CN1795418A - Photosensitive composition and process for production of printed wiring boards with the same - Google Patents
Photosensitive composition and process for production of printed wiring boards with the same Download PDFInfo
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- CN1795418A CN1795418A CNA2004800144680A CN200480014468A CN1795418A CN 1795418 A CN1795418 A CN 1795418A CN A2004800144680 A CNA2004800144680 A CN A2004800144680A CN 200480014468 A CN200480014468 A CN 200480014468A CN 1795418 A CN1795418 A CN 1795418A
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- G—PHYSICS
- G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
- G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
- G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
- G03F7/004—Photosensitive materials
- G03F7/027—Non-macromolecular photopolymerisable compounds having carbon-to-carbon double bonds, e.g. ethylenic compounds
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- G—PHYSICS
- G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
- G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
- G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
- G03F7/004—Photosensitive materials
- G03F7/027—Non-macromolecular photopolymerisable compounds having carbon-to-carbon double bonds, e.g. ethylenic compounds
- G03F7/032—Non-macromolecular photopolymerisable compounds having carbon-to-carbon double bonds, e.g. ethylenic compounds with binders
- G03F7/033—Non-macromolecular photopolymerisable compounds having carbon-to-carbon double bonds, e.g. ethylenic compounds with binders the binders being polymers obtained by reactions only involving carbon-to-carbon unsaturated bonds, e.g. vinyl polymers
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- G—PHYSICS
- G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
- G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
- G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
- G03F7/004—Photosensitive materials
- G03F7/038—Macromolecular compounds which are rendered insoluble or differentially wettable
Abstract
The invention relates to a photosensitive resin composition characterized by containing at least one resin which has photopolymerizable ethylenically unsaturated groups on the side chains and a photosensitive compound which has three or more ethylenically unsaturated groups and exhibits a viscosity of 2000mPa s or above at 25 DEG C under one atm; and a process for the production of wiring boards with the same.
Description
Technical field
The present invention relates to photosensitive polymer combination and use it to make the method for tellite.
Background technology
For can be easy and the reliability highland make printed circuit board (PCB) with trickle and highdensity conductive pattern, the photonasty resist liquid that has performances such as excellent resolution rate is in essence directly coated formed the etching resist layer on the metal conductor layer on insulated substrate surface, this etching resist layer is widely known by the people according to the infusion process (dip) that the resist pattern of appointment forms.This method is easy and owing to do not produce pin hole on formed etching resist layer, therefore, is requiring to make under several microns～20 microns the thick situation than film, and this method is an effective method.
But, by the formed etching resist layer of photonasty resist liquid that uses so far, particularly have three or ethene unsaturated group more than it and under the situation of viscosity under 25 ℃, 1 atmospheric pressure using as 2000mPas or the photosensitive compounds more than it, although the etching resist layer can not pasted each other, but exposure sensitivity is low, must use a large amount of light quantities.If need a large amount of light quantities, then exist the time shutter elongated, productivity is not good and be difficult to the problem of practicability.
Summary of the invention
In view of the above problems, the object of the present invention is to provide a kind of material that is used to form the etching resist layer, formed etching resist layer can not pasted each other, and exposure sensitivity is good.
The result that the inventor etc. have carried out further investigation has finished the present invention.
Promptly, first invention is a kind of photosensitive polymer combination, it is characterized by, contain the resin of at least a ethene unsaturated group that in molecule, has photopolymerization on the side chain and have three or the ethene unsaturated group more than it and the viscosity under 25 ℃, 1 atmospheric pressure is 2000mPas or the photosensitive compounds more than it.
Preferably, the ethene unsaturated group equivalent of the resin of the ethene unsaturated group that has photopolymerization in molecule on the side chain that contains in the above-mentioned photosensitive polymer combination is 100～1000g/eq.
In addition, consider from the alkali development angle, preferably, resin combination of the present invention and then contain the resin that can in alkaline aqueous solution, dissolve, the weight-average molecular weight of this resin is 5000～200,000, acid number is 20mg KOH/g～300mg KOH/g,
And then the solvent that contains in the above-mentioned photosensitive polymer combination is preferably 30 weight %～95 weight %.
Second invention is a kind of manufacture method of tellite, it is characterized by, after the substrate that will be formed with metal conductor layer on the insulated substrate surface impregnated in the aforesaid photosensitive polymer combination, from photosensitive polymer combination, mention substrate, photosensitive resin coating composition on substrate surface exposes, develops by photomask thus, behind the etching resist layer of formation resist pattern, substrate is imposed etch processes, thereby make metal conductor layer form the conductive pattern of appointment.
Feature of the present invention is to contain that viscosity is 2000mPas or the photosensitive compounds molecule more than it under 25 ℃, 1 atmospheric pressure, and at least a resin that on side chain, has the ethene unsaturated group of photopolymerization, can form etching resist layer inviscid and that exposure sensitivity is good.
Embodiment
Below, be described in detail at the present invention.
Photosensitive polymer combination of the present invention be have on the side chain that contains in molecule photopolymerization the ethene unsaturated group resin and have three or the ethene unsaturated group more than it and the viscosity under 25 ℃, 1 atmospheric pressure is the photosensitive polymer combination of 2000mPas or above photosensitive compounds.Preferably, further contain the resin that is dissolvable in water alkaline aqueous solution, and the photosensitive polymer combination of Photoepolymerizationinitiater initiater and solvent.
As the resin that is dissolvable in water alkaline aqueous solution, can enumerate the maleic anhydride multipolymer of styrene maleic resin etc.; Or the co-polymer of the ethylene unsaturated monomer with carboxyl of the ester compounds with ethene unsaturated group of (methyl) methyl acrylate, (methyl) ethyl acrylate, (methyl) propyl acrylate etc. and (methyl) acrylic acid etc.; The ethylene unsaturated monomer of the no carboxyl of styrene etc., the co-polymer of the ethylene unsaturated monomer with carboxyl of the ester compounds with ethene unsaturated group of (methyl) methyl acrylate, (methyl) ethyl acrylate, (methyl) propyl acrylate etc. and (methyl) acrylic acid etc. etc.These co-polymer resins can be used alone or as a mixture.
Be dissolvable in water the weight-average molecular weight of the resin of alkaline aqueous solution, it is suitable being generally 5000～200,000, is preferably 10,000～100,000.Weight-average molecular weight is less than under 5000 the situation, anti-development as the weak alkaline aqueous solution of the aqueous sodium carbonate of developer solution or sodium silicate aqueous solution etc. is relatively poor, in order to utilize developer solution to make sustainable the carrying out of dissolving of exposure portion, need make wiring (circuit) thin to more than a certain degree, according to the situation difference, have because of developer solution is regardless of exposure portion and unexposed portion and they are all dissolved peel off, and cause the situation of difficult that becomes of describing of resist pattern.On the other hand, if weight-average molecular weight surpasses 200,000, then as the weak alkaline aqueous solution of developer solution to the dissolving of the unexposed portion difficulty that becomes, the situation that has or not method to develop.And, if weight-average molecular weight surpasses 200,000, then peel off in the operation of resist of exposure portion with strong alkaline aqueous solutions such as sodium hydrate aqueous solutions after etching, peeling off of resist film can be very slow, has the situation that can't use the stripper wire (stripper line) that in the past often used.
In addition, these are dissolvable in water the acid number of the resin of alkaline aqueous solution, are suitable in 20～300mgKOH/g scope usually, are preferred in 50～200mgKOH/g scope.Under the situation of acid number, adopt as the weak alkaline aqueous solution of the aqueous sodium carbonate of developer solution or sodium silicate aqueous solution etc. the dissolving of the unexposed portion difficulty that becomes less than 20mg KOH/g.In addition, in stripping process, have peeling off of the resist film situation very slowly that becomes.On the other hand, if acid number surpasses 300mg KOH/g, then identical with the low situation of above-mentioned weight-average molecular weight, the anti-development of weak alkaline aqueous solution is relatively poor, in order to utilize developer solution to make sustainable the carrying out of dissolving of exposure portion, need make wiring (circuit) thin to a certain degree or more than it, according to the situation difference, have because of developer solution is regardless of exposure portion and unexposed portion and they are all dissolved peel off, cause the situation of difficult that becomes of describing of resist pattern.The mensuration of acid number for example can be with the sample of the KOH absolute methanol titration unit weight of 0.1N, and uses indicator such as phenolphthalein to measure.
Be dissolvable in water the resin of the ethene unsaturated group of no photopolymerization in the molecule of alkaline aqueous solution, in the solid constituent of composition, preferably contain 10～80 weight %, more preferably contain 20～60 weight %.
As the resin that on side chain, has the ethene unsaturated group, can enumerate the resin that the ethene unsaturated monocarboxylic of epoxy resin addition (methyl) acrylic acid of linear phenol aldehyde type epoxy resin of bisphenol A type epoxy resin, bisphenol f type epoxy resin, phenol or the linear phenol aldehyde type epoxy resin of cresols etc. etc. and unsaturated multi-anhydride are obtained; Resin that maleic anhydride multipolymer addition hydroxyethyl (methyl) acrylate or glycidyl (methyl) acrylate of styrene maleic resin etc. formed etc.Perhaps, can enumerate, the co-polymer addition of the ethylene unsaturated monomer with carboxyl of the ester compounds with ethene unsaturated group of (methyl) methyl acrylate, (methyl) ethyl acrylate, (methyl) propyl acrylate etc. and (methyl) acrylic acid etc. is had hydroxyl hydroxyethyl (methyl) acrylate etc., have hydroxyl and have the compound of ethene unsaturated group and the multipolymer that obtains; To copolymer resin addition hydroxyethyl (methyl) acrylate of the ester compounds with ethene unsaturated group of (methyl) methyl acrylate, (methyl) ethyl acrylate, (methyl) propyl acrylate etc. and glycidyl acrylate or have the co-polymer that the compound of carboxyl obtains with ethene unsaturated group; Or (methyl) acrylic acid etc. had the ethylene unsaturated monomer of carboxyl, the ester compounds with ethene unsaturated group of (methyl) methyl acrylate, (methyl) ethyl acrylate, (methyl) propyl acrylate etc. and copolymer resin addition hydroxyethyl (methyl) acrylate of glycidyl acrylate or have co-polymer that the compound of carboxyl obtains etc. with ethene unsaturated group.
Maybe can enumerate, co-polymer addition glycidyl (methyl) acrylate with carboxyl etc. be contained resin that the ethylene unsaturated monomer of glycidyl forms etc.These resins and co-polymer can be used alone or as a mixture.
The ethene unsaturated group equivalent that has the resin of ethene unsaturated group on the side chain is to be good with 100～1000g/eq.If ethene unsaturated group equivalent greater than 1000g/eq, has the situation that exposure sensitivity can't improve.Be more preferred from 200～700g/eq.
Ethene unsaturated group equivalent is the use amount of the resin of 100～1000g/eq, preferably contains 5～60 weight % in the solid constituent of composition, more preferably contains 10～50 weight %.
In addition, the photosensitive compounds that is used for photosensitive polymer combination of the present invention has following character: cause reactions such as crosslinked, polymerization or dimerization by exposure, form the etching resist insoluble to developer solution by the dry overlay film by the formed photosensitive polymer combination of photosensitive polymer combination is exposed.The viscosity of the major component of photosensitive compounds is under 1 atmospheric pressure, 25 ℃, during less than 2000mPas, if the etching resist layer of made is overlapped each other and apply weight, then photosensitive compounds can move to film coated surface, and the etching resist layer is bondd each other.The viscosity of the major component of photosensitive compounds is preferably 2000mPas or more than it, and more preferably 4000mPas or more than it also can be solid forms.
As preferable photosensitive compounds with three or its above ethene unsaturated group, can enumerate triallyl isocyanuric acid ester, cyamelide EO modification triacrylate, multi-functional urethanes adduct, multifunctional polyester acrylate, pentaerythrite four (methyl) acrylate, dipentaerythritol five (methyl) acrylate, dipentaerythritol six (methyl) acrylate etc.
The ethene unsaturated group is two or its following photosensitive compounds, because of the worry that exposure sensitivity is reduced is arranged, so not preferred.
When using viscosity under 25 ℃, 1 atmospheric pressure less than the photosensitive compounds of 2000mPas, the use total amount of photosensitive compounds is preferably 30 weight % or below it, more preferably 20 weight % or below it.As above-mentioned compound with ethene unsaturated group; unsaturated compound with an ethene unsaturated compound; can enumerate for example 2-hydroxyethyl (methyl) acrylate; 2-hydroxypropyl (methyl) acrylate; 4-hydroxybutyl (methyl) acrylate; the N-vinyl pyrrolidone; (methyl) acryloyl morpholine; methoxyl TEG (methyl) acrylate; methoxy poly (ethylene glycol) (methyl) acrylate; N; N-dimethyl (methyl) acrylamide; N-methylol (methyl) acrylamide; N; N-dimethyl amido propyl group (methyl) acrylamide; N; N-dimethyl amido ethyl (methyl) acrylate; N, N-dimethyl amido propyl group (methyl) acrylate; phenoxy group ethyl (methyl) acrylate; cyclohexyl (methyl) acrylate; isobornyl (イ ソ ボ ニ Le) acrylate etc.In addition, as unsaturated compound with two ethene unsaturated compounds, can enumerate EO addition product two (methyl) acrylate of diethylene glycol two (methyl) acrylate, triethylene glycol two (methyl) acrylate, tripropylene glycol two (methyl) acrylate, trimethylolpropane two (methyl) acrylate, bisphenol-A etc.As unsaturated compound with three ethene unsaturated compounds, can enumerate, trimethylolpropane tris (methyl) acrylate, trimethylolpropane PO modification three (methyl) acrylate, trimethylolpropane EO modification three (methyl) acrylate, pentaerythritol triacrylate etc., can with these with have three or ethene unsaturated group more than it and under 25 ℃, 1 atmospheric pressure viscosity be that 2000mPas or the photosensitive compounds more than it are used in combination.
With respect to photosensitive polymer combination of the present invention, the ratio of photosensitive compounds is preferably 5～60 weight % in the solid state component of said composition, more preferably 7～50 weight %.During less than 5 weight %, the sclerosis during exposure is insufficient, and the tendency of dissolving is arranged when developing.If surpass 60 weight %, can cause bonding during then overlapping resist film.
The solid component concentration of photosensitive polymer combination of the present invention is preferably less than 70 weight %.If more than or equal to 70 weight %, then the viscosity of photonasty resist liquid uprises, and can can't form uniform etching resist layer, and the sclerosis during less than 5 weight % during because of exposure is insufficient, and the situation of dissolving is arranged when developing.Be preferably 7～50 weight %.
As being used in organic solvent composition of the present invention, can enumerate as, straight chain, side chain, secondary or the polynary alcohols of methyl alcohol, ethanol, propyl alcohol, isopropyl alcohol, 2-butanols, hexanol, ethylene glycol etc.; The ketone of acetone, methyl ethyl ketone, cyclohexanone, isophorone etc.; Toluene, dimethylbenzene etc. aromatic hydrocarbon based; The cellosolve class of cellosolve, butyl cellosolve etc.; Reach the carbitol class of carbitol, butyl carbitol etc.; The propylene glycol alkyl ethers of methyl proxitol class etc.; The polypropylene glycol alkyl ether of dipropylene glycol methyl ether etc.; The acetates of ethyl acetate, butyl acetate, cellosolve acetate, butyl cellosolve acetate, butyl carbitol acetate, propylene glycol monomethyl ether acetate etc.; The lactic acid ester of ethyl lactate, butyl lactate etc.; Propionic acid ester, pyruvate class, ethoxy-c acid esters class and dioxane glycol ethers etc., and normal hexane, cyclohexane, tetrahydrofuran etc. can make up them multiple the use.
As Photoepolymerizationinitiater initiater,, all can use as long as the active ray by ultraviolet ray, visible light etc. shines the initiating agent that the polymerization that can make unsaturated compound begins.Can enumerate diphenyl ketone as benzophenone, Michler's keton (Michler ' s ketone) etc.; The benzoin alkylether class of benzoin, benzoin isobutyl ether etc.; 2,2-dimethoxy-2-phenyl acetophenone, 2,2-diethoxy acetophenone, 2, the acetophenones of 2-ring-4-metaphenoxy acetophenone etc.; The phenylpropyl alcohol ketone of 2-hydroxy-2-methyl propiophenone, 4-isopropyl-2-hydroxy-2-methyl propiophenone etc.; The anthraquinone class of 2-EAQ, 2-tert-butyl group anthraquinone etc.; The thioxanthene ketone of diethyl thioxanthone, diisopropyl thioxanthones, chlorination thioxanthones etc.; And other benzil, 1-hydroxy-cyclohexyl phenyl ketone, 2-methyl-[4-(methyl sulfenyl) phenyl]-2-morpholinyl (モ Le Off オ リ ノ)-propane-1-ketone, to the dimethyl amido ethyl benzoate, to dimethyl amido isoamyl benzoate etc.These Photoepolymerizationinitiater initiaters can be used alone or as a mixture.With respect to photosensitive polymer combination of the present invention, the ratio of Photoepolymerizationinitiater initiater accounts for 0.2～20 weight % in the solid state component of said composition be good, and 1～10 weight % is for better.
In addition, in the photosensitive resin composition of the present invention, can further optionally add dye leveller, defoamer, shake change agent (thixotropic agent), colour former, dyestuff, pigment, inorganic filler, organic filler etc.
Be coated with the etching resist layer that photonasty resist liquid of the present invention forms by impregnation method, in developing procedure and etch processes operation, the intensity of the contact in order fully to keep and the injection of developer solution or etching solution to conveyance, the thickness of the resist layer of base plan portion is at 3 μ m or suit more than it, can be tough especially when 5 μ m or its are above thereby become the resist layer of elching resistant excellence.In addition, in order to realize extra high resolution and etching precision, the thickness of resist layer is 30 μ m in base plan portion or suits below it, is 20 μ m or preferred especially below it.
Photosensitive polymer combination of the present invention, can be to be formed with on the substrate of metal conductor layer on the surface of general hard (rigidity) circuit board and flexible circuit board, metal substrate etc., form film and photonasty resist film uniformly by rolling method or infusion process.Resin combination of the present invention is particularly suitable for forming the photonasty resist film with infusion process.Usually, by the substrate conductor surface is handled with acid such as sulfuric acid, or use abrasive metal surface such as brush and with behind the cleaning surfaces, on the conductor layer of substrate, be coated with photosensitive polymer combination of the present invention with rolling method or infusion process, follow dry solvent, forming thickness is 3～20 μ m, the film of preferred 8～15 μ m and uniform photonasty resist film, then, the circuit pattern of appointment being exposed with ultraviolet ray or visible light by photomask makes it to solidify, and removes unexposed portion with dissolving in the weak alkaline aqueous solutions such as aqueous sodium carbonate about 0.5～3.0 weight %.Then, after the conductor layer that will expose is removed by etch processes, the photonasty resist film that has solidified on the conductor layer surface that the left behind strong alkaline aqueous solutions such as sodium hydrate aqueous solution about with 1.0～5.0 weight % are peeled off removal, thereby obtain the object conductor circuit.
If use photosensitive polymer combination of the present invention, then the etching resist layer of Zhi Zuoing can not bond each other and exposure sensitivity good, can form the superior etching resist layer of anti-development fluidity, corrosion liquid resistance, fissility of exposure portion.
Embodiment
The present invention is described in detail in detail by the following examples.If be not particularly limited, then part is represented the meaning of weight portion.
Measure and appraisal procedure
Molecular resin amount: measure with GPC, try to achieve weight-average molecular weight.
Resinous acid value: with the KOH absolute methanol solution titration 1g sample of 0.1N, use indicator such as phenolphthalein to measure, show with the milligram numerical table of KOH.
Quantity of solvent: the solvent in the photosensitive polymer combination solution is represented with weight %.
Thickness: use the simple and easy film thickness gauge of eddy current type (イ ソ ス コ one プ MP30; Off イ Star シ ヤ one イ Application ス ト Le メ Application Star corporate system) measures.
Development: use 30 ℃, the aqueous sodium carbonate of 1.0 weight %, under the pressure of 0.18pa, carry out 60 seconds spray development, unexposed portion is carried out following judgement.
Zero is the situation of no residue, * for the situation of residue is arranged.
Exposure sensitivity: expose with two-sided while exposure machine HMW-532D ((strain) オ one Network is made made) by photoresist, ultraviolet ray with integration light quantity 100mJ exposes, then with the aqueous sodium carbonate of 30 ℃ 1.0 weight %, press in spraying to be 2kg/cm
2Condition under, after carrying out spraying in 60 seconds, confirm the rank hop count (the remaining hop counts of filming that ス ト one Off ア is one 21 sections) of filming this moment.
Susceptibility be 2 sections or its following table be shown *; 3～4 segment tables are shown zero, 5 section or be expressed as ◎ more than it.
Cohesiveness: coated substrates is cut into square 10cm * 10cm, and overlapping coated surface applies 20g/cm
2Weight placed one day, will not have bonding person and be expressed as ◎, have bonding person to be expressed as zero slightly, produce a large amount of bonding persons to be expressed as *.
Coating: substrate is immersed in when mentioning in the photonasty resist liquid, and the thickness of film coated surface does not have inhomogeneous person and is expressed as zero, thickness have inhomogeneous person be expressed as *.
Resin solution A's is synthetic
16.9 parts of 55.0 parts of methyl methacrylates, 10.0 parts of 2-hydroxyethylmethacry,ate, 18.1 parts of n-butyl acrylates and methacrylic acids are dissolved in 150.0 parts of the methyl ethyl ketones, in nitrogen atmosphere, stirring, using polymerization initiator to carry out polymerization under the counterflow condition, obtain with the polystyrene conversion weight-average molecular weight be 28000, acid number is that 110mg KOH/g, solid component concentration are the resin solution A of 40.0 weight %.
Resin solution B's is synthetic
20.0 parts of 55.0 parts of methyl methacrylates, 10.0 parts of 2-ethylhexyl acrylate, 15.0 parts of benzyl methacrylates and methacrylic acids are dissolved in 15.0 parts of the methyl ethyl ketones, in nitrogen atmosphere, stirring, using polymerization initiator to carry out polymerization under the counterflow condition, obtain with the polystyrene conversion weight-average molecular weight be 63000, acid number is that 130mg KOH/g, solid component concentration are the resin solution B of 40.0 weight %.
Resin solution C's is synthetic
With the dissolving in 150.0 parts of methyl ethyl ketones of 23.0 parts of 58.0 parts of methyl methacrylates, 9.0 parts of 2-ethylhexyl acrylate, 10.0 parts of benzyl methacrylates and methacrylic acids, in nitrogen atmosphere, stirring, using polymerization initiator to carry out polymerization under the counterflow condition, obtain with the polystyrene conversion weight-average molecular weight be 107000, acid number is that 150mg KOH/g, solid component concentration are the resin solution C of 40.0 weight %.
The modulation of photonasty resist stoste E
With resin solution A30.0 part, 3.0 parts of cyamelide EO modification triacrylates (solid/25 ℃), 4.0 parts of dipentaerythritol acrylates (viscosity: 4200mPas/25 ℃), resin (the molecular weight: 15000 that has the ethene unsaturated group on the side chain, unsaturated group equivalent: 350 (g/eq), solid state component: 60 weight %) 10 parts, 1.5 parts of 2-methyl-[4-(methyl sulfenyl) phenyl]-2-morpholinyl-propane-1-ketone, 0.5 part of diethyl thioxanthone and UV-Blue 236 (Mitsui Chemicals corporate system) mix for 0.1 part, and being modulated into solid component concentration is the photonasty resist stoste E of 55.2 weight %.
The modulation of photonasty resist stoste F
With resin solution B30.0 part, 4.0 parts of dipentaerythritol acrylates (viscosity: 4200mPas/25 ℃), 3.0 parts of tetramethylol methane tetraacrylates (solid/25 ℃), compound (the molecular weight: 15000 that has the ethene unsaturated group on the side chain, ethene unsaturated group equivalent: 350 (g/eq), solid state component: 60 weight %) 10 parts, 1.5 parts of 2-methyl-[4-(methyl sulfenyl) phenyl]-2-morpholinyl-propane-1-ketone, 0.5 part of diethyl thioxanthone and UV-Blue 236 (Mitsui Chemicals corporate system) mix for 0.1 part, and being modulated into solid component concentration is the photonasty resist stoste F of 55.2 weight %.
The modulation of photonasty resist stoste G
With resin solution C30.0 part, 3.0 parts of dipentaerythritol acrylates (viscosity: 4200mPas/25 ℃), 4.0 parts of tetramethylol methane tetraacrylates (solid/25 ℃), compound (the molecular weight: 15000 that has the ethene unsaturated group on the side chain, ethene unsaturated group equivalent: 450 (g/eq), solid state component: 60 weight %) 10 parts, 1.5 parts of 2-methyl-[4-(methyl sulfenyl) phenyl]-2-morpholinyl-propane-1-ketone, 0.5 part of diethyl thioxanthone and UV-Blue 236 (Mitsui Chemicals corporate system) mix for 0.1 part, and being modulated into solid component concentration is the photonasty resist stoste G of 55.2 weight %.
The modulation of photonasty resist stoste H
40.0 parts of resin solution B, dipentaerythritol acrylate 7.0 parts of (viscosity: 4200mPas/25 ℃), 2-methyl-[4-(methyl sulfenyl) phenyl]-2-morpholinyl-propane-1.5 parts of 1-ketone, 0.5 part of diethyl thioxanthone and UV-Blue 236 (Mitsui Chemicals corporate system) are mixed for 0.1 part, and being modulated into solid component concentration is the photonasty resist stoste H of 51.1 weight %.
The modulation of photonasty resist stoste I
Compound (the molecular weight: 15000 of ethene unsaturated group will be had on 30.0 parts of resin solution B, trimethylolpropane triacrylate 7.0 parts (viscosity: 65mPas/25 ℃), the side chain, ethene unsaturated group equivalent: 350 (g/eq), solid state component: 60 weight %) 10 parts, 2-methyl-[4-(methyl sulfenyl) phenyl]-2-morpholinyl-propane-1.5 parts of 1-ketone, 0.5 part of diethyl thioxanthone and UV-Blue 236 (Mitsui Chemicals corporate system) mix for 0.1 part, and being modulated into solid component concentration is the photonasty resist stoste I of 55.2 weight %.
The modulation of photonasty resist stoste Z
Compound (the ethene unsaturated group equivalent: 10 parts of 86 (g/eq) of ethene unsaturated group will be had on 5.0 parts of 30.0 parts of resin solution A, dipentaerythritol acrylate 2.0 parts (viscosity: 4500mPas/25 ℃), tetramethylol methane tetraacrylates (solid/25 ℃), the side chain, 2-methyl-[4-(methyl sulfenyl) phenyl]-2-morpholinyl-propane-1.5 parts of 1-ketone, 0.5 part of diethyl thioxanthone and UV-Blue 236 (Mitsui Chemicals corporate system) mix for 0.1 part, and being modulated into solid component concentration is the photonasty resist stoste Z of 63.3 weight %.
The modulation of photonasty resist stoste AA
Compound (the ethene unsaturated group equivalent: 10 parts of 1260 (g/eq) of ethene unsaturated group will be had on 2.0 parts of resin solution B30.0 part, dipentaerythritol acrylate 5.0 parts (viscosity: 4500mPas/25 ℃), tetramethylol methane tetraacrylates (solid/25 ℃), the side chain, 2-methyl-[4-(methyl sulfenyl) phenyl]-2-morpholinyl-propane-1.5 parts of 1-ketone, 0.5 part of diethyl thioxanthone and UV-Blue 236 (Mitsui Chemicals corporate system) mix for 0.1 part, and being modulated into solid component concentration is the photonasty resist stoste AA of 55.2 weight %.
Embodiment 1
The modulation of photonasty resist liquid K
35.0 parts of MEK (methyl ethyl ketone) and propylene glycol monomethyl ether acetate are sneaked among the photonasty resist stoste E for 15.9 parts, stir and be modulated into photonasty resist liquid K.
Embodiment 2
The modulation of photonasty resist liquid L
Direct usability photosensitiveness resist stoste E.
Embodiment 3
The modulation of photonasty resist liquid M
35.0 parts of MEK and propylene glycol monomethyl ether acetate are sneaked among the photonasty resist stoste F for 15.9 parts, stir and be modulated into photonasty resist liquid M.
Embodiment 4
The modulation of photonasty resist liquid N
Direct usability photosensitiveness resist stoste F.
Embodiment 5
The modulation of photonasty resist liquid O
35.0 parts of MEK and propylene glycol monomethyl ether acetate are sneaked among the photonasty resist stoste G for 15.9 parts, stir and be modulated into photonasty resist liquid O.
Embodiment 6
The modulation of photonasty resist liquid P
Direct usability photosensitiveness resist stoste G.
Comparative example 1
The modulation of photonasty resist liquid Q
35.0 parts of MEK and propylene glycol monomethyl ether acetate are sneaked among the photonasty resist stoste H for 15.9 parts, stir and be modulated into photonasty resist liquid Q.
Comparative example 2
The modulation of photonasty resist liquid R
35.0 parts of MEK and propylene glycol monomethyl ether acetate are sneaked among the photonasty resist stoste I for 15.9 parts, stir and be modulated into photonasty resist liquid R.
Embodiment 7
The modulation of photonasty resist liquid AE
46.2 parts of MEK and propylene glycol monomethyl ether acetate are sneaked among the photonasty resist stoste Z for 19.8 parts, stir and be modulated into photonasty resist liquid AE.
Embodiment 8
The modulation of photonasty resist liquid AF
35.0 parts of MEK and propylene glycol monomethyl ether acetate are sneaked among the photonasty resist stoste AA for 15.9 parts, stir and be modulated into photonasty resist liquid AF.
Comparative example 3
The modulation of photonasty resist liquid AG
Change 3.0 parts of the cyamelide EO modification triacrylates among the photonasty resist stoste F (solid/25 ℃) into polyethyleneglycol diacrylate (50mPas/25 ℃) 3.0 parts of addings, further 35.0 parts of MEK and propylene glycol monomethyl ether acetate are sneaked into for 15.9 parts, stir and be modulated into photonasty resist liquid AG.
The manufacture method of tellite
Prepare glass epoxide double-sided copper-clad laminate plate (thickness of slab 0.2mm, the thick 18 μ m of copper, the printed circuit substrate of substrate size 370mm * 260mm).
Then, in stainless container, store photonasty resist liquid and stoste (G), make dipping bath.Then, will be as the printed circuit substrate of above-mentioned preparation, with direction perpendicular to liquid level, flood with the speed that 50cm/ divides, flood so that the substrate upper end exceeds the state of liquid level 1cm, dipping is in case after finishing, just thereby the pulling speed of dividing with 50cm/ rises to liquid level top coating photonasty resist liquid with whole substrates, and with heated air drier 80 ℃ dry 10 minutes down, then, be cooled to room temperature.
Use two masks of describing to form the figure of conductive pattern, so that the orthogonal mode of wiring pattern direction of each mask, make mask near the substrate two sides, expose with two-sided while exposure machine HMW-532D ((strain) オ one Network is made institute) by photoresist, ultraviolet ray with integration light quantity 100～500mJ exposes, afterwards, use 2kg/cm
2Atomisation pressure aqueous sodium carbonate, the development of spraying 30 ℃ 1.0 weight %, form the etching resist layer of the resist pattern of appointment.
Then, use 40 ℃ cupric chloride etching solution, the etching of copper exposed portions serve is removed, after the washing, use 2kg/cm
2Atomisation pressure spray the sodium hydrate aqueous solution of 40 ℃ 3.0 weight %, remove the etching resist layer, form the metal conductor layer of conductive pattern, be made into tellite.
The test findings of the tellite that obtains in the manner described above is shown in table 1.
(utilizing on the industry possibility)
Because can form the etching resist layer that nothing bonds, exposure sensitivity is good according to the present invention, therefore, the present invention is very important invention on industry.
Table 1
| Resin solution | Alkali dissolution molecular resin amount | Alkali dissolution resinous acid value mgKOH/g | Resist liquid stoste | Ethene unsaturated group equivalent (g/eq) | Quantity of solvent (%) | Photosensitive compounds viscosity (mPas/25 ℃) | Development | Exposure sensitivity | Cohesiveness | Coating | Thickness (μ m) | |
| Embodiment 1 | A | 28000 | 110 | E | 350 | 73 | Solid 4200 | ○ | ◎ | ◎ | ○ | 9 |
| Embodiment 2 | A | 28000 | 110 | E | 350 | 45 | Solid 4200 | ○ | ◎ | ◎ | ○ | 10 |
| Embodiment 3 | B | 63000 | 130 | F | 350 | 73 | Solid 4200 | ○ | ◎ | ◎ | ○ | 10 |
| Embodiment 4 | B | 63000 | 130 | F | 350 | 45 | Solid 4200 | ○ | ◎ | ◎ | ○ | 11 |
| Embodiment 5 | C | 107000 | 150 | G | 450 | 73 | Solid 4200 | ○ | ◎ | ◎ | ○ | 10 |
| Embodiment 6 | C | 107000 | 150 | G | 450 | 45 | Solid 4200 | ○ | ◎ | ◎ | ○ | 9 |
| Embodiment 7 | A | 28000 | 110 | Z | 86 | 73 | Solid 4200 | ○ | ◎ | ○ | ○ | 10 |
| Embodiment 8 | B | 63000 | 130 | AA | 1260 | 73 | Solid 4200 | ○ | ○ | ◎ | ○ | 9 |
| Comparative example 1 | B | 63000 | 130 | H | - | 75 | 4200 | ○ | × | ◎ | ○ | 9 |
| Comparative example 2 | B | 63000 | 130 | I | 350 | 73 | 65 | ○ | ◎ | × | ○ | 10 |
| Comparative example 3 | B | 63000 | 130 | - | 350 | 73 | 50 | ○ | × | × | ○ | 10 |
Claims (4)
1. photosensitive polymer combination, it is characterized by, contain at least a resin and the photosensitive compounds that has the ethene unsaturated group of photopolymerization in molecule on the side chain, it is 2000mPas or more than it that this photosensitive compounds has the above ethene unsaturated group of three or its and the viscosity under 25 ℃, 1 atmospheric pressure.
2. photosensitive polymer combination as claimed in claim 1, it is characterized by, the ethene unsaturated group equivalent in the resin of the ethene unsaturated group that has photopolymerization in molecule on the side chain that described photosensitive polymer combination contains is 100～1000g/eq.
3. photosensitive polymer combination as claimed in claim 1 is characterized by, and the solvent that contains in described photosensitive polymer combination is 30 weight %～95 weight %.
4. the manufacture method of a tellite, it is characterized by, impregnated in claim 1 or the 2 described photosensitive polymer combinations by the substrate that will on the insulated substrate surface, be formed with metal conductor layer, from photosensitive polymer combination, mention substrate, thereby photosensitive resin coating composition on substrate surface, expose, develop by photomask, form the etching resist layer of the resist pattern of appointment, afterwards, by substrate is implemented etch processes, make metal conductor layer form the conductive pattern of appointment.
Applications Claiming Priority (3)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2003177411 | 2003-06-23 | ||
| JP177411/2003 | 2003-06-23 | ||
| PCT/JP2004/008852 WO2004114021A1 (en) | 2003-06-23 | 2004-06-17 | Photosensitive composition and process for production of printed wiring boards with the same |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN1795418A true CN1795418A (en) | 2006-06-28 |
| CN100595672C CN100595672C (en) | 2010-03-24 |
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| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN200480014468A Expired - Fee Related CN100595672C (en) | 2003-06-23 | 2004-06-17 | Photosensitive resin composition and process for production of printed wiring boards with the same |
Country Status (5)
| Country | Link |
|---|---|
| JP (1) | JPWO2004114021A1 (en) |
| KR (3) | KR100903465B1 (en) |
| CN (1) | CN100595672C (en) |
| TW (1) | TWI298731B (en) |
| WO (1) | WO2004114021A1 (en) |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105331928A (en) * | 2012-01-12 | 2016-02-17 | 大日本印刷株式会社 | Vapor deposition mask and method for producing organic semiconductor element |
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| KR100826148B1 (en) * | 2006-12-29 | 2008-04-30 | 박행임 | Face care |
Family Cites Families (15)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS6485655A (en) * | 1987-09-28 | 1989-03-30 | Ishikawajima Harima Heavy Ind | Sterilizing and washing apparatus |
| JPH05179462A (en) * | 1991-12-27 | 1993-07-20 | Sharp Corp | Resist applying method |
| JPH05327181A (en) * | 1992-05-19 | 1993-12-10 | Dainippon Toryo Co Ltd | Manufacture of printed circuit board |
| JPH075687A (en) * | 1993-06-18 | 1995-01-10 | Mitsui Toatsu Chem Inc | Liquid etching resist and copper-plated laminate board coated with etching resist film |
| JPH0777800A (en) * | 1993-09-09 | 1995-03-20 | Ajinomoto Co Inc | Photosensitive resin composition |
| JP2819279B2 (en) * | 1996-09-13 | 1998-10-30 | 東京化工機株式会社 | Photosensitive resist coating method and coating apparatus |
| JP3652053B2 (en) * | 1997-03-07 | 2005-05-25 | サツマ通信工業株式会社 | Method for forming thin film on substrate for electronic circuit |
| JPH1172914A (en) * | 1997-08-27 | 1999-03-16 | Toagosei Co Ltd | Photo-polymerizable resin composition |
| JP2000187322A (en) * | 1998-10-15 | 2000-07-04 | Mitsubishi Chemicals Corp | Photosensitive composition, image forming material and image forming method using same |
| JP2000155416A (en) * | 1998-11-19 | 2000-06-06 | Mitsui Chemicals Inc | Photosensitive liquid composition and its use |
| JP2000330278A (en) * | 1999-05-25 | 2000-11-30 | Taiyo Ink Mfg Ltd | Photosensitive resin composition |
| JP3880252B2 (en) * | 1999-08-09 | 2007-02-14 | 東洋インキ製造株式会社 | Photosensitive coloring composition for color filter and color filter using the same |
| JP2002107926A (en) * | 2000-09-29 | 2002-04-10 | Taiyo Ink Mfg Ltd | Photosensitive resin composition |
| JP2002241440A (en) * | 2001-02-19 | 2002-08-28 | Toppan Printing Co Ltd | Alkaline soluble polymer and photosensitive resin composition |
| JP2002251007A (en) * | 2001-02-23 | 2002-09-06 | Toppan Printing Co Ltd | Photosensitive resin composition |
-
2004
- 2004-06-17 JP JP2005507276A patent/JPWO2004114021A1/en active Pending
- 2004-06-17 CN CN200480014468A patent/CN100595672C/en not_active Expired - Fee Related
- 2004-06-17 KR KR1020077014404A patent/KR100903465B1/en not_active IP Right Cessation
- 2004-06-17 WO PCT/JP2004/008852 patent/WO2004114021A1/en active Application Filing
- 2004-06-17 KR KR1020087007767A patent/KR20080035022A/en not_active Application Discontinuation
- 2004-06-17 KR KR1020057020889A patent/KR20060006831A/en active Search and Examination
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Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105331928A (en) * | 2012-01-12 | 2016-02-17 | 大日本印刷株式会社 | Vapor deposition mask and method for producing organic semiconductor element |
Also Published As
| Publication number | Publication date |
|---|---|
| KR100903465B1 (en) | 2009-06-18 |
| TW200504136A (en) | 2005-02-01 |
| KR20060006831A (en) | 2006-01-19 |
| CN100595672C (en) | 2010-03-24 |
| TWI298731B (en) | 2008-07-11 |
| KR20080035022A (en) | 2008-04-22 |
| WO2004114021A1 (en) | 2004-12-29 |
| JPWO2004114021A1 (en) | 2006-08-03 |
| KR20070086618A (en) | 2007-08-27 |
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