)
- Epoxy Resins (AREA)
- Non-Metallic Protective Coatings For Printed Circuits (AREA)
Abstract
The present invention relates to ink areas, to solve the problems, such as that it is excessive that tradition FPC solder mask dielectric constant/dielectric is consumed, the invention proposes a kind of application with imide structure photosensitive-ink and its in flexible circuit board, there is one kind imide structure photosensitive-ink to be mixed by following components system: photosensitive resin 30-55, the epoxy resin 5-20 with imide structure, photoinitiator 2.5-8.5, acrylic monomers 2-10, filler material 10-35, solvent 20-40, pigment 0.5-50, auxiliary agent 1-7.It not only ensure that photosensitive-ink dielectric constant on wiring board/dielectric consume is lower, but also ink has heat resistance and chemical resistance and anti-flammability, while ensure that bending resistance after ink solidification.
Description
Technical field
The present invention relates to ink areas, and in particular to one kind has imide structure photosensitive-ink and its in flexible circuit board
On application.
Background technique
FPC is also known as flexible printed circuit board, is the printed circuit board made of insulating substrate flexible, its Distribution density
It is high, light-weight, thickness is thin, bending is good, it can allow the volume of electronic product to become smaller significantly, meet electronic product to highly dense
Degree, miniaturization, high reliability direction are developed.Therefore, FPC space flight, military affairs, mobile communication, laptop computer, computer peripheral equipment,
It is widely used on the fields such as smart phone, digital camera or product.Under consumer electronics demand for development, FPC is also
It will develop to ultra high density direction.5G is compared with the 4G epoch, from the technical point of view, whole is high-frequency high-speed, loss, differential loss etc.
Index promotes a level further along, currently, the material that is lost in still using, behind can move towards low-loss material application.
Traditional FPC solder mask is former for starting with modified bisphenol A type epoxy resin or modified bisphenol F type epoxy resin
It is photosensitive resin that material, which connects unsaturated bond and carboxylic group, the heat resistance and endurance of the photosensitive resin of synthesis and resistant to bending
Property, but dielectric constant/dielectric consume is excessive.
Summary of the invention
To solve the problems, such as that tradition FPC solder mask dielectric constant/dielectric is consumed excessive, the invention proposes one kind to have
Imide structure photosensitive-ink not only ensure that photosensitive-ink dielectric constant on wiring board/dielectric consume is lower.And ink has
There are heat resistance and chemical resistance, while ensure that bending resistance after ink solidification.
The present invention has also gone out the application with imide structure photosensitive-ink in flexible circuit board.
The present invention is achieved by the following technical solutions: one kind has imide structure photosensitive-ink by following components system
It is mixed, in parts by weight:
It is preferably, a kind of that there is imide structure photosensitive-ink to be mixed by following components system, in parts by weight:
The epoxy resin with imide structure the preparation method comprises the following steps: substance containing acid anhydrides and structural material containing NCO
It reacts and is reacted 1-10 hours at 80-200 DEG C in the presence of solvent, is added in dissolved fluorinated epoxy resin in a solvent
In 60-150 DEG C of reaction time 1-10 hour, obtain the epoxy resin with imide structure.
Wherein, the parts by weight of each reactant are as follows:
Preferably, the parts by weight of each reactant are as follows:
The photosensitive resin has the modified bisphenol A epoxy acrylic resin that can be purchased in the market, modified bisphenol F epoxy
Acrylic resin, polyester acrylate resin, acrylic copolymeric resin can also be using the fluorine-containing photosensitive tree with imide structure
Rouge, the preparation method comprises the following steps: by fluorinated epoxy resin, after fluorine-containing epoxy resin does not dissolve in a solvent, under the action of catalyst and not
Saturated monocarboxylic acid and after being reacted 1-10 hours at 70-140 DEG C of reaction temperature it is stand-by；With substance containing acid anhydrides and NCO structure
Mixture reacts in the presence of solvent reacted 1-10 hours at 80-200 DEG C after be added in above-mentioned stand-by resin, reaction temperature 50-
140 DEG C, time 1-10 hour, then with substance reaction containing acid anhydrides, 70-140 DEG C of reaction temperature, time 1-10 hour, had
The photosensitive resin of imide structure, it is however preferred to have the photosensitive resin of imide structure.
Wherein, the parts by weight of the photosensitive resin reaction each component with imide structure are as follows:
Preferably, the parts by weight of reaction each component are as follows:
It is above-mentioned to state substance containing acid anhydrides and be selected from phthalic anhydride, tetrabydrophthalic anhydride, hexahydrophthalic anhydride, suitable
Anhydride maleique, tung oil acid anhydride, alkylene succinic anhydride, methyl tetrahydro phthalic anhydride, methylhexahydrophthalic anhydride, nadic acid
Acid anhydride, methylnadic anhydride, glutaric anhydride, terpenes acid anhydrides, methyl cyclohexene tetracarboxylic dianhydride, dodecenylsuccinic acid acid anhydride, partially
Benzenetricarboxylic acid acid anhydride, hydrogenation trimellitic anhydride, pyromellitic acid anhydride, hydrogenated pyromellitic anhydride, benzophenone tetracarboxylic dianhydride,
The double trimellitic anhydride esters of poly- azelaic acid acid anhydride, poly- sebacic acid acid anhydride, ethylene glycol, inclined three acid anhydride ester of glycerine three, diphenyl sulfone tetracarboxylic acid
Acid dianhydride, polyadipate acid anhydride, poly- azelaic acid acid anhydride, poly- sebacic acid acid anhydride, trialkyl for one of tetrabydrophthalic anhydride or
It is several.
Above-mentioned structural material containing NCO be selected from methyl diisocyanate (TDI), methyl diphenylene diisocyanate (MDI),
Poly methylene poly phenyl poly isocyanate (PAPI), dicyclohexyl methyl hydride diisocyanate (HMDI), 1,5- naphthalene diisocyanate
(NDI), hexamethylene diisocyanate (HDI), isophorone diisocyanate (IPDI), triphenylmethane triisocyanate
(TTI), benzene dimethylene diisocyanate (XDI), paraphenylene diisocyanate (PPDI), 3,3 '-dimethyl diphenyl -4,4 '-two
Isocyanates (TODI), front three group diisocyanate (TMDI), hydrogenation XDI, hydrogenation MDI, tri o cresyl thiophosphate phenyl isocyanate
(TPTI) and its addition product of isocyanate compound listed above, biuret modified isocyanates are (such as biuret modified
HDI etc.) and isocyanuric acid tripolymer (such as HDI trimer, IPDI tripolymer), organic-silicon-modified isocyanates (can be by two
Isocyanates and organic siliconresin reaction), one or more of isocyanate derivates.
The fluorinated epoxy resin is selected from diphenylol hexafluoropropane diglycidyl ether, bis- (the 3- glycidol ethers of 1,3-
Base tetrafluoro phenoxy group) -2- hydroxy propane, bis- (hydroxyl hexafluoro isopropyl) the benzene diglycidyl ethers of Isosorbide-5-Nitrae -, bis- (the hydroxyl hexafluoros of 1,3-
Isopropyl) benzene diglycidyl ether, the positive perfluoro propyl benzene diglycidyl ether of 1,3- bis- (hydroxyl hexafluoro isopropyls), Isosorbide-5-Nitrae-be bis-
(hydroxyl hexafluoro isopropyl) phenyl tetrafluoride diglycidyl ether, 4,4, two contracting glycerin ether of-dihydroxy octafluorobiphenyl, 4,4 ,-bis- (hydroxyls
Hexafluoro isopropyl) two one or more of contracting glycerin ether of octafluorobiphenyl, as long as the category of the fluorine richness epoxy resin scope
In.
In order to reduce cost, non-fluorine-containing epoxy resin can be partially selected, non-fluorine-containing epoxy resin includes bisphenol-A epoxy tree
Rouge, bisphenol F epoxy resin, bisphenol-A D epoxy resin, bisphenol-s epoxy resin, resorcinol type epoxy resin, hydrogenated bisphenol A ring
Oxygen resin, biphenyl epoxy resin, modifying epoxy resin by organosilicon, o-cresol formaldehyde epoxy resin, phenol formaldehyde (PF) epoxy resin,
Resorcinol formaldehyde epoxy resin, other more phenolic tetraglycidel ether epoxy resins, aliphatic glycidyl ether epoxy resin, epoxy
Change olefin(e) compound, non-fluorine-containing epoxy resin can not select or select according to demand one of or several.
The solvent is a kind of in ketone, alcohols, esters, ethers, benzene class, petroleum-type equal solvent, and usage amount is to make
The amount of solute dissolution, but prepared in the epoxy resin with imide structure with the fluorine-containing photosensitive resin with imide structure
In the process, total solvent usage amount is limited, and is because solid content needs to control.Preferably ethylene glycol monoethylether acetate,
Ethylene glycol monomethyl ether acetate, diethylene glycol monomethyl ether acetic acid esters, diethylene glycol monoethyl ether acetic acid esters, diethylene glycol monobutyl ether second
Acid esters, propylene glycol methyl ether acetate, propylene glycol monoethyl ether acetate, propylene glycol monobutyl ether acetic acid esters, dipropylene glycol monomethyl ether
Acetic acid esters, dipropylene glycol monoethyl ether acetic acid esters, Dipropylene glycol mono-n-butyl Ether acetic acid esters, glycol monoethyl ether, second in ether solvent
2-ethoxyethanol, ethylene glycol monobutyl ether, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, diethylene glycol monobutyl ether, propylene glycol list
Methyl ether, dihydroxypropane single-ether, propylene glycol monobutyl ether, dipropylene glycol monomethyl ether, dipropylene glycol monoethyl ether, Dipropylene glycol mono-n-butyl Ether,
Gamma-butyrolacton, n-methyl-2-pyrrolidone, dimethylformamide, dimethyl acetamide, dimethylpropionamide one of
Or it is a variety of.
The photoinitiator is selected from 2- hydroxy-methyl phenyl-propane -1- ketone (photoinitiator -1173), 1- hydroxy-cyclohexyl
Phenyl ketone (photoinitiator-184), 2- methyl-1-(4- methyl mercapto phenyl)-2- morpholinyl-1- acetone (photoinitiator-907),
Benzoin dimethylether BDK (photoinitiator -651), 2,4,6-trimethylbenzoyldiphenylphosphine oxide (photoinitiator -
1110), isopropyl thioxanthone (mixing of 2,4 isomeries) ITX (photoinitiator -1105), 4- (N, N- dimethylamino) benzoic acid second
Ester EPD (photoinitiator -1101), EDAB, benzophenone BP, BZO (photoinitiator -1220), 4- chlorobenzophenone are (light-initiated
Agent -1046), methyl o-benzoylbenzoate (photoinitiator -1156), diphenyl iodnium hexafluorophosphate (photoinitiator -
810), 4- phenyl benzophenone (photoinitiator-PBZ), 2,4,6- trimethylbenzoy-dipheny phosphine oxide (photoinitiators-
TPO), 2,4,6- trimethylbenzoyl phenyl phosphinic acid ethyl esters (photoinitiator-TPO-L), 20%1- hydroxycyclohexylphenyl first
Ketone 80%2- methyl -2- hydroxyl -1- phenyl -1- acetone (photoinitiator -1000), 50%TPO；50%1173 (photoinitiators-
4265), photoinitiator-DETX, contraposition N, the different monooctyl ester of N- dimethylaminobenzoic acid (photoinitiator-EHA), 4- methyl benzophenone
(photoinitiator-MBZ), o-benzoyl yl benzoic acid methyl esters (photoinitiator-OMBB), bis- (1- (2,4- difluorophenyl) -3- pyrroles
Base) titanocenes, one of Hexaarylbiimidazole or a variety of.
The acrylic monomers is selected from tetrahydrofuran acrylate, 2- phenoxyethyl acrylate, acrylic acid, methyl-prop
Olefin(e) acid isobornyl thiocyanoacetate, methacrylic acid, caprolactone, isobornyl acrylate, trimethylolpropane formal acrylic acid
Ester, alkoxy nonyl phenol acrylate, triethylene-glycol dimethylacrylate, 1,6- hexanediyl ester, 1,
3- butanediol dimethylacrylate, trimethylolpropane trimethacrylate, pentaerythritol triacrylate, (3) ethoxylation
Trimethylolpropane trimethacrylate (EO3TMPTA), (9) ethoxylated trimethylolpropane triacrylate (EO9TMPTA),
(3) propoxylation trimethylolpropane trimethacrylate (PO3TMPTA), dipentaerythritol hexaacrylate, caprolactone modification two
Six acrylate of pentaerythrite, pentaerythritol tetraacrylate, Dipentaerythritol Pentaacrylate, three (2- ethoxy) isocyanic acids
Urea ester, trimethylol-propane trimethacrylate, trimethylolpropane trimethacrylate, (2) propoxyl group neopentyl glycol dipropyl
One of olefin(e) acid ester (PO2-NPGDA), polyethylene glycol (600) diacrylate, 1,3-BDO dimethylacrylate or
It is a variety of.
The filler material is selected from there are commonly barium sulfate, silicates and Calcium carbonates；Preferably clay, talcum powder, cloud
Female powder, flake asbestos, there are also silica, calcium hydroxide, magnesium hydroxide, calcium carbonate, blanc fixe, montmorillonite, one or more.
The pigment includes organic pigment and inorganic pigment.Inorganic pigment is selected from oxide, chromate, sulfate, carbonic acid
Salt, silicate, borate, molybdate, phosphate, vanadate, ferricyanate, hydroxide, sulfide, metal, in carbon black
It is a kind of.It is more that organic pigment can be divided into azo pigments, phthalocyanine color, anthraquinone, indigoids, quinacridone etc. by the chemical structure of compound
One of ring pigment, fragrant methaneseries pigment etc..
The auxiliary agent is selected from one of promotor, defoaming agent, levelling agent, dispersing agent or a variety of.Defoaming agent is mainly
Organic silicon defoaming agent or acryl-based antifoaming agent, the use of defoaming agent, levelling agent, dispersing agent are for photosensitive covering material
It is smooth glossy to print rear surface.
There is one kind imide structure photosensitive-ink can add fire retardant, and phosphorus flame retardant includes inorganic phosphorus flame retardant
And organic phosphorus flame retardant, nitrogenated flame retardant general types have melamine, melamine cyanurate (MCA) etc., can not add
Add or add one or more.
The unsaturated monocarboxylic acid is selected from fluorine-containing, acrylic acid, methacrylic acid, undecenoic acid, 5- hexene
One of acid, butenoic acid, penetenoic acid are a variety of.
The catalyst is selected from dimethylbenzyl ammonia, (R)-NN- dimethyl -1- ((S) -2- diphenylphosphine) ferrocene) second
Amine, 1,1 '-bis- (diphenylphosphine) ferrocene, 2- (diphenylphosphino) ethamine, N, N- dimethylethanolamine, N, N- dimethyl formyl
Amine, triethylamine, triethanolamine, trimethyl benzyl ammonia chloride, tri-methyl benzyl ammonium bromide, triethyl benzyl ammonia chloride, triethyl group
Benzylphosphonium Bromide ammonium, cobalt naphthenate, manganese naphthenate, lead naphthenate, zinc naphthenate, calcium naphthenate, copper naphthenate, iron naphthenate, ring
One of alkanoic acid barium, zirconium naphthenate, magnesium naphthenate, nickel naphthenate are a variety of.
A kind of application with imide structure photosensitive-ink on flexible printed circuit board.The present invention uses one
There is kind the epoxy resin of imide structure to pass through photocuring and heat cure for the liquid photosensitive solder mask of main raw material(s), it
Existing excellent heat resistance, endurance, flexibility, are also equipped with certain anti-flammability, are applicable in the circuit board.
Compared with prior art, the beneficial effects of the present invention are:
(1) the advantages that photosensitive resin of the invention, photocurable, liquid alkali developing；
(2) there is lower dielectric constant/dielectric dissipation factor using the photosensitive-ink that photosensitive resin of the invention produces,
Flexibility is excellent, heat-resist, chemical-resistance and has many advantages, such as certain anti-flammability.
Specific embodiment
Technical solution of the present invention is described further below with reference to embodiment, it is raw materials used commercially available in embodiment or
It is prepared using conventional method.
Preparation example 1: there is imide structure photosensitive resin 1
50 grams of Solvents N-methyl -2-Pyrrolidone are poured into three-necked flask, and 40 grams of IPDI and tetrahydro O-phthalic is added
27.4 grams of acid anhydrides, stand-by, 60 grams of Solvents N-methyl -2-Pyrrolidone of the addition in another flask in 10 hours is reacted at 80 DEG C,
100 grams of diphenylol hexafluoropropane diglycidyl ether, is heated to 140 DEG C, 32.4 grams of acrylic acid is added after dissolution, triphen
1 gram of base phosphorus is reacted 1 hour at 140 DEG C, is cooled to 50 DEG C, and above-mentioned stand-by resin is added, keeps the temperature 10 hours at 50 DEG C, adds and contain
40 grams of acid anhydrides substance tetrabydrophthalic anhydride is heated to 140 DEG C and reacts 1 hour, obtains with imide structure photosensitive resin
1。
Preparation example 2: there is imide structure photosensitive resin 2
60 grams of solvent gamma-butyrolacton are poured into three-necked flask, are added 10 grams and 6.3 grams of pyromellitic acid anhydride of TDI,
Stand-by, 40 grams of solvent gamma-butyrolacton of the addition in another flask in 4 hours, 4,4 '-dihydroxy octafluoros of addition are reacted at 150 DEG C
30 grams of two contracting glycerin ether of biphenyl, is slowly heated to 120 DEG C, and dissolution finishes, and adds 10.6 grams of methacrylic acid, dimethylbenzyl ammonia
10 grams are reacted 4 hours at 120 DEG C, are cooled to 100 DEG C, and above-mentioned stand-by resin is added, keeps the temperature 4 hours at 100 DEG C, adds containing acid
It 9.0 grams of succinic anhydride of acid anhydride substance alkylene, is heated to 100 DEG C and reacts 5 hours, obtain with imide structure photosensitive resin 2.
Preparation example 3: there is imide structure photosensitive resin 3
50 grams of solvent dimethylformamide are added in three-necked flask, is added 10 grams of HDI, is warming up to 200 degrees Celsius, half
Hour average rate is added 6.78 grams of glutaric anhydride, keeps the temperature 1 hour for use, dimethylformamide 100 is poured into another three-necked flask
Gram, 90 grams of -2- hydroxy propane of addition 1,3- bis- (3- glycidyl ether tetrafluoro phenoxy groups), 10 grams of biphenyl epoxy resin, slowly
70 DEG C are heated to, dissolution finishes, and adds 34 grams of butenoic acid, and 20 grams of trimethyl benzyl ammonia chloride are reacted 9 hours at 70 DEG C, heating
To 140 DEG C, above-mentioned stand-by resin is added, keeps the temperature 1 hour at 140 DEG C, adds the methylhexahydrophthaacid acid of substance containing acid anhydrides
50 grams of acid anhydride, 10 hours are kept the temperature at 70 DEG C, is obtained with imide structure photosensitive resin 3.
Preparation example 4: the epoxy resin 1 with imide structure
50 grams of Solvents N-methyl -2-Pyrrolidone are poured into three-necked flask, and 40 grams of IPDI and phthalic anhydride is added
26.0 grams, 10 hours are reacted at 80 DEG C for use, 60 grams of Solvents N-methyl -2-Pyrrolidone of the addition in another flask, 1,3-
Bis- (hydroxyl hexafluoro isopropyls) positive 100 grams of diglycidyl ether of perfluoro propyl benzene, is heated to 100 DEG C, adds after dissolution
Above-mentioned stand-by resin keeps the temperature 5 hours at 100 DEG C, obtains the epoxy resin 1 with imide structure.
Preparation example 5: the epoxy resin 2 with imide structure
40 grams of solvent dimethylformamide are poured into three-necked flask, are added 60 grams and 55 grams of methyl tetrahydro phthalic anhydride of MDI,
5 hours stand-by, 70 grams of solvent dimethylformamide of addition, diphenylol hexafluoropropane two in another flask are reacted at 150 DEG C
160 grams of glycidol ether, 140 DEG C are heated to, above-mentioned stand-by resin is added after dissolution, 8 hours is kept the temperature at 80 DEG C, obtains
Epoxy resin 3 with imide structure.
Preparation example 6: the epoxy resin 3 with imide structure
50 grams of solvent dimethylformamide are added in three-necked flask, is added 10 grams of HDI, is warming up to 200 degrees Celsius, half
Hour average rate is added 6.78 grams of glutaric anhydride, keeps the temperature 1 hour for use, dimethylformamide 100 is poured into another three-necked flask
Gram, it is added 80 grams of phenyl tetrafluoride diglycidyl ether of Isosorbide-5-Nitrae-bis- (hydroxyl hexafluoro isopropyls), 15 grams of biphenyl epoxy resin, slowly heats
To 70 DEG C, dissolution is finished, and is added above-mentioned stand-by resin, is kept the temperature 1 hour at 150 DEG C, obtain the epoxy with imide structure
Resin 3.
Embodiment 1-5
The photosensitive resin 1-3 of imide structure prepared by preparation example 1,2,3, prepared by preparation example 4,5,6 has acid imide
The epoxy resin of structure and commercially available photosensitive resin are mixed with initiator, acrylic monomers, filler material, solvent, pigment, auxiliary agent respectively
It grinds to obtain different photosensitive-ink numbers to be respectively that A, B, C, D, E, F, G implement formula table such as table by three-roller after closing uniformly
Shown in 1, it is in parts by weight.
Table 1:
Experimental performance evaluation
By above-mentioned A-H, totally 8 tests are respectively printed on PI (polyimides), and ink thickness is 20-25 μm, 75 DEG C of bakings
30 minutes, using 500mj/cm2Energy exposure, finally solidify 60 minutes in 150 DEG C of heated-air circulation roaster.It presses respectively
According to following performance test:
One, chemical resistance:
Two, heat resistance
Three, electrical characteristic
Four, environmental characteristics
| A | B | C | D | E | F | G | |
| Dk | 2.6 | 2.7 | 2.6 | 3.1 | 3.0 | 3.9 | 3.6 |
| Df | 0.001 | 0.001 | 0.001 | 0.005 | 0.005 | 0.015 | 0.019 |
Five, bending resistance: 180 ° of angle doublings, not have slight crack as standard.
| A | B | C | D | E | F | G | |
| Number resistant to bending | 20 | 20 | 22 | 3 | 3 | 0 | 0 |
Six, anti-flammability is tested: test basis: UL94, the vertical burn test of Chapter 11 thin material
From experimental result above it is found that more than 7 tests chemical resistance, flexibility, resistance to after photocuring and heat cure
Hot, electrical characteristic, environmental characteristics can meet the requirements.With the sense with imide-modified epoxy resin, imide structure
A kind of photosensitive covering material for mixture that photopolymer resin, photoinitiator, filler material, solvent, unsaturated monomer, toner and auxiliary agent form
Material flexility reaches the application requirement on wiring board, and anti-flammability can be by VTM-1, and dielectric constant/dielectric dissipation factor is less than
3.0/0.003.With with imide-modified epoxy resin, commercially available bisphenol-A epoxy acrylic resin, photoinitiator, filling
A kind of photosensitive covering material flexility for mixture that material, solvent, unsaturated monomer, toner and auxiliary agent form reaches wiring board
On application requirement, anti-flammability can by VTM-2, dielectric constant/dielectric dissipation factor be less than 3.2/0.010.Commercially available epoxy
A kind of mixing of resin, epoxy acrylic resin, photoinitiator, filler material, solvent, unsaturated monomer, toner and auxiliary agent composition
The photosensitive covering material performance of object reaches the application requirement of wiring board, cannot be fire-retardant, and dielectric constant/dielectric dissipation factor is greater than
3.5/0.010, the photosensitive resin than the synthesis of not fluorine-containing epoxy resin is low.
Claims (9)
1. one kind has imide structure photosensitive-ink, which is characterized in that the photosensitive-ink is mixed by following components system and made
At:
Photosensitive resin 25-60,
Epoxy resin 2-35 with imide structure,
Photoinitiator 2-10,
Acrylic monomers 1-15,
Filler material 5-45,
Solvent 20-60,
Pigment 0-50,
Auxiliary agent 0-20.
2. according to claim 1 a kind of with imide structure photosensitive-ink, which is characterized in that described has acyl sub-
The epoxy resin of amine structure the preparation method comprises the following steps: substance containing acid anhydrides reacts 80-200 in the presence of solvent with structural material containing NCO
It reacts 1-10 hours, is added to small in 60-150 DEG C of reaction time 1-10 in dissolved fluorinated epoxy resin in a solvent at DEG C
When, obtain the epoxy resin with imide structure.
3. according to claim 2 a kind of with imide structure photosensitive-ink, which is characterized in that the weight of each reactant
Part are as follows:
Fluorinated epoxy resin 10-90,
Not fluorine-containing epoxy resin 0-30,
Solvent 10-60,
The 1-30 of substance containing acid anhydrides,
The 1-30 of structural material containing NCO.
4. according to claim 3 a kind of with imide structure photosensitive-ink, which is characterized in that the substance containing acid anhydrides
Selected from phthalic anhydride, tetrabydrophthalic anhydride, hexahydrophthalic anhydride, maleic anhydride, tung oil acid anhydride, alkene
Base succinic anhydride, methyl tetrahydro phthalic anhydride, methylhexahydrophthalic anhydride, carbic anhydride, methylnadic anhydride, glutaric acid
Acid anhydride, terpenes acid anhydrides, methyl cyclohexene tetracarboxylic dianhydride, dodecenylsuccinic acid acid anhydride, trimellitic anhydride, hydrogenation trimellitic acid
Acid anhydride, pyromellitic acid anhydride, hydrogenated pyromellitic anhydride, benzophenone tetracarboxylic dianhydride, poly- azelaic acid acid anhydride, poly- sebacic acid acid anhydride, second
The double trimellitic anhydride esters of glycol, inclined three acid anhydride ester of glycerine three, diphenyl sulfone tetracarboxylic dianhydride, polyadipate acid anhydride, poly- nonyl two
Acid anhydrides, poly- sebacic acid acid anhydride, trialkyl are for one of tetrabydrophthalic anhydride or several.
5. according to claim 3 a kind of with imide structure photosensitive-ink, which is characterized in that described ties containing NCO
Structure substance is selected from methyl diisocyanate, methyl diphenylene diisocyanate, poly methylene poly phenyl poly isocyanate, two hexamethylenes
Dicyclohexylmethane diisocyanate, 1,5- naphthalene diisocyanate, hexamethylene diisocyanate, isophorone diisocyanate, triphen
Methylmethane triisocyanate, benzene dimethylene diisocyanate, paraphenylene diisocyanate, 3,3 '-dimethyl diphenyls -4,4 '-two
Isocyanates, front three group diisocyanate, hydrogenation XDI, hydrogenation MDI, tri o cresyl thiophosphate phenyl isocyanate and its listed above
Isocyanate compound addition product, biuret modified isocyanates, isocyanuric acid tripolymer, organic-silicon-modified isocyanic acid
One or more of ester, isocyanate derivates.
6. according to claim 3 a kind of with imide structure photosensitive-ink, which is characterized in that the fluorinated epoxy
Resin includes diphenylol hexafluoropropane diglycidyl ether, bis- (3- glycidyl ether tetrafluoro the phenoxy group) -2- hydroxyls third of 1,3-
Bis- (hydroxyl hexafluoro isopropyl) the benzene diglycidyl ethers of alkane, 1,4-, bis- (hydroxyl hexafluoro isopropyl) the benzene diglycidyl ethers of 1,3-,
The positive perfluoro propyl benzene diglycidyl ether of 1,3- bis- (hydroxyl hexafluoro isopropyls), bis- (hydroxyl hexafluoro isopropyl) phenyl tetrafluorides two of 1,4-
Glycidol ether, 4,4,Two contracting glycerin ether of dihydroxy octafluorobiphenyl, 4,4,Bis- (hydroxyl hexafluoro isopropyl) octafluorobiphenyls two contract sweet
One or more of oily ether.
7. according to claim 1 a kind of with imide structure photosensitive-ink, it is characterised in that: the photoinitiator choosing
From 2- hydroxy-methyl phenyl-propane-1- ketone, 1- hydroxy-cyclohexyl phenyl ketone, 2- methyl-1-(4- methyl mercapto phenyl)-2-
Quinoline base -1- acetone, benzoin dimethylether BDK, 2,4,6- trimethyl benzoyl diphenyl base phosphine oxide, isopropyl thioxanthone
(mixing of 2,4 isomeries) ITX, 4- (N, N- dimethylamino) ethyl benzoate EPD, EDAB, benzophenone BP, BZO, 4- chlorodiphenyl
Ketone, methyl o-benzoylbenzoate, diphenyl iodnium hexafluorophosphate, 4- phenyl benzophenone, 2,4,6- trimethylbenzene
Formoxyl-diphenyl phosphine oxide, 2,4,6- trimethylbenzoyl phenyl phosphinic acid ethyl ester, 20%1- hydroxycyclohexyl phenyl ketone
80%2- methyl -2- hydroxyl -1- phenyl -1- acetone, 50% TPO;50% 1173, photoinitiator-DETX, contraposition N, N- diformazan ammonia
The different monooctyl ester of yl benzoic acid, 4- methyl benzophenone, o-benzoyl yl benzoic acid methyl esters, bis- (1- (2,4 difluorobenzene base) -3- pyrroles
Cough up base) titanocenes, one of Hexaarylbiimidazole or a variety of.
8. according to claim 1 a kind of with imide structure photosensitive-ink, it is characterised in that: acrylic monomers is selected from
Tetrahydrofuran acrylate, 2- phenoxyethyl acrylate, acrylic acid, isobornyl methacrylate, methacrylic acid, third
Olefin(e) acid caprolactone, isobornyl acrylate, trimethylolpropane formal acrylate, alkoxy nonyl phenol acrylate,
Triethylene-glycol dimethylacrylate, 1,6 hexanediol diacrylate, 1,3 butylene glycol dimethylacrylate, three hydroxyls
Propane tri, pentaerythritol triacrylate, (3) ethoxylated trimethylolpropane triacrylate, (9) second
Oxygroup trimethylolpropane trimethacrylate, (3) propoxylation trimethylolpropane trimethacrylate, dipentaerythritol 6 third
Olefin(e) acid ester, caprolactone modification dipentaerythritol hexaacrylate, pentaerythritol tetraacrylate, five acrylic acid of dipentaerythritol
Ester, three (2- ethoxy) isocyanic acid urea esters, trimethylol-propane trimethacrylate, trimethylolpropane trimethacrylate,
(2) propoxyl group neopentylglycol diacrylate, polyethylene glycol (600) diacrylate, 1,3 butylene glycol dimethylacrylate
One of or it is a variety of.
9. a kind of a kind of answering on flexible printed circuit board with imide structure photosensitive-ink according to claim 1
With.
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Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN113604099A (en) * | 2021-07-08 | 2021-11-05 | 江苏海田电子材料有限公司 | Low-dielectric-constant solder resist ink and preparation method thereof |
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