CN102650826B - Dry film photoresist containing special adhesive additive and plasticizer - Google Patents
Dry film photoresist containing special adhesive additive and plasticizer Download PDFInfo
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- CN102650826B CN102650826B CN201110047382.XA CN201110047382A CN102650826B CN 102650826 B CN102650826 B CN 102650826B CN 201110047382 A CN201110047382 A CN 201110047382A CN 102650826 B CN102650826 B CN 102650826B
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Abstract
The invention provides a dry film photoresist for aqueous solution development. The components thereof include a macromolecule adhesive, a free radical photoinitiator, monomers capable of having addition polymerization, a plasticizer and a thermal polymerization inhibitor. The dry film photoresist is characterized in that the macromolecule adhesive is an adhesive containing a carboxylic group and capable of forming a film, and is formed by polymerizing a mixture including components as follows (a) a monomer having a molecular formula of H2C=CRCOO[(CnH2n)X(CpH2p)]R', wherein R refers to hydrogen or methyl, R' refers to saturated or unsaturated C5-C12 crosslink alkyl which also can be replaced by at least one C1-C4 alkyl or hydrogen, x refers to an oxygen or sulfur atom, n ranges from 2 to 4, p ranges from 0 to 4, and m ranges from 0 to 2; and (b) at least one C3-C15, alpha, beta-unsaturated monomer containing a carboxyl group and 3-15 carbon atoms. The plasticizer contains carboxy polyurethane, the molecular weight ranges from 10,000 to 100,000, a free carboxyl group is introduced onto a main chain, and at least one olefinic bond unsaturated terminal group is provided.
Description
Technical field
What the present invention relates to contain in dry film photoresist, especially dry film photoresist that a kind of aqueous solution develops a kind of carboxyl can film forming polymer binder and the dry film photoresist that develops of a kind of aqueous solution of the polyurethane that contains carboxyl.
Background technology
The dry film photoresist that aqueous solution is developed is the component of photopolymerization, uses in the production of printed-wiring board (PWB), and these photoresists are normally applied to the solution of impedance thing on a kind of transparent mylar carrier, then forming dry film after solvent evaporates.In normal circumstances; dry film photoresist is to use together with carrier on the base thing covering at copper; in certain region, through carrier and egative film exposure, dry film is solidified; then with alkaline aqueous solution, wash Polyester and remove unexposed dry film from copper surface; the copper aspect exposing is removed with etching solution etching again; the dry film of exposure curing can be peeled off with stripper, and remaining is exactly is cured dry film protection and the copper face that do not etch away and form electronic circuit.
In process of production, fluidity etching and electrogilding normally involve alkali condition, thereby can cause some problem, and for example curing photoresist loses viscosity, so that curing photoresist has the character of good this process of resistance is just extremely important.Thereby unexposed photoresist can be washed off rapidly on copper coin, to reach as far as possible rapid development also very important, in order easily to remove unexposed uncured photoresist, in photoresist, just should contain a kind of film-forming polymer binder that contains carboxyl.
Photopolymerization component for photoresistance preferably can make time shutter and development time the shortest, and guarantee that this photopolymerization component is adhered on carrier thin film rather than on cover film, the flexibility of guaranteeing the material that solidified is very important, and in operating process, curing material can not split broken like this.But, in the partition of photopolymerization component, must keep the fine balance of various compositions, the flexibility of photoresist has been played to the material of effect, even if the amount of using seldom, still may have negative effect or the degree that pasting of this component is had to negative impact the time of exposure and development time.The plastifier using at present, went to increase flexibility as N-ethyl-toluene sulfanilamide (SN) is once added in the formula of phtotpolymerizable component, yet, thereby this plastifier can be from component seepage go out and placed restrictions on its validity.
Summary of the invention
The object of this invention is to provide a kind of contain carboxyl can film forming polymer binder the dry film photoresist that develops of aqueous solution, in this dry film photoresist, also include the carboxylic polyurethane that at least contains a unsaturated terminal of vinyl of flexibility of a material of guaranteeing to have solidified as plastifier, the dry film photoresist that this aqueous solution is developed can overcome the part that comes with some shortcomings in prior art.
Of the present invention contain carboxyl can film forming polymer binder the aqueous solution dry film photoresist technical scheme of developing be achieved in that the dry film photoresist that a kind of aqueous solution is developed, in its component, contain polymer binder, free radical light trigger, can addition polymerization monomer, plastifier and thermal polymerization inhibitor, it is characterized in that:
Described polymer binder is a kind of can being obtained by following polymerization of mixtures by film forming bonding agent of carboxyl of containing:
(a) the monomer H that molecular formula is following
2c=CRCOO ((C
nh
2n) X (C
ph
2p))
mr '
Wherein R is hydrogen or methyl, and R ' sends from following groups: different norborny, bornyl, borneol thiazolinyl, different norbornene, norbornene, dicyclo undecyl, three cyclo-dodecyl, three ring eight alkyl, 2-cyanogen water sheet base, 2.3 1 dihydro norbornies, X is oxygen or sulphur, n is 2.4, p is 0-4, and m is 0-2;
(b) have the monomer of a 3-15 charcoal atom at least, this monomer has α, β-unsaturated link and include carboxyl or anhydride group;
(c) has a C at least
1-C
8alkyl acrylate;
(d) has a C at least
1-C
8alkylmethacrylate;
Described plastifier is for containing carboxyl polyurethane, and its molecular weight is 1000-100000, and free carboxyl group group, on main polymer chain, and at least contains a undersaturated terminal group of ethylene linkage.
A kind ofly contain can being made by least two monomers by film forming polymer binder of carboxyl, first monomer, (a) has molecular formula H
2c=CRCOO ((C
nh
2n) X (C
ph
2p))
mr ', wherein R is hydrogen or methyl, and R ' is saturated or undersaturated C5-C12 bridging alkyl, can be also alkyl or hydrogen replacement at least 1 C1-C4, and X is oxygen or sulphur atom, and n is 2-4, and p is 0-4, and m is 0-2.This saturated or unsaturation C5-C12 bridging alkyl R ' is many rings hydrocarbon that has 5-12 sulphur atom, has a ring or condensed ring, has a valency chain in ring, and atom or atomic link are bound up on the different piece of ring.This C1-C4 alkyl can be methyl, ethyl, propyl group, isopropyl, normal-butyl or isobutyl, also halogen as chlorine, bromine, iodine or fluorine atom.The example of random replacement bridging alkyl comprises monocycle bridging system, and example is isobornyl, bornyl, borneol thiazolinyl, isoborneol thiazolinyl, norbornene, dicyclo (4.3.2) undecyl, three ring (5.3.1.
2,6) dodecyl, three ring (3.2.1.0
2,7) 12 octyls, 2-chlorine norborny, 2.3-dichloro norborny, and condensed ring bridging system, example is two cyclopentyl, 1,2,3,4,4a, 5,8,8a-octahydro-outer-1.4; Outward-5,8-dimethylnaphthalene.Isosorbide-5-Nitrae-methylpent thiazolinyl.Make the acrylate of above-mentioned bridging group and the esterification that methacrylate also can be general, for example the esterification of the acrylic or methacrylic of the alcohol of above-mentioned bridging gene.
First kind monomer example comprises isoborneol propylene and metering system ester, and its structure is as follows
Wherein R is to be above-mentioned defined.
Dimerization cyclopentene oxygen ethyl propylene acid esters or methacrylate, its structure is as follows:
Wherein R also has regulation in the above.
Dimerization cyclopentene acrylate and base acrylate, its structure is as follows:
Wherein R also has regulation in the above.
Other examples of monomers comprises dimerization cyclopentene methylthio ethyl acrylate and methacrylate, norborny acrylate and methacrylate, different norborneol oxygen ethyl propylene acid esters and methacrylate.
Second monomer (b) is in order to composite adhesives, is the α that at least one contains 3 to 15 carbon atoms that has using according to the present invention, and β-unsaturated comprises the monomer of carboxyl or acid anhydrides.The example of the monomer that contains carboxyl is cinnamon acid, crotonic acid, and sorbic acid, acrylic acid, methacrylic acid, wherein take acrylic acid and methylmethyiene acid as better.
Be more preferably use the 3rd monomer (c) in this bonding agent synthetic, the 3rd monomer can be a kind of compound (i) C
1-C
8alkyl acrylate or methacrylate, (ii) C
2-C
8hydroxy alkyl cyclopropanecarboxylic acid ester or methacrylate, or (iii) styrene, α-C
1-C
6ring-alkylated styrenes, α-halogen styrene, or a kind of ring substitutive derivative.
This compound (i) is any alkyl acrylate or methacrylate, and this alkyl is that straight or branched group contains 1-8 carbon atom, is methyl, ethyl, propyl group, sec-butyl, tertiary amyl, n-hexyl, n-heptyl, or α ethylhexyl acrylate or methacrylate.This compound (ii) is any hydroxy alkyl acrylic or methacrylic acid, and hydroxy alkyl is wherein the straight or branched group that contains 2-8 carbon atom, as 2-hydroxyethyl, and 2-hydroxypropyl, or 2-hydroxyl-n-butyl acrylate or methacrylic acid.This compound (iii) is the adjacent base styrene of styrene, p-methylstyrene or to sec-butylbenzene ethene.Phenyl ring in compound (iii) can be replaced by 1 to 5 functional group, and the alkyl of 1-6 carbon atom, as methyl; ethyl, sec-butyl, 1-6 carbon atom alkoxy; the acyl group of carbon atom that there is 1-6; the carboxyl that contains 1-6 carbon atom, sulfenyl, hydroxyl or halogen group; as fluorine; chlorine, bromine, iodo.
The bonding agent using in the present invention can go to synthesize with the general optical molecule polymer reaction in organic solvent, situation is that the weight average molecule content of this bonding agent is 40000-200000 preferably, best weight average molecular weight is 7000-100000, this molecular weight is to measure with gel permeation chromatograph, with polystyrene, it is calibration standard thing, in bonding agent synthetic, the binding agent based weight of consumption of monomer (a), its mobility scale is in 15-50 % by weight, better in 15-30 % by weight, preferably in 20-29 % by weight.
The binding agent based weight of consumption of monomer (b), when preparing bonding agent, usable range is 15-50 % by weight, preferably in 18-32 % by weight, the binding agent based weight of consumption of alternative monomer (c), when preparing bonding agent, usable range is 0-40 % by weight,, be better 10-40 % by weight, preferably in the scope of 15-35 % by weight.
In the component of photoresist in the present invention, comprised polymer binder, free-radical initiator, can addition polymerization monomer, and thermal polymerization inhibitor, also includes the plastifier that contains carboxyl in a kind of the present invention.Other alternative adjuvant comprises dyestuff and sticky limit reinforcing agent.Solvent when " doing " film and referring to film forming is evaporated.In formula, polymer binder accounts for the 40-70% of dry film photoresist general assembly (TW), be more preferably and account for 50-60%, photoionization base initiating agent accounts for 0.5-10%, is more preferably 3-7%, addition polymerization monomer accounts for 5-40%, be more preferably and account for 15-35%, plastifier accounts for 0.2-10%, is more preferably and accounts for 0.5-2.0%, hot polymerization inhibitor accounts for 0.003%-0.04%, is more preferably 0.01%-0.02%.
The plastifier using is in the present invention a kind of polyurethane that contains carboxyl, and this polyurethane has the unsaturated terminal group of an ethylene linkage at least.When light is poly-, unsaturated ethylene linkage in macromolecule just can with the substance reaction in phtotpolymerizable component, so form a part of curing system, so the flexibility of solidfied material is just improved, and as a part of whole curing system, just from then on seepage is not gone out.Carboxylic group has increased the solvent borne of this superpolymer, has promoted not have removing of superpolymer in cured portion in washing Polyester process.The present invention further provides the method for the poly-component of dry film light of using this available water solution development, comprise the following steps: the phtotpolymerizable component being placed on carrier thin film to be pressed onto on a copper clad laminate, see through carrier and egative film and with radiating light, go the phtotpolymerizable component of curing exposure part, from the component that light is poly-, remove carrier thin film, thereby wash the poly-component of Polyester light with alkaline aqueous solution, from substrate, removed uncured phtotpolymerizable component.Improvement is herein exactly to have comprised further the polyurethane that contains carboxyl in the poly-component of light, because this polyurethane contains again at least one terminal ethylene linkage group.The quantity of polyurethane plastifier is 0.5-30%, is 2-30% preferably, is preferably 9-15%, and hot polymerization inhibitor quantity is 0.003-0.04%, preferably 0.01-0.02%.It is 1-150 that polyurethane in the present invention has acid number (neutralization one gram of photopolymer institute must the milligram oil of KOH), is 2-140 preferably, is preferably about 10, and molecular weight is 5000-50000, preferably 10000-100000.This polyurethane is by following monomer synthesized: (1) at least two aliphatic diol and an aliphatics dihydroxy, list or dicarboxyl acidic group and an excessive aliphatics, lopps aliphatics or aromatic series two isocyanic acid polyreactions, need add catalyzer, the polyurethane high molecule that isocyanic acid is terminal is take in formation, also contains hydroxy-acid group freely on the main chain of this polyurethane.(2) the terminal isocyanate group of the product producing in step (1) reacts with aliphatics monohydroxy methacrylate.
Diol mixture in above-mentioned steps (1) comprises at least two aliphatic diols, and weight average molecular weight is 1000-4000, and suitable aliphatic diol comprises polyglycol; Polypropylene glycol; By oxirane and propylene oxide reaction and the segmented copolymer forming, polytetrahydrofuran diol, poly-hexane diacid propylene glycol hexanediol neopentyl glycol 1,4-butylene glycol/ethylene glycol/adipate diol 1,6-hexanediol/ester of phthalic acid adipate, neopentyl phthalic acid vinegar/ethane diacid esterdiol and hexanediol adipate diol, the potpourri of glycol also comprises hexane diacid dihydroxy list pentane dicarboxylic acid.Suitable dicarboxyl carboxylic acid comprises two hydroxymethyl propionic acids, 2,3-dihydroxypropionic acid, 2,4-dihydroxy-3,3-acid dimethyl, 2,3-dihydroxy Palmitic acid, dihydroxy butyric acid, tartrate and 2,3-dihydroxy-2 methylpropanoic acid, two-hydroxymethyl propionic acid is that better the concentration of hydroxycarboxylic acid is 0.2%-30%.Be 2-5% (take in the general assembly (TW) of preparing each composition of polyurethane elbow is benchmark) preferably.
Diol mixture and excessive aliphatics, lopps aliphatics or aromatic diisocyanate.Suitable diisocyanate comprises: 2,4-or 2,6-toluene diisocyanate, isophorone diisocyanate, 1,6-hexamethylene diisocyanate, 2,4-trimethyl vegolysen, 6-diisocyanate p, the potpourri of p '-methylene-bis-phenyl isocyanate or above example.
The ratio 1.1 to 2.0 of hydroxyl and the reaction equivalent of isocyanates is 1.4 preferably.Preferably 40 ℃-90 ℃ of the temperature of reaction, are preferably 70 ℃-80 ℃, and reaction is preferably in and adds the organo-tin compound of 50-300ppm or 0.1-3% ester fat amines as carrying out under catalyzer.For example, suitable catalyzer comprises: dioctyl tin two (iso-octyl thioglycollic acid ester).Dibutyl tin two lauryls, dibutyl tin diisooctyl richness is carried out ester, triethylenediamine, triethanolamine and triethylamine.
Two (sulfuration) diacetic acid di-isooctyls of the sub-tin of dioctyl are better, and formed polyurethane is with carboxylic acid group on polymer main chain, and isocyanate group is at the two ends of main polymer chain.
Second step in reaction is product and aliphatics monohydroxy acrylate or the methacrylate being used in the first step (1), quantity is wanted enough different hydracid radical reactions going with main chain two ends, is that the excessive hydroxyl-metacrylate of 0.2 to 10 equivalent is for better.Suitable acrylate and methacrylate comprise: as 2-hydroxypropyl acrylate and methacrylate, single-butanediol acrylate and monomethacrylates, polyglycol (10-20 moles of ethylene oxide) mono acrylic ester and monomethacrylates, polypropylene glycol (5-20 mole of epoxypropane) acrylate and methacrylate.Organo-tin compound or aliphatics ammoniate, its kind and quantity are shown in above-mentioned, as the catalyzer of reaction needed.The macromolecule polyurethane producing is liquid, in polymer chain terminal, has acrylate or methacrylate, and carboxylic group is on high polymer main chain freely, and acid number is 1 to 150.
In the present invention spendable free radical light trigger be a kind of routine by light-initiated initiating agent, this initiating agent is being non-lower activity lower than 185 ℃, available light trigger can be selected from aromatic ketone class, as benzophenone, dimethoxy benzene benzoylformaldoxime, also can select other useful free radical light trigger.
That uses in the present invention can addition polymerization monomer, at least will have 1, better at least will have 2, better at least will have 2 to 4, most preferably 2 to 3 vinyl double bonds, or the potpourri of these compounds.
Available addition polymerization monomer comprises alkylene base or poly-alkane omega-diol diacrylate, has with the compound of the ethenylidene group of ester bond conjugation at this particularly suitable.Below that application of the present invention is not limited only to these examples, glycol diacrylate as the example of demonstration, diethylene glycol diacrylate, glycerine diacrylate, glycerol tri-acrylate, 1,3-PD dimethylacrylate, 1,2,4-butantriol trimethyl acrylic ester, 1,4-benzenediol diacrylate, Isosorbide-5-Nitrae-cyclohexanediol diacrylate, pentaerythrite three and tetramethyl acrylate.Pentaerythrite three and tetraacrylate, tetraethylene glycol dimethacrylate, trimethylol propane trimethyl propionic ester, triethylene glycol diacrylate, tetraethylene glycol diacrylate, pentaerythritol triacrylate, tricarboxylic methylpropane triacrylate, tetramethylol methane tetraacrylate, 1,3-propyl group omega-diol diacrylate, 1,5-PD dimethylacrylate, polypropylene glycol, polyglycol, and molecular weight is from 100 to about 500 diacrylates of (number is average) and the multipolymer of dimethylacrylate.Also can choose other available addition polymerization monomer.
The hot polymerization inhibitor that used in the present invention can prevent the thermal polymerization when dry and storage, useful hot polymerization inhibitor is exemplified below: p methoxy phenol, Pyrogentisinic Acid, p-dihydroxy-benzene and benzoquinones that alkyl or aryl replaces, t-butyl catechol, 1,2,3,-thrihydroxy-benzene, resin copper, the acid of β-phenol, 2,4-d-tert-butyl-p-cresol, 2,2-methine-bis-(4-ethyl-6-t-butyl phenol), to toluene benzoquinones, tetrahydrochysene is for 1,4-benzoquinone, aryl phosphite, and alkylaryl phosphite, also can choose other available hot polymerization and suppress.
In photoresist in the present invention, also have some selectable adjuvants in the poly-component of light, colourless (printing off) dyestuff for example, background dye, adhesion promoter, and antioxidant all have narration in disclosed data.Other adjuvant also can be selected, but these selectable adjuvants are not necessary.
The preparation of photoresist is in the present invention that different components is mixed in solvent, alcohol, and ketone, halogenated alkane and ether are all suitable solvents, other solvent also can be selected.After mixing, this solution coat on carrier thin film, solvent evaporates then, the thickness of this photoresist, between 10-100 micron, is preferably between 12.2-50.8 micron, the thickness of carrier thin film is preferably between about 0.0254-0.0508mm.And then adding cover film, dry film originally, between pliable and tough supporting film and coverlay, can be made stacking thin slice and drum.
Photoresist is in the present invention the making for printed-wiring board (PWB); generally speaking; photoresist is hot-pressed on the base thing of Copper Foil covering together with carrier thin film; by egative film, expose and cause a kind of surely and not existing video that can polymers; remove carrier thin film and then in alkaline water developer solution, develop, wash away at the unpolymerized material of copper foil surface, the part then exposing just can be done following processing; as electroplated or etching, the poly-photoresist of light still covers on shielded copper surface.This poly-part of light finally can wash away with known removing solution.
Generally speaking, for the exposure of this component of polymerization and amount large at 150mJ/cm
2between, accurate exposure depends on the adjusting of special component mathematics.
Alkaline water developer solution is alkali metal hydroxide, as lithium hydroxide, and NaOH and lithium hydroxide, alkaline solution can be strong base weak acid brine solution, as sodium carbonate, and sodium bicarbonate, be preferably with sodium carbonate with alkali metal phosphate and pyrophosphate, concentration is preferably 0.5-1.0 % by weight.Generally speaking, the effect that the past dry film surface pressing having exposed sprays this alkaline water developer solution is better.
Generally speaking, the photoresist material that the stripper mating with the present invention removes polymerization is the alkaline solution of heating, but concentration the same with the alkaline solution developing wants high, and generally speaking, concentration is 1-10 % by weight, be about 1%-3% preferably, generally speaking, this stripper is heated to 45-65 ℃, is preferably and is heated to 50-55 ℃, available stripper sprays substrate, is preferably substrate is immersed in the stripper of the stirring in peel groove of heating.
Photoresist of the present invention is because the plastifier that contains special adhesive and match is with it specially adapted to alkali etching, in the production of the printed-wiring board (PWB) of gold-plated and chemical grinding, the bonding agent in the present invention has obdurability and can resist the ammoniacal liquor used in production run.
Embodiment
In order more clearly to describe the present invention, spy provides following example, and in following example, unless otherwise indicated, all deal and percentage all represent with weight.
Embodiment 1-4
Be used for the preparation of the bonding agent of photoresist, its formula is listed in table 1.
Table 1
1: methylacrylic acid
2: methyl methacrylate
3: ethyl propylene acid esters
4: isobornyl methacrylate
Bonding agent synthetic as described below, by 422g butanone and 555g, the mix monomer in table 1 adds a reaction vessel, and reactant stirs and is heated to 80 ℃ under nitrogen.Add 7ml azoisobutyronitrile, butanone solution (concentration is 0.05g azoisobutyronitrile/g butanone) is in reaction vessel, after 5 hours, add again 19ml azoisobutyronitrile butanone solution (concentration is 0.05g azoisobutyronitrile/g butanone), continue within 1 hour, to stir and heating, after having reacted, reactant transfer, in glass container, adds appropriate butanone, regulates solid content to 31%.
Photoresist is pressed the preparation of component in list 2, the combination in table is added in the binder solution of 31% solid content, and correspondingly, in form, amount of binder comprises actual bonding agent and solvent.
Table 2
1, the interior olefin(e) acid ester of alkane three in hydroxyethyl trihydroxy methyl.
2, hydroxyethyl biphenol A and metering system phenol reaction preparation (EBECRYL3702, REDCURE APECIATG INC.)
3, diethanolamine improvement toluene triazole, (CIBA-GEIGY, REOMET42)
4, ethyl dimethyl amido amido benzene methyl
5, isopropyl thioxanthone
Photoresist is prepared by the following method.Material in table 2 mixes with about 600 revs/min of speed in ribbon mixer.
This potpourri is removed air bubble for centrifugal three minutes in hydro-extractor.
On the thick mylar of 23.4um, be coated with, equal 38.1 microns of thickness is dried after heat in the baking oven of 100 ℃, about 3-6 minute, and then coating layer is pressed onto the two-sided copper coin (56.7g copper, on insulated substrate) deoiling after scrubbing.The about 0.79mm of its thickness.Laminating sheet is to use hot cylinder trigger squeeze with approximately 121 ℃ of temperature, the about 2.1kg/cm of pressure
2, with the speed of 121.9cm/min, be pressed into, then by egative film, expose, depth of exposure is stouffer 6-7 level (with 12 grades of stouffer depth of exposure tables).After 15 minutes, remove mylar, and by developing machine (Chemcut 547 developing machines), developer solution is 0.90%w/w sodium carbonate single-crystal water solution, approximately 35 ℃ of temperature, the about 0.138MPa of top flushing pressure, the about 0.138MPa of drip washing pressure, speed should be adjusted to 50% the solution point that rushes.
Then, plate is placed on (Chemcut 547) in travelling belt drip washing etching machine, the about 91.4cm of length of its etching chamber, pollute the about 61cm of control section long, the about 30.5cm of drip washing part is long, approximately 49 ℃ of temperature. when depth of exposure during in stouffer6-7 level the speed of etching machine be 45.72cm/min (the 1st time by) and 91.44cm/min (passing through for the 2nd time).The speed of etching travelling belt should make adjustments, make the 1st time by time etching degree approximately 90%, and etching completely after passing through for the second time, noresidue copper, etching is to use MacDermind ULTRAETCH50 etching solution, concentration is 427.95-570.6g copper/3.785g etching solution, contains 4.5-5.0ppm chlorine, and pH8.0-8.5 can produce optimal etch speed.Polluting in pulpit uses the supplementary liquid (ammonium hydroxide and hydrogenation ammonium potpourri) of MacDermind ULTRAETCH50 to keep the pH that pollutes pulpit 11.In operation when plate from etching machine out after with supplementary liquid drip washing, then this supplementary liquid returns and is directed in etching bath.
The level of adhesion that plate after etching need be measured photoresist is evaluated at the resistibility under fluidity etching condition, and level of adhesion can, depending on seeing the degree that depends on of test board, be that one group of live width is 40,50 on this test board, 60,70,80,90, the line-spacing of 100,125,150,200 and 250 microns.The assessment of the performance of photoresist is the thinnest line based on existing under each etching speed just.The circuit existing is narrower, and the resistibility to liquid etching solution just representing is stronger.The thinnest residual in each embodiment live width is set forth in table 3.
Table 3
| Embodiment | Live width (um) |
| 1 | 70 |
| 2 | 90 |
| 3 | 125 |
| 4 | ＞250 |
Embodiment 5-8
The bonding agent made from the formula of enumerating in table 1, the formula of enumerating with table 5 is prepared photoresist.
Table 5
1. use the bonding agent of embodiment 1
2. use the bonding agent of embodiment 2
3. use the bonding agent of embodiment 3
4. use the bonding agent of embodiment 4
5.PUT polyurethane, embodiment is shown in preparation
*. same with table 2 embodiment 1-4.
As described in above-described embodiment 1-4, photoresist is pressed on copper clad laminate, through exposure, develop, and etching and test, it the results are shown in table 6.
Table 6
| Embodiment | Live width (um) |
| 5 | 63 |
| 6 | 80 |
| 7 | 99 |
| 8 | 200 |
Embodiment 9-13
Bonding agent in embodiment 9-13 is pressed the formula preparation of table 7.
Table 7
1: methacrylic acid
2: methyl methacrylate
3: ethyl propylene acid esters
4: dimerization cyclopentene oxygen methacrylate
With the bonding agent of row and the photoresist of the method Preparation Example 9-13 described in embodiment 1-4 in table 7.
Table 8
*. same with embodiment 1-4
As described in above-described embodiment 1-4, photoresist is pressed on copper clad laminate, through exposure, develop, and etching and test, it the results are shown in table 9.
Table 9
| Embodiment | Live width (um) |
| 9 | 50 |
| 10 | 90 |
| 11 | 80 |
| 12 | 60 |
| 13 | 60 |
Embodiment 14-18
With the bonding agent of row and the photoresist of the method Preparation Example 14-18 described in embodiment 1-4 in table 7, the photoresist of embodiment 14-18 is pressed the listed formula preparation of table 10.
As described in above-described embodiment 1-4, photoresist is pressed on copper clad laminate, through exposure, develop, and etching and test, it the results are shown in table 11.
Table 10
1. use the bonding agent of embodiment 9
2. use the bonding agent of embodiment 10
3. use the bonding agent of embodiment 11
4. use the bonding agent of embodiment 12
5. use the bonding agent of embodiment 13
6. polyurethane, prepares and sees embodiment
*. same with table 2 embodiment 1-4
Table 11
| Embodiment | Live width (um) |
| 14 | 45 |
| 15 | 81 |
| 16 | 68 |
| 17 | 51 |
| 18 | 49 |
Result in above embodiment can be found out, has used after special adhesive of the present invention, and phtotpolymerizable dry film photoresist level of adhesion on Copper Foil after solidifying has greatly improved, thereby the ability of opposing alkaline etching liquid is improved significantly.Especially it should be noted that, in special adhesive of the present invention, added after a kind of polyurethane that contains carboxyl, phtotpolymerizable dry film photoresist level of adhesion on Copper Foil after solidifying has further improvement, is reflected in the ability of opposing alkaline etching liquid has been had further and improved.
Embodiment 19
In the present invention, polyurethane is by formula preparation in table 12 below.
Potpourri gathers propylene diester, and segmented copolymer and two hydroxyl formic acid are heated to about 60 ℃, and logical nitrogen makes it dry in 12 hours, adds two (sulfuration) diacetic acid dioctyl ester catalyzer of 0.015% dioctyl tin, then adds the different hydrogen acid ether (hydrogen acid ester) of toluene two.This reaction mixing is put thing and under nitrogen protection, is heated to 75 ℃ to 80 ℃. and get and wave minute folding of making different hydrogen acid ether (hydrogen acid ester); it is 1.8% different hydrogen acid ether (hydrogen acid ester); then under air Polyester part, add 2-hydroxypropyl methyl acrylate; contain 0.1% butylated hydroxy-methylbenzene, stabilizing agent and 0.015% above-mentioned catalyzer.
Table 12
| Molecular weight | Quantity % | Mole | |
| Polypropylene glycol 1 | 195 | 29.28 | 0.0294 |
| One section of multipolymer of embedding 2 | 996 | 42.63 | 0.0428 |
| Two hydroxymethyl propionic acids | 67 | 2.37 | 0.0353 |
| Toluene diisocynate | 87.1 | 14.07 | 0.1615 |
| 2-hydroxypropyl methacrylate | 144 | 3.88 | 0.0269 |
1. weight average molecular weight 2000, poly G55-53, and olin chemical company produces
2. weight average molecular weight 2000, poly G20-56, and olin chemical company produces, and reacts preparation from oxirane with polypropylene glycol.
Embodiment 20
The present embodiment has shown the preparation process of the dry film of the photopolymerization component in the present invention, wherein that the polyurethane of use in embodiment 19 is as the using method of plastifier, this dry film is make with photoresist the interlayer in polyester support film and tygon coverlay and be rolled into tubular, this phtotpolymerizable component is with following part of preparation: 77 parts of acrylate polymerics (31% solid content), 13% ethyl propylene acid esters, 65% Methyl methyacrlate, 22% methacrylic acid, in solvent butanone, with AIBN (azoisobutyronitrile), make initiating agent, at 60 ℃-65 ℃, be polymerized.0.23 part of sticker (molecular weight 22000, partial hydrolysis, vinyl chloride/hexenoic acid ester copolymer of hydroxyl improvement, wherein vinyl chloride approximately 90%, vinyl acetate acid approximately 4%, 2.3% hydroxyl composition, title UCAR VAGD, is produced by UMION CARBIDE company).3% methoxylation bisphenol a dimethacrylate (title BPE500 is produced by SHIN-NAKAMURA CHEMIAD company).2.9 parts of urine amine macromolecules; 7 parts of trimethylolpropane triacrylates (being produced by Sartomer chemical company); 1.5 parts of dimethoxy benzene benzoylformaldoximes (production of Ciba-Geigy company); 1.5 parts of ethyl dimethylamine benzoic ethers of 0.3 part of isopropyl thioxanthone (production of ACETO chemical company) (production of ACETO chemical company); 0.6 part of pentabromo-monochloro cyclic ethylene (PCBH is produced by Japanese NISSEI chemical company); 0.6 part of ethoxylation ethylidene diamino (title QHADROL is produced by BASF AG); 0.02 part of butylation cresols, 0.4 part of itaconic acid; The toluene assorted luxuriant (title REOM ET42, Ciba-Geigy company produces) of 0.08 part of diethanolamine improvement; 0.05 part of dye solution one (2.44% BG, 6.72% Victoria blue, and 91.29% methyl alcohol); 0.4 part of dye solution two (5% BG, 95% methyl alcohol) and 0.2 part of leuco crystal violet.Above component is through fully mixing, and on the thick transparent mylar of 23.4um, is coated with.Thickness is about 38.1 microns.Then put into baking oven except desolventizing, the poly-component of this dried light is pressed on the polyethylene film of 25.4 micron thickness and rolls up on cylinder.
Claims (4)
1. the dry film photoresist that aqueous solution is developed, in its component, contain polymer binder, free radical light trigger, can addition polymerization monomer, plastifier and thermal polymerization inhibitor, it is characterized in that:
Described polymer binder be a kind of contain carboxyl can film forming bonding agent, by following polymerization of mixtures, obtained:
(a) the monomer H that molecular formula is following
2c=CRCOO ((C
nh
2n) X (C
ph2
p))
mr '
Wherein R is hydrogen or methyl, and R ' is selected from following groups: different norborny, bornyl, borneol thiazolinyl, different norbornene, norbornene, dicyclo undecyl, three cyclo-dodecyl, three ring eight alkyl, 2,3-dihydro norborny, X is oxygen or sulphur, and n is 2-4, and p is 0-4, and m is 2;
(b) have the monomer of a 3-15 carbon atom at least, this monomer has α, β-unsaturated link and include carboxyl or anhydride group;
(c) has a C at least
1-C
8alkyl acrylate;
(d) has a C at least
1-C
8alkylmethacrylate;
Described plastifier contains carboxyl polyurethane, and its molecular weight is 1000-100000, and free carboxyl group group is connected on main polymer chain, and at least contains a undersaturated terminal group of ethylene linkage.
2. by the dry film photoresist of a kind of aqueous solution development described in claim 1, it is characterized in that, polymer binder accounts for the 40-70% of dry film photoresist general assembly (TW), free radical light trigger accounts for 0.5-10%, can account for 5-40% by addition polymerization monomer, plastifier accounts for 0.2-10%, and thermal polymerization inhibitor accounts for 0.003%-0.04%.
3. by the dry film photoresist of a kind of aqueous solution development described in claim 1 or 2, it is characterized in that, polymer binder accounts for the 50-60% of dry film photoresist general assembly (TW), free radical light trigger accounts for 3-7%, can account for 15-35% by addition polymerization monomer, plastifier accounts for 0.5-2.0%, and thermal polymerization inhibitor accounts for 0.01%-0.02%.
4. by the dry film photoresist of a kind of aqueous solution development described in claim 1, described in it is characterized in that can addition polymerization monomer be to be selected from: glycol diacrylate, diethylene glycol diacrylate, glycerine diacrylate, glycerol tri-acrylate, 1, ammediol dimethylacrylate, 1, 2, 4-butantriol trimethyl acrylic ester, 1, 4-benzenediol diacrylate, 1, 4-cyclohexandiol diacrylate, pentaerythritol acrylate trimethyl, pentaerythritol tetramethylacrylate, tetraethylene glycol dimethacrylate, trimethylol-propane trimethacrylate, triethylene glycol diacrylate, tetraethylene glycol diacrylate, pentaerythritol triacrylate, tetramethylol methane tetraacrylate, 1, ammediol diacrylate, 1, 5-pentanediol dimethylacrylate.
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| KR101675822B1 (en) * | 2013-08-07 | 2016-11-15 | 코오롱인더스트리 주식회사 | Photosensitive Resin Composition for Dry Film Photoresist |
| CN108255014B (en) * | 2017-12-11 | 2019-07-02 | 珠海市能动科技光学产业有限公司 | A kind of dry film photoresist containing modified polyurethane and photo-curing monomer |
| CN110941141A (en) * | 2019-12-28 | 2020-03-31 | 珠海市能动科技光学产业有限公司 | Aqueous solution developing dry film photoresist |
| CN115639723A (en) * | 2022-11-15 | 2023-01-24 | 珠海市能动科技光学产业有限公司 | Photosensitive dry film photoresist for printed circuit board and preparation method thereof |
Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1245908A (en) * | 1998-05-29 | 2000-03-01 | 日合-莫顿株式会社 | Optical imageadable composite with improved flexibility |
| CN101105626A (en) * | 2006-07-10 | 2008-01-16 | 太阳油墨制造株式会社 | Light solidifying/heat solidifying resin composition, condensate of the same and printing circuit board |
| CN101458452A (en) * | 2007-12-14 | 2009-06-17 | Jsr株式会社 | X-ray sensitive resin composition, barrier body and protection film of liquid crystal display member and their forming methods |
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|---|---|---|---|---|
| US6852466B2 (en) * | 1998-12-23 | 2005-02-08 | Shipley Company, L.L.C. | Photoresist compositions particularly suitable for short wavelength imaging |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1245908A (en) * | 1998-05-29 | 2000-03-01 | 日合-莫顿株式会社 | Optical imageadable composite with improved flexibility |
| CN101105626A (en) * | 2006-07-10 | 2008-01-16 | 太阳油墨制造株式会社 | Light solidifying/heat solidifying resin composition, condensate of the same and printing circuit board |
| CN101458452A (en) * | 2007-12-14 | 2009-06-17 | Jsr株式会社 | X-ray sensitive resin composition, barrier body and protection film of liquid crystal display member and their forming methods |
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