CN109913030A - A kind of preparation method and applications with imide structure photosensitive resin - Google Patents
A kind of preparation method and applications with imide structure photosensitive resin Download PDFInfo
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Abstract
The present invention relates to photosensitive material fields, in order to solve the problems, such as that it is excessive that the photosensitive resin synthesized at present dielectric constant/dielectric is consumed, it is proposed a kind of preparation method with imide structure photosensitive resin, prepare a kind of not only low-k/dielectric consume, but also photosensitive resin that bending resistance is good, chemical-resistance is good.The present invention also proposes the application with the photosensitive-ink for preparing with imide structure photosensitive resin in the circuit board, not only ensure that the heat resistance and chemical resistance of wiring board curing ink, but also have excellent bending resistance after guaranteeing ink solidification.
Description
Technical field
The present invention relates to photosensitive material fields, and in particular to a kind of preparation method with imide structure photosensitive resin and
Its application of photosensitive-ink prepared in the circuit board.
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,
The requirements such as processing, precision, the tolerance of FPC can all increase；Meanwhile the magnitude of value of single base station also will increase, so entirely
Market scale can be described as the variation of matter, the development of high frequency FPC for 4G, it is desirable that FPC has low-k/dielectric
Dissipation factor (Dk/Df) performance.
Low-k/dielectric dissipation factor industry in material uses LCP (Liquid Crystal Polymer liquid crystal
High molecular polymer) perhaps tetrafluoroethene but the solder mask on these materials remains cover film or solder mask.Covering
Film is PI (polyimides) film, the dielectric constant 3.5 of conventional polyimide or more than, dielectric dissipation factor is more than 0.010, and
Solder mask is largely Conventional epoxy acrylic resin, and dielectric constant is largely also greater than 3.5, and dielectric dissipation factor is more than
0.010, industry is highly desirable low-k/dielectric dissipation factor solder mask or cover film.
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
In order to solve the problems, such as that the photosensitive resin synthesized at present dielectric constant/dielectric is consumed excessive, the present invention proposes one kind
Preparation method with imide structure photosensitive resin prepares not only low-k/dielectric consume, but also bending resistance
A kind of photosensitive resin good, chemical-resistance is good.
The present invention also proposes the application with the photosensitive-ink for preparing with imide structure photosensitive resin in the circuit board, no
It only ensure that the heat resistance and chemical resistance of wiring board curing ink, and have excellent bending resistance after guaranteeing ink solidification.
What the invention is realized by the following technical scheme: it is a kind of with imide structure photosensitive resin the preparation method comprises the following steps:
After fluorinated epoxy resin, non-fluorine-containing epoxy resin are dissolved in a solvent, under the action of catalyst with unsaturated monocarboxylic acid and
It is stand-by after being reacted 1-10 hours at 70-140 DEG C of reaction temperature；Exist with substance containing acid anhydrides and structural material containing NCO in solvent
It is added in above-mentioned stand-by resin after being reacted 1-10 hours at lower 80-200 DEG C of reaction, 50-140 DEG C of reaction temperature, the time, 1-10 was small
When, then with substance reaction containing acid anhydrides, 70-140 DEG C of reaction temperature, time 1-10 hour obtains a kind of having imide structure sense
Photopolymer resin.
React the parts by weight of each component are as follows:
Preferably, the parts by weight of reaction each component are as follows:
The fluorinated epoxy resin includes 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 '-dihydroxy octafluorobiphenyl, two contracting glycerin ether, 4,4 '-bis- (hydroxyls
Hexafluoro isopropyl) two one or more of contracting glycerin ether of octafluorobiphenyl；
In order to reduce cost, non-fluorine-containing epoxy resin can be partially selected, the non-fluorine-containing epoxy resin includes bisphenol-A epoxy
Resin, bisphenol F epoxy resin, bisphenol-A D epoxy resin, bisphenol-s epoxy resin, resorcinol type epoxy resin, hydrogenated bisphenol A
Epoxy resin, modifying epoxy resin by organosilicon, o-cresol formaldehyde epoxy resin, phenol formaldehyde (PF) epoxy resin, resorcinol formaldehyde
Epoxy resin, biphenyl epoxy resin, more phenolic tetraglycidel ether epoxy resins, aliphatic glycidyl ether epoxy resin, epoxy
Change one or more of olefin(e) compound；
The unsaturated monocarboxylic acid be selected from fluorine-containing, acrylic acid, methacrylic acid, undecenoic acid, 5- hexenoic acid,
One of 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；
The solvent is selected from one or more of ketone, alcohols, esters, ethers, benzene class, petroleum-type, and usage amount is
The amount for dissolving solute, but total solvent usage amount is limited, and is because solid content needs to control.Preferably, solvent
Including ethylene glycol monoethylether acetate, ethylene glycol monomethyl ether acetate, diethylene glycol monomethyl ether acetic acid esters, diethylene glycol monoethyl ether
Acetic acid esters, butyl carbitol acetate, propylene glycol methyl ether acetate, propylene glycol monoethyl ether acetate, propyleneglycol monobutyl
Ether acetic acid ester, dipropylene glycol monomethyl ether acetic acid esters, dipropylene glycol monoethyl ether acetic acid esters, Dipropylene glycol mono-n-butyl Ether acetic acid esters, ethers
Glycol monoethyl ether, ethylene glycol monoethyl ether, ethylene glycol monobutyl ether, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether in solvent,
Diethylene glycol monobutyl ether, propylene glycol monomethyl ether, dihydroxypropane single-ether, propylene glycol monobutyl ether, dipropylene glycol monomethyl ether, dipropylene glycol
Single ether, Dipropylene glycol mono-n-butyl Ether, gamma-butyrolacton, n-methyl-2-pyrrolidone, dimethylformamide, DBE, dimethylacetamide
One of amine, dimethylpropionamide are a variety of, in photosensitive resin preparation to use solvent at two can be unanimously also inconsistent.
The substance containing acid anhydrides is selected from phthalic anhydride, tetrabydrophthalic anhydride, hexahydrophthalic anhydride, suitable fourth
Enedioic acid acid anhydride, tung oil acid anhydride, alkylene succinic anhydride, methyl tetrahydro phthalic anhydride, methylhexahydrophthalic anhydride, nadic acid
Acid anhydride, methylnadic anhydride, glutaric anhydride, terpenes acid anhydrides, methylcyclohexene 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；Substance containing acid anhydrides can be unanimously also different at two used in photosensitive resin preparation, but total substance migration containing acid anhydrides
Amount is limited.
The 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
(not I), 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.
Application with imide structure photosensitive resin preparation photosensitive-ink in the circuit board, the present invention use a kind of fluorine-containing
Epoxy resin or fluorine-containing epoxy resin and not fluorine-containing epoxy resin mix and match are photosensitive resin starting material, are thus main former
The liquid photosensitive solder mask of material passes through photocuring and heat cure, its existing excellent heat resistance, endurance, flexibility are gone back
Have certain anti-flammability, is applicable in the circuit board.Photosensitive-ink is mixed by following each component, the parts by weight of each component
Are as follows:
Preferably, photosensitive-ink is mixed by following each component, the parts by weight of each component are as follows:
The epoxy resin is selected from diphenylol hexafluoropropane diglycidyl ether, bis- (the 3- glycidyl ethers four of 1,3-
Fluorophenoxy) -2- hydroxy propane, bis- (hydroxyl hexafluoro isopropyl) the benzene diglycidyl ethers of Isosorbide-5-Nitrae -, bis- (the hydroxyl hexafluoro isopropyls of 1,3-
Base) benzene diglycidyl ether, the positive perfluoro propyl benzene diglycidyl ether of 1,3- bis- (hydroxyl hexafluoro isopropyls), the bis- (hydroxyls of Isosorbide-5-Nitrae-
Hexafluoro isopropyl) phenyl tetrafluoride diglycidyl ether, 4,4 '-dihydroxy octafluorobiphenyl, two contracting glycerin ether, 4,4 '-bis- (hydroxyl hexafluoros
Isopropyl) two contracting glycerin ether of octafluorobiphenyl, bisphenol A epoxide resin, bisphenol F epoxy resin, bisphenol-A D epoxy resin, bisphenol S ring
Oxygen resin, resorcinol type epoxy resin, hydrogenated bisphenol A epoxy resin, biphenyl epoxy resin, modifying epoxy resin by organosilicon,
O-cresol formaldehyde epoxy resin, phenol formaldehyde (PF) epoxy resin, resorcinol formaldehyde epoxy resin, other polyphenol type glycidol ethers
One or more of epoxy resin, aliphatic glycidyl ether epoxy resin, epoxidation of olefins compound；
Photoinitiator is selected from 2- hydroxy-methyl phenyl-propane -1- ketone (photoinitiator -1173), 1- hydroxycyclohexylphenyl
Ketone (photoinitiator-184), is rested in peace at 2- methyl-1-(4- methyl mercapto phenyl)-2- morpholinyl-1- acetone (photoinitiator-907)
It is fragrant double methyl ether BDK (photoinitiator -651), 2,4,6-trimethylbenzoyldiphenylphosphine oxide (photoinitiator -1110), different
Propyl thioxanthone (mixing of 2,4 isomeries) ITX (photoinitiator -1105), 4- (N, N- dimethylamino) ethyl benzoate EPD (light
Initiator -1101), EDAB, benzophenone BP, BZO (photoinitiator -1220), 4- chlorobenzophenone (photoinitiator -1046),
Methyl o-benzoylbenzoate (photoinitiator -1156), diphenyl iodnium hexafluorophosphate (photoinitiator -810), 4- phenyl
Benzophenone (photoinitiator-PBZ), 2,4,6- trimethylbenzoy-dipheny phosphine oxides (photoinitiator-TPO), 2,4,6-
Trimethylbenzoyl phenyl phosphinic acid ethyl ester (photoinitiator-TPO-L), 20%1- hydroxycyclohexyl phenyl ketone 80%2- first
Base -2- hydroxyl -1- phenyl -1- acetone (photoinitiator -1000), 50%TPO；It is 50%1173 (photoinitiators -4265), light-initiated
Agent-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- pyrrole radicals) titanocenes,
One of Hexaarylbiimidazole is a variety of.
Acrylic monomers is selected from tetrahydrofuran acrylate, 2- phenoxyethyl acrylate, acrylic acid, methacrylic acid
Isobornyl thiocyanoacetate, methacrylic acid, caprolactone, isobornyl acrylate, trimethylolpropane formal acrylate, alkane
Oxygroup nonyl phenol acrylate, triethylene-glycol dimethylacrylate, 1,6- hexanediyl ester, 1,3- fourth two
Alcohol dimethylacrylate, trimethylolpropane trimethacrylate, pentaerythritol triacrylate, three hydroxyl first of (3) ethoxylation
Base propane triacrylate (EO3TMPTA), (9) ethoxylated trimethylolpropane triacrylate (EO9TMPTA), (3) third
Oxygroup trimethylolpropane trimethacrylate (PO3TMPTA), dipentaerythritol hexaacrylate, two season penta of caprolactone modification
Six acrylate of tetrol, pentaerythritol tetraacrylate, Dipentaerythritol Pentaacrylate, three (2- ethoxy) isocyanic acid ureas
Ester, trimethylol-propane trimethacrylate, trimethylolpropane trimethacrylate, two propylene of (2) propoxyl group neopentyl glycol
One of acid esters (PO2-NPGDA), polyethylene glycol (600) diacrylate, 1,3-BDO dimethylacrylate are more
Kind.
The filler material includes one or more of barium sulfate, silicates, Calcium carbonate；Preferably barium sulfate,
Clay, talcum powder, mica powder, flake asbestos, silica, calcium hydroxide, magnesium hydroxide, calcium carbonate, blanc fixe, in montmorillonite
It is one or more.
The organic solvent includes one or more of ketone, alcohols, esters, ethers, benzene class, petroleum-type；As
It is preferred that the organic solvent is selected from ethylene glycol monoethylether acetate, ethylene glycol monomethyl ether acetate, diethylene glycol monomethyl ether second
Acid esters, diethylene glycol monoethyl ether acetic acid esters, butyl carbitol acetate, propylene glycol methyl ether acetate, propylene glycol list second
Ether acetic acid ester, propylene glycol monobutyl ether acetic acid esters, dipropylene glycol monomethyl ether acetic acid esters, dipropylene glycol monoethyl ether acetic acid esters, dipropyl two
Alcohol monobutyl ether-acetate, glycol monoethyl ether, ethylene glycol monoethyl ether, ethylene glycol monobutyl ether, diethylene glycol list in ether solvent
Methyl ether, diethylene glycol monoethyl ether, diethylene glycol monobutyl ether, propylene glycol monomethyl ether, dihydroxypropane single-ether, propylene glycol monobutyl ether, two
Propylene glycol monomethyl ether, dipropylene glycol monoethyl ether, Dipropylene glycol mono-n-butyl Ether, gamma-butyrolacton, n-methyl-2-pyrrolidone, dimethyl
It is formamide, dimethyl acetamide, one or more among dimethylpropionamide.
The pigment includes one of organic pigment, inorganic pigment；Inorganic pigment is selected from oxide, chromate, sulfuric acid
Salt, carbonate, silicate, borate, molybdate, phosphate, vanadate, ferricyanate, hydroxide, sulfide, metal, charcoal
One of black, organic pigment can be divided into azo pigments, phthalocyanine color, anthraquinone, indigoids, quinacridine by the chemical structure of compound
One of the polycyclic pigments such as ketone, fragrant methaneseries pigment etc..
The auxiliary agent includes one of promotor, defoaming agent, levelling agent, dispersing agent or a variety of.Defoaming agent predominantly has
Machine silicon class defoaming agent or acryl-based antifoaming agent, the use of defoaming agent, levelling agent, dispersing agent are for photosensitive covering material print
Brush rear surface is smooth glossy.
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,
Again because containing imide structure flexibility is more preferable, heat-resist, chemical-resistance is more preferable, imide structure itself has certain
Anti-flammability the advantages that.
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.
Embodiment 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。
Embodiment 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
9.0 grams of acid anhydride substance hexahydrophthalic anhydride is heated to 100 DEG C and reacts 5 hours, obtains with imide structure photosensitive resin 2.
Embodiment 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.
Comparative example 1
DBE100 grams is poured into three-necked flask, is added 100 grams of bisphenol A epoxide resin, is slowly heated to 120 DEG C, dissolution
It finishes, adds 30 grams of acrylic acid, 1 gram of triphenyl phosphorus is reacted 4 hours at 120 DEG C, adds the tetrahydrophthalic anhydride of substance containing acid anhydrides 50
Gram, it is heated to 120 DEG C and reacts 5 hours, obtain photosensitive resin 1.Comparative example 2
100 grams of DBE are poured into three-necked flask, is added 100 grams of bisphenol F epoxy resin, are slowly heated to 120 DEG C, dissolution
It finishes, adds 35 grams of acrylic acid, 1 gram of triphenyl phosphorus is reacted 4 hours at 120 DEG C, adds the tetrahydrophthalic anhydride of substance containing acid anhydrides 50
Gram, it is heated to 120 DEG C and reacts 5 hours, obtain photosensitive resin 2.
Test case
Photosensitive resin prepared by embodiment 1,2,3 and comparative example 1, comparative example 2 respectively with 2- methyl-1-(4- methylthio phenyl
Base) -2- morpholinyl -1- acetone, polyethylene glycol (600) diacrylate, carbon black, magnesium hydroxide, biphenyl epoxy resin (YX-
4000), bis- (hydroxyl hexafluoro isopropyl) the benzene diglycidyl ethers of 1,3-, melamine, defoaming agent KS-66, in N- methyl -2- pyrrole
Pyrrolidone passes through three-roller after mixing and grinds to obtain different photosensitive-ink numbers to be respectively A, B, C, D, E.Implement formula
Table is as shown in table 1, is in parts by weight.
Table 1:
Experimental performance evaluation
By above-mentioned A-E, totally 5 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
Five, bending resistance: 180 ° of angle doublings, not have slight crack as standard.
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 5 tests chemical resistance, flexibility, resistance to after photocuring and heat cure
Hot, electrical characteristic, environmental characteristics can meet the requirements.With fluorine-containing photosensitive material, photoinitiator, epoxy resin, filler material,
A kind of photosensitive covering material flexility for mixture that solvent, unsaturated monomer, toner and auxiliary agent form reaches on wiring board
Application requirement, anti-flammability can by VTM-1, dielectric constant/dielectric dissipation factor be less than 3.0/0.003.With will be fluorine-containing and not
The photosensitive resin of fluorine-containing epoxy resin synthesis, photoinitiator, epoxy resin, filler material, solvent, unsaturated monomer, toner and
A kind of photosensitive covering material performance of mixture of auxiliary agent composition reaches the application requirement of wiring board, anti-flammability can by VTM-1,
Dielectric constant/dielectric dissipation factor is 2.9/0.003, and the photosensitive resin than the synthesis of not fluorine-containing epoxy resin is low, bending resistance
It is better than not fluorine-containing comparative example.
Claims (10)
1. a kind of preparation method with imide structure photosensitive resin, it is characterised in that: the preparation method is that: ring will be fluorinated
It is warm with unsaturated monocarboxylic acid and reacting under the action of catalyst after oxygen resin, non-fluorine-containing epoxy resin dissolve in a solvent
It is stand-by after being reacted 1-10 hours at 70-140 DEG C of degree；80- is reacted in the presence of solvent with substance containing acid anhydrides with structural material containing NCO
Be added in above-mentioned stand-by resin after being reacted 1-10 hours at 200 DEG C, 50-140 DEG C of reaction temperature, time 1-10 hour, then with contain
Acid anhydrides substance reaction, 70-140 DEG C of reaction temperature, time 1-10 hour obtains a kind of with imide structure photosensitive resin.
2. a kind of preparation method with imide structure photosensitive resin according to claim 1, it is characterised in that: reaction
The parts by weight of each component are as follows:
3. a kind of preparation method with imide structure photosensitive resin according to claim 2, it is characterised in that: reaction
The parts by weight of each component are as follows:
4. a kind of preparation method with imide structure photosensitive resin according to claim 1 or 2 or 3, feature exist
In: the fluorinated epoxy resin includes diphenylol hexafluoropropane diglycidyl ether, bis- (the 3- glycidyl ether tetrafluoros of 1,3-
Phenoxy group) -2- hydroxy propane, bis- (hydroxyl hexafluoro isopropyl) the benzene diglycidyl ethers of Isosorbide-5-Nitrae -, bis- (the hydroxyl hexafluoro isopropyls of 1,3-
Base) benzene diglycidyl ether, the positive perfluoro propyl benzene diglycidyl ether of 1,3- bis- (hydroxyl hexafluoro isopropyls), the bis- (hydroxyls of Isosorbide-5-Nitrae-
Hexafluoro isopropyl) phenyl tetrafluoride diglycidyl ether, 4,4 '-dihydroxy octafluorobiphenyl, two contracting glycerin ether, 4,4 '-bis- (hydroxyl hexafluoros
Isopropyl) two one or more of contracting glycerin ether of octafluorobiphenyl.
5. a kind of preparation method with imide structure photosensitive resin according to claim 1 or 2 or 3, feature exist
In: the non-fluorine-containing epoxy resin includes bisphenol A epoxide resin, bisphenol F epoxy resin, bisphenol-A D epoxy resin, bisphenol S epoxy
Resin, resorcinol type epoxy resin, biphenyl epoxy resin, hydrogenated bisphenol A epoxy resin, modifying epoxy resin by organosilicon, neighbour
Cresol formaldehyde epoxy resin, phenol formaldehyde (PF) epoxy resin, resorcinol formaldehyde epoxy resin, other polyphenol type glycidol ether rings
One or more of oxygen resin, aliphatic glycidyl ether epoxy resin, epoxidation of olefins compound.
6. a kind of preparation method with imide structure photosensitive resin according to claim 1 or 2 or 3, feature exist
In: the unsaturated monocarboxylic acid is selected from fluorine-containing, acrylic acid, methacrylic acid, undecenoic acid, 5- hexenoic acid, butylene
One of acid, penetenoic acid are a variety of.
7. a kind of preparation method with imide structure photosensitive resin according to claim 1 or 2 or 3, feature exist
In: the catalyst is selected from dimethylbenzyl ammonia, triphenylphosphine, two cyclopentadienyl of (S)-(+)-N, N- dimethyl -1- (2- biphenyl phosphino-)
Iron ethamine, (R)-NN- dimethyl -1- ((S) -2- diphenylphosphine) ferrocene) ethamine, 1,1 '-bis- (diphenylphosphine) ferrocene, 2-
(diphenylphosphino) ethamine, N, N- dimethylethanolamine, n,N-Dimethylformamide, triethylamine, triethanolamine, trimethyl benzyl
Ammonium chloride, tri-methyl benzyl ammonium bromide, triethyl benzyl ammonia chloride, triethylbenzyl ammonium bromide, cobalt naphthenate, manganese naphthenate,
Lead naphthenate, zinc naphthenate, calcium naphthenate, copper naphthenate, iron naphthenate, barium naphthanate, zirconium naphthenate, magnesium naphthenate, cycloalkanes
One of sour nickel is a variety of.
8. a kind of preparation method with imide structure photosensitive resin according to claim 1 or 2 or 3, feature exist
In: the substance containing acid anhydrides is selected from phthalic anhydride, tetrabydrophthalic anhydride, hexahydrophthalic anhydride, maleic two
Acid anhydrides, tung oil acid anhydride, alkylene succinic anhydride, methyl tetrahydro phthalic anhydride, methylhexahydrophthalic anhydride, carbic anhydride, first
Base carbic anhydride, glutaric anhydride, terpenes acid anhydrides, methylcyclohexene tetracarboxylic dianhydride, dodecenylsuccinic acid acid anhydride, inclined benzene front three
Acid anhydrides, hydrogenation trimellitic anhydride, pyromellitic acid anhydride, hydrogenated pyromellitic anhydride, benzophenone tetracarboxylic dianhydride, poly- nonyl two
The double trimellitic anhydride ester of acid anhydrides, poly- sebacic acid acid anhydride, ethylene glycol, inclined three acid anhydride ester of glycerine three, diphenyl sulfone tetracarboxylic dianhydride,
Polyadipate acid anhydride, poly- azelaic acid acid anhydride, poly- sebacic acid acid anhydride, trialkyl are for one of tetrabydrophthalic anhydride or several.
9. a kind of preparation method with imide structure photosensitive resin according to claim 1 or 2 or 3, feature exist
In: the structural material containing NCO is selected from methyl diisocyanate, methyl diphenylene diisocyanate, polymethylene polyphenyl
Polyisocyanates, dicyclohexyl methyl hydride diisocyanate, 1,5- naphthalene diisocyanate, hexamethylene diisocyanate, different Fo Er
Ketone diisocyanate, triphenylmethane triisocyanate, benzene dimethylene diisocyanate, paraphenylene diisocyanate, 3,3 '-two
4,4 '-diisocyanate of methyl biphenyl-, front three group diisocyanate, hydrogenation XDI, hydrogenation MDI, thiophosphoric acid triphenyl isocyanide
The addition product of acid esters and its isocyanate compound listed above, biuret modified isocyanates, isocyanuric acid tripolymer,
One or more of organic-silicon-modified isocyanates, isocyanate derivates.
10. a kind of tool that the preparation method using described in claims 1 or 22 or 3 with imide structure photosensitive resin obtains
There is the application of imide structure photosensitive resin preparation photosensitive-ink in the circuit board.
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